Sunteți pe pagina 1din 114

Oil Refining

Contents

1 Oil refinery 1
1.1 Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Major products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Common process units found in a refinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3.1 Flow diagram of typical refinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3.2 The crude oil distillation unit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Specialty end products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.5 Siting/locating of petroleum refineries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.6 Safety and environmental concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.7 Corrosion problems and prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.8 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.8.1 Oil refining in the United States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.11 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

2 Continuous distillation 9
2.1 Industrial application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3 Design and operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.1 Column feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.2 Improving separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.3 Overhead system arrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4.1 Continuous distillation of crude oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

3 Vacuum distillation 15
3.1 Laboratory-scale applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.1.1 Rotary evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.1.2 Distillation of high-boiling and/or air sensitive materials . . . . . . . . . . . . . . . . . . . 16

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3.2 Industrial-scale applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16


3.2.1 Vacuum distillation in petroleum refining . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.3 Molecular distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.4 Gallery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

4 Hydrodesulfurization 19
4.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.2 Process chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.3 Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.4 Sulfur compounds in refinery HDS feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.4.1 Thiophenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5 Catalysts and mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5.1 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.5.2 Supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6 Other uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.1 Hydrodenitrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.2 Saturation of olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.6.3 Hydrogenation in the food industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.7 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

5 Catalytic reforming 23
5.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
5.2 Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.2.1 Typical naphtha feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.2.2 The reaction chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
5.3 Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5.4 Catalysts and mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.5 Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

6 Fluid catalytic cracking 28


6.1 Flow diagram and process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
6.1.1 Reactor and Regenerator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.1.2 Distillation column . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.1.3 Regenerator flue gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
6.2 Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
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6.2.1 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6.3 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
6.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
6.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

7 Cracking (chemistry) 35
7.1 History and patents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
7.2 Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.1 Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.2 Hydrogen abstraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.3 Radical decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.4 Radical addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.5 Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2.6 Example: cracking butane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.3 Cracking methodologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.3.1 Thermal methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.3.2 Catalytic methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
7.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
7.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

8 Visbreaker 40
8.1 Process objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2 Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2.1 Coil visbreaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2.2 Soaker visbreaking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
8.2.3 Process options . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.2.4 Soaker visbreaking versus coil visbreaking . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3 Quality and yields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3.1 Feed quality and product quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3.2 Yields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.3.3 Fuel oil stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.4 Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.4.1 Viscosity blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
8.4.2 Example economics for a two-component blend . . . . . . . . . . . . . . . . . . . . . . . 42
8.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
8.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

9 Merox 43
9.1 Types of Merox process units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
9.2 Conventional Merox for extracting mercaptans from LPG . . . . . . . . . . . . . . . . . . . . . . 44
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9.2.1 Flow diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44


9.3 Conventional Merox for sweetening jet fuel or kerosene . . . . . . . . . . . . . . . . . . . . . . . 45
9.3.1 Flow diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
9.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
9.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
9.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

10 Coker unit 47
10.1 Types of coker units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
10.2 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
10.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
10.4 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

11 Alkylation 48
11.1 Alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
11.1.1 Nucleophilic alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
11.1.2 Electrophilic alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
11.1.3 Carbene alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
11.2 In biology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
11.3 Oil refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
11.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
11.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
11.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

12 Dimer (chemistry) 51
12.1 Noncovalent dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
12.2 Covalent dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
12.3 Polymer chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
12.4 Biochemical dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
12.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
12.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

13 Isomerization 53
13.1 Instances of isomerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
13.2 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
13.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

14 Amine gas treating 55


14.1 Description of a typical amine treater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
14.2 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
14.3 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
14.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
14.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
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14.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

15 Claus process 58
15.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
15.2 Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
15.2.1 Thermal step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
15.2.2 Catalytic step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
15.2.3 Sub dew point Claus process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
15.3 Process performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
15.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
15.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

16 Hydrogen sulfide 61
16.1 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
16.2 Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
16.3 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.1 Production of thioorganic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.2 Alkali metal sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.3 Analytical chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.4 Precursor to metal sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
16.4.5 Miscellaneous applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
16.5 Removal from fuel gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
16.6 Removal from water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
16.7 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
16.7.1 Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
16.7.2 Incidents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.7.3 Suicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.8 Function in the body . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.9 Involvement in diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.9.1 Hydrogen sulfide deficiency after heart attack . . . . . . . . . . . . . . . . . . . . . . . . . 65
16.9.2 Other diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
16.10Induced hypothermia and suspended animation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
16.11Participant in the sulfur cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.12Mass extinctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.13See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.14References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
16.15Additional resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
16.16External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70

17 Cooling tower 71
17.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
vi CONTENTS

17.2 Classification by use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72


17.2.1 Heating, ventilation and air conditioning (HVAC) . . . . . . . . . . . . . . . . . . . . . . 72
17.2.2 Industrial cooling towers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
17.3 Classification by build . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
17.3.1 Package type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
17.3.2 Field erected type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
17.4 Heat transfer methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
17.5 Air flow generation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
17.6 Categorization by air-to-water flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
17.6.1 Crossflow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
17.6.2 Counterflow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
17.6.3 Common aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
17.7 Wet cooling tower material balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
17.7.1 Cycles of concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
17.7.2 Water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
17.8 Legionnaires’ disease . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
17.9 Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
17.10Fog production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
17.11Salt emission pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
17.12Use as a flue-gas stack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
17.13Operation in freezing weather . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
17.14Fire hazard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
17.15Structural stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
17.16See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
17.17References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
17.18External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

18 Steam 84
18.1 Types of steam and conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.1 Agricultural . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.2 Domestic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.3 Electricity generation (and cogeneration) . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
18.2.4 Energy storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.5 Lifting gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.6 Mechanical effort . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.7 Sterilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.8 Steam in piping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.9 Wood treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.10 Concrete treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.2.11 Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
18.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
CONTENTS vii

18.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
18.5 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

19 Boiler 87
19.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
19.2 Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
19.3 Configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
19.4 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
19.5 Superheated steam boilers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
19.5.1 Supercritical steam generator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
19.6 Hydronic boilers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
19.7 Accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.1 Boiler fittings and accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.2 Steam accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.3 Combustion accessories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.7.4 Other essential items . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
19.8 Draught . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
19.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
19.10References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
19.11Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

20 API oil-water separator 95


20.1 Description of the design and operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
20.2 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
20.3 Other oil-water separation applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
20.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
20.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
20.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

21 Dissolved air flotation 97


21.1 Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
21.2 Drinking water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
21.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
21.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
21.5 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
21.6 Text and image sources, contributors, and licenses . . . . . . . . . . . . . . . . . . . . . . . . . . 99
21.6.1 Text . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
21.6.2 Images . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
21.6.3 Content license . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Chapter 1

Oil refinery

Anacortes Refinery (Tesoro), on the north end of March Point


southeast of Anacortes, Washington

An oil refinery or petroleum refinery is an industrial


process plant where crude oil is processed and refined
Crude oil is separated into fractions by fractional distillation.
into more useful products such as petroleum naphtha,
The fractions at the top of the fractionating column have lower
gasoline, diesel fuel, asphalt base, heating oil, kerosene boiling points than the fractions at the bottom. The heavy bottom
and liquefied petroleum gas.[1][2] Oil refineries are typ- fractions are often cracked into lighter, more useful products. All
ically large, sprawling industrial complexes with exten- of the fractions are processed further in other refining units.
sive piping running throughout, carrying streams of fluids
between large chemical processing units. In many ways,
oil refineries use much of the technology of, and can be different hydrocarbon molecules in crude oil are sepa-
thought of, as types of chemical plants. The crude oil rated in a refinery into components which can be used
feedstock has typically been processed by an oil produc- as fuels, lubricants, and as feedstocks in petrochemical
tion plant. There is usually an oil depot (tank farm) at or processes that manufacture such products as plastics,
near an oil refinery for the storage of incoming crude oil detergents, solvents, elastomers and fibers such as nylon
feedstock as well as bulk liquid products. and polyesters.
An oil refinery is considered an essential part of the Petroleum fossil fuels are burned in internal combustion
downstream side of the petroleum industry. engines to provide power for ships, automobiles, aircraft
engines, lawn mowers, chainsaws, and other machines.
Different boiling points allow the hydrocarbons to be sep-
1.1 Operation arated by distillation. Since the lighter liquid products are
in great demand for use in internal combustion engines,
Raw or unprocessed crude oil is not generally useful in a modern refinery will convert heavy hydrocarbons and
industrial applications, although “light, sweet” (low vis- lighter gaseous elements into these higher value products.
cosity, low sulfur) crude oil has been used directly as a Oil can be used in a variety of ways because it con-
burner fuel to produce steam for the propulsion of seago- tains hydrocarbons of varying molecular masses, forms
ing vessels. The lighter elements, however, form ex- and lengths such as paraffins, aromatics, naphthenes (or
plosive vapors in the fuel tanks and are therefore haz- cycloalkanes), alkenes, dienes, and alkynes. While the
ardous, especially in warships. Instead, the hundreds of molecules in crude oil include different atoms such as

1
2 CHAPTER 1. OIL REFINERY

dle distillates (kerosene, diesel), heavy distillates and


residuum (heavy fuel oil, lubricating oils, wax, asphalt).
This classification is based on the way crude oil is dis-
tilled and separated into fractions (called distillates and
residuum) as in the above drawing.[2]

• Liquified petroleum gas (LPG)


• Gasoline (also known as petrol)
• Naphtha
• Kerosene and related jet aircraft fuels
• Diesel fuel
The oil refinery in Haifa, Israel is capable of processing about • Fuel oils
9 million tons (66 million barrels) of crude oil a year. Its two
cooling towers are landmarks of the city’s skyline. • Lubricating oils
• Paraffin wax
sulfur and nitrogen, the hydrocarbons are the most com-
• Asphalt and tar
mon form of molecules, which are molecules of vary-
ing lengths and complexity made of hydrogen and carbon • Petroleum coke
atoms, and a small number of oxygen atoms. The dif-
ferences in the structure of these molecules account for • Sulfur
their varying physical and chemical properties, and it is
this variety that makes crude oil useful in a broad range Oil refineries also produce various intermediate prod-
of several applications. ucts such as hydrogen, light hydrocarbons, reformate and
pyrolysis gasoline. These are not usually transported but
Once separated and purified of any contaminants and im-
instead are blended or processed further on-site. Chem-
purities, the fuel or lubricant can be sold without fur-
ical plants are thus often adjacent to oil refineries. For
ther processing. Smaller molecules such as isobutane and
example, light hydrocarbons are steam-cracked in an
propylene or butylenes can be recombined to meet spe-
ethylene plant, and the produced ethylene is polymerized
cific octane requirements by processes such as alkylation,
to produce polyethene.
or less commonly, dimerization. Octane grade of gaso-
line can also be improved by catalytic reforming, which
involves removing hydrogen from hydrocarbons pro-
ducing compounds with higher octane ratings such as 1.3 Common process units found
aromatics. Intermediate products such as gasoils can even in a refinery
be reprocessed to break a heavy, long-chained oil into a
lighter short-chained one, by various forms of cracking
such as fluid catalytic cracking, thermal cracking, and
hydrocracking. The final step in gasoline production is
the blending of fuels with different octane ratings, vapor
pressures, and other properties to meet product specifica-
tions.
Oil refineries are large scale plants, processing about a
hundred thousand to several hundred thousand barrels of
crude oil a day. Because of the high capacity, many of the
units operate continuously, as opposed to processing in
batches, at steady state or nearly steady state for months to
years. The high capacity also makes process optimization
and advanced process control very desirable.

Storage tanks and towers at Shell Puget Sound Refinery (Shell Oil
1.2 Major products Company), Anacortes, Washington

Petroleum products are usually grouped into three cat- • Desalter unit washes out salt from the crude oil be-
egories: light distillates (LPG, gasoline, naphtha), mid- fore it enters the atmospheric distillation unit.
1.3. COMMON PROCESS UNITS FOUND IN A REFINERY 3

• Atmospheric distillation unit distills crude oil into • Steam reforming unit produces hydrogen for the hy-
fractions. See continuous distillation. drotreaters or hydrocracker.
• Vacuum distillation unit further distills residual bot- • Liquified gas storage vessels store propane and sim-
toms after atmospheric distillation. ilar gaseous fuels at pressure sufficient to maintain
them in liquid form. These are usually spherical ves-
• Naphtha hydrotreater unit uses hydrogen to desul- sels or “bullets” (i.e., horizontal vessels with rounded
furize naphtha from atmospheric distillation. Must ends).
hydrotreat the naphtha before sending to a catalytic
reformer unit. • Storage tanks store crude oil and finished products,
usually cylindrical, with some sort of vapor emis-
• Catalytic reformer unit is used to convert the sion control and surrounded by an earthen berm to
naphtha-boiling range molecules into higher octane contain spills.
reformate (reformer product). The reformate has
higher content of aromatics and cyclic hydrocar- • Amine gas treater, Claus unit, and tail gas treatment
bons). An important byproduct of a reformer is hy- convert hydrogen sulfide from hydrodesulfurization
drogen released during the catalyst reaction. The into elemental sulfur.
hydrogen is used either in the hydrotreaters or the • Utility units such as cooling towers circulate cooling
hydrocracker. water, boiler plants generates steam, and instrument
air systems include pneumatically operated control
• Distillate hydrotreater desulfurizes distillates (such
valves and an electrical substation.
as diesel) after atmospheric distillation.
• Wastewater collection and treating systems consist
• Fluid Catalytic Cracker (FCC) unit upgrades heavier of API separators, dissolved air flotation (DAF)
fractions into lighter, more valuable products. units and further treatment units such as an activated
• Hydrocracker unit uses hydrogen to upgrade heavier sludge biotreater to make water suitable for reuse or
fractions into lighter, more valuable products. for disposal.[3]
• Solvent refining units use solvent such as cresol or
• Visbreaking unit upgrades heavy residual oils by
furfural to remove unwanted, mainly aromatics from
thermally cracking them into lighter, more valuable
lubricating oil stock or diesel stock.
reduced viscosity products.
• Solvent dewaxing units remove the heavy waxy con-
• Merox unit treats LPG, kerosene or jet fuel by oxi-
stituents petrolatum from vacuum distillation prod-
dizing mercaptans to organic disulfides.
ucts.
• Alternative processes for removing mercaptans are
known, e.g. doctor sweetening process and caustic
washing.
1.3.1 Flow diagram of typical refinery

• Coking units (delayed coking, fluid coker, and flexi- The image below is a schematic flow diagram of a typi-
coker) process very heavy residual oils into gasoline cal oil refinery[4] that depicts the various unit processes
and diesel fuel, leaving petroleum coke as a residual and the flow of intermediate product streams that oc-
product. curs between the inlet crude oil feedstock and the final
end products. The diagram depicts only one of the lit-
• Alkylation unit uses sulfuric acid or hydrofluoric erally hundreds of different oil refinery configurations.
acid to produce high-octane components for gaso- The diagram also does not include any of the usual re-
line blending. finery facilities providing utilities such as steam, cool-
ing water, and electric power as well as storage tanks for
• Dimerization unit converts olefins into higher-
crude oil feedstock and for intermediate products and end
octane gasoline blending components. For example,
products.[1][5][6][7]
butenes can be dimerized into isooctene which may
subsequently be hydrogenated to form isooctane. There are many process configurations other than that de-
There are also other uses for dimerization. Gasoline picted above. For example, the vacuum distillation unit
produced through dimerization is highly unsaturated may also produce fractions that can be refined into end-
and very reactive. It tends spontaneously to form products such as: spindle oil used in the textile industry,
gums. For this reason the effluent from the dimer- light machinery oil, motor oil, and various waxes.
ization need to be blended into the finished gasoline
pool immediately or hydrogenated.
1.3.2 The crude oil distillation unit
• Isomerization unit converts linear molecules to
higher-octane branched molecules for blending into The crude oil distillation unit (CDU) is the first processing
gasoline or feed to alkylation units. unit in virtually all petroleum refineries. The CDU distills
4 CHAPTER 1. OIL REFINERY

Schematic flow diagram of a typical crude oil distillation unit as


used in petroleum crude oil refineries.

1.4 Specialty end products


Schematic flow diagram of a typical oil refinery These require blending various feedstocks, mixing appro-
priate additives, providing short term storage, and prepa-
ration for bulk loading to trucks, barges, product ships,
and railcars:
the incoming crude oil into various fractions of different
boiling ranges, each of which are then processed further
in the other refinery processing units. The CDU is often • Gaseous fuels such as propane, stored and shipped
referred to as the atmospheric distillation unit because it in liquid form under pressure in specialized railcars
operates at slightly above atmospheric pressure.[1][2][8] to distributors.
Below is a schematic flow diagram of a typical crude oil • Lubricants (produces light machine oils, motor oils,
distillation unit. The incoming crude oil is preheated by and greases, adding viscosity stabilizers as required),
exchanging heat with some of the hot, distilled fractions usually shipped in bulk to an offsite packaging plant.
and other streams. It is then desalted to remove inorganic
salts (primarily sodium chloride). • Wax (paraffin), used in the packaging of frozen
Following the desalter, the crude oil is further heated by foods, among others. May be shipped in bulk to a
exchanging heat with some of the hot, distilled fractions site to prepare as packaged blocks.
and other streams. It is then heated in a fuel-fired furnace
• Sulfur (or sulfuric acid), byproducts of sulfur re-
(fired heater) to a temperature of about 398 °C and routed
moval from petroleum which may have up to a cou-
into the bottom of the distillation unit.
ple percent sulfur as organic sulfur-containing com-
The cooling and condensing of the distillation tower over- pounds. Sulfur and sulfuric acid are useful indus-
head is provided partially by exchanging heat with the trial materials. Sulfuric acid is usually prepared and
incoming crude oil and partially by either an air-cooled shipped as the acid precursor oleum.
or water-cooled condenser. Additional heat is removed
from the distillation column by a pumparound system as • Bulk tar shipping for offsite unit packaging for use
shown in the diagram below. in tar-and-gravel roofing.
As shown in the flow diagram, the overhead distillate • Asphalt unit. Prepares bulk asphalt for shipment.
fraction from the distillation column is naphtha. The frac-
tions removed from the side of the distillation column at • Petroleum coke, used in specialty carbon products
various points between the column top and bottom are or as solid fuel.
called sidecuts. Each of the sidecuts (i.e., the kerosene,
light gas oil and heavy gas oil) is cooled by exchanging • Petrochemicals or petrochemical feedstocks, which
heat with the incoming crude oil. All of the fractions are often sent to petrochemical plants for further
(i.e., the overhead naphtha, the sidecuts and the bottom processing in a variety of ways. The petrochemicals
residue) are sent to intermediate storage tanks before be- may be olefins or their precursors, or various types
ing processed further. of aromatic petrochemicals.
1.7. CORROSION PROBLEMS AND PREVENTION 5

1.5 Siting/locating of petroleum re- accompanies the presence of a refinery. Aside from air
pollution impacts there are also wastewater concerns,[3]
fineries risks of industrial accidents such as fire and explosion,
and noise health effects due to industrial noise.
A party searching for a site to construct a refinery or a
chemical plant needs to consider the following issues: Many governments worldwide have mandated restric-
tions on contaminants that refineries release, and most
refineries have installed the equipment needed to com-
• The site has to be reasonably far from residential ar- ply with the requirements of the pertinent environmental
eas. protection regulatory agencies. In the United States, there
is strong pressure to prevent the development of new re-
• Infrastructure should be available for supply of raw fineries, and no major refinery has been built in the coun-
materials and shipment of products to markets. try since Marathon’s Garyville, Louisiana facility in 1976.
However, many existing refineries have been expanded
• Energy to operate the plant should be available. during that time. Environmental restrictions and pressure
to prevent construction of new refineries may have also
contributed to rising fuel prices in the United States.[9]
• Facilities should be available for waste disposal.
Additionally, many refineries (more than 100 since the
1980s) have closed due to obsolescence and/or merger
Refineries which use a large amount of steam and cool- activity within the industry itself.
ing water need to have an abundant source of water. Oil
refineries therefore are often located nearby navigable Environmental and safety concerns mean that oil refiner-
rivers or on a sea shore, nearby a port. Such location also ies are sometimes located some distance away from ma-
gives access to transportation by river or by sea. The ad- jor urban areas. Nevertheless, there are many instances
vantages of transporting crude oil by pipeline are evident, where refinery operations are close to populated areas and
and oil companies often transport a large volume of fuel pose health risks In California's Contra Costa County and
to distribution terminals by pipeline. Pipeline may not Solano County, a shoreline necklace of refineries, built
be practical for products with small output, and rail cars, in the early 20th century before this area was populated,
road tankers, and barges are used. and associated chemical plants are adjacent to urban ar-
eas in Richmond, Martinez, Pacheco, Concord, Pittsburg,
Petrochemical plants and solvent manufacturing (fine Vallejo and Benicia, with occasional accidental events
fractionating) plants need spaces for further processing that require "shelter in place" orders to the adjacent pop-
of a large volume of refinery products for further pro- ulations.
cessing, or to mix chemical additives with a product at
source rather than at blending terminals.

1.7 Corrosion problems and pre-


1.6 Safety and environmental con- vention
cerns

Refinery of Slovnaft in Bratislava.


Fire-extinguishing operations after the Texas City refinery explo-
sion. Petroleum refineries run as efficiently as possible to re-
duce costs. One major factor that decreases efficiency is
The refining process releases a number of different chem- corrosion of the metallic components found throughout
icals into the atmosphere (see AP 42 Compilation of Air refining process. Corrosion causes the failure of equip-
Pollutant Emission Factors) and a notable odor normally ment items as well as dictating the maintenance schedule
6 CHAPTER 1. OIL REFINERY

of the refinery, during which part or all of the refinery tory material such as standard Portland cement or other
must be shut down. The corrosion-related direct costs in special acid-resistant cements that are shot onto the inner
the U.S. petroleum industry as of 1996 was estimated as surface of the vessel. Also available are thin overlays of
US$3.7 billion per year.[10][11] more expensive metals that protect cheaper metal against
[15]
Corrosion occurs in various forms in the refining pro- corrosion without requiring lots of material.
cess, such as pitting corrosion from water droplets, em-
brittlement from hydrogen, and stress corrosion cracking
from sulfide attack.[12] From a materials standpoint, car- 1.8 History
bon steel is used for upwards of 80 per cent of refin-
ery components, which is beneficial due to its low cost.
The world’s first refinery opened at Ploiești, Romania, in
Carbon steel is resistant to the most common forms of
1856-1857,[16] with United States investment. After be-
corrosion, particularly from hydrocarbon impurities at
ing taken over by Nazi Germany, the Ploiești refineries
temperatures below 205 °C, but other corrosive chemi-
were bombed in Operation Tidal Wave by the Allies dur-
cals and environments prevent its use everywhere. Com-
ing the Oil Campaign of World War II.
mon replacement materials are low alloy steels contain-
ing chromium and molybdenum, with stainless steels con- At one point, the refinery in Ras Tanura, Saudi Arabia
taining more chromium dealing with more corrosive en- owned by Saudi Aramco was claimed to be the largest
vironments. More expensive materials commonly used oil refinery in the world. For most of the 20th cen-
are nickel, titanium, and copper alloys. These are pri- tury, the largest refinery was the Abadan Refinery in
marily saved for the most problematic areas where ex- Iran. This refinery suffered extensive damage during
tremely high temperatures and/or very corrosive chemi- the Iran-Iraq war. The world’s largest refinery complex
cals are present.[13] is the Jamnagar Refinery Complex, consisting of two
refineries side by side operated by Reliance Industries
Corrosion is fought by a complex system of monitoring,
Limited in Jamnagar, India with a combined production
preventative repairs and careful use of materials. Mon-
capacity of 1,240,000 barrels per day (197,000 m3 /d).
itoring methods include both off-line checks taken dur-
PDVSA's Paraguaná Refinery Complex in Paraguaná
ing maintenance and on-line monitoring. Off-line checks
Peninsula, Venezuela with a capacity of 956,000 bbl/d
measure corrosion after it has occurred, telling the en-
(152,000 m3 /d) and SK Energy's Ulsan in South Korea
gineer when equipment must be replaced based on the
with 840,000 bbl/d (134,000 m3 /d) are the second and
historical information he has collected. This is referred
third largest, respectively.
to as preventative management.
On-line systems are a more modern development, and
are revolutionizing the way corrosion is approached. 1.8.1 Oil refining in the United States
There are several types of on-line corrosion monitor-
ing technologies such as linear polarization resistance, In the 19th century, refineries in the U.S. processed crude
electrochemical noise and electrical resistance. On-Line oil primarily to recover the kerosene. There was no
monitoring has generally had slow reporting rates in the market for the more volatile fraction, including gasoline,
past (minutes or hours) and been limited by process con- which was considered waste and was often dumped di-
ditions and sources of error but newer technologies can rectly into the nearest river. The invention of the automo-
report rates up to twice per minute with much higher ac- bile shifted the demand to gasoline and diesel, which re-
curacy (referred to as real-time monitoring). This allows main the primary refined products today. Today, national
process engineers to treat corrosion as another process and state legislation requires refineries to meet stringent
variable that can be optimized in the system. Immediate air and water cleanliness standards. In fact, oil companies
responses to process changes allow the control of corro- in the U.S. perceive obtaining a permit to build a modern
sion mechanisms, so they can be minimized while also refinery to be so difficult and costly that no new refiner-
maximizing production output.[14] In an ideal situation ies were built (though many have been expanded) in the
having on-line corrosion information that is accurate and U.S. from 1976 until 2014, when the small Dakota Prairie
real-time will allow conditions that cause high corrosion Refinery in North Dakota is set to begin operation.[17]
rates to be identified and reduced. This is known as pre- More than half the refineries that existed in 1981 are
dictive management. now closed due to low utilization rates and accelerating
Materials methods include selecting the proper material mergers.[18] As a result of these closures total US refin-
for the application. In areas of minimal corrosion, cheap ery capacity fell between 1981 to 1995, though the oper-
materials are preferable, but when bad corrosion can oc- ating capacity stayed fairly constant in that time period at
cur, more expensive but longer lasting materials should around 15,000,000 barrels per day (2,400,000 m3 /d).[19]
be used. Other materials methods come in the form of Increases in facility size and improvements in efficiencies
protective barriers between corrosive substances and the have offset much of the lost physical capacity of the in-
equipment metals. These can be either a lining of refrac- dustry. In 1982 (the earliest data provided), the United
States operated 301 refineries with a combined capacity
1.11. EXTERNAL LINKS 7

of 17.9 million barrels (2,850,000 m3 ) of crude oil each [4] Crude Oil Solids Removal
calendar day. In 2010, there were 149 operable U.S. re-
[5] Guide to Refining from Chevron Oil's website
fineries with a combined capacity of 17.6 million barrels
(2,800,000 m3 ) per calendar day.[20] [6] Refinery flowchart from Universal Oil Products' website
In 2009 through 2010, as revenue streams in the oil busi-
[7] An example flowchart of fractions from crude oil at a re-
ness dried up and profitability of oil refineries fell due finery
to lower demand for product and high reserves of supply
preceding the economic recession, oil companies began [8] Kister, Henry Z. (1992). Distillation Design (1st Edition
to close or sell refineries. ed.). McGraw-Hill. ISBN 978-0-07-034909-4.

[9] By Steve Hargreaves, CNNMoney.com staff writer (2007-


04-17). “Behind high gas prices: The refinery crunch”.
Money.cnn.com. Retrieved 2011-11-05.

[10] Corrosion Costs and Preventive Strategies in the United


States, a publication of NACE International.
ExxonMobil oil refinery in Baton Rouge (the second-largest in the
United States) [11] R.D. Kane, Corrosion in Petroleum Refining and Petro-
chemical Operations, Corrosion: Environments and In-
dustries, Vol 13C, ASM Handbook, ASM International,
2006, p 967–1014.
1.9 See also [12] E.N. Skinner, J.F. Mason, and J.J. Moran, High Temper-
ature Corrosion in Refinery and Petrochemical Service,
• Acid gas Corrosion, Vol 16 (No. 12), 1960, p 593t–600t.

• H-Bio [13] E.L. Hildebrand, Materials Selection for Petroleum Re-


fineries and Petrochemical Plants, Mater. Prot. Perform.,
• AP 42 Compilation of Air Pollutant Emission Fac- Vol 11 (No. 7), 1972, p19–22.
tors
[14] R.D. Kane, D.C. Eden, and D.A. Eden, Innovative Solu-
• API oil-water separator tions Integrate Corrosion Monitoring with Process Con-
trol, Mater. Perform., Feb 2005, p 36–41.
• Ethanol fuel
[15] W.A. McGill and M.J. Weinbaum, Aluminum-Diffused
• Butanol fuel Steel Lasts Longer, Oil Gas J., Vol 70, Oct 9, 1972, p
66–69.
• Gas flare
[16] “WORLD EVENTS: 1844-1856”. PBS.org. Retrieved
• Industrial wastewater treatment 2009-04-22. world’s first oil refinery

• K factor crude oil refining [17] “North Dakota Builds A Refinery, First In The U.S. Since
'76”. Investors Business Daily. April 11, 2013. Retrieved
• List of oil refineries August 24, 2014.

• Natural-gas processing [18] White Paper on Refining Capacity, Federal Trade Com-
mission, April, 2007.
• Nelson complexity index
[19] “U. S. Operating Crude Oil Distillation Capacity (Thou-
• Sour gas sand Barrels per Day)". Eia.doe.gov. 2011-07-28. Re-
trieved 2011-11-05.

[20] “2011 The U.S. Petroleum Industry: Statistics & Defini-


1.10 References tions” (PDF). Retrieved 2011-11-05.

[1] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-


ing Technology and Economics (2nd Edition ed.). Marcel
Dekker, Inc. ISBN 0-8247-7150-8.
1.11 External links
[2] Leffler, W.L. (1985). Petroleum refining for the nontech- • Interactive map of UK refineries
nical person (2nd Edition ed.). PennWell Books. ISBN
0-87814-280-0. • Searchable United States Refinery Map
[3] Beychok, Milton R. (1967). Aqueous Wastes from • Complete, detailed refinery description
Petroleum and Petrochemical Plants (1st Edition ed.).
John Wiley & Sons. LCCN 67019834. • Ecomuseum Bergslagen - history of Oljeön, Sweden
8 CHAPTER 1. OIL REFINERY

• Fueling Profits: Report on Industry Consolidation


(publication of the Consumer Federation of Amer-
ica)

• Price Spikes, Excess Profits and Excuses (publica-


tion of the Consumer Federation of America)

• Basics of Oil Refining Overview of crude oil refining


process

• Refining NZ Learning Centre Oil Refinery Process


Animations,Videos & 360 Degree Views
Chapter 2

Continuous distillation

Image 1: Typical industrial distillation towers

Continuous distillation, a form of distillation, is an on-


going separation in which a mixture is continuously (with-
out interruption) fed into the process and separated frac-
tions are removed continuously as output streams. A dis-
tillation is the separation or partial separation of a liquid
feed mixture into components or fractions by selective
boiling (or evaporation) and condensation. A distillation Image 2: A crude oil vacuum distillation column as used in oil
produces at least two output fractions. These fractions refineries
include at least one volatile distillate fraction, which has
boiled and been separately captured as a vapor condensed
to a liquid, and practically always a bottoms (or residuum) different times, only one distillate exit point (location) is
fraction, which is the least volatile residue that has not needed for a batch distillation and the distillate can just
been separately captured as a condensed vapor. be switched to a different receiver, a fraction-collecting
An alternative to continuous distillation is batch distilla- container. Batch distillation is often used when smaller
tion, where the mixture is added to the unit at the start of quantities are distilled. In a continuous distillation, each
the distillation, distillate fractions are taken out sequen- of the fraction streams is taken simultaneously through-
tially in time (one after another) during the distillation, out operation; therefore, a separate exit point is needed
and the remaining bottoms fraction is removed at the end. for each fraction. In practice when there are multiple dis-
Because each of the distillate fractions are taken out at tillate fractions, each of the distillate exit points are lo-

9
10 CHAPTER 2. CONTINUOUS DISTILLATION

cated at different heights on a fractionating column. The


bottoms fraction can be taken from the bottom of the dis-
tillation column or unit, but is often taken from a reboiler
connected to the bottom of the column.
Each fraction may contain one or more components
(types of chemical compounds). When distilling crude
oil or a similar feedstock, each fraction contains many
components of similar volatility and other properties. Al-
though it is possible to run a small-scale or laboratory con-
tinuous distillation, most often continuous distillation is
used in a large-scale industrial process.

2.1 Industrial application


Distillation is one of the unit operations of chemical engi-
neering.[1][2] Continuous distillation is used widely in the
chemical process industries where large quantities of liq-
uids have to be distilled.[3][4][5] Such industries are the
natural gas processing, petrochemical production, coal
tar processing, liquor production, liquified air separation,
hydrocarbon solvents production and similar industries,
but it finds its widest application in petroleum refineries.
In such refineries, the crude oil feedstock is a very com-
plex multicomponent mixture that must be separated and
yields of pure chemical compounds are not expected, only
groups of compounds within a relatively small range of Image 3: Chemical engineering schematic of Continuous Binary
Fractional Distillation tower. A binary distillation separates a
boiling points, which are called fractions. These frac-
feed mixture stream into two fractions: one distillate and one
tions are the origin of the term fractional distillation or bottoms fractions.
fractionation. It is often not worthwhile separating the
components in these fractions any further based on prod-
uct requirements and economics.
again.
Industrial distillation is typically performed in large, ver-
tical cylindrical columns (as shown in images 1 and 2) Image 3 depicts a simple continuous fractional distillation
known as “distillation towers” or “distillation columns” tower for separating a feed stream into two fractions, an
with diameters ranging from about 65 centimeters to 11 overhead distillate product and a bottoms product. The
meters and heights ranging from about 6 meters to 60 me- “lightest” products (those with the lowest boiling point or
ters or more. highest volatility) exit from the top of the columns and the
“heaviest” products (the bottoms, those with the highest
boiling point) exit from the bottom of the column. The
overhead stream may be cooled and condensed using a
2.2 Principle water-cooled or air-cooled condenser. The bottoms re-
boiler may be a steam-heated or hot oil-heated heat ex-
Main article: Distillation changer, or even a gas or oil-fired furnace.
The principle for continuous distillation is the same as In a continuous distillation, the system is kept in a steady
for normal distillation: when a liquid mixture is heated so state or approximate steady state. Steady state means that
that it boils, the composition of the vapor above the liquid quantities related to the process do not change as time
differs from the liquid composition. If this vapor is then passes during operation. Such constant quantities include
separated and condensed into a liquid, it becomes richer feed input rate, output stream rates, heating and cool-
in the lower boiling component(s) of the original mixture. ing rates, reflux ratio, and temperatures, pressures, and
This is what happens in a continuous distillation column. compositions at every point (location). Unless the pro-
A mixture is heated up, and routed into the distillation cess is disturbed due to changes in feed, heating, ambi-
column. On entering the column, the feed starts flowing ent temperature, or condensing, steady state is normally
down but part of it, the component(s) with lower boiling maintained. This is also the main attraction of continu-
point(s), vaporizes and rises. However, as it rises, it cools ous distillation, apart from the minimum amount of (eas-
and while part of it continues up as vapor, some of it (en- ily instrumentable) surveillance; if the feed rate and feed
riched in the less volatile component) begins to descend composition are kept constant, product rate and quality
2.3. DESIGN AND OPERATION 11

are also constant. Even when a variation in conditions


occurs, modern process control methods are commonly
able to gradually return the continuous process to another
steady state again.
Since a continuous distillation unit is fed constantly with
a feed mixture and not filled all at once like a batch distil-
lation, a continuous distillation unit does not need a siz-
able distillation pot, vessel, or reservoir for a batch fill.
Instead, the mixture can be fed directly into the column,
where the actual separation occurs. The height of the feed
point along the column can vary on the situation and is
designed so as to provide optimal results. See McCabe–
Thiele method.
A continuous distillation is often a fractional distillation
and can be a vacuum distillation or a steam distillation.

2.3 Design and operation


Design and operation of a distillation column depends
on the feed and desired products. Given a simple, bi-
nary component feed, analytical methods such as the
McCabe–Thiele method[5][6][7] or the Fenske equation[5]
can be used to assist in the design. For a multi-component
feed, computerized simulation models are used both for
design and subsequently in operation of the column as
well. Modeling is also used to optimize already erected
columns for the distillation of mixtures other than those
the distillation equipment was originally designed for. Image 4: Simplified chemical engineering schematic of Contin-
When a continuous distillation column is in operation, it uous Fractional Distillation tower separating one feed mixture
stream into four distillate and one bottoms fractions
has to be closely monitored for changes in feed compo-
sition, operating temperature and product composition.
Many of these tasks are performed using advanced com-
steel vessels (see images 1 and 2) known as “distillation
puter control equipment.
towers” or “distillation columns”. To improve the sepa-
ration, the tower is normally provided inside with hori-
2.3.1 Column feed zontal plates or trays as shown in image 5, or the column
is packed with a packing material. To provide the heat
The column can be fed in different ways. If the feed is required for the vaporization involved in distillation and
from a source at a pressure higher than the distillation col- also to compensate for heat loss, heat is most often added
umn pressure, it is simply piped into the column. Other- to the bottom of the column by a reboiler, and the purity
wise, the feed is pumped or compressed into the column. of the top product can be improved by recycling some of
The feed may be a superheated vapor, a saturated vapor, a the externally condensed top product liquid as reflux. De-
partially vaporized liquid-vapor mixture, a saturated liq- pending on their purpose, distillation columns may have
uid (i.e., liquid at its boiling point at the column’s pres- liquid outlets at intervals up the length of the column as
sure), or a sub-cooled liquid. If the feed is a liquid at a shown in image 4.
much higher pressure than the column pressure and flows
through a pressure let-down valve just ahead of the col-
umn, it will immediately expand and undergo a partial Reflux
flash vaporization resulting in a liquid-vapor mixture as it
enters the distillation column. Large-scale industrial fractionation towers use reflux to
achieve more efficient separation of products.[3][5] Re-
flux refers to the portion of the condensed overhead liquid
2.3.2 Improving separation product from a distillation tower that is returned to the up-
per part of the tower as shown in images 3 and 4. Inside
Although small size units, mostly made of glass, can be the tower, the downflowing reflux liquid provides cooling
used in laboratories, industrial units are large, vertical, and partial condensation of the upflowing vapors, thereby
12 CHAPTER 2. CONTINUOUS DISTILLATION

increasing the efficacy of the distillation tower. The more Distillation towers (such as in images 3 and 4) use var-
reflux that is provided, the better is the tower’s separation ious vapor and liquid contacting methods to provide the
of the lower boiling from the higher boiling components required number of equilibrium stages. Such devices are
of the feed. A balance of heating with a reboiler at the commonly known as “plates” or “trays”.[8] Each of these
bottom of a column and cooling by condensed reflux at plates or trays is at a different temperature and pressure.
the top of the column maintains a temperature gradient The stage at the tower bottom has the highest pressure
(or gradual temperature difference) along the height of and temperature. Progressing upwards in the tower, the
the column to provide good conditions for fractionating pressure and temperature decreases for each succeeding
the feed mixture. Reflux flows at the middle of the tower stage. The vapor–liquid equilibrium for each feed com-
are called pumparounds. ponent in the tower reacts in its unique way to the dif-
ferent pressure and temperature conditions at each of the
Changing the reflux (in combination with changes in feed
and product withdrawal) can also be used to improve the stages. That means that each component establishes a dif-
ferent concentration in the vapor and liquid phases at each
separation properties of a continuous distillation column
while in operation (in contrast to adding plates or trays, of the stages, and this results in the separation of the com-
ponents. Some example trays are depicted in image 5. A
or changing the packing, which would, at a minimum,
require quite significant downtime). more detailed, expanded image of two trays can be seen
in the theoretical plate article. The reboiler often acts as
an additional equilibrium stage.
Plates or trays If each physical tray or plate were 100% efficient, then
the number of physical trays needed for a given sepa-
ration would equal the number of equilibrium stages or
theoretical plates. However, that is very seldom the case.
Hence, a distillation column needs more plates than the
required number of theoretical vapor–liquid equilibrium
stages.

Packing

Another way of improving the separation in a distilla-


tion column is to use a packing material instead of trays.
These offer the advantage of a lower pressure drop across
the column (when compared to plates or trays), benefi-
cial when operating under vacuum. If a distillation tower
uses packing instead of trays, the number of necessary
theoretical equilibrium stages is first determined and then
the packing height equivalent to a theoretical equilibrium
stage, known as the height equivalent to a theoretical plate
(HETP), is also determined. The total packing height re-
quired is the number theoretical stages multiplied by the
HETP.
This packing material can either be random dumped
packing such as Raschig rings or structured sheet metal.
Liquids tend to wet the surface of the packing and the
vapors pass across this wetted surface, where mass trans-
fer takes place. Unlike conventional tray distillation in
which every tray represents a separate point of vapor–
liquid equilibrium, the vapor–liquid equilibrium curve in
a packed column is continuous. However, when model-
ing packed columns it is useful to compute a number of
theoretical plates to denote the separation efficiency of
the packed column with respect to more traditional trays.
Differently shaped packings have different surface areas
and void space between packings. Both of these factors
affect packing performance.
Image 5: Cross-sectional diagram of a binary fractional distil-
lation tower with bubble-cap trays. (See theoretical plate for Another factor in addition to the packing shape and sur-
enlarged tray image.) face area that affects the performance of random or struc-
2.5. SEE ALSO 13

tured packing is liquid and vapor distribution entering the a higher octane rating value.
packed bed. The number of theoretical stages required to The naphtha cut, as that fraction is called, contains many
make a given separation is calculated using a specific va- different hydrocarbon compounds. Therefore it has an
por to liquid ratio. If the liquid and vapor are not evenly initial boiling point of about 35 °C and a final boiling
distributed across the superficial tower area as it enters point of about 200 °C. Each cut produced in the frac-
the packed bed, the liquid to vapor ratio will not be cor- tionating columns has a different boiling range. At some
rect in the packed bed and the required separation will distance below the overhead, the next cut is withdrawn
not be achieved. The packing will appear to not be work- from the side of the column and it is usually the jet fuel
ing properly. The height equivalent to a theoretical plate
cut, also known as a kerosene cut. The boiling range of
(HETP) will be greater than expected. The problem is that cut is from an initial boiling point of about 150 °C
not the packing itself but the mal-distribution of the flu-
to a final boiling point of about 270 °C, and it also con-
ids entering the packed bed. Liquid mal-distribution is tains many different hydrocarbons. The next cut further
more frequently the problem than vapor. The design of
down the tower is the diesel oil cut with a boiling range
the liquid distributors used to introduce the feed and re- from about 180 °C to about 315 °C. The boiling ranges
flux to a packed bed is critical to making the packing
between any cut and the next cut overlap because the dis-
perform at maximum efficiency. Methods of evaluating tillation separations are not perfectly sharp. After these
the effectiveness of a liquid distributor can be found in come the heavy fuel oil cuts and finally the bottoms prod-
references.[9][10] uct, with very wide boiling ranges. All these cuts are pro-
cessed further in subsequent refining processes.
2.3.3 Overhead system arrangements

Images 4 and 5 assume an overhead stream that is to-


2.5 See also
tally condensed into a liquid product using water or air-
cooling. However, in many cases, the tower overhead is • Azeotropic distillation
not easily condensed totally and the reflux drum must in-
• Extractive distillation
clude a vent gas outlet stream. In yet other cases, the
overhead stream may also contain water vapor because ei- • Fractional distillation
ther the feed stream contains some water or some steam
is injected into the distillation tower (which is the case • Fractionating column
in the crude oil distillation towers in oil refineries). In
• Steam distillation
those cases, if the distillate product is insoluble in water,
the reflux drum may contain a condensed liquid distillate
phase, a condensed water phase and a non-condensible
gas phase, which makes it necessary that the reflux drum 2.6 References
also have a water outlet stream.
[1] Editors: Jacqueline I. Kroschwitz and Arza Seidel (2004).
Kirk-Othmer Encyclopedia of Chemical Technology (5th
ed.). Hoboken, New Jersey: Wiley-Interscience. ISBN
2.4 Examples 0-471-48810-0.

[2] McCabe, W., Smith, J. and Harriott, P. (2004). Unit Op-


2.4.1 Continuous distillation of crude oil erations of Chemical Engineering (7th ed.). McGraw Hill.
ISBN 0-07-284823-5.
Petroleum crude oils contain hundreds of different
hydrocarbon compounds: paraffins, naphthenes and [3] Kister, Henry Z. (1992). Distillation Design (1st ed.).
McGraw-Hill. ISBN 0-07-034909-6.
aromatics as well as organic sulfur compounds, organic
nitrogen compounds and some oxygen containing hydro- [4] King, C.J. (1980). Separation Processes (2nd ed.). Mc-
carbons such as phenols. Although crude oils generally Graw Hill. ISBN 0-07-034612-7.
do not contain olefins, they are formed in many of the
processes used in a petroleum refinery.[11] [5] Perry, Robert H. and Green, Don W. (1984). Perry’s
Chemical Engineers’ Handbook (6th ed.). McGraw-Hill.
The crude oil fractionator does not produce products ISBN 0-07-049479-7.
having a single boiling point; rather, it produces frac-
tions having boiling ranges.[11][12] For example, the crude [6] Beychok, Milton (May 1951). “Algebraic Solution
oil fractionator produces an overhead fraction called of McCabe-Thiele Diagram”. Chemical Engineering
Progress.
"naphtha" which becomes a gasoline component after it
is further processed through a catalytic hydrodesulfurizer [7] Seader, J. D., and Henley, Ernest J. (1998). Separa-
to remove sulfur and a catalytic reformer to reform its hy- tion Process Principles. New York: Wiley. ISBN 0-471-
drocarbon molecules into more complex molecules with 58626-9.
14 CHAPTER 2. CONTINUOUS DISTILLATION

[8] Photographs of bubble cap and other tray types (Website


of Raschig Gmbh)

[9] Random Packing, Vapor and Liquid Distribution: Liquid


and gas distribution in commercial packed towers, Moore,
F., Rukovena, F., Chemical Plants & Processing, Edition
Europe, August 1987, p. 11-15

[10] Structured Packing, Liquid Distribution: A new method to


assess liquid distributor quality, Spiegel, L., Chemical En-
gineering and Processing 45 (2006), p. 1011-1017

[11] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-


ing Technology and Economics (2nd ed.). Marcel Dekker,
Inc. ISBN 0-8247-7150-8.

[12] Nelson, W.L. (1958). Petroleum Refinery Engineering


(4th ed.). McGraw Hill. LCCN 57010913.

2.7 External links


• Distillation Theory by Ivar J. Halvorsen and Sigurd
Skogestad, Norwegian University of Science and
Technology, Norway
• Distillation, An Introduction by Ming Tham, New-
castle University, UK
• Distillation by the Distillation Group, USA

• Distillation Lecture Notes by Prof. Randall M. Price


at Christian Brothers University

• Petroleum Distillation by Wayne Pafco


• Distillation simulation software
Chapter 3

Vacuum distillation

terials (such as beta carotene) also require vacuum distil-


lation to remove solvents from the mixture without dam-
aging the product. Another reason vacuum distillation is
used is that compared to steam distillation there is a lower
level of residue build up. This is important in commercial
applications where heat transfer is produced using heat
exchangers.
Vacuum distillation is sometimes referred to as low tem-
perature distillation.
There are many laboratory applications for vacuum dis-
tillation as well as many types of distillation set-ups and
apparatuses.
Safety is an important consideration when using glass-
ware as part of the set-up. All of the glass components
should be carefully examined for scratches and cracks
which could result in implosions when the vacuum is ap-
plied. Wrapping as much of the glassware with tape as
is practical helps to prevent dangerous scattering of glass
shards in the event of an implosion.

Figure 1: At atmospheric pressure, dimethyl sulfoxide boils at


189°C. Under a vacuum, it distills off into the connected receiver
at only 70°C.

Vacuum distillation is a method of distillation whereby


3.1.1 Rotary evaporation
the pressure above the liquid mixture to be distilled is re-
duced to less than its vapor pressure (usually less than
atmospheric pressure) causing evaporation of the most Rotary evaporation[5] is a type of vacuum distillation ap-
volatile liquid(s) (those with the lowest boiling points).[1] paratus used to remove bulk solvents from the liquid be-
This distillation method works on the principle that boil- ing distilled. It is also used by environmental regulatory
ing occurs when the vapor pressure of a liquid exceeds agencies for determining the amount of solvents in paint,
the ambient pressure. Vacuum distillation is used with or coatings and inks.[6]
without heating the mixture. Rotary evaporation set-ups include an apparatus referred
to as a Rotovap which rotates the distillation flask (some-
times called the still pot) to enhance the distillation. Ro-
3.1 Laboratory-scale applications tating the flask throws up liquid on the walls of the flask
and thus increases the surface area for evaporation.
Laboratory-scale vacuum distillation is used when liq- Heat is often applied to the rotating distillation flask by
uids to be distilled have high atmospheric boiling points partially immersing it in a heated bath of water or oil.
or chemically change at temperatures near their atmo- Typically, the vacuum in such systems is generated by a
spheric boiling points.[2][3][4] Temperature sensitive ma- water aspirator or a vacuum pump of some type.

15
16 CHAPTER 3. VACUUM DISTILLATION

3.1.2 Distillation of high-boiling and/or air 3.2 Industrial-scale applications


sensitive materials

Some compounds have high boiling point temperatures


as well as being air sensitive. A simple laboratory vac-
uum distillation glassware set-up can be used, in which
the vacuum can be replaced with an inert gas after the
distillation is complete.
However, this is not a completely satisfactory system if it
is desired to collect fractions under a reduced pressure.
For better results or for very air sensitive compounds, ei-
ther a Perkin triangle distillation set-up or a short-path
distillation set-up can be used.

Perkin triangle distillation set-up


Figure 2: Simplified animation of a typical dry vacuum distilla-
The Perkin triangle set-up (Image 5) uses a series of tion column as used in oil refineries
Teflon valves to allow the distilled fractions to be isolated
from the distillation flask without the main body of the
distillation set-up being removed from either the vacuum
or the heat source, and thus can remain in a state of reflux.
To do this, the distillate receiver vessel is first isolated
from the vacuum by means of the Teflon valves.
The vacuum over the sample is then replaced with an inert
gas (such as nitrogen or argon) and the distillate receiver
can then be stoppered and removed from the system.

Vacuum distillation set-up using a short-path head

Vacuum distillation of moderately air/water-sensitive liq-


uid can be done using standard Schlenk-line techniques
(Image 6). When assembling the set-up apparatus, all of
the connecting lines are clamped so that they cannot pop
off.
Once the apparatus is assembled, and the liquid to be
distilled is in the still pot, the desired vacuum is estab-
lished in the system by using the vacuum connection on
the short-path distillation head. Care is taken to prevent
potential “bumping” as the liquid in the still pot degases.
While establishing the vacuum, the flow of coolant is
started through the short-path distillation head. Once the
desired vacuum is established, heat is applied to the still
pot.
If needed, the first portion of distillate can be discarded
by purging with inert gas and changing out the distillate
receiver.
When the distillation is complete: the heat is removed,
the vacuum connection is closed, and inert gas is purged Figure 3: Large-scale vacuum distillation tower at the Fawley oil
through the distillation head and the distillate receiver. refinery[7]
While under the inert gas purge, remove the distillate re-
ceiver and cap it with an air-tight cap. The distillate re- Industrial-scale vacuum distillation[8] has several ad-
ceiver can be stored under vacuum or under inert gas by vantages. Close boiling mixtures may require many
using the side-arm on the distillation flask. equilibrium stages to separate the key components. One
3.3. MOLECULAR DISTILLATION 17

tool to reduce the number of stages needed is to utilize The constraint imposed by limiting the column inlet
vacuum distillation.[9] Vacuum distillation columns (as crude oil to a temperature of less than 370 to 380 °C
depicted in Figures 2 and 3) typically used in oil refineries yields a residual oil from the bottom of the atmospheric
have diameters ranging up to about 14 metres (46 feet), distillation column consisting entirely of hydrocarbons
heights ranging up to about 50 metres (164 feet), and feed that boil above 370 to 380 °C.
rates ranging up to about 25,400 cubic metres per day To further distill the residual oil from the atmospheric
(160,000 barrels per day). distillation column, the distillation must be performed at
Vacuum distillation increases the relative volatility of the absolute pressures as low as 10 to 40 mmHg (also referred
key components in many applications. The higher the rel- to as Torr) so as to limit the operating temperature to less
ative volatility, the more separable are the two compo- than 370 to 380 °C.
nents; this connotes fewer stages in a distillation column Figure 2 is a simplified process diagram of a petroleum
in order to effect the same separation between the over- refinery vacuum distillation column that depicts the inter-
head and bottoms products. Lower pressures increase rel- nals of the column and Figure 3 is a photograph of a large
ative volatilities in most systems. vacuum distillation column in a petroleum refinery.
A second advantage of vacuum distillation is the reduced The 10 to 40 mmHg absolute pressure in a vacuum distil-
temperature requirement at lower pressures. For many lation column increases the volume of vapor formed per
systems, the products degrade or polymerize at elevated volume of liquid distilled. The result is that such columns
temperatures. have very large diameters.[13]
Vacuum distillation can improve a separation by: Distillation columns such those in Images 1 and 2, may
have diameters of 15 meters or more, heights ranging up
• Prevention of product degradation or polymer for-
to about 50 meters, and feed rates ranging up to about
mation because of reduced pressure leading to lower
25,400 cubic meters per day (160,000 barrels per day).
tower bottoms temperatures,
The vacuum distillation column internals must provide
• Reduction of product degradation or polymer for- good vapor–liquid contacting while, at the same time,
mation because of reduced mean residence time es- maintaining a very low pressure increase from the top
pecially in columns using packing rather than trays. of the column top to the bottom. Therefore, the vac-
uum column uses distillation trays only where withdraw-
• Increasing capacity, yield, and purity. ing products from the side of the column (referred to as
side draws). Most of the column uses packing material
Another advantage of vacuum distillation is the reduced for the vapor–liquid contacting because such packing has
capital cost, at the expense of slightly more operating a lower pressure drop than distillation trays. This packing
cost. Utilizing vacuum distillation can reduce the height material can be either structured sheet metal or randomly
and diameter, and thus the capital cost of a distillation dumped packing such as Raschig rings.
column. The absolute pressure of 10 to 40 mmHg in the vacuum
column is most often achieved by using multiple stages of
steam jet ejectors.[14]
3.2.1 Vacuum distillation in petroleum re-
fining Many industries, other than the petroleum refining indus-
try, use vacuum distillation on a much a smaller scale.
Petroleum crude oil is a complex mixture of hundreds
of different hydrocarbon compounds generally having
from 3 to 60 carbon atoms per molecule, although there 3.3 Molecular distillation
may be small amounts of hydrocarbons outside that
range.[10][11][12] The refining of crude oil begins with dis- Molecular distillation is vacuum distillation below the
tilling the incoming crude oil in a so-called atmospheric pressure of 0.01 torr[15] (1.3 Pa). 0.01 torr is one or-
distillation column operating at pressures slightly above der of magnitude above high vacuum, where fluids are in
atmospheric pressure.[8][10][11] the free molecular flow regime, i.e. the mean free path
In distilling the crude oil, it is important not to subject the of molecules is comparable to the size of the equipment.
crude oil to temperatures above 370 to 380 °C because The gaseous phase no longer exerts significant pressure
the high molecular weight components in the crude oil on the substance to be evaporated, and consequently, rate
will undergo thermal cracking and form petroleum coke of evaporation no longer depends on pressure. That is,
at temperatures above that. Formation of coke would re- because the continuum assumptions of fluid dynamics no
sult in plugging the tubes in the furnace that heats the longer apply, mass transport is governed by molecular dy-
feed stream to the crude oil distillation column. Plug- namics rather than fluid dynamics. Thus, a short path be-
ging would also occur in the piping from the furnace to tween the hot surface and the cold surface is necessary,
the distillation column as well as in the column itself. typically by suspending a hot plate covered with a film of
18 CHAPTER 3. VACUUM DISTILLATION

feed next to a cold plate with a line of sight in between. [9] Karl Kolmetz, Andrew W. Sloley et al. (2004), Design-
Molecular distillation is used industrially for purification ing Distillation Columns for Vacuum Service, 11th India
of oils. Oil and Gas Symposium and International Exhibition,
September 2004, Mumbai, India (also published in Hy-
drocarbon Processing, May 2005)

3.4 Gallery [10] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-
ing Technology and Economics (2nd Edition ed.). Marcel
Dekker, Inc. ISBN 0-8247-7150-8.
• A simple short path vacuum distillation apparatus
[11] Leffler, W.L. (1985). Petroleum refining for the nontech-
• Kugelrohr - a short path vacuum distillation appara- nical person (2nd Edition ed.). PennWell Books. ISBN
tus 0-87814-280-0.

• Perkin triangle - for air-sensitive vacuum distillation [12] James G, Speight (2006). The Chemistry and Technology
of Petroleum (Fourth Edition ed.). CRC Press. 0-8493-
• Vacuum distillation apparatus 9067-2.

[13] Karl Kolmetz, Andrew W. Sloley et al (2004), Design-


ing Distillation Columns for Vacuum Service, 11th India
3.5 See also Oil and Gas Symposium and International Exhibition,
September 2004, Mumbai, India (also published in Hy-
drocarbon Processing, May 2005)
• Continuous distillation
[14] Photo gallery (from website of Graham Manufacturing
• Fractionating column Company)

• Fractional distillation [15] Vogel’s 5th ed.

• Kugelrohr
3.7 External links
3.6 References • D1160 Vacuum Distillation

This article incorporates material from the


Citizendium article "Vacuum distillation",
which is licensed under the Creative Commons
Attribution-ShareAlike 3.0 Unported License
but not under the GFDL.

[1] Laurence M. Harwood, Christopher J. Moody (13 June


1989). Experimental organic chemistry: Principles and
Practice (Illustrated edition ed.). WileyBlackwell. pp.
147–149. ISBN 978-0-632-02017-1.

[2] Distillation (CU Boulder Organic Chemistry Teaching


Labs)

[3] Vacuum Distillation: New Method for Analyzing Organic


Chemicals in a Wide Array of Samples (United States En-
vironmental Protection Agency)

[4] What is vacuum distillation? (Argonne National Labora-


tory's NEWTON Ask-A-Scientist)

[5] Operation of a Rotary Evaporator (Rotovap) (from the


website of the University of British Columbia)

[6] SCAQMD Test method 302-91

[7] Energy Institute website page

[8] Kister, Henry Z. (1992). Distillation Design (1st Edition


ed.). McGraw-Hill. ISBN 0-07-034909-6.
Chapter 4

Hydrodesulfurization

Not to be confused with Flue-gas desulfurization. metal, laying the foundation of the modern catalytic hy-
drogenation process.
Hydrodesulfurization (HDS) is a catalytic chemical Soon after Sabatier’s work, a German chemist, Wilhelm
process widely used to remove sulfur (S) from natural gas Normann, found that catalytic hydrogenation could be
and from refined petroleum products such as gasoline or used to convert unsaturated fatty acids or glycerides in
petrol, jet fuel, kerosene, diesel fuel, and fuel oils.[1][2] the liquid phase into saturated ones. He was awarded a
The purpose of removing the sulfur is to reduce the sulfur patent in Germany in 1902[7] and in Britain in 1903,[8]
dioxide (SO which was the beginning of what is now a worldwide in-
2) emissions that result from using those fuels in auto- dustry.
motive vehicles, aircraft, railroad locomotives, ships, gas In the mid-1950s, the first noble metal catalytic reforming
or oil burning power plants, residential and industrial process (the Platformer process) was commercialized. At
furnaces, and other forms of fuel combustion. the same time, the catalytic hydrodesulfurization of the
Another important reason for removing sulfur from the naphtha feed to such reformers was also commercialized.
naphtha streams within a petroleum refinery is that sulfur, In the decades that followed, various proprietary catalytic
even in extremely low concentrations, poisons the noble hydrodesulfurization processes, such as the one depicted
metal catalysts (platinum and rhenium) in the catalytic re- in the flow diagram below, have been commercialized.
forming units that are subsequently used to upgrade the Currently, virtually all of the petroleum refineries world-
octane rating of the naphtha streams. wide have one or more HDS units.
The industrial hydrodesulfurization processes include fa- By 2006, miniature microfluidic HDS units had been im-
cilities for the capture and removal of the resulting plemented for treating JP-8 jet fuel to produce clean feed
hydrogen sulfide (H stock for a fuel cell hydrogen reformer.[9] By 2007, this
2S) gas. In petroleum refineries, the hydrogen sulfide gas had been integrated into an operating 5 kW fuel cell gen-
is then subsequently converted into byproduct elemental eration system.[10]
sulfur or sulfuric acid (H
2SO
4). In fact, the vast majority of the 64,000,000 metric
tons of sulfur produced worldwide in 2005 was byproduct 4.2 Process chemistry
sulfur from refineries and other hydrocarbon processing
plants.[3][4] Hydrogenation is a class of chemical reactions in
An HDS unit in the petroleum refining industry is also which the net result is the addition of hydrogen (H).
often referred to as a hydrotreater. Hydrogenolysis is a type of hydrogenation and results in
the cleavage of the C-X chemical bond, where C is a
carbon atom and X is a sulfur (S), nitrogen (N) or oxygen
4.1 History (O) atom. The net result of a hydrogenolysis reaction is
the formation of C-H and H-X chemical bonds. Thus,
hydrodesulfurization is a hydrogenolysis reaction. Using
Although some reactions involving catalytic hydrogena- ethanethiol (C
tion of organic substances were already known, the prop- 2H
erty of finely divided nickel to catalyze the fixation of hy- 5SH), a sulfur compound present in some petroleum
drogen on hydrocarbon (ethylene, benzene) double bonds products, as an example, the hydrodesulfurization reac-
was discovered by the French chemist Paul Sabatier in tion can be simply expressed as
1897.[5][6] Through this work, he found that unsaturated
hydrocarbons in the vapor phase could be converted into
saturated hydrocarbons by using hydrogen and a catalytic

19
20 CHAPTER 4. HYDRODESULFURIZATION

For the mechanistic aspects of, and the catalysts used in 2S that it contains. The H
this reaction see the section catalysts and mechanisms 2S-free hydrogen-rich gas is then recycled back for reuse
in the reactor section. Any excess gas from the gas sep-
arator vessel joins the sour gas from the stripping of the
4.3 Process description reaction product liquid.
The liquid from the gas separator vessel is routed through
In an industrial hydrodesulfurization unit, such as in a re- a reboiled stripper distillation tower. The bottoms prod-
finery, the hydrodesulfurization reaction takes place in a uct from the stripper is the final desulfurized liquid prod-
fixed-bed reactor at elevated temperatures ranging from uct from hydrodesulfurization unit.
300 to 400 °C and elevated pressures ranging from 30 The overhead sour gas from the stripper contains hydro-
to 130 atmospheres of absolute pressure, typically in the gen, methane, ethane, hydrogen sulfide, propane, and,
presence of a catalyst consisting of an alumina base im- perhaps, some butane and heavier components. That sour
pregnated with cobalt and molybdenum (usually called a gas is sent to the refinery’s central gas processing plant
CoMo catalyst). Occasionally, a combination of nickel for removal of the hydrogen sulfide in the refinery’s main
and molybdenum (called NiMo) is used, in addition to the amine gas treating unit and through a series of distilla-
CoMo catalyst, for specific difficult-to-treat feed stocks, tion towers for recovery of propane, butane and pentane
such as those containing a high level of chemically bound or heavier components. The residual hydrogen, methane,
nitrogen. ethane, and some propane is used as refinery fuel gas. The
The image below is a schematic depiction of the equip- hydrogen sulfide removed and recovered by the amine gas
ment and the process flow streams in a typical refinery treating unit is subsequently converted to elemental sulfur
HDS unit. in a Claus process unit or to sulfuric acid in a wet sulfuric
acid process or in the conventional Contact Process.
Note that the above description assumes that the HDS
unit feed contains no olefins. If the feed does contain
olefins (for example, the feed is a naphtha derived from a
refinery fluid catalytic cracker (FCC) unit), then the over-
head gas from the HDS stripper may also contain some
ethene, propene, butenes and pentenes, or heavier com-
ponents.
It should also be noted that the amine solution to and from
the recycle gas contactor comes from and is returned to
the refinery’s main amine gas treating unit.

Schematic diagram of a typical Hydrodesulfurization (HDS) unit


in a petroleum refinery
4.4 Sulfur compounds in refinery
The liquid feed (at the bottom left in the diagram) is HDS feedstocks
pumped up to the required elevated pressure and is joined
by a stream of hydrogen-rich recycle gas. The resulting The refinery HDS feedstocks (naphtha, kerosene, diesel
liquid-gas mixture is preheated by flowing through a heat oil, and heavier oils) contain a wide range of organic
exchanger. The preheated feed then flows through a fired sulfur compounds, including thiols, thiophenes, organic
heater where the feed mixture is totally vaporized and sulfides and disulfides, and many others. These organic
heated to the required elevated temperature before enter- sulfur compounds are products of the degradation of sul-
ing the reactor and flowing through a fixed-bed of catalyst fur containing biological components, present during the
where the hydrodesulfurization reaction takes place. natural formation of the fossil fuel, petroleum crude oil.
The hot reaction products are partially cooled by flow- When the HDS process is used to desulfurize a refinery
ing through the heat exchanger where the reactor feed naphtha, it is necessary to remove the total sulfur down
was preheated and then flows through a water-cooled heat to the parts per million range or lower in order to prevent
exchanger before it flows through the pressure controller poisoning the noble metal catalysts in the subsequent cat-
(PC) and undergoes a pressure reduction down to about alytic reforming of the naphthas.
3 to 5 atmospheres. The resulting mixture of liquid and When the process is used for desulfurizing diesel oils, the
gas enters the gas separator vessel at about 35 °C and 3 latest environmental regulations in the United States and
to 5 atmospheres of absolute pressure. Europe, requiring what is referred to as ultra-low sul-
Most of the hydrogen-rich gas from the gas separator ves- fur diesel (ULSD), in turn requires that very deep hy-
sel is recycle gas, which is routed through an amine con- drodesulfurization is needed. In the very early 2000s, the
tactor for removal of the reaction product H governmental regulatory limits for highway vehicle diesel
4.6. OTHER USES 21

was within the range of 300 to 500 ppm by weight of to- cobalt-modified MoS2 catalyst, nickel and tungsten are
tal sulfur. As of 2006, the total sulfur limit for highway also used, depending on the nature of the feed. For ex-
diesel is in the range of 15 to 30 ppm by weight.[11] ample, Ni-W catalysts are more effective for hydrodeni-
trogenation (HDN).

4.4.1 Thiophenes
4.5.2 Supports
A family of substrates that are particularly common
in petroleum are the aromatic sulfur-containing hete- Metal sulfides are “supported” on materials with high
rocycles called thiophenes. Many kinds of thiophenes surface areas. A typical support for HDS catalyst is γ-
occur in petroleum ranging from thiophene itself to alumina. The support allows the more expensive catalyst
more condensed derivatives called benzothiophenes and to be more widely distributed, giving rise to a larger frac-
dibenzothiophenes. Thiophene itself and its alkyl deriva- tion of the MoS
tives are easier to hydrogenolyse, whereas dibenzoth- 2 that is catalytically active. The interaction between the
iophene, especially its 4,6-disubstituted derivatives, are support and the catalyst is an area of intense interest, since
considered the most challenging substrates. Benzothio- the support is often not fully inert but participates in the
phenes are midway between the simple thiophenes and catalysis.
dibenzothiophenes in their susceptibility to HDS.

4.6 Other uses


4.5 Catalysts and mechanisms
The basic hydrogenolysis reaction has a number of uses
The main HDS catalysts are based on molybdenum disul- other than hydrodesulfurization.
fide (MoS
2) together with smaller amounts of other metals.[12] The
nature of the sites of catalytic activity remains an active 4.6.1 Hydrodenitrogenation
area of investigation, but it is generally assumed basal
planes of the MoS The hydrogenolysis reaction is also used to reduce the ni-
2 structure are not relevant to catalysis, rather the edges trogen content of a petroleum stream in a process referred
or rims of these sheet.[13] At the edges of the MoS to as hydrodenitrogenation (HDN). The process flow is
2 crystallites, the molybdenum centre can stabilize a co- the same as that for an HDS unit.
ordinatively unsaturated site (CUS), also known as an an-
ion vacancy. Substrates, such as thiophene, bind to this Using pyridine (C
site and undergo a series a reactions that result in both C- 5H
S scission and C=C hydrogenation. Thus, the hydrogen 5N), a nitrogen compound present in some petroleum
serves multiple roles—generation of anion vacancy by re- fractionation products, as an example, the hydrodeni-
moval of sulfide, hydrogenation, and hydrogenolysis. A trogenation reaction has been postulated as occurring in
simplified diagram for the cycle is shown: three steps:[15][16]

and the overall reaction may be simply expressed as:

Many HDS units for desulfurizing naphthas within


petroleum refineries are actually simultaneously denitro-
Simplified diagram of a HDS cycle for thiophene genating to some extent as well.

4.5.1 Catalysts 4.6.2 Saturation of olefins

Most metals catalyse HDS, but it is those at the mid- The hydrogenolysis reaction may also be used to saturate
dle of the transition metal series that are most active. or convert olefins (alkenes) into paraffins (alkanes). The
Ruthenium disulfide appears to be the single most active process used is the same as for an HDS unit.
catalyst, but binary combinations of cobalt and molyb- As an example, the saturation of the olefin pentene can
denum are also highly active.[14] Aside from the basic be simply expressed as:
22 CHAPTER 4. HYDRODESULFURIZATION

[12] Topsøe, H.; Clausen, B. S.; Massoth, F. E., Hydrotreat-


ing Catalysis, Science and Technology, Springer-Verlag:
Berlin, 1996.
Some hydrogenolysis units within a petroleum refinery or
a petrochemical plant may be used solely for the satu- [13] Daage, M.; Chianelli, R. R., “Structure-Function Rela-
ration of olefins or they may be used for simultaneously tions in Molybdenum Sulfide Catalysts - the Rim-Edge
desulfurizing as well as denitrogenating and saturating Model”, J. of Catalysis, 1994, 149, 414-427.
olefins to some extent.
[14] Chianelli, R. R.; Berhault, G.; Raybaud, P.; Kasztelan,
S.; Hafner, J. and Toulhoat, H., “Periodic trends in hy-
drodesulfurization: in support of the Sabatier principle”,
4.6.3 Hydrogenation in the food industry Applied Catalysis, A, 2002, volume 227, pages 83-96.

Further information: Hydrogenation, Wilhelm Normann [15] Kinetics and Interactions of the Simultaneous Catalytic Hy-
and Trans fat drodenitrogenation of Pyridine and Hydrodesulfurization
of Thiophene (John Wilkins, PhD Thesis, MIT, 1977)

The food industry uses hydrogenation to completely or [16] Simultaneous Catalytic Hydrodenitrogenation of Pyridine
partially saturate the unsaturated fatty acids in liquid and Hydrodesulfurization of Thiophene (Satterfield,C.N.,
vegetable fats and oils to convert them into solid or semi- Modell, M. and Wilkens, J.A., Ind. Eng. Chem. Process
solid fats, such as those in margarine and shortening. Des. Dev., 1980 Vol. 19, pages 154-160)

4.7 See also 4.9 External links


• Criterion Catalysts (Hydroprocessing Catalyst Sup-
• Claus process
plier)
• Hydrogen pinch • Haldor Topsoe (Catalyzing Your Business)
• Timeline of hydrogen technologies • Albemarle Catalyst Company (Petrochemical cata-
lysts supplier)

• UOP-Honeywell (Engineering design and construc-


4.8 References tion of large-scale, industrial HDS plants)
[1] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin- • Hydrogenation for Low Trans and High Conjugated
ing Technology and Economics (2nd ed.). Marcel Dekker, Fatty Acids by E.S. Jang, M.Y. Jung, D.B. Min,
Inc. ISBN 0-8247-7150-8. Comprehensive Reviews in Food Science and Food
Safety, Vol.1, 2005
[2] Hydrodesulfurization Technologies and Costs Nancy Ya-
maguchi, Trans Energy Associates, William and Flora • Oxo Alcohols (Engineered and constructed by Aker
Hewlett Foundation Sulfur Workshop, Mexico City, May Kvaerner)
29–30, 2003
• Catalysts and technology for Oxo-Alcohols
[3] Sulfur production report by the United States Geological
Survey

[4] Discussion of recovered byproduct sulfur

[5] C.R.Acad.Sci. 1897, 132, 210

[6] C.R.Acad.Sci. 1901, 132, 210

[7] DE Patent DE141029 (Espacenet, record not available)

[8] UK Patent GB190301515 GB190301515 (Espacenet)

[9] Microchannel HDS (March 2006)

[10] Fuel cells help make noisy, hot generators a thing of the
past (December 2007) Pacific Northwest National Labo-
ratory

[11] Diesel Sulfur published online by the National Petrochem-


ical & Refiners Association (NPRA)
Chapter 5

Catalytic reforming

used industrially to produce products such as hydrogen,


ammonia, and methanol from natural gas, naphtha or
other petroleum-derived feedstocks. Nor is this process
to be confused with various other catalytic reforming pro-
cesses that use methanol or biomass-derived feedstocks to
produce hydrogen for fuel cells or other uses.

5.1 History
In the 1940s, Vladimir Haensel,[1] a research chemist
working for Universal Oil Products (UOP), developed
a catalytic reforming process using a catalyst containing
platinum. Haensel’s process was subsequently commer-
cialized by UOP in 1949 for producing a high octane
gasoline from low octane naphthas and the UOP process
become known as the Platforming process.[2] The first
Platforming unit was built in 1949 at the refinery of the
A catalytic reformer unit in a petroleum refinery. © BP p.l.c Old Dutch Refining Company in Muskegon, Michigan.
In the years since then, many other versions of the pro-
Catalytic reforming is a chemical process used to con-
cess have been developed by some of the major oil com-
vert petroleum refinery naphthas distilled from crude oil
panies and other organizations. Today, the large majority
(typically having low octane ratings) into high-octane
of gasoline produced worldwide is derived from the cat-
liquid products called reformates, which are premium
alytic reforming process.
blending stocks for high-octane gasoline. The process
converts low-octane linear hydrocarbons (paraffins) into To name a few of the other catalytic reforming versions
branched alkanes (isoparaffins) and cyclic naphthenes, that were developed, all of which utilized a platinum
which are then partially dehydrogenated to produce high- and/or a rhenium catalyst:
octane aromatic hydrocarbons. The dehydrogenation
also produces significant amounts of byproduct hydrogen • Rheniforming: Developed by Chevron Oil Com-
gas, which is fed into other refinery processes such as pany.
hydrocracking. A side reaction is hydrogenolysis, which
• Powerforming: Developed by Esso Oil Company,
produces light hydrocarbons of lower value, such as
currently known as ExxonMobil.
methane, ethane, propane and butanes.
In addition to a gasoline blending stock, reformate is the • Magnaforming: Developed by Engelhard and
main source of aromatic bulk chemicals such as benzene, Atlantic Richfield Oil Company.
toluene, xylene and ethylbenzene which have diverse • Ultraforming: Developed by Standard Oil of Indi-
uses, most importantly as raw materials for conversion ana, now a part of the British Petroleum Company.
into plastics. However, the benzene content of reformate
makes it carcinogenic, which has led to governmental reg- • Houdriforming: Developed by the Houdry Process
ulations effectively requiring further processing to reduce Corporation.
its benzene content. • CCR Platforming: A Platforming version, designed
This process is quite different from and not to be for continuous catalyst regeneration, developed by
confused with the catalytic steam reforming process UOP.

23
24 CHAPTER 5. CATALYTIC REFORMING

• Octanizing: A catalytic reforming version developed The table just below lists some fairly typical straight-
by Axens, a subsidiary of Institut francais du petrole run heavy naphtha feedstocks, available for catalytic re-
(IFP), designed for continuous catalyst regeneration. forming, derived from various crude oils. It can be seen
that they differ significantly in their content of paraffins,
naphthenes and aromatics:
5.2 Chemistry .....
Some refinery naphthas include olefinic hydrocarbons,
Before describing the reaction chemistry of the catalytic such as naphthas derived from the fluid catalytic crack-
reforming process as used in petroleum refineries, the ing and coking processes used in many refineries. Some
typical naphthas used as catalytic reforming feedstocks refineries may also desulfurize and catalytically reform
will be discussed. those naphthas. However, for the most part, catalytic re-
forming is mainly used on the straight-run heavy naph-
thas, such as those in the above table, derived from the
5.2.1 Typical naphtha feedstocks
distillation of crude oils.
A petroleum refinery includes many unit operations and
unit processes. The first unit operation in a refinery 5.2.2 The reaction chemistry
is the continuous distillation of the petroleum crude oil
being refined. The overhead liquid distillate is called There are many chemical reactions that occur in the cat-
naphtha and will become a major component of the re- alytic reforming process, all of which occur in the pres-
finery’s gasoline (petrol) product after it is further pro- ence of a catalyst and a high partial pressure of hydrogen.
cessed through a catalytic hydrodesulfurizer to remove Depending upon the type or version of catalytic reform-
sulfur-containing hydrocarbons and a catalytic reformer ing used as well as the desired reaction severity, the reac-
to reform its hydrocarbon molecules into more complex tion conditions range from temperatures of about 495 to
molecules with a higher octane rating value. The naphtha 525 °C and from pressures of about 5 to 45 atm.[10]
is a mixture of very many different hydrocarbon com-
pounds. It has an initial boiling point of about 35 °C The commonly used catalytic reforming catalysts con-
and a final boiling point of about 200 °C, and it contains tain noble metals such as platinum and/or rhenium,
paraffin, naphthene (cyclic paraffins) and aromatic hydro- which are very susceptible to poisoning by sulfur and
carbons ranging from those containing 4 carbon atoms to nitrogen compounds. Therefore, the naphtha feedstock
those containing about 10 or 11 carbon atoms. to a catalytic reformer is always pre-processed in a
hydrodesulfurization unit which removes both the sulfur
The naphtha from the crude oil distillation is often further and the nitrogen compounds. Most catalysts require both
distilled to produce a “light” naphtha containing most (but sulphur and nitrogen content to be lower than 1 ppm.
not all) of the hydrocarbons with 6 or fewer carbon atoms
[11]
and a “heavy” naphtha containing most (but not all) of the The four major catalytic reforming reactions are:
hydrocarbons with more than 6 carbon atoms. The heavy
naphtha has an initial boiling point of about 140 to 150 1: The dehydrogenation of naphthenes to con-
°C and a final boiling point of about 190 to 205 °C. The vert them into aromatics as exemplified in the
naphthas derived from the distillation of crude oils are conversion methylcyclohexane (a naphthene)
referred to as “straight-run” naphthas. to toluene (an aromatic), as shown below:
It is the straight-run heavy naphtha that is usually pro-
cessed in a catalytic reformer because the light naphtha
has molecules with 6 or fewer carbon atoms which, when + 3 H2
reformed, tend to crack into butane and lower molecular
weight hydrocarbons which are not useful as high-octane
gasoline blending components. Also, the molecules with
6 carbon atoms tend to form aromatics which is undesir-
able because governmental environmental regulations in a 2: The isomerization of normal paraffins to
number of countries limit the amount of aromatics (most isoparaffins as exemplified in the conversion
particularly benzene) that gasoline may contain.[3][4][5] of normal octane to 2,5-Dimethylhexane (an
isoparaffin), as shown below:
It should be noted that there are a great many petroleum
crude oil sources worldwide and each crude oil has its
own unique composition or “assay”. Also, not all refiner-
ies process the same crude oils and each refinery produces
its own straight-run naphthas with their own unique ini-
tial and final boiling points. In other words, naphtha is a
generic term rather than a specific term.
5.3. PROCESS DESCRIPTION 25

3: The dehydrogenation and aromatization of once each 6 to 24 months. Such a unit is referred to as a
paraffins to aromatics (commonly called dehy- semi-regenerative catalytic reformer (SRR).
drocyclization) as exemplified in the conver- Some catalytic reforming units have an extra spare or
sion of normal heptane to toluene, as shown swing reactor and each reactor can be individually iso-
below: lated so that any one reactor can be undergoing in situ
regeneration while the other reactors are in operation.
When that reactor is regenerated, it replaces another re-
actor which, in turn, is isolated so that it can then be re-
generated. Such units, referred to as cyclic catalytic re-
formers, are not very common. Cyclic catalytic reformers
serve to extend the period between required shutdowns.
The latest and most modern type of catalytic reform-
ers are called continuous catalyst regeneration (CCR) re-
formers. Such units are characterized by continuous in-
4: The hydrocracking of paraffins into smaller
situ regeneration of part of the catalyst in a special regen-
molecules as exemplified by the cracking of
erator, and by continuous addition of the regenerated cat-
normal heptane into isopentane and ethane, as
alyst to the operating reactors. As of 2006, two CCR ver-
shown below:
sions available: UOP’s CCR Platformer process[13] and
Axens’ Octanizing process.[14] The installation and use of
CCR units is rapidly increasing.
Many of the earliest catalytic reforming units (in the
1950s and 1960s) were non-regenerative in that they did
not perform in situ catalyst regeneration. Instead, when
needed, the aged catalyst was replaced by fresh catalyst
The hydrocracking of paraffins is the only one of the and the aged catalyst was shipped to catalyst manufac-
above four major reforming reactions that consumes hy- turers to be either regenerated or to recover the platinum
drogen. The isomerization of normal paraffins does not content of the aged catalyst. Very few, if any, catalytic
consume or produce hydrogen. However, both the de- reformers currently in operation are non-regenerative.
hydrogenation of naphthenes and the dehydrocyclization The process flow diagram below depicts a typical semi-
of paraffins produce hydrogen. The overall net produc- regenerative catalytic reforming unit.
tion of hydrogen in the catalytic reforming of petroleum
naphthas ranges from about 50 to 200 cubic meters of
hydrogen gas (at 0 °C and 1 atm) per cubic meter of
liquid naphtha feedstock. In the United States custom-
ary units, that is equivalent to 300 to 1200 cubic feet of
hydrogen gas (at 60 °F and 1 atm) per barrel of liquid
naphtha feedstock.[12] In many petroleum refineries, the
net hydrogen produced in catalytic reforming supplies a
significant part of the hydrogen used elsewhere in the re-
finery (for example, in hydrodesulfurization processes).
The hydrogen is also necessary in order to hydrogenolyze
any polymers that form on the catalyst. Schematic diagram of a typical semi-regenerative catalytic re-
In practice, the higher the content of naphtenes in the former unit in a petroleum refinery
naphtha feedstock, the better will be the quality of the
reformate and the higher the production of hydrogen. The liquid feed (at the bottom left in the diagram) is
Crude oils containing the best naphtha for reforming are pumped up to the reaction pressure (5–45 atm) and is
typically from Western Africa or the North Sea, such as joined by a stream of hydrogen-rich recycle gas. The re-
Bonny light or Troll. sulting liquid–gas mixture is preheated by flowing through
a heat exchanger. The preheated feed mixture is then to-
tally vaporized and heated to the reaction temperature
(495–520 °C) before the vaporized reactants enter the
5.3 Process description first reactor. As the vaporized reactants flow through the
fixed bed of catalyst in the reactor, the major reaction is
The most commonly used type of catalytic reforming unit the dehydrogenation of naphthenes to aromatics (as de-
has three reactors, each with a fixed bed of catalyst, and scribed earlier herein) which is highly endothermic and
all of the catalyst is regenerated in situ during routine cat- results in a large temperature decrease between the in-
alyst regeneration shutdowns which occur approximately let and outlet of the reactor. To maintain the required
26 CHAPTER 5. CATALYTIC REFORMING

reaction temperature and the rate of reaction, the vapor- 5.4 Catalysts and mechanisms
ized stream is reheated in the second fired heater before it
flows through the second reactor. The temperature again Most catalytic reforming catalysts contain platinum or
decreases across the second reactor and the vaporized rhenium on a silica or silica-alumina support base, and
stream must again be reheated in the third fired heater be- some contain both platinum and rhenium. Fresh catalyst
fore it flows through the third reactor. As the vaporized is chlorided (chlorinated) prior to use.
stream proceeds through the three reactors, the reaction
rates decrease and the reactors therefore become larger. The noble metals (platinum and rhenium) are consid-
At the same time, the amount of reheat required between ered to be catalytic sites for the dehydrogenation reac-
the reactors becomes smaller. Usually, three reactors are tions and the chlorinated alumina provides the acid sites
all that is required to provide the desired performance of needed for isomerization, cyclization and hydrocracking
the catalytic reforming unit. reactions.[11] The biggest care has to be exercised dur-
ing the chlorination. Indeed if not chlorinated (or in-
Some installations use three separate fired heaters as sufficiently chlorinated) the platinum and rhenium in the
shown in the schematic diagram and some installations catalyst would be reduced almost immediately to metal-
use a single fired heater with three separate heating coils. lic state by the hydrogen in the vapour phase. On the
The hot reaction products from the third reactor are par- other an excessive chlorination could depress excessively
tially cooled by flowing through the heat exchanger where the activity of the catalyst.
the feed to the first reactor is preheated and then flow The activity (i.e., effectiveness) of the catalyst in a semi-
through a water-cooled heat exchanger before flowing regenerative catalytic reformer is reduced over time dur-
through the pressure controller (PC) into the gas sepa- ing operation by carbonaceous coke deposition and chlo-
rator. ride loss. The activity of the catalyst can be periodically
Most of the hydrogen-rich gas from the gas separator ves- regenerated or restored by in situ high temperature ox-
sel returns to the suction of the recycle hydrogen gas com- idation of the coke followed by chlorination. As stated
pressor and the net production of hydrogen-rich gas from earlier herein, semi-regenerative catalytic reformers are
the reforming reactions is exported for use in the other regenerated about once per 6 to 24 months. The higher
refinery processes that consume hydrogen (such as hy- the severity of the reacting conditions (temperature), the
drodesulfurization units and/or a hydrocracker unit). higher is the octane of the produced reformate but also
the shorter will be the duration of the cycle between two
The liquid from the gas separator vessel is routed into a
regenerations. Catalyst’s cycle duration is also very de-
fractionating column commonly called a stabilizer. The
pendent on the quality of the feedstock. However, in-
overhead offgas product from the stabilizer contains the
dependently of the crude oil used in the refinery, all cata-
byproduct methane, ethane, propane and butane gases
lysts require a maximum final boiling point of the naphtha
produced by the hydrocracking reactions as explained
feedstock of 180 °C.
in the above discussion of the reaction chemistry of a
catalytic reformer, and it may also contain some small Normally, the catalyst can be regenerated perhaps 3 or
amount of hydrogen. That offgas is routed to the refin- 4 times before it must be returned to the manufacturer
ery’s central gas processing plant for removal and recov- for reclamation of the valuable platinum and/or rhenium
ery of propane and butane. The residual gas after such content.[11]
processing becomes part of the refinery’s fuel gas system.
The bottoms product from the stabilizer is the high-
octane liquid reformate that will become a component of 5.5 Economics
the refinery’s product gasoline. Reformate can be blended
directly in the gasoline pool but often it is separated in
two or more streams. A common refining scheme con-
5.6 References
sists in fractionating the reformate in two streams, light
and heavy reformate. The light reformate has lower oc- [1] A Biographical Memoir of Vladimir Haensel written by
tane and can be used as isomerization feedstock if this Stanley Gembiki, published by the National Academy of
Sciences in 2006.
unit is available. The heavy reformate is high in octane
and low in benzene, hence it is an excellent blending com- [2] Platforming described on UOP’s website
ponent for the gasoline pool.
[3] Canadian regulations on benzene in gasoline
Benzene is often removed with a specific operation to re-
duce the content of benzene in the reformate as the fin- [4] United Kingdom regulations on benzene in gasoline
ished gasoline has often an upper limit of benzene content
(in the UE this is 1% volume). The benzene extracted can [5] USA regulations on benzene in gasoline
be marketed as feedstock for the chemical industry. [6] Barrow Island crude oil assay

[7] Mutineer-Exeter crude oil assay


5.7. EXTERNAL LINKS 27

[8] CPC Blend crude oil assay

[9] Draugen crude oil assay

[10] OSHA Technical Manual, Section IV, Chapter 2,


Petroleum refining Processes (A publication of the
Occupational Safety and Health Administration)

[11] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-


ing Technology and Economics (2nd Edition ed.). Marcel
Dekker, Inc. ISBN 0-8247-7150-8.

[12] US Patent 5011805, Dehydrogenation, dehydrocyclization


and reforming catalyst (Inventor: Ralph Dessau, Assignee:
Mobil Oil Corporation)

[13] CCR Platforming (UOP website)

[14] Octanizing Options (Axens website)

5.7 External links


• Oil Refinery Processes, A Brief Overview
• Colorado School of Mines, Lecture Notes (Chapter
10, Refining Processes, Catalytic Refinery by John
Jechura, Adjunct Professor)

• Students’ Guide to Refining (scroll down to Plat-


forming)

• Modern Refinery Website of Delft University of


Technology, Netherlands (use search function for
Reforming)
• Major scientific and technical challenges about de-
velopment of new refining processes (IFP website)
Chapter 6

Fluid catalytic cracking

and breaks the long-chain molecules of the high-boiling


hydrocarbon liquids into much shorter molecules by con-
tacting the feedstock, at high temperature and moderate
pressure, with a fluidized powdered catalyst.
In effect, refineries use fluid catalytic cracking to correct
the imbalance between the market demand for gasoline
and the excess of heavy, high boiling range products re-
sulting from the distillation of crude oil.
As of 2006, FCC units were in operation at 400
petroleum refineries worldwide and about one-third of
the crude oil refined in those refineries is processed in an
FCC to produce high-octane gasoline and fuel oils.[2][4]
During 2007, the FCC units in the United States pro-
cessed a total of 5,300,000 barrels (840,000 m3 ) per day
of feedstock[5] and FCC units worldwide processed about
twice that amount.

6.1 Flow diagram and process de-


scription
The modern FCC units are all continuous processes
which operate 24 hours a day for as long as 3 to 5 years
A typical fluid catalytic cracking unit in a petroleum refinery.
between scheduled shutdowns for routine maintenance.
There are several different proprietary designs that have
Fluid catalytic cracking (FCC) is one of the most im- been developed for modern FCC units. Each design is
portant conversion processes used in petroleum refiner- available under a license that must be purchased from the
ies. It is widely used to convert the high-boiling, high- design developer by any petroleum refining company de-
molecular weight hydrocarbon fractions of petroleum siring to construct and operate an FCC of a given design.
crude oils to more valuable gasoline, olefinic gases, and
other products.[1][2][3] Cracking of petroleum hydrocar- There are two different configurations for an FCC unit:
bons was originally done by thermal cracking, which has the “stacked” type where the reactor and the catalyst re-
been almost completely replaced by catalytic cracking generator are contained in a single vessel with the reactor
because it produces more gasoline with a higher octane above the catalyst regenerator and the “side-by-side” type
rating. It also produces byproduct gases that are more where the reactor and catalyst regenerator are in two sep-
olefinic, and hence more valuable, than those produced arate vessels. These are the major FCC designers and
by thermal cracking. licensors:[1][3][4][6]
The feedstock to an FCC is usually that portion of the Side-by-side configuration:
crude oil that has an initial boiling point of 340 °C or
higher at atmospheric pressure and an average molecular • CB&I
weight ranging from about 200 to 600 or higher. This
• ExxonMobil Research and Engineering (EMRE)
portion of crude oil is often referred to as heavy gas oil
or vacuum gas oil (HVGO). The FCC process vaporizes • Shell Global Solutions

28
6.1. FLOW DIAGRAM AND PROCESS DESCRIPTION 29

• Axens / Stone & Webster Process Technology — The hot catalyst (at about 715 °C) leaving the regenerator
currently owned by Technip flows into a catalyst withdrawal well where any entrained
combustion flue gases are allowed to escape and flow back
• Universal Oil Products (UOP) — currently fully into the upper part to the regenerator. The flow of regen-
owned subsidiary of Honeywell erated catalyst to the feedstock injection point below the
catalyst riser is regulated by a slide valve in the regener-
Stacked configuration: ated catalyst line. The hot flue gas exits the regenerator
after passing through multiple sets of two-stage cyclones
that remove entrained catalyst from the flue gas,
• Kellogg Brown & Root (KBR)
The amount of catalyst circulating between the regen-
Each of the proprietary design licensors claims to have erator and the reactor amounts to about 5 kg per kg of
unique features and advantages. A complete discussion of feedstock, which [1][7]
is equivalent to about 4.66 kg per litre
the relative advantages of each of the processes is beyond of feedstock. Thus, an FCC unit processing 75,000
the scope of this article. Suffice it to say that all of the barrels per day (11,900 m3 /d) will circulate about 55,900
licensors have designed and constructed FCC units that tonnes per day of catalyst.
have operated quite satisfactorily.

6.1.1 Reactor and Regenerator

The reactor and regenerator are considered to be the heart


of the fluid catalytic cracking unit. The schematic flow
diagram of a typical modern FCC unit in Figure 1 below
is based upon the “side-by-side” configuration. The pre-
heated high-boiling petroleum feedstock (at about 315 to
430 °C) consisting of long-chain hydrocarbon molecules
is combined with recycle slurry oil from the bottom of
the distillation column and injected into the catalyst riser
where it is vaporized and cracked into smaller molecules
of vapor by contact and mixing with the very hot pow-
dered catalyst from the regenerator. All of the cracking
reactions take place in the catalyst riser within a period of
2–4 seconds. The hydrocarbon vapors “fluidize” the pow- Figure 1: A schematic flow diagram of a Fluid Catalytic Crack-
dered catalyst and the mixture of hydrocarbon vapors and ing unit as used in petroleum refineries
catalyst flows upward to enter the reactor at a temperature
of about 535 °C and a pressure of about 1.72 barg.
The reactor is a vessel in which the cracked product va- 6.1.2 Distillation column
pors are: (a) separated from the so-called spent catalyst
The reaction product vapors (at 535 °C and a pressure
by flowing through a set of two-stage cyclones within the
reactor and (b) the spent catalyst flows downward through of 1.72 barg) flow from the top of the reactor to the
bottom section of the distillation column (commonly re-
a steam stripping section to remove any hydrocarbon va-
pors before the spent catalyst returns to the catalyst re- ferred to as the main fractionator) where they are distilled
into the FCC end products of cracked naphtha, fuel oil,
generator. The flow of spent catalyst to the regenerator is
regulated by a slide valve in the spent catalyst line. and offgas. After further processing for removal of sulfur
compounds, the cracked naphtha becomes a high-octane
Since the cracking reactions produce some carbonaceous component of the refinery’s blended gasolines.
material (referred to as catalyst coke) that deposits on the
catalyst and very quickly reduces the catalyst reactivity, The main fractionator offgas is sent to what is called a
the catalyst is regenerated by burning off the deposited gas recovery unit where it is separated into butanes and
coke with air blown into the regenerator. The regenera- butylenes, propane and propylene, and lower molecular
tor operates at a temperature of about 715 °C and a pres- weight gases (hydrogen, methane, ethylene and ethane).
sure of about 2.41 barg. The combustion of the coke is Some FCC gas recovery units may also separate out some
exothermic and it produces a large amount of heat that of the ethane and ethylene.
is partially absorbed by the regenerated catalyst and pro- Although the schematic flow diagram above depicts the
vides the heat required for the vaporization of the feed- main fractionator as having only one sidecut stripper and
stock and the endothermic cracking reactions that take one fuel oil product, many FCC main fractionators have
place in the catalyst riser. For that reason, FCC units are two sidecut strippers and produce a light fuel oil and a
often referred to as being 'heat balanced'. heavy fuel oil. Likewise, many FCC main fractiona-
30 CHAPTER 6. FLUID CATALYTIC CRACKING

tors produce a light cracked naphtha and a heavy cracked The flue gas is finally processed through an electrostatic
naphtha. The terminology light and heavy in this context precipitator (ESP) to remove residual particulate matter
refers to the product boiling ranges, with light products to comply with any applicable environmental regulations
having a lower boiling range than heavy products. regarding particulate emissions. The ESP removes par-
The bottom product oil from the main fractionator con- ticulates in the size range of 2 to 20 µm from the flue
tains residual catalyst particles which were not completely gas.[3] Particulate filter systems, known as Fourth Stage
removed by the cyclones in the top of the reactor. For that Separators (FSS) are sometimes required to meet partic-
reason, the bottom product oil is referred to as a slurry oil. ulate emission limits. These can replace the ESP when
particulate emissions are the only concern.
Part of that slurry oil is recycled back into the main frac-
tionator above the entry point of the hot reaction product The steam turbine in the flue gas processing system
vapors so as to cool and partially condense the reaction (shown in the above diagram) is used to drive the regener-
product vapors as they enter the main fractionator. The ator’s combustion air compressor during start-ups of the
remainder of the slurry oil is pumped through a slurry set- FCC unit until there is sufficient combustion flue gas to
tler. The bottom oil from the slurry settler contains most take over that task.
of the slurry oil catalyst particles and is recycled back into
the catalyst riser by combining it with the FCC feedstock
oil. The so-called clarified slurry oil or decant oil is with- 6.2 Chemistry
drawn from the top of slurry settler for use elsewhere in
the refinery, as a heavy fuel oil blending component, or
Before delving into the chemistry involved in catalytic
as carbon black feedstock.
cracking, it will be helpful to briefly discuss the compo-
sition of petroleum crude oil.
Petroleum crude oil consists primarily of a mixture of
6.1.3 Regenerator flue gas hydrocarbons with small amounts of other organic com-
pounds containing sulfur, nitrogen and oxygen. The crude
Depending on the choice of FCC design, the combustion oil also contains small amounts of metals such as copper,
in the regenerator of the coke on the spent catalyst may or iron, nickel and vanadium.[2]
may not be complete combustion to carbon dioxide CO
The elemental composition ranges of crude oil are sum-
2. The combustion air flow is controlled so as to pro-
marized in Table 1 and the hydrocarbons in the crude oil
vide the desired ratio of carbon monoxide (CO) to carbon
can be classified into three types:[1][2]
dioxide for each specific FCC design.[1][4]
In the design shown in Figure 1, the coke has only been • Paraffins or alkanes: saturated straight-chain or
partially combusted to CO branched hydrocarbons, without any ring structures
2. The combustion flue gas (containing CO and CO
2) at 715 °C and at a pressure of 2.41 barg is routed • Naphthenes or cycloalkanes: saturated hydrocar-
through a secondary catalyst separator containing swirl bons having one or more ring structures with one
tubes designed to remove 70 to 90 percent of the or more side-chain paraffins
particulates in the flue gas leaving the regenerator.[8] This
is required to prevent erosion damage to the blades in the • Aromatics: hydrocarbons having one or more un-
turbo-expander that the flue gas is next routed through. saturated ring structures such as benzene or unsatu-
rated polycyclic ring structures such as naphthalene
The expansion of flue gas through a turbo-expander pro- or phenanthrene, any of which may also have one or
vides sufficient power to drive the regenerator’s combus- more side-chain paraffins.
tion air compressor. The electrical motor-generator can
consume or produce electrical power. If the expansion of
the flue gas does not provide enough power to drive the Olefins or alkenes, which are unsaturated straight-chain
air compressor, the electric motor/generator provides the or branched hydrocarbons, do not occur naturally in crude
needed additional power. If the flue gas expansion pro- oil.
vides more power than needed to drive the air compres- In plain language, the fluid catalytic cracking pro-
sor, than the electric motor/generator converts the excess cess breaks large hydrocarbon molecules into smaller
power into electric power and exports it to the refinery’s molecules by contacting them with powdered catalyst at
electrical system.[3] a high temperature and moderate pressure which first va-
The expanded flue gas is then routed through a steam- porizes the hydrocarbons and then breaks them. The
generating boiler (referred to as a CO boiler) where the cracking reactions occur in the vapor phase and start im-
carbon monoxide in the flue gas is burned as fuel to pro- mediately when the feedstock is vaporized in the catalyst
vide steam for use in the refinery as well as to comply with riser.
any applicable environmental regulatory limits on carbon Figure 2 is a very simplified schematic diagram
monoxide emissions.[3] that exemplifies how the process breaks high boiling,
6.2. CHEMISTRY 31

in the technical literature.[1][2][3][4]

6.2.1 Catalysts

Modern FCC catalysts are fine powders with a bulk


density of 0.80 to 0.96 g/cm3 and having a particle size
distribution ranging from 10 to 150 µm and an average
particle size of 60 to 100 μm.[9][10] The design and oper-
ation of an FCC unit is largely dependent upon the chem-
ical and physical properties of the catalyst. The desirable
properties of an FCC catalyst are:

• Good stability to high temperature and to steam

• High activity

• Large pore sizes

• Good resistance to attrition


Figure 2: Diagrammatic example of the catalytic cracking of • Low coke production
petroleum hydrocarbons

A modern FCC catalyst has four major components:


straight-chain alkane (paraffin) hydrocarbons into smaller crystalline zeolite, matrix, binder, and filler. Zeolite is
straight-chain alkanes as well as branched-chain alkanes, the primary active component and can range from about
branched alkenes (olefins) and cycloalkanes (naphthenes). 15 to 50 weight percent of the catalyst. The zeolite used in
The breaking of the large hydrocarbon molecules into FCC catalysts is referred to as faujasite or as Type Y and
smaller molecules is more technically referred to by or- is composed of silica and alumina tetrahedra with each
ganic chemists as scission of the carbon-to-carbon bonds. tetrahedron having either an aluminum or a silicon atom
at the center and four oxygen atoms at the corners. It is
As depicted in Figure 2, some of the smaller alkanes are a molecular sieve with a distinctive lattice structure that
then broken and converted into even smaller alkenes and allows only a certain size range of hydrocarbon molecules
branched alkenes such as the gases ethylene, propylene, to enter the lattice. In general, the zeolite does not allow
butylenes, and isobutylenes. Those olefinic gases are molecules larger than 8 to 10 nm (i.e., 80 to 90 ångströms)
valuable for use as petrochemical feedstocks. The propy- to enter the lattice.[9][10]
lene, butylene and isobutylene are also valuable feed-
stocks for certain petroleum refining processes that con- The catalytic sites in the zeolite are strong acids (equiv-
vert them into high-octane gasoline blending compo- alent to 90% sulfuric acid) and provide most of the cat-
nents. alytic activity. The acidic sites are provided by the alu-
mina tetrahedra. The aluminum atom at the center of
As also depicted in Figure 2, the cycloalkanes (naph- each alumina tetrahedra is at a +3 oxidation state sur-
thenes) formed by the initial breakup of the large
rounded by four oxygen atoms at the corners which are
molecules are further converted to aromatics such as shared by the neighboring tetrahedra. Thus, the net
benzene, toluene, and xylenes, which boil in the gasoline
charge of the alumina tetrahedra is −1 which is bal-
boiling range and have much higher octane ratings than anced by a sodium ion during the production of the cat-
alkanes. alyst. The sodium ion is later replaced by an ammonium
In the cracking process carbon is also produced which ion, which is vaporized when the catalyst is subsequently
gets deposited on the catalyst (catalyst coke). The carbon dried, resulting in the formation of Lewis and Brønsted
formation tendency or amount of carbon in a crude or acidic sites. In some FCC catalysts, the Brønsted sites
FCC feed is measured with methods such as Micro Car- may be later replaced by rare earth metals such as cerium
bon Residue, Conradson Carbon Residue or Ramsbottom and lanthanum to provide alternative activity and stability
Carbon Residue. levels.[9][10]
By no means does Figure 2 include all the chemistry of The matrix component of an FCC catalyst contains amor-
the primary and secondary reactions taking place in the phous alumina which also provides catalytic activity sites
fluid catalytic process. There are a great many other re- and in larger pores that allows entry for larger molecules
actions involved. However, a full discussion of the highly than does the zeolite. That enables the cracking of higher-
technical details of the various catalytic cracking reac- boiling, larger feedstock molecules than are cracked by
tions is beyond the scope of this article and can be found the zeolite.
32 CHAPTER 6. FLUID CATALYTIC CRACKING

The binder and filler components provide the physical 6.3 History
strength and integrity of the catalyst. The binder is usu-
ally silica sol and the filler is usually a clay (kaolin).
Nickel, vanadium, iron, copper and other metal contami- The first commercial use of catalytic cracking occurred in
nants, present in FCC feedstocks in the parts per million 1915 when Almer M. McAfee of Gulf Refining Company
range, all have detrimental effects on the catalyst activity developed a batch process using aluminum chloride (a
and performance. Nickel and vanadium are particularly Friedel Crafts catalyst known since 1877) to catalytically
troublesome. There are a number of methods for miti- crack heavy petroleum oils. However, the prohibitive cost
gating the effects of the contaminant metals:[11][12] of the catalyst prevented the widespread use of McAfee’s
process at that time.[2][14]
In 1922, a French mechanical engineer named Eugene
• Avoid feedstocks with high metals content: This
Jules Houdry and a French pharmacist named E.A. Prud-
seriously hampers a refinery’s flexibility to process
homme set up a laboratory near Paris to develop a cat-
various crude oils or purchased FCC feedstocks.
alytic process for converting lignite coal to gasoline. Sup-
ported by the French government, they built a small
• Feedstock feed pretreatment: Hydrodesulfurization
demonstration plant in 1929 that processed about 60 tons
of the FCC feedstock removes some of the metals
per day of lignite coal. The results indicated that the pro-
and also reduces the sulfur content of the FCC prod-
cess was not economically viable and it was subsequently
ucts. However, this is quite a costly option.
shut down.[15][16][17]
• Increasing fresh catalyst addition: All FCC units Houdry had found that Fuller’s earth, a clay mineral con-
withdraw some of the circulating equilibrium cata- taining aluminosilicates, could convert oil derived from
lyst as spent catalyst and replaces it with fresh cata- the lignite to gasoline. He then began to study the cataly-
lyst in order to maintain a desired level of activity. sis of petroleum oils and had some success in converting
Increasing the rate of such exchange lowers the level vaporized petroleum oil to gasoline. In 1930, the Vacuum
of metals in the circulating equilibrium catalyst, but Oil Company invited him to come to the United States
this is also quite a costly option. and he moved his laboratory to Paulsboro, New Jersey.
In 1931, the Vacuum Oil Company merged with Standard
• Demetallization: The commercial proprietary Oil of New York (Socony) to form the Socony-Vacuum
Demet Process removes nickel and vanadium from Oil Company. In 1933, a small Houdry unit processed
the withdrawn spent catalyst. The nickel and 200 barrels per day (32 m3 /d) of petroleum oil. Because
vanadium are converted to chlorides which are of the economic depression of the early 1930s, Socony-
then washed out of the catalyst. After drying, the Vacuum was no longer able to support Houdry’s work and
demetallized catalyst is recycled into the circulating gave him permission to seek help elsewhere.
catalyst. Removals of about 95 percent nickel
removal and 67 to 85 percent vanadium have been In 1933, Houdry and Socony-Vacuum joined with Sun
reported. Despite that, the use of the Demet process Oil Company in developing the Houdry process. Three
has not become widespread, perhaps because of the years later, in 1936, Socony-Vacuum converted an older
high capital expenditure required. thermal cracking unit in their Paulsboro refinery in New
Jersey to a small demonstration unit using the Houdry
• Metals passivation: Certain materials can be used as process
3
to catalytically crack 2,000 barrels per day (320
additives which can be impregnated into the catalyst m /d) of petroleum oil.
or added to the FCC feedstock in the form of metal- In 1937, Sun Oil began operation of a new Houdry unit
organic compounds. Such materials react with the processing 12,000 barrels per day (1,900 m3 /d) in their
metal contaminants and passivate the contaminants Marcus Hook refinery in Pennsylvania. The Houdry pro-
by forming less harmful compounds that remain on cess at that time used reactors with a fixed bed of catalyst
the catalyst. For example, antimony and bismuth and was a semi-batch operation involving multiple reac-
are effective in passivating nickel and tin is effective tors with some of the reactors in operation while other
in passivating vanadium. A number of proprietary reactors were in various stages of regenerating the cata-
passivation processes are available and fairly widely lyst. Motor-driven valves were used to switch the reactors
used. between online operation and offline regeneration and a
cycle timer managed the switching. Almost 50 percent of
The major suppliers of FCC catalysts worldwide in- the cracked product was gasoline as compared with about
[15][16][17]
clude Albemarle Corporation, W.R. Grace Company and 25 percent from the thermal cracking processes.
BASF Catalysts (formerly Engelhard). The price for By 1938, when the Houdry process was publicly an-
lanthanum oxide used in fluid catalytic cracking has risen nounced, Socony-Vacuum had eight additional units un-
from $5 per kilogram in early 2010 to $140 per kilogram der construction. Licensing the process to other compa-
in June 2011.[13] nies also began and by 1940 there were 14 Houdry units
6.4. SEE ALSO 33

in operation processing 140,000 barrels per day (22,000 alytic cracking unit. Their U.S. Patent No. 2,451,804,
m3 /d). A Method of and Apparatus for Contacting Solids and
The next major step was to develop a continuous process Gases, describes their milestone invention. Based on their
rather than the semi-batch Houdry process. That step work, M. W. Kellogg Company constructed a large pilot
was implemented by advent of the moving-bed process plant in the Baton Rouge, Louisiana refinery of the Stan-
known as the Thermofor Catalytic Cracking (TCC) pro- dard Oil of New Jersey. The pilot plant began operation
cess which used a bucket conveyor-elevator to move the in May 1940.
catalyst from the regeneration kiln to the separate reac- Based on the success of the pilot plant, the first commer-
tor section. A small semicommercial demonstration TCC cial fluid catalytic cracking plant (known as the Model
unit was built in Socony-Vacuum’s Paulsboro refinery in I FCC) began processing 13,000 barrels per day (2,100
1941 and operated successfully, producing 500 barrels m3 /d) of petroleum oil in the Baton Rouge refinery on
per day (79 m3 /d). Then a full-scale commercial TCC May 25, 1942, just four years after the CRA consortium
unit processing 10,000 barrels per day (1,600 m3 /d) be- was formed and in the midst of World War II. A little
gan operation in 1943 at the Beaumont, Texas refinery of more than a month later, in July 1942, it was processing
Magnolia Oil Company, an affiliate of Socony-Vacuum. 17,000 barrels per day (2,700 m3 /d). In 1963, that first
By the end of World War II in 1945, the processing ca- Model I FCC unit was shut down after 21 years of oper-
pacity of the TCC units in operation was about 300,000 ation and subsequently dismantled.[15][16][17][18]
barrels per day (48,000 m3 /d). In the many decades since the Model I FCC unit be-
It is said that the Houdry and TCC units were a ma- gan operation, the fixed bed Houdry units have all been
jor factor in the winning of World War II by supply- shut down as have most of the moving bed units (such
ing the high-octane gasoline needed by the air forces of as the TCC units) while hundreds of FCC units have
Great Britain and the United States for the more efficient been built. During those decades, many improved FCC
higher compression ratio engines of the Spitfire and the designs have evolved and cracking catalysts have been
Mustang.[15][16][17] greatly improved, but the modern FCC units are essen-
In the years immediately after World War II, the Houdri- tially the same as that first Model I FCC unit.
flow process and the air-lift TCC process were developed Note: All of the refinery and company names in this his-
as improved variations on the moving-bed theme. Just tory section (with the exception of Universal Oil Prod-
like Houdry’s fixed-bed reactors, the moving-bed designs ucts) have changed over time by mergers and buyouts.
were prime examples of good engineering by developing Some have changed a number of times.
a method of continuously moving the catalyst between the
reactor and regeneration sections. The first air-lift TCC
unit began operation in October 1950 at the Beaumont,
Texas refinery.
6.4 See also
This fluid catalytic cracking process had first been investi-
• Oil refinery
gated in the 1920s by Standard Oil of New Jersey, but re-
search on it was abandoned during the economic depres- • Petroleum
sion years of 1929 to 1939. In 1938, when the success of
Houdry’s process had become apparent, Standard Oil of • Cracking (chemistry)
New Jersey resumed the project as part of a consortium
of that include five oil companies (Standard Oil of New • Catalysis
Jersey, Standard Oil of Indiana, Anglo-Iranian Oil, Texas
Oil and Dutch Shell), two engineering-construction com-
panies (M.W. Kellogg and Universal Oil Products) and
a German chemical company (I.G. Farben). The consor- 6.5 References
tium was called Catalytic Research Associates (CRA) and
its purpose was to develop a catalytic cracking process [1] James H. Gary and Glenn E. Handwerk (2001). Petroleum
which would not impinge on Houdry’s patents.[15][16][17] Refining: Technology and Economics (4th ed.). CRC
Press. ISBN 0-8247-0482-7.
Chemical engineering professors Warren K. Lewis and
Edwin R. Gilliland of the Massachusetts Institute of [2] James. G. Speight (2006). The Chemistry and Technology
Technology (MIT) suggested to the CRA researchers that of Petroleum (4th ed.). CRC Press. ISBN 0-8493-9067-2.
a low velocity gas flow through a powder might “lift” it
enough to cause it to flow in a manner similar to a liquid. [3] Reza Sadeghbeigi (2000). Fluid Catalytic Cracking Hand-
Focused on that idea of a fluidized catalyst, researchers book (2nd ed.). Gulf Publishing. ISBN 0-88415-289-8.
Donald Campbell, Homer Martin, Eger Murphree and
Charles Tyson of the Standard Oil of New Jersey (now [4] David S.J. Jones and Peter P. Pujado (Editors) (2006).
Handbook of Petroleum Processing (First ed.). Springer.
Exxon-Mobil Company) developed the first fluidized cat-
ISBN 1-4020-2819-9.
34 CHAPTER 6. FLUID CATALYTIC CRACKING

[5] U.S. Downstream Processing of Fresh Feed Input by Cat- • North American Catalysis Society
alytic Cracking Units (Energy Information Administra-
tion, U.S. Dept. of Energy) • Fluid Catalytic Cracking (University of British
Columbia, Quak Foo, Lee )
[6] Editorial Staff (November 2002). “Refining Processes
2002”. Hydrocarbon Processing: 108–112. ISSN 0887- • CFD Simulation of a Full-Scale Commercial FCC
0284. Regenerator
[7] Fluid Catalytic Cracking

[8] Alex C. Hoffmann and Lewis E. Stein (2002). Gas Cy-


clones and Swirl Tubes:Principles, Design and Operation
(1st ed.). Springer. ISBN 3-540-43326-0.

[9] Jessica Elzea Kogel, Nikhil C. Trivedi, James M. Bar-


ber and Stanley T. Krukowsk (Editors) (2006). Industrial
Minerals & Rocks: Commodities, Markets and Uses (Sev-
enth ed.). Society of Mining, Metallurgy and Exploration.
ISBN 0-87335-233-5.

[10] Wen-Ching Yang (2003). Handbook of Fluidization and


Fluid Particle Systems. CRC Press. ISBN 0-8247-0259-
X.

[11] Passivate Vanadium on FCC Catalysts for Improved Re-


finery Profitability (1997 Annual National Petrochemical
and Refiners Association (NPRA) Meeting)

[12] Julius Scherzer (1990). Octane-enhancing Zeolitic FCC


Catalysts: Scientific ans Technical Aspects. CRC Press.
ISBN 0-8247-8399-9.

[13] Chu, Steven. Critical Materials Strategy page 17 United


States Department of Energy, December 2011. Accessed:
23 December 2011.

[14] Pioneer of Catalytic Cracking: Almer McAfee at Gulf Oil


(North American Catalysis Society website)

[15] Tim Palucka (Winter 2005). “The Wizard of Octane: Eu-


gene Houdry”. Invention & Technology 20 (3).

[16] Amos A. Avidan, Michael Edwards and Hartley Owen


(Mobil Research and Development) (January 8, 1990).
“Innovative Improvements Highlight FCC’s Past and Fu-
ture”. Oil & Gas Journal 88 (2).

[17] “Houdry Process for Catalytic Cracking”. American


Chemical Society. Retrieved April 27, 2012.

[18] Eger Murphree and the Four Horsemen: FCC, Fluid Cat-
alytic Cracking (North American Catalysis Society web-
site)

6.6 External links


• Valero Refinery Tour (Houston, TX) Description
and diagram of power train
• CD Tech website discussion of Lummus FCC and
hydrotreating of catalytically cracked naphtha.
• The FCC Network
• Recovery of CO from a FCC using the COPureSM
Process
Chapter 7

Cracking (chemistry)

In petroleum geology and chemistry, cracking is the 7.1 History and patents
process whereby complex organic molecules such as
kerogens or heavy hydrocarbons are broken down into
Among several variants of thermal cracking methods
simpler molecules such as light hydrocarbons, by the
(variously known as the "Shukhov cracking process",
breaking of carbon-carbon bonds in the precursors. The
"Burton cracking process", “Burton-Humphreys crack-
rate of cracking and the end products are strongly de-
ing process”, and “Dubbs cracking process”) Vladimir
pendent on the temperature and presence of catalysts.
Shukhov, a Russian engineer, invented and patented the
Cracking is the breakdown of a large alkane into smaller,
first in 1891 (Russian Empire, patent no. 12926, Novem-
more useful alkanes and alkenes. Simply put, hydrocar-
ber 27, 1891).[1] One installation was used to a lim-
bon cracking is the process of breaking a long-chain of
ited extent in Russia, but development was not followed
hydrocarbons into short ones.
up. In the first decade of the 20th century the Amer-
More loosely, outside the field of petroleum chemistry, ican engineers William Merriam Burton and Robert E.
the term “cracking” is used to describe any type of split- Humphreys independently developed and patented a sim-
ting of molecules under the influence of heat, catalysts ilar process as U.S. patent 1,049,667 on June 8, 1908.
and solvents, such as in processes of destructive distilla- Among its advantages was the fact that both the condenser
tion or pyrolysis. and the boiler were continuously kept under pressure.[2]
Fluid catalytic cracking produces a high yield of gasoline In its earlier versions however, it was a batch process,
and LPG, while hydrocracking is a major source of jet rather than continuous, and many patents were to follow
fuel, Diesel fuel, naphtha, and LPG. in the USA and Europe, though not all were practical.[1]
In 1924, a delegation from the American Sinclair Oil Cor-
poration visited Shukhov. Sinclair Oil apparently wished
to suggest that the patent of Burton and Humphreys, in
use by Standard Oil, was derived from Shukhov’s patent
for oil cracking, as described in the Russian patent. If that
could be established, it could strengthen the hand of rival
American companies wishing to invalidate the Burton-
Humphreys patent. In the event Shukhov satisfied the
Americans that in principle Burton’s method closely re-
sembled his 1891 patents, though his own interest in the
matter was primarily to establish that “the Russian oil in-
dustry could easily build a cracking apparatus according
to any of the described systems without being accused by
the Americans of borrowing for free”.[3]
At that time, just a few years after the Russian Revolu-
tion, Russia was desperate to develop industry and earn
foreign exchange, so their oil industry eventually did ob-
tain much of their technology from foreign companies,
largely American.[3] At about that time however, fluid
catalytic cracking was being explored and developed and
soon replaced most of the purely thermal cracking pro-
Refinery using the Shukhov cracking process, Baku, Soviet Union, cesses in the fossil fuel processing industry. The replace-
1934. ment was however not complete; many types of crack-
ing, including pure thermal cracking, still are in use, de-
pending on the nature of the feedstock and the products

35
36 CHAPTER 7. CRACKING (CHEMISTRY)

required to satisfy market demands. Thermal cracking CH3 CH2 • + CH2 =CH2 →
remains important however, for example in producing CH3 CH2 CH2 CH2 •
naphtha, gas oil, and coke, and more sophisticated forms
of thermal cracking have been developed for various pur-
poses. These include visbreaking, steam cracking, and 7.2.5 Termination
coking.[4]
In these reactions two free radicals react with each other
to produce products that are not free radicals. Two com-
mon forms of termination are recombination, where the
7.2 Chemistry two radicals combine to form one larger molecule, and
disproportionation, where one radical transfers a hydro-
A large number of chemical reactions take place during gen atom to the other, giving an alkene and an alkane.
the cracking process, most of them based on free radi-
cals. Computer simulations aimed at modeling what takes CH3 • + CH3 CH2 • → CH3 CH2 CH3
place during steam cracking have included hundreds or
even thousands of reactions in their models. The main CH3 CH2 • + CH3 CH2 • → CH2 =CH2 +
reactions that take place include: CH3 CH3

7.2.1 Initiation 7.2.6 Example: cracking butane

In these reactions a single molecule breaks apart into two There are three places where a butane molecule (CH3 -
free radicals. Only a small fraction of the feed molecules CH2 -CH2 -CH3 ) might be split. Each has a distinct like-
actually undergo initiation, but these reactions are neces- lihood:
sary to produce the free radicals that drive the rest of the
reactions. In steam cracking, initiation usually involves • 48%: break at the CH3 -CH2 bond.
breaking a chemical bond between two carbon atoms,
rather than the bond between a carbon and a hydrogen CH3 * / *CH2 -CH2 -CH3
atom.
Ultimately this produces an alkane and an
alkene: CH4 + CH2 =CH-CH3
CH3 CH3 → 2 CH3 •
• 38%: break at a CH2 -CH2 bond.
7.2.2 Hydrogen abstraction
CH3 -CH2 * / *CH2 -CH3
In these reactions a free radical removes a hydrogen atom Ultimately this produces an alkane and an
from another molecule, turning the second molecule into alkene of different types: CH3 -CH3 +
a free radical. CH2 =CH2

CH3 • + CH3 CH3 → CH4 + CH3 CH2 • • 14%: break at a terminal C-H bond

H/CH2 -CH2 -CH2 -CH3


7.2.3 Radical decomposition
Ultimately this produces an alkene and hydro-
In these reactions a free radical breaks apart into two gen gas: CH2 =CH-CH2 -CH3 + H2
molecules, one an alkene, the other a free radical. This is
the process that results in alkene products.
7.3 Cracking methodologies
CH3 CH2 • → CH2 + CH2 + H•
7.3.1 Thermal methods
7.2.4 Radical addition Thermal cracking was the first category of hydrocarbon
cracking to be developed. Thermal cracking is an ex-
In these reactions, the reverse of radical decomposition ample of a reaction whose energetics are dominated by
reactions, a radical reacts with an alkene to form a sin- entropy (∆S°) rather than by enthalpy (∆H°) in the Gibbs
gle, larger free radical. These processes are involved in Free Energy equation ∆G°=∆H°-T∆S°. Although the
forming the aromatic products that result when heavier bond dissociation energy D for a carbon-carbon single
feedstocks are used. bond is relatively high (about 375 kJ/mol) and cracking is
7.3. CRACKING METHODOLOGIES 37

highly endothermic, the large positive entropy change re- depend on the composition of the feed, the hydrocarbon-
sulting from the fragmentation of one large molecule into to-steam ratio, and on the cracking temperature and fur-
several smaller pieces, together with the extremely high nace residence time.[7]
temperature, makes T∆S° term larger than the ∆H° term, In steam cracking, a gaseous or liquid hydrocarbon feed
thereby favoring the cracking reaction. like naphtha, LPG or ethane is diluted with steam and
briefly heated in a furnace without the presence of oxy-
Thermal cracking gen. Typically, the reaction temperature is very high, at
around 850°C, but the reaction is only allowed to take
Modern high-pressure thermal cracking operates at ab- place very briefly. In modern cracking furnaces, the res-
solute pressures of about 7,000 kPa. An overall pro- idence time is reduced to milliseconds to improve yield,
cess of disproportionation can be observed, where “light”, resulting in gas velocities faster than the speed of sound.
hydrogen-rich products are formed at the expense of After the cracking temperature has been reached, the gas
heavier molecules which condense and are depleted of hy- is quickly quenched to stop the reaction in a transfer line
drogen. The actual reaction is known as homolytic fission heat exchanger or inside a quenching header using quench
and produces alkenes, which are the basis for the econom- oil.
ically important production of polymers. The products produced in the reaction depend on the
Thermal cracking is currently used to “upgrade” very composition of the feed, the hydrocarbon to steam ratio
heavy fractions or to produce light fractions or distil- and on the cracking temperature and furnace residence
lates, burner fuel and/or petroleum coke. Two ex- time. Light hydrocarbon feeds such as ethane, LPGs
tremes of the thermal cracking in terms of product range or light naphtha give product streams rich in the lighter
are represented by the high-temperature process called alkenes, including ethylene, propylene, and butadiene.
“steam cracking” or pyrolysis (ca. 750 °C to 900 °C or Heavier hydrocarbon (full range and heavy naphthas as
higher) which produces valuable ethylene and other feed- well as other refinery products) feeds give some of these,
stocks for the petrochemical industry, and the milder- but also give products rich in aromatic hydrocarbons and
temperature delayed coking (ca. 500 °C) which can pro- hydrocarbons suitable for inclusion in gasoline or fuel oil.
duce, under the right conditions, valuable needle coke, a A higher cracking temperature (also referred to as sever-
highly crystalline petroleum coke used in the production ity) favors the production of ethene and benzene, whereas
of electrodes for the steel and aluminium industries. lower severity produces higher amounts of propene, C4-
The first thermal cracking method, the Shukhov crack- hydrocarbons and liquid products. The process also re-
ing process, was invented by Russian engineer Vladimir sults in the slow deposition of coke, a form of carbon,
Shukhov, in the Russian empire, Patent No. 12926, on the reactor walls. This degrades the efficiency of the
November 27, 1891.[5] reactor, so reaction conditions are designed to minimize
this. Nonetheless, a steam cracking furnace can usually
William Merriam Burton developed one of the earliest only run for a few months at a time between de-cokings.
thermal cracking processes in 1912 which operated at Decokes require the furnace to be isolated from the pro-
700–750 °F (371–399 °C) and an absolute pressure of cess and then a flow of steam or a steam/air mixture is
90 psi (620 kPa) and was known as the Burton process. passed through the furnace coils. This converts the hard
Shortly thereafter, in 1921, C.P. Dubbs, an employee of solid carbon layer to carbon monoxide and carbon diox-
the Universal Oil Products Company, developed a some- ide. Once this reaction is complete, the furnace can be
what more advanced thermal cracking process which op- returned to service.
erated at 750–860 °F (399–460 °C) and was known as
the Dubbs process.[6] The Dubbs process was used ex-
tensively by many refineries until the early 1940s when
catalytic cracking came into use.
7.3.2 Catalytic methods

The catalytic cracking process involves the presence of


Steam cracking acid catalysts (usually solid acids such as silica-alumina
and zeolites) which promote a heterolytic (asymmet-
Steam cracking is a petrochemical process in which sat- ric) breakage of bonds yielding pairs of ions of oppo-
urated hydrocarbons are broken down into smaller, often site charges, usually a carbocation and the very unstable
unsaturated, hydrocarbons. It is the principal industrial hydride anion. Carbon-localized free radicals and cations
method for producing the lighter alkenes (or commonly are both highly unstable and undergo processes of chain
olefins), including ethene (or ethylene) and propene (or rearrangement, C-C scission in position beta as in crack-
propylene). Steam cracker units are facilities in which ing, and intra- and intermolecular hydrogen transfer. In
a feedstock such as naphtha, liquefied petroleum gas both types of processes, the corresponding reactive in-
(LPG), ethane, propane or butane is thermally cracked termediates (radicals, ions) are permanently regenerated,
through the use of steam in a bank of pyrolysis furnaces and thus they proceed by a self-propagating chain mech-
to produce lighter hydrocarbons. The products obtained anism. The chain of reactions is eventually terminated by
38 CHAPTER 7. CRACKING (CHEMISTRY)

radical or ion recombination. fuel, and heavy fuel oil.


During the trip up the riser, the cracking catalyst is
Fluid Catalytic cracking “spent” by reactions which deposit coke on the catalyst
and greatly reduce activity and selectivity. The “spent”
Main article: Fluid catalytic cracking catalyst is disengaged from the cracked hydrocarbon va-
Fluid catalytic cracking is a commonly used process, and pors and sent to a stripper where it is contacts steam to re-
move hydrocarbons remaining in the catalyst pores. The
“spent” catalyst then flows into a fluidized-bed regenera-
tor where air (or in some cases air plus oxygen) is used to
burn off the coke to restore catalyst activity and also pro-
vide the necessary heat for the next reaction cycle, crack-
ing being an endothermic reaction. The “regenerated”
catalyst then flows to the base of the riser, repeating the
cycle.
The gasoline produced in the FCC unit has an ele-
vated octane rating but is less chemically stable com-
pared to other gasoline components due to its olefinic
profile. Olefins in gasoline are responsible for the forma-
tion of polymeric deposits in storage tanks, fuel ducts and
injectors. The FCC LPG is an important source of C3 -
C4 olefins and isobutane that are essential feeds for the
alkylation process and the production of polymers such
as polypropylene.
Schematic flow diagram of a fluid catalytic cracker

a modern oil refinery will typically include a cat cracker, Hydrocracking


particularly at refineries in the US, due to the high de-
mand for gasoline.[8][9][10] The process was first used Hydrocracking is a catalytic cracking process assisted
around 1942 and employs a powdered catalyst. During by the presence of added hydrogen gas. Unlike a
WWII, in contrast to the Axis Forces which suffered se- hydrotreater, where hydrogen is used to cleave C-S and
vere shortages of gasoline and artificial rubber, the Allied C-N bonds, hydrocracking uses hydrogen to break C-C
Forces were supplied with plentiful supplies of the mate- bonds (hydrotreatment is conducted prior to hydrocrack-
rials. Initial process implementations were based on low ing to protect the catalysts in a hydrocracking).
activity alumina catalyst and a reactor where the catalyst
particles were suspended in a rising flow of feed hydro- The products of this process are saturated hydrocar-
carbons in a fluidized bed. bons; depending on the reaction conditions (tempera-
ture, pressure, catalyst activity) these products range from
Alumina-catalyzed cracking systems are still in use in ethane, LPG to heavier hydrocarbons consisting mostly
high school and university laboratories in experiments of isoparaffins. Hydrocracking is normally facilitated by
concerning alkanes and alkenes. The catalyst is usu- a bifunctional catalyst that is capable of rearranging and
ally obtained by crushing pumice stones, which contain breaking hydrocarbon chains as well as adding hydro-
mainly aluminium oxide and silica into small, porous gen to aromatics and olefins to produce naphthenes and
pieces. In the laboratory, aluminium oxide (or porous alkanes.
pot) must be heated.
The major products from hydrocracking are jet fuel and
In newer designs, cracking takes place using a very ac- diesel, but low sulphur naphta fractions and LPG are also
tive zeolite-based catalyst in a short-contact time verti- produced.[11] All these products have a very low content
cal or upward-sloped pipe called the “riser”. Pre-heated of sulfur and other contaminants.
feed is sprayed into the base of the riser via feed noz-
zles where it contacts extremely hot fluidized catalyst at It is very common in Europe and Asia because those re-
1,230 to 1,400 °F (666 to 760 °C). The hot catalyst va- gions have high demand for diesel and kerosene. In the
porizes the feed and catalyzes the cracking reactions that US, fluid catalytic cracking is more common because the
break down the high-molecular weight oil into lighter demand for gasoline is higher.
components including LPG, gasoline, and diesel. The The hydrocracking process depends on the nature of the
catalyst-hydrocarbon mixture flows upward through the feedstock and the relative rates of the two competing
riser for a few seconds, and then the mixture is separated reactions, hydrogenation and cracking. Heavy aromatic
via cyclones. The catalyst-free hydrocarbons are routed feedstock is converted into lighter products under a wide
to a main fractionator for separation into fuel gas, LPG, range of very high pressures (1,000-2,000 psi) and fairly
gasoline, naphtha, light cycle oils used in diesel and jet high temperatures (750°−1,500° F), in the presence of
7.6. EXTERNAL LINKS 39

hydrogen and special catalysts. • Hydrocarbon Cracking — A Quick Summary for


The primary function of hydrogen is, thus: a) If feed- High School Students from canadaconnects.ca
stock has a high paraffinic content, the primary function • www.shukhov.org/shukhov.html — Vladimir Grig-
of hydrogen is to prevent the formation of polycyclic aro- orievich Shukhov biography
matic compounds. b) Reduced tar formation c) Reduced
Impurities d) Prevent buildup of coke on the catalyst. e)
High cetane fuel is achieved.

7.4 See also


• Fossil fuel reforming

7.5 References
[1] M. S. Vassiliou (2 March 2009). Historical Dictionary of
the Petroleum Industry. Scarecrow Press. pp. 459–. ISBN
978-0-8108-6288-3.

[2] Newton Copp; Andrew Zanella (1993). Discovery, Inno-


vation, and Risk: Case Studies in Science and Technology.
MIT Press. pp. 172–. ISBN 978-0-262-53111-5.

[3] Oil of Russia. American Cracking for Soviet Refining.


Yury Evdoshenko.

[4] Kraus, Richard S. Petroleum Refining Process in 78. Oil


and Natural Gas, Kraus, Richard S., Editor, Encyclopedia
of Occupational Health and Safety, Jeanne Mager Stell-
man, Editor-in-Chief. International Labor Organization,
Geneva. © 2011.

[5] Vladimir Grigorievich Shukhov (Biography)

[6] U.S. Supreme Court Cases & Opinions, Volume 322,


UNIVERSAL OIL PRODUCTS CO. V. GLOBE OIL &
REFINING CO., 322 U. S. 471 (1944)

[7] Propylene From Ethylene and Butene via Metathesis

[8] James H. Gary and Glenn E. Handwerk (2001). Petroleum


Refining: Technology and Economics (4th ed.). CRC
Press. ISBN 0-8247-0482-7.

[9] James. G. Speight (2006). The Chemistry and Technology


of Petroleum (4th ed.). CRC Press. ISBN 0-8493-9067-2.

[10] Reza Sadeghbeigi (2000). Fluid Catalytic Cracking Hand-


book (2nd ed.). Gulf Publishing. ISBN 0-88415-289-8.

[11] Sadighi, S., Ahmad, A., Shirvani, M. (2011) Comparison


of lumping approaches to predict the product yield in a
dual bed VGO hydrocracker. , International Journal of
Chemical Reactor Engineering, 9, art. no. A4.

7.6 External links


• Information on cracking in oil refining from how-
stuffworks.com
Chapter 8

Visbreaker

A visbreaker is a processing unit in an oil refinery whose 8.2.1 Coil visbreaking


purpose is to reduce the quantity of residual oil produced
in the distillation of crude oil and to increase the yield of
more valuable middle distillates (heating oil and diesel)
by the refinery. A visbreaker thermally cracks large
hydrocarbon molecules in the oil by heating in a furnace
to reduce its viscosity and to produce small quantities of
light hydrocarbons (LPG and gasoline).[1][2][3] The pro-
cess name of “visbreaker” refers to the fact that the pro-
cess reduces (i.e., breaks) the viscosity of the residual oil.
The process is non-catalytic.

8.1 Process objectives


The objectives of visbreaking are:
A schematic diagram of a Visbreaker unit
• Reduce the viscosity of the feed stream: Typi-
cally this is the residue from vacuum distillation
The term coil (or furnace) visbreaking is applied to units
of crude oil but can also be the residue from
where the cracking process occurs in the furnace tubes
hydroskimming operations, natural bitumen from
(or “coils”). Material exiting the furnace is quenched to
seeps in the ground or tar sands, and even certain
halt the cracking reactions: frequently this is achieved by
high viscosity crude oils.
heat exchange with the virgin material being fed to the
furnace, which in turn is a good energy efficiency step, but
• Reduce the amount of residual fuel oil produced by sometimes a stream of cold oil (usually gas oil) is used to
a refinery: Residual fuel oil is generally regarded as the same effect. The gas oil is recovered and re-used. The
a low value product. Demand for residual fuel con- extent of the cracking reaction is controlled by regulation
tinues to decrease as it is replaced in its traditional of the speed of flow of the oil through the furnace tubes.
markets, such as fuel needed to generate steam in The quenched oil then passes to a fractionator where the
power stations, by cleaner burning alternative fuels products of the cracking (gas, LPG, gasoline, gas oil and
such as natural gas. tar) are separated and recovered.

• Increase the proportion of middle distillates in the


refinery output: Middle distillate is used as a dilu- 8.2.2 Soaker visbreaking
ent with residual oils to bring their viscosity down
to a marketable level. By reducing the viscosity of In soaker visbreaking, the bulk of the cracking reaction
the residual stream in a visbreaker, a fuel oil can occurs not in the furnace but in a drum located after the
be made using less diluent and the middle distillate furnace called the soaker. Here the oil is held at an ele-
saved can be diverted to higher value diesel or heat- vated temperature for a pre-determined period of time to
ing oil manufacture. allow cracking to occur before being quenched. The oil
then passes to a fractionator. In soaker visbreaking, lower
temperatures are used than in coil visbreaking. The com-
8.2 Technology paratively long duration of the cracking reaction is used
instead.

40
8.4. ECONOMICS 41

8.2.3 Process options 8.3.2 Yields


Visbreaker tar can be further refined by feeding it to The yields of the various hydrocarbon products will de-
a vacuum fractionator. Here additional heavy gas oil pend on the “severity” of the cracking operation as de-
may be recovered and routed either to catalytic cracking, termined by the temperature the oil is heated to in the
hydrocracking or thermal cracking units on the refinery. visbreaker furnace. At the low end of the scale, a furnace
The vacuum-flashed tar (sometimes referred to as pitch) heating to 425 °C would crack only mildly, while opera-
is then routed to fuel oil blending. In a few refinery loca- tions at 500 °C would be considered as very severe. Ara-
tions, visbreaker tar is routed to a delayed coker for the bian light crude residue when visbroken at 450 °C would
production of certain specialist cokes such as anode coke yield around 76% (by weight) of tar, 15% middle distil-
or needle coke. lates, 6% gasolines and 3% gas and LPG.

8.2.4 Soaker visbreaking versus coil vis- 8.3.3 Fuel oil stability
breaking
The severity of visbreaker operation is normally lim-
From the standpoint of yield, there is little or nothing to ited by the need to produce a visbreaker tar that can be
choose between the two approaches. However, each of- blended to make a stable fuel oil.
fers significant advantages in particular situations: Stability in this case is taken to mean the tendency of a
fuel oil to produce sediments when stored. These sed-
• De-coking: The cracking reaction forms petroleum
iments are undesirable as they can quickly foul the fil-
coke as a byproduct. In coil visbreaking, this de-
ters of pumps used to move the oil necessitating time-
posits in the tubes of the furnace and will eventu-
consuming maintenance.
ally lead to fouling or blocking of the tubes. The
same will occur in the drum of a soaker visbreaker, Vacuum residue fed to a visbreaker can be considered to
though the lower temperatures used in the soaker be composed of the following:
drum lead to fouling at a much slower rate. Coil vis-
breakers therefore require frequent de-coking. This • Asphaltenes: large polycyclic molecules that are
is quite labour-intensive, but can be developed into a suspended in the oil in a coloidal form
routine where tubes are de-coked sequentially with-
out the need to shutdown the visbreaking operation. • Resins: also polycyclic but of a lower molecular
Soaker drums require far less frequent attention but weight than asphaltenes
their being taken out of service normally requires a
complete halt to the operation. Which is the more • Aromatic hydrocarbons: derivatives of benzene,
disruptive activity will vary from refinery to refinery. toluene and xylenes

• Fuel Economy: The lower temperatures used in the • Parafinic hydrocarbons: alkanes
soaker approach mean that these units use less fuel.
In cases where a refinery buys fuel to support process Visbreaking preferentially cracks aliphatic compounds
operations, any savings in fuel consumption could be which have relatively low sulphur contents, low density
extremely valuable. In such cases, soaker visbreak- and high viscosity and the effect of their removal can be
ing may be advantageous. clearly seen in the change in quality between feed and
product. A too severe cracking in a visbreaker will lead to
the asphaltene colloid becoming metastable. Subsequent
8.3 Quality and yields addition of a diluent to manufacture a finished fuel oil can
cause the colloid to break down, precipitating asphaltenes
8.3.1 Feed quality and product quality as a sludge. It has been observed that a paraffinic diluent
is more likely to cause precipitation than an aromatic one.
The quality of the feed going into a visbreaker will vary Stability of fuel oil is assessed using a number of propri-
considerably with the type of crude oil that the refinery etary tests (for example “P” value and SHF tests).
is processing. The following is a typical quality for the
vacuum distillation residue of Arabian light (a crude oil
from Saudi Arabia and widely refined around the world): 8.4 Economics
Once this material has been run through a visbreaker
(and, again, there will be considerable variation from vis- 8.4.1 Viscosity blending
breaker to visbreaker as no two will operate under ex-
actly the same conditions) the reduction in viscosity is The viscosity blending of two or more liquids having
dramatic: different viscosities is a three-step procedure. The first
42 CHAPTER 8. VISBREAKER

step is to calculate the Viscosity Blending Index (VBI) of oil manufacture. For example, if the cutter stock is taken
each component of the blend using the following equation to have a value of $300 per tonne and fuel oil $150 per
(known as a Refutas equation): [2][4] ton (oil prices naturally change quickly, but these prices,
and more importantly the differences between them, are
(1) VBN = 14.534 × ln[ln(v + 0.8)] + 10.975 not unrealistic), it is a simple matter to calculate the value
of the different residues in this example as being:
where v is the viscosity in square millimeters per second Virgin residue: $93.1 per tonne
(mm²/s) or centistokes (cSt) and ln is the natural loga- Visbroken residue: $127.0 per tonne
rithm (logₑ). It is important that the viscosity of each
component of the blend be obtained at the same temper-
ature.
8.5 References
The next step is to calculate the VBN of the blend, using
this equation: [1] James H. Gary and Glenn E. Handwerk (1984). Petroleum
Refining Technology and Economics (2nd Edition ed.).
(2) VBNB ₑ = [wA × VBNA] + [wB × Marcel Dekker, Inc. ISBN 0-8247-7150-8.
VBNB] + ... + [wX × VBNX] [2] Robert E. Maples (2000). Petroleum Refinery Process
Economics (2nd Edition ed.). Pennwell Books. ISBN 0-
where w is the weight fraction (i.e., % ÷ 100) of each 87814-779-9.
component of the blend.
[3] James G. Speight (2006). The Chemistry and Technology
Once the viscosity blending number of a blend has been of Petroleum (4th Edition ed.). CRC Press. ISBN 0-8493-
calculated using equation (2), the final step is to determine 9067-2.
the viscosity of the blend by using the invert of equation
[4] C.T. Baird (1989), Guide to Petroleum Product Blending,
(1):
HPI Consultants, Inc. HPI website
(VBN - 10.975) ÷ 14.534
(3) v = ee − 0.8
8.6 External links
where VBN is the viscosity blending number of the blend
and e is the transcendental number 2.71828, also known • Foster Wheeler Visbreaking Overview
as Euler’s number.
• Shell Thermal Conversion

8.4.2 Example economics for a two- • Shell Soaker Visbreaking


component blend • Shell Deep Thermal Conversion

A marketable fuel oil, such as for fueling a power station, • Shell Thermal Gasoil Unit (TGU)
might be required to have a viscosity of 40 centistokes at
100 °C. It might be prepared using either the virgin or • Fuel Oil Stability Testing
visbroken residue described above combined with a dis- • Bunkerworld: “Sediment Stability and Compatibil-
tillate diluent (“cutter stock”). Such a cutter stock could ity - The Structure of Fuel Oil”
typically have a viscosity at 100 °C of 1.3 centistokes.
Rearranging equation (2) above for a simple two compo-
nent blend shows that the percentage of cutterstock re-
quired in the blend is found by:
(4) %cutter stock = [VBN40 − VBNᵣₑ ᵢ ᵤₑ] ÷ [VBN ᵤ ₑᵣ
ₒ − VBNᵣₑ ᵢ ᵤₑ]
Using the viscosities quoted in the tables above for the
residues from Arab Light crude oil and calculating VBNs
according to equation (1) gives:
For virgin residue (i.e., the unconverted feed to the vis-
breaker): 27.5% cutter stock in the blend
For visbroken residue: 13.3% cutter stock in the blend.
As middle distillates have a far higher value in the market
place than fuel oils, it can be seen that the use of a vis-
breaker will considerably improve the economics of fuel
Chapter 9

Merox

Merox is an acronym for mercaptan oxidation. It is a kerosenes.[3]


proprietary catalytic chemical process developed by UOP
used in oil refineries and natural gas processing plants to • Merox for extraction of mercaptans from refinery
remove mercaptans from LPG, propane, butanes, light and natural gases.[4]
naphthas, kerosene and jet fuel by converting them to liq-
uid hydrocarbon disulfides.[1] • Minalk Merox for sweetening of naphthas.[5] This
process continuously injects just a few ppm of
The Merox process requires an alkaline environment caustic into the feed naphtha.
which, in some process versions, is provided by an aque-
ous solution of sodium hydroxide (NaOH), a strong base, • Caustic-free Merox for sweetening jet fuels and
commonly referred to as caustic. In other versions of the kerosenes.[6] This process injects small amounts of
process, the alkalinity is provided by ammonia, which is ammonia and water (rather than caustic) into the
a weak base. feed naphtha to provide the required alkalinity.
The catalyst in some versions of the process is a water-
soluble liquid. In other versions, the catalyst is impreg- • Caustic-free Merox for sweetening of naphthas.[7]
nated onto charcoal granules. This process also injects small amounts of ammonia
and water (rather than caustic) into the feed naphtha
Processes within oil refineries or natural gas processing to provide the required alkalinity.
plants that remove mercaptans and/or hydrogen sulfide
(H2 S) are commonly referred to as sweetening processes In all of the above Merox versions, the overall oxida-
because they results in products which no longer have the tion reaction that takes place in converting mercaptans
sour, foul odors of mercaptans and hydrogen sulfide. The to disulfides is:
liquid hydrocarbon disulfides may remain in the sweet-
ened products, they may be used as part of the refinery 4 RSH + O2 → 2RSSR + 2H2 O
or natural gas processing plant fuel, or they may be pro-
cessed further. The most common mercaptans removed are:
Especially when dealing with kerosene, the Merox pro-
• Methanethiol - CH3 SH [m-mercaptan]
cess is usually more economical than using a catalytic
hydrodesulfurization process for much the same purpose. • Ethanethiol - C2 H5 SH [e- mercaptan]
Indeed, it is rarely (if ever) required to reduce the sulphur
• 1-Propanethiol - C3 H7 SH [n-P mercaptan]
content of a straight-run kerosene to respect the sulphur
specification of Jet Fuel as the specification is 3000 ppm • 2-Propanethiol - CH3 CH(SH)CH3 [2C3 mercap-
and very few crude oils have a kerosene cut with a higher tan]
content of sulphur than this limit.
• Butanethiol - C4 H9 SH [n-butyl mercaptan]
• tert-Butyl mercaptan - C(CH3 )3 SH [t-butyl mercap-
9.1 Types of Merox process units tan]
• Pentanethiol - C5 H11 SH [pentyl mercaptan]
UOP has developed many versions of the Merox process
for various applications: In some of the above Merox process versions, the cata-
lyst is a liquid. In others, the catalyst is in the form of
• Conventional Merox for extraction of mercaptans impregnated charcoal granules.
from LPG, propane, butanes or light naphthas.[2] Process flow diagrams and descriptions of the two con-
ventional versions of the Merox process are presented in
• Conventional Merox for sweetening jet fuels and the following sections.

43
44 CHAPTER 9. MEROX

9.2 Conventional Merox for ex- naphtha) feedstock enters the prewash vessel and flows
upward through a batch of caustic which removes any
tracting mercaptans from LPG H2 S that may be present in the feedstock. The coalescer
at the top of the prewash vessel prevents caustic from be-
The conventional Merox process for extraction and re- ing entrained and carried out of the vessel.
moval of mercaptans from liquefied petroleum gases
(LPG), such as propane, butanes and mixtures of propane The feedstock then enters the mercaptan extractor and
and butanes, can also be used to extract and remove mer- flows upward through the contact trays where the LPG
captans from light naphthas.[2] It is a two-step process. In intimately contacts the downflowing Merox caustic that
the first step, the feedstock LPG or light naphtha is con- extracts the mercaptans from the LPG. The sweetened
tacted in the trayed extractor vessel with an aqueous caus- LPG exits the tower and flows through: a caustic settler
tic solution containing UOP’s proprietary liquid catalyst. vessel to remove any entrained caustic, a water wash ves-
The caustic solution reacts with mercaptans and extracts sel to further remove any residual entrained caustic and
them. The reaction that takes place in the extractor is: a vessel containing a bed of rock salt to remove any en-
trained water. The dry sweetened LPG exits the Merox
2RSH + 2 NaOH → 2NaSR + 2 H O unit.
2
The caustic solution leaving the bottom of the mercaptan
In the above reaction, RSH is a mercaptan and R signifies extractor (“rich” Merox caustic) flows through a control
an organic group such as a methyl, ethyl, propyl or other valve which maintains the extractor pressure needed to
group. For example, the ethyl mercaptan (ethanethiol) keep the LPG liquified. It is then injected with UOP’s
has the formula C2 H5 SH. proprietary liquid catalyst (on an as needed basis), flows
The second step is referred to as regeneration and it in- through a steam-heated heat exchanger and is injected
volves heating and oxidizing of the caustic solution leav- with compressed air before entering the oxidizer vessel
ing the extractor. The oxidations results in converting the where the extracted mercaptans are converted to disul-
extracted mercaptans to organic disulfides (RSSR) which fides. The oxidizer vessel has a packed bed to keep
are liquids that are water-insoluble and are then separated the aqueous caustic and the water-insoluble disulfide well
and decanted from the aqueous caustic solution. The re- contacted and well mixed.
action that takes place in the regeneration step is: The caustic-disulfide mixture then flows into the separa-
tor vessel where it is allowed to form a lower layer of
4NaSR + O2 + 2H2 O → 2RSSR + 4NaOH “lean” Merox caustic and an upper layer of disulfides. The
vertical section of the separator is for the disengagement
After decantation of the disulfides, the regenerated “lean” and venting of excess air and includes a Raschig ring sec-
caustic solution is recirculated back to the top of the ex- tion to prevent entrainment of any disulfides in the vented
tractor to continue extracting mercaptans. air. The disulfides are withdrawn from the separator and
routed to fuel storage or to a hydrotreater unit. The re-
The net overall Merox reaction covering the extraction
generated lean Merox caustic is then pumped back to the
and the regeneration step may be expressed as:
top of the extractor for reuse.
4 RSH + O2 → 2RSSR + 2H2 O

The feedstock entering the extractor must be free of any


H2 S. Otherwise, any H2 S entering the extractor would
react with the circulating caustic solution and interfere
with the Merox reactions. Therefore, the feedstock is first
“prewashed” by flowing through a batch of aqueous caus-
tic to remove any H2 S. The reaction that takes place in
the prewash vessel is:

H2 S + NaOH → NaSH + H2 O

The batch of caustic solution in the prewash vessel is pe-


riodically discarded as "spent caustic" and replaced by
fresh caustic as needed.

9.2.1 Flow diagram


Flow diagram of a conventional Merox process unit for extracting
The flow diagram below depicts the equipment and the mercaptans from liquified petroleum gas (LPG).
flow paths involved in the process.[2] The LPG (or light
9.4. SEE ALSO 45

9.3 Conventional Merox for sweet- The pressure maintained in the reactor is chosen so that
the injected air will completely dissolve in the feedstock
ening jet fuel or kerosene at the operating temperature.

The conventional Merox process for the removal of mer-


captans (i.e., sweetening) of jet fuel or kerosene is a one-
step process.[3] The mercaptan oxidation reaction takes
place in an alkaline environment as the feedstock jet fuel
or kerosene, mixed with compressed air, flows through
a fixed bed of catalyst in a reactor vessel. The catalyst
consists of charcoal granules that have been impregnated
with UOP’s proprietary catalyst. The oxidation reaction
that takes place is:

4 RSH + O2 → 2RSSR + 2H2 O

As is the case with the conventional Merox process for


treating LPG, the jet fuel or kerosene sweetening process
also requires that the feedstock be prewashed to remove
Conventional Merox process unit for sweetening jet fuel or
any H2 S that would interfere with the sweetening. The re- kerosene
action that takes place in the batch caustic prewash vessel
is:

H2 S + NaOH → NaSH + H2 O 9.4 See also


• 2006 Côte d'Ivoire toxic waste spill
9.3.1 Flow diagram
• Disulfide bond
The Merox reactor is a vertical vessel containing a bed
of charcoal granules that have been impregnated with the
UOP catalyst. The charcoal granules may be impregnated 9.5 References
with the catalyst in situ or they may be purchased from
UOP as pre-impregnated with the catalyst. An alkaline [1] Treating Technology Solutions
environment is provided by caustic being pumped into
[2] Merox Process for Mercaptan Extraction
reactor on an intermittent, as needed basis.[3]
The jet fuel or kerosene feedstock from the top of the [3] Merox Process for Kerosene/Jet Fuel Sweetening
caustic prewash vessel is injected with compressed air [4] Merox Process for Gas Extraction
and enters the top of the Merox reactor vessel along with
any injected caustic. The mercaptan oxidation reaction [5] Minalk Process for Fixed-Bed Naphtha Sweetening
takes place as the feedstock percolates downward over [6] Caustic-free Merox Process for Kerosene/Jet Fuel Sweet-
the catalyst. The reactor effluent flows through a caus- ening
tic settler vessel where it forms a bottom layer of aque-
ous caustic solution and an upper layer of water-insoluble [7] Caustic-Free Merox Process for Fixed-Bed Naphtha
sweetened product. Sweetening

The caustic solution remains in the caustic settler so that


the vessel contains a reservoir for the supply of caustic
that is intermittently pumped into the reactor to maintain 9.6 External links
the alkaline environment.
• Energy and Environmental Profile of the U.S.
The sweetened product from the caustic settler vessel Petroleum Refining Industry, U.S. Department of
flows through a water wash vessel to remove any entrained Energy Office of Industrial Technologies, Decem-
caustic as well as any other unwanted water-soluble sub- ber 1998. (Use the keyword “Merox” in the PDF
stances, followed by flowing through a salt bed vessel to search function)
remove any entrained water and finally through a clay fil-
ter vessel. The clay filter removes any oil-soluble sub- • Applications of the MeroxSM Process for Extrac-
stances, organometallic compounds (especially copper) tion of Mercaptan Sulfur Abstract of a paper pre-
and particulate matter, which might prevent meeting jet sented at the 1999 Annual Meeting of the American
fuel product specifications. Institute of Chemical Engineers.
46 CHAPTER 9. MEROX

• Profile of the Petroleum Refining Industry, Sec-


tor Notebook Project, Office of Enforcement and
Compliance Assurance, U.S. Environmental Pro-
tection Agency, September 1995. (Use the keyword
“Merox” in the PDF search function)
Chapter 10

Coker unit

A coker or coker unit is an oil refinery processing unit


that converts the residual oil from the vacuum distillation
column or the atmospheric distillation column into low
molecular weight hydrocarbon gases, naphtha, light and
heavy gas oils, and petroleum coke. The process ther-
mally cracks the long chain hydrocarbon molecules in the
residual oil feed into shorter chain molecules leaving be-
hind the excess carbon in the form of petroleum coke.
This petroleum coke can either be fuel grade (high in sul-
phur and metals) or anode grade (low in sulphur and met-
als). The raw coke from the coker is often referred to
as green coke.[1] In this context, “green” means unpro-
cessed. The further processing of green coke by calcining
in a rotary kiln removes residual volatile hydrocarbons
from the coke. The calcined petroleum coke can be fur-
ther processed in an anode baking oven in order to pro- A typical schematic flow diagram of a delayed coking unit
duce anode coke of the desired shape and physical prop-
erties. The anodes are mainly used in the aluminium and
steel industry.
10.3 References
[1] Petroleum coke on the website of the IUPAC Com-
pendium of Chemical Terminology
10.1 Types of coker units
[2] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-
ing Technology and Economics (2nd ed.). Marcel Dekker,
Main article: Delayed coker Inc. ISBN 0-8247-7150-8. OCLC 10323572.

[3] Hydrocarbon Refining staff (November 1998). “Refining


There are three types of cokers used in oil refineries: Processes '98”. Hydrocarbon Processing: pages 62–64.
Delayed coker, Fluid coker and Flexicoker.[2][3] The one ISSN 0887-0284.
that is by far the most commonly used is the delayed
coker.
The schematic flow diagram below depicts a typical de- 10.4 External links
layed coker:
• Detailed description of cokers and related topics

10.2 See also • Quality specifications for petroleum cokes

• Delayed coker

• Shukhov cracking process

• Burton process

• Visbreaker

• Petroleum coke

47
Chapter 11

Alkylation

Alkylation is the transfer of an alkyl group from one use of organometallic compounds such as Grignard
molecule to another. The alkyl group may be trans- (organomagnesium), organolithium, organocopper, and
ferred as an alkyl carbocation, a free radical, a carbanion organosodium reagents. These compounds typically can
or a carbene (or their equivalents).[1] Alkylating agents add to an electron-deficient carbon atom such as at a
are widely used in chemistry because the alkyl group is carbonyl group. Nucleophilic alkylating agents can also
probably the most common group encountered in organic displace halide substituents on a carbon atom. In the pres-
molecules. Many biological target molecules or their syn- ence of catalysts, they also alkylate alkyl and aryl halides,
thetic precursors are composed of an alkyl chain with spe- as exemplified by Suzuki couplings.
cific functional groups in a specific order. Selective alky-
lation, or adding parts to the chain with the desired func-
tional groups, is used, especially if there is no commonly 11.1.2 Electrophilic alkylating agents
available biological precursor. Alkylation with only one
carbon is termed methylation. Electrophilic alkylating agents deliver the equivalent of
an alkyl cation. Examples include the use of alkyl halides
In oil refining contexts, alkylation refers to a particular with a Lewis acid catalyst to alkylate aromatic substrates
alkylation of isobutane with olefins. For upgrading of in Friedel-Crafts reactions. Alkyl halides can also react
petroleum, alkylation produces synthetic C7 –C8 alkylate, directly with amines to form C-N bonds; the same holds
which is a premium blending stock for gasoline.[2] true for other nucleophiles such as alcohols, carboxylic
In medicine, alkylation of DNA is used in chemotherapy acids, thiols, etc.
to damage the DNA of cancer cells. Alkylation is accom- Electrophilic, soluble alkylating agents are often very
plished with the class of drugs called alkylating antineo- toxic, due to their ability to alkylate DNA. They should be
plastic agents. handled with proper PPE. This mechanism of toxicity is
also responsible for the ability of some alkylating agents
to perform as anti-cancer drugs in the form of alkylating
antineoplastic agents, and also as chemical weapons such
as mustard gas. Alkylated DNA either does not coil or
uncoil properly, or cannot be processed by information-
decoding enzymes. This results in cytotoxicity with the
Benzene Friedel-Crafts alkylation. effects of inhibition the growth of the cell, initiation of
programmed cell death or apoptosis. However, mutations
are also triggered, including carcinogenic mutations, ex-
plaining the higher incidence of cancer after exposure.
11.1 Alkylating agents
Alcohols and phenols can be alkylated to give alkyl ethers:
“Alkylating agent” redirects here. For the class R-OH + R'-X → R-O-R' + H-X
of drugs, see alkylating antineoplastic agent.
The produced acid HX is removed with a base, or, al-
Alkylating agents are classified according to their ternatively, the alcohol is deprotonated first to give an
nucleophilic or electrophilic character. alkoxide or phenoxide. For example, dimethyl sulfate
alkylates the sodium salt of phenol to give anisole, the
methyl ether of phenol. The dimethyl sulfate is dealky-
11.1.1 Nucleophilic alkylating agents lated to sodium methylsulfate.[3]

Nucleophilic alkylating agents deliver the equivalent Ph-O– Na+ + Me2 SO4 → Ph-O-Me + Na+
of an alkyl anion (carbanion). Examples include the MeSO4 –

48
11.3. OIL REFINING 49

On the contrary, the alkylation of amines introduces the


problem that the alkylation of an amine makes it more nu-
cleophilic. Thus, when an electrophilic alkylating agent is
introduced to a primary amine, it will preferentially alky-
late all the way to a quaternary ammonium cation. Alkylation of alkenes (shown here is propene) by isobutane is a
major process in refineries. It is catalysed by strong acids such as
+ HF and sulfuric acid.
R-NH2 → R-NH-R' → R-N(R')2 → R-N(R')3
(alkylating agent omitted for clarity)
isobutane. The reaction is carried out at mild tempera-
If the quaternary ammonium is not the desired product, tures (0 and 30 °C) in a two-phase reaction. Because the
more circuitious routes such as reductive amination are reaction is exothermic, cooling is needed: SAAU plants
necessary. require lower temperatures so the cooling medium needs
to be chilled, for HFAU normal refinery cooling water
will suffice. It is important to keep a high ratio of isobu-
11.1.3 Carbene alkylating agents
tane to alkene at the point of reaction to prevent side re-
Carbenes are extremely reactive and are known to attack actions which produces a lower octane product, so the
even unactivated C-H bonds. Carbenes can be generated plants have a high recycle of isobutane back to feed. The
by elimination of a diazo group. A metal can form a car- phases separate spontaneously, so the acid phase is vigor-
bene equivalent called a transition metal carbene com- ously mixed with the hydrocarbon phase to create suffi-
plex. cient contact surface.

Trimethyloxonium tetrafluoroborate and triethyloxonium The product is called alkylate and is composed of
tetrafluoroborate belong to one of these categories. a mixture of high-octane, branched-chain paraffinic
hydrocarbons (mostly isoheptane and isooctane). Alky-
late is a premium gasoline blending stock because it has
exceptional antiknock properties and is clean burning.
11.2 In biology Alkylate is also a key component of avgas. The octane
number of the alkylate depends mainly upon the kind
Main article: methylation of alkenes used and upon operating conditions. For ex-
ample, isooctane results from combining butylene with
Methylation is the most common type of alkylation, being isobutane and has an octane rating of 100 by definition.
associated with the transfer of a methyl group. Methy- There are other products in the alkylate, so the octane
lation is distinct from alkylation in that it is specifically rating will vary accordingly.
the transfer of one carbon, whereas alkylation can re- Since crude oil generally contains only 10 to 40 per-
fer to the transfer of long chain carbon groups. Methy- cent of hydrocarbon constituents in the gasoline range,
lation in nature is typically effected by vitamin B12- refineries use a fluid catalytic cracking process to con-
derived enzymes, where the methyl group is carried by vert high molecular weight hydrocarbons into smaller and
cobalt. In methanogenesis, coenzyme M is methylated more volatile compounds, which are then converted into
by tetrahydromethanopterin. liquid gasoline-size hydrocarbons. Alkylation processes
Electrophilic compounds may alkylate different nucle- transform low molecular-weight alkenes and iso-paraffin
ophiles in the body. The toxicity, carcinogenity, and molecules into larger iso-paraffins with a high octane
paradoxically, cancer cell-killing abilities of different number.
DNA alkylating agents are an example. Combining cracking, polymerization, and alkylation can
result in a gasoline yield representing 70 percent of
the starting crude oil. More advanced processes, such
11.3 Oil refining as cyclicization of paraffins and dehydrogenation of
naphthenes forming aromatic hydrocarbons in a catalytic
Main article: alkylation unit reformer, have also been developed to increase the oc-
In a standard oil refinery process, isobutane is alkylated tane rating of gasoline. Modern refinery operation can
with low-molecular-weight alkenes (primarily a mixture be shifted to produce almost any fuel type with specified
of propene and butene) in the presence of a Bronsted acid performance criteria from a single crude feedstock.
catalyst, either sulfuric acid or hydrofluoric acid.[4] In an Refineries examine whether it makes sense economically
oil refinery it is referred to as a sulfuric acid alkylation to install alkylation units. Alkylation units are complex,
unit (SAAU) or a hydrofluoric alkylation unit, (HFAU). with substantial economy of scale. In addition to a suit-
Refinery workers may simply refer to it as the alky or able quantity of feedstock, the price spread between the
alky unit. The catalyst protonates the alkenes (propene, value of alkylate product and alternate feedstock disposi-
butene) to produce reactive carbocations, which alkylate tion value must be large enough to justify the installation.
50 CHAPTER 11. ALKYLATION

Alternative outlets for refinery alklylation feedstocks in- [2] Stefanidakis, G.; Gwyn, J.E. (1993). “Alkylation”. In
clude sales as LPG, blending of C4 streams directly into John J. McKetta. Chemical Processing Handbook. CRC
gasoline and feedstocks for chemical plants. Local mar- Press. pp. 80–138. ISBN 0-8247-8701-3.
ket conditions vary widely between plants. Variation in [3] G. S. Hiers and F. D. Hager (1941), “Anisole”, Org.
the RVP specification for gasoline between countries and Synth.; Coll. Vol. 1: 58
between seasons dramatically impacts the amount of bu-
tane streams that can be blended directly into gasoline. [4] Michael Röper, Eugen Gehrer, Thomas Narbeshuber,
The transportation of specific types of LPG streams can Wolfgang Siegel “Acylation and Alkylation” in Ull-
be expensive so local disparities in economic conditions mann’s Encyclopedia of Industrial Chemistry, Wiley-
are often not fully mitigated by cross market movements VCH, Weinheim, 2000. doi:10.1002/14356007.a01_185
of alkylation feedstocks. [5] Sulphur recovery; (2007). The Process Principles, de-
The availability of a suitable catalyst is also an important tails advances in sulphur recovery by the WSA process.
factor in deciding whether to build an alkylation plant. Denmark: Jens Kristen Laursen, Haldor Topsøe A/S.
Reprinted from Hydrocarbonengineering August 2007
If sulfuric acid is used, significant volumes are needed.
Access to a suitable plant is required for the supply of
fresh acid and the disposition of spent acid. If a sulfuric
acid plant must be constructed specifically to support an 11.6 External links
alkylation unit, such construction will have a significant
impact on both the initial requirements for capital and on- • Macrogalleria page on polycarbonate production
going costs of operation. Alternatively it is possible to in-
stall a WSA Process unit to regenerate the spent acid. No • Alkylating agents at the US National Library of
drying of the gas takes place. This means that there will Medicine Medical Subject Headings (MeSH)
be no loss of acid, no acidic waste material and no heat is
lost in process gas reheating. The selective condensation
in the WSA condenser ensures that the regenerated fresh
acid will be 98% w/w even with the humid process gas.
It is possible to combine spent acid regeneration with dis-
posal of hydrogen sulfide by using the hydrogen sulfide as
internal fuel in the refinery or elsewhere.[5]
The second main catalyst option is hydrofluoric acid. In
typical alkylation plants, rates of consumption for acid
are much lower than for sulfuric acid. These plants also
produce alkylate with better octane rating than do sulfuric
plants. However, due to its hazardous nature, HF acid is
produced at very few locations and transportation must be
managed rigorously.

11.4 See also


• Hydrodealkylation

• Transalkylation

• Friedel–Crafts reaction

• Category:Alkylating agents

• Category:Ethylating agents
• Category:Methylating agents

11.5 References
[1] March Jerry; (1985). Advanced Organic Chemistry re-
actions, mechanisms and structure (3rd ed.). New York:
John Wiley & Sons, inc. ISBN 0-471-85472-7
Chapter 12

Dimer (chemistry)

Dimers of carboxylic acids are often found in vapour phase.

A dimer (/ˈdaɪmər/) (di-, “two” + -mer, “parts”) is an


oligomer consisting of two structurally similar monomers
joined by bonds that can be either strong or weak,
covalent or intermolecular. The term homodimer is used
when the two molecules are identical (e.g. A-A) and het-
erodimer when they are not (e.g. A-B). The reverse of
dimerisation is often called dissociation.

12.1 Noncovalent dimers


The dimer of cyclopentadiene although this might not be readily
Carboxylic acids form dimers by hydrogen bonding of apparent on initial inspection
the acidic hydrogen and the carbonyl oxygen when an-
hydrous. For example, acetic acid forms a dimer in the
gas phase, where the monomer units are held together 2 C(NR2 )2 → (R2 N)2 C=C(NR2 )2
by hydrogen bonds. Under special conditions, most OH-
containing molecules form dimers, e.g. the water dimer.
Borane (“BH3 ") occurs as the dimer diborane (B2 H6 ), Carbenes are highly reactive and readily form bonds.
due to the high Lewis acidity of the boron center.
Dicyclopentadiene is an asymmetrical dimer of two
Excimers and exciplexes are excited structures with a cyclopentadiene molecules that have reacted in a Diels-
short lifetime. For example, noble gases do not form Alder reaction to give the product. Upon heating, it
stable dimers, but do form the excimers Ar2 *, Kr2 * and “cracks” (undergoes a retro-Diels-Alder reaction) to give
Xe2 * under high pressure and electrical stimulation. identical monomers:

12.2 Covalent dimers C10 H12 → 2 C5 H6

Molecular dimers are often formed by the reaction of two


identical compounds e.g.: 2A → A-A. In this example, Many nonmetallic elements occur as dimers: hydrogen,
monomer “A” is said to dimerise to give the dimer “A- nitrogen, oxygen, the halogens, i.e. fluorine, chlorine,
A”. An example is a diaminocarbene, which dimerise to bromine and iodine. Mercury occurs as a mercury(I)
give a tetraaminoethylene: cation (Hg2 2+ ), formally a heterodimer.

51
52 CHAPTER 12. DIMER (CHEMISTRY)

12.3 Polymer chemistry


In the context of polymers, “dimer” also refers to the
degree of polymerization 2, regardless of the stoichiom-
etry or condensation reactions. This is particularly appli-
cable to disaccharides. For example, cellobiose is a dimer
of glucose, even though the formation reaction produces
water:

2C6 H12 O6 → C12 H22 O11 + H2 O

Here, the dimer has a stoichiometry different from the


pair of monomers.

12.4 Biochemical dimers


Pyrimidine dimers are formed by a photochemical re-
action from pyrimidine DNA bases. This cross-linking
causes DNA mutations, which can be carcinogenic, caus-
ing skin cancers.

12.5 See also


• Monomer
• Trimer

• Polymer
• Protein dimer

12.6 References
• “IUPAC “Gold Book” definition”. Retrieved 2009-
04-30.
Chapter 13

Isomerization

In chemistry isomerization (also isomerisation) is the


process by which one molecule is transformed into an-
other molecule which has exactly the same atoms, but the
atoms have a different arrangement e.g. A-B-C → B-
A-C (these related molecules are known as isomers [1] ).
In some molecules and under some conditions, isomer-
ization occurs spontaneously. Many isomers are equal
or roughly equal in bond energy, and so exist in roughly
equal amounts, provided that they can interconvert rela-
tively freely, that is the energy barrier between the two
“Trans-cis isomerism” is where in certain compounds an
isomers is not too high. When the isomerization occursinterconversion of cis and trans isomers can be observed,
intramolecularly it is considered a rearrangement reac-
for instance, with maleic acid and with azobenzene often
tion. by photoisomerization. Another example is the photo-
An example of an organometallic isomerization is the chemical conversion of the trans isomer to the cis isomer
[4]
5
production of decaphenylferrocene, [(η -C5 Ph5 )2 Fe] of resveratrol:
from its linkage isomer.[2][3]

Other instances are Aldose-ketose isomerism in biochem-


istry; isomerizations between conformational isomers,
which take place without an actual rearrangement for in-
stance inconversion of two cyclohexane conformations;
fluxional molecules which display rapid interconversion
of isomers e.g. bullvalene; and “valence isomerization":
the isomerization of molecules which involve structural
changes resulting only from a relocation of single and
double bonds. If a dynamic equilibrium is established
between the two isomers it is also referred to as valence
13.1 Instances of isomerization tautomerism [5]
In a cycloisomerization a cyclic compound is formed.
Isomerizations in hydrocarbon cracking is usually em- The energy difference between two isomers is called “iso-
ployed in organic chemistry, where fuels, such as pentane, merization energy”. Isomerizations with low energy dif-
a straight-chain isomer, are heated in the presence of a ference both experimental and computational (in paren-
platinum catalyst. The resulting mixture of straight- and theses) are endothermic trans-cis isomerization of 2-
branched-chain isomers then have to be separated. An in- butene with 2.6 (1.2) kcal/mol, cracking of isopentane to
dustrial process is also the isomerisation of n-butane into n-pentane with 3.6 (4.0) kcal/mol or conversion of trans-
isobutane. 2-butene to 1-butene with 2.6 (2.4) kcal/mol.[6]

53
54 CHAPTER 13. ISOMERIZATION

13.2 See also


• Racemization

• Epimerization

13.3 References
[1] IUPAC, Compendium of Chemical Terminology, 2nd ed.
(the “Gold Book”) (1997). Online corrected version:
(2006–) "isomerization".

[2] Brown, K. N.; Field, L. D.; Lay, P. A.; Lin-


dall, C. M.; Masters, A. F. (1990). "(η5 -
Pentaphenylcyclopentadienyl){1-(η6 -phenyl)−2,3,4,5-
tetraphenylcyclopentadienyl}iron(II), [Fe(η5 -
6
C5 Ph5 ){(η -C6 H5 )C5 Ph4 }], a linkage isomer of
decaphenylferrocene”. J. Chem. Soc., Chem. Commun.
(5): 408–410. doi:10.1039/C39900000408.

[3] Field, L. D.; Hambley, T. W.; Humphrey, P. A.; Lindall,


C. M.; Gainsford, G. J.; Masters, A. F.; Stpierre, T. G.;
Webb, J. (1995). “Decaphenylferrocene”. Aust. J. Chem.
48 (4): 851–860. doi:10.1071/CH9950851.

[4] Resveratrol Photoisomerization: An Integrative Guided-


Inquiry Experiment Elyse Bernard, Philip Britz-
McKibbin, Nicholas Gernigon Vol. 84 No. 7 July 2007
Journal of Chemical Education 1159.

[5] Common Definitions and Terms in Organic Chemistry


(from the website of Cartage.org.lb)

[6] How to Compute Isomerization Energies of Organic


Molecules with Quantum Chemical Methods Ste-
fan Grimme, Marc Steinmetz, and Martin Korth J.
Org. Chem.; 2007; 72(6) pp 2118 - 2126; (Article)
doi:10.1021/jo062446p
Chapter 14

Amine gas treating

Amine gas treating, also known as amine scrubbing, noethanolamine (MEA) denoted as RNH2 , the chemistry
gas sweetening and acid gas removal, refers to a may be expressed as:
group of processes that use aqueous solutions of various
alkylamines (commonly referred to simply as amines) to RNH2 + H2 S ⇔ RNH+
remove hydrogen sulfide (H2 S) and carbon dioxide (CO2 ) 3 + SH-
from gases.[1][2][3] It is a common unit process used
in refineries, and is also used in petrochemical plants, A typical amine gas treating process (as shown in the flow
natural gas processing plants and other industries. diagram below) includes an absorber unit and a regen-
Processes within oil refineries or chemical processing erator unit as well as accessory equipment. In the ab-
plants that remove hydrogen sulfide are referred to as sorber, the downflowing amine solution absorbs H2 S and
“sweetening” processes because the odor of the processed CO2 from the upflowing sour gas to produce a sweetened
products is improved by the absence of hydrogen sulfide. gas stream (i.e., a gas free of hydrogen sulfide and carbon
An alternative to the use of amines involves membrane dioxide) as a product and an amine solution rich in the
technology. However, membranes are less attractive absorbed acid gases. The resultant “rich” amine is then
since the relatively high capital and operation costs as well routed into the regenerator (a stripper with a reboiler) to
as other technical factors. [4] produce regenerated or “lean” amine that is recycled for
reuse in the absorber. The stripped overhead gas from the
Many different amines are used in gas treating: regenerator is concentrated H2 S and CO2 .

• Diethanolamine (DEA)
• Monoethanolamine (MEA)
• Methyldiethanolamine (MDEA)
• Diisopropanolamine (DIPA)
• Aminoethoxyethanol (Diglycolamine) (DGA)

The most commonly used amines in industrial plants


are the alkanolamines DEA, MEA, and MDEA. These
amines are also used in many oil refineries to remove
sour gases from liquid hydrocarbons such as liquified
petroleum gas (LPG).

14.1 Description of a typical amine Process flow diagram of a typical amine treating process used
treater in petroleum refineries, natural gas processing plants and other
industrial facilities.

Gases containing H2 S or both H2 S and CO2 are com-


monly referred to as sour gases or acid gases in the
hydrocarbon processing industries. 14.2 Amines
The chemistry involved in the amine treating of such
gases varies somewhat with the particular amine be- The amine concentration in the absorbent aqueous solu-
ing used. For one of the more common amines, mo- tion is an important parameter in the design and operation

55
56 CHAPTER 14. AMINE GAS TREATING

of an amine gas treating process. Depending on which of the 64,000,000 metric tons of sulfur produced world-
one of the following four amines the unit was designed to wide in 2005 was byproduct sulfur from refineries and
use and what gases it was designed to remove, these are other hydrocarbon processing plants.[6][7] Another sulfur-
some typical amine concentrations, expressed as weight removing process is the WSA Process which recovers sul-
percent of pure amine in the aqueous solution:[1] fur in any form as concentrated sulfuric acid. In some
plants, more than one amine absorber unit may share a
• Monoethanolamine: About 20 % for re- common regenerator unit. The current emphasis on re-
moving H2 S and CO2 , and about 32 % moving CO2 from the flue gases emitted by fossil fuel
for removing only CO2 . power plants has led to much interest in using amines for
• Diethanolamine: About 20 to 25 % for removing CO2 . (See also: Carbon capture and storage
removing H2 S and CO2 and Conventional coal-fired power plant.)
• Methyldiethanolamine: About 30 to 55% In the specific case of the industrial synthesis of
% for removing H2 S and CO2 ammonia, for the steam reforming process of hydrocar-
• Diglycolamine: About 50 % for remov- bons to produce gaseous hydrogen, amine treating is one
ing H2 S and CO2 of the commonly used processes for removing excess car-
bon dioxide in the final purification of the gaseous hydro-
The choice of amine concentration in the circulating gen.
aqueous solution depends upon a number of factors and
may be quite arbitrary. It is usually made simply on the
basis of experience. The factors involved include whether 14.4 See also
the amine unit is treating raw natural gas or petroleum
refinery by-product gases that contain relatively low con- • Ammonia production
centrations of both H2 S and CO2 or whether the unit • Hydrodesulfurization
is treating gases with a high percentage of CO2 such
as the offgas from the steam reforming process used • WSA Process
in ammonia production or the flue gases from power • Claus process
plants.[1]
• Selexol
Both H2 S and CO2 are acid gases and hence corrosive to
carbon steel. However, in an amine treating unit, CO2 is • Rectisol
the stronger acid of the two. H2 S forms a film of iron
• Amine
sulfide on the surface of the steel that acts to protect the
steel. When treating gases with a high percentage of CO2 , • Ionic liquids
corrosion inhibitors are often used and that permits the
• Solid sorbents for carbon capture
use of higher concentrations of amine in the circulating
solution.
Another factor involved in choosing an amine concentra- 14.5 References
tion is the relative solubility of H2 S and CO2 in the se-
lected amine.[1] The choice of the type of amine will af- [1] Arthur Kohl and Richard Nielson (1997). Gas Purification
fect the required circulation rate of amine solution, the (5th ed.). Gulf Publishing. ISBN 0-88415-220-0.
energy consumption for the regeneration and the ability
[2] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-
to selectively remove either H2 S alone or CO2 alone if
ing Technology and Economics (2nd ed.). Marcel Dekker,
desired. For more information about selecting the amine
Inc. ISBN 0-8247-7150-8.
concentration, the reader is referred to Kohl and Nielsen’s
book. [3] US 4080424, Loren N. Miller & Thomas S. Zawacki,
“Process for acid gas removal from gaseous mixtures”, is-
Activated MDEA or aMDEA uses piperazine as a catalyst sued 21 Mar 1978, assigned to Institute of Gas Technol-
to increase the speed of the reaction with CO2. It has ogy
been commercially successful.[5]
[4] Baker, R. W. “Future Directions of Membrane Gas Sepa-
ration Technology” Ind. Eng. Chem. Res. 2002, volume
41, pages 1393-1411. doi:10.1021/ie0108088
14.3 Uses
[5] “Piperazine – Why It’s Used and How It Works”. The
Contactor 2 (4). 2008. Retrieved 2013-10-23. |first1=
In oil refineries, that stripped gas is mostly H2 S, much missing |last1= in Authors list (help)
of which often comes from a sulfur-removing process
called hydrodesulfurization. This H2 S-rich stripped gas [6] Sulfur production report by the United States Geological
Survey
stream is then usually routed into a Claus process to con-
vert it into elemental sulfur. In fact, the vast majority [7] Discussion of recovered byproduct sulfur
14.6. EXTERNAL LINKS 57

14.6 External links


• Description of Gas Sweetening Equipment and Op-
erating Conditions
• Selecting Amines for Sweetening Units, Polasek, J.
(Bryan Research & Engineering) and Bullin, J.A.
(Texas A&M University), Gas Processors Associ-
ation Regional Meeting, Sept. 1994.

• Natural Gas Supply Association Scroll down to Sul-


fur and Carbon Dioxide Removal

• Description of the classic book on gas treating by


Arthur Kohl & Richard Nielsen. Gas Purification
(Fifth ed.). Gulf Publishing. ISBN 0-88415-220-0.
Chapter 15

Claus process

plants.[3][4][5] Sulfur is used for manufacturing sulfuric


acid, medicine, cosmetics, fertilizers and rubber prod-
ucts. Elemental sulfur is used as fertilizer and pesticide.

15.1 History
The process was invented by Carl Friedrich Claus, a
chemist working in England. A British patent was issued
to him in 1883. The process was later significantly mod-
Piles of sulfur produced in Alberta by the Claus process awaiting ified by a German company called IG Farben[6]
shipment at docks in Vancouver, Canada.

The Claus process is the most significant gas 15.2 Process description
desulfurizing process, recovering elemental sulfur
from gaseous hydrogen sulfide. First patented in 1883 by A schematic process flow diagram of a basic 2+1-reactor
the scientist Carl Friedrich Claus, the Claus process has (converter) SuperClaus unit is shown below:
become the industry standard.
The multi-step Claus process recovers sulfur from the
gaseous hydrogen sulfide found in raw natural gas and
from the by-product gases containing hydrogen sulfide
derived from refining crude oil and other industrial pro-
cesses. The by-product gases mainly originate from phys-
ical and chemical gas treatment units (Selexol, Rectisol,
Purisol and amine scrubbers) in refineries, natural gas
processing plants and gasification or synthesis gas plants.
These by-product gases may also contain hydrogen
cyanide, hydrocarbons, sulfur dioxide or ammonia. Schematic flow diagram of a straight-through, 3 reactor (con-
Gases with an H2 S content of over 25% are suitable for verter), Claus sulfur recovery unit.
the recovery of sulfur in straight-through Claus plants
The Claus technology can be divided into two process
while alternate configurations such as a split-flow set up
steps, thermal and catalytic.
or feed and air preheating can be used to process leaner
[1]
feeds.
Hydrogen sulfide produced, for example, in the hydro- 15.2.1 Thermal step
desulfurization of refinery naphthas and other petroleum
oils, is converted to sulfur in Claus plants.[2] The overall In the thermal step, hydrogen sulfide-laden gas reacts in a
main reaction equation is: substoichiometric combustion at temperatures above 850
°C [7] such that elemental sulfur precipitates in the down-
2 H2 S + O2 → 2 S + 2 H2 O stream process gas cooler.
The H2 S content and the concentration of other com-
In fact, the vast majority of the 64,000,000 metric tons bustible components (hydrocarbons or ammonia) deter-
of sulfur produced worldwide in 2005 was byproduct mine the location where the feed gas is burned. Claus
sulfur from refineries and other hydrocarbon processing gases (acid gas) with no further combustible contents

58
15.2. PROCESS DESCRIPTION 59

apart from H2 S are burned in lances surrounding a central Side reactions


muffle by the following chemical reaction:
Other chemical processes taking place in the thermal step
2 H S + 3 O → 2 SO + 2 H O (ΔH = of the Claus reaction are:[5]
2 2 2 2
−4147.2 kJ mol−1 )
• The formation of hydrogen gas:
This is a strongly exothermic free-flame total oxidation
of hydrogen sulfide generating sulfur dioxide that reacts 2 H2 S → S2 + 2 H2 (ΔH > 0)
away in subsequent reactions. The most important one is CH4 + 2 H2 O → CO2 + 4 H2
the Claus reaction:

• The formation of carbonyl sulfide:


2 H2 S + SO2 → 3 S + 2 H2 O

H2 S + CO2 → S=C=O + H2 O
The overall equation is:[5]

• The formation of carbon disulfide:


10 H2 S + 5 O2 → 2 H2 S + SO2 + 7/2 S2 + 8
H2 O
CH4 + 2 S2 → S=C=S + 2 H2 S
This equation shows that in the thermal step alone two-
thirds of the hydrogen sulfide can be converted to sulfur. 15.2.2 Catalytic step
Gases containing ammonia, such as the gas from the re-
finery’s sour water stripper (SWS), or hydrocarbons are The Claus reaction continues in the catalytic step with ac-
converted in the burner muffle. Sufficient air is injected tivated aluminum(III) or titanium(IV) oxide, and serves
into the muffle for the complete combustion of all hy- to boost the sulfur yield. More hydrogen sulfide (H2 S) re-
drocarbons and ammonia. The air to the acid gas ratio acts with the SO2 formed during combustion in the reac-
is controlled such that in total 1/3 of all hydrogen sulfide tion furnace in the Claus reaction, and results in gaseous,
(H2 S) is converted to SO2 . This ensures a stoichiometric elemental sulfur.
reaction for the Claus reaction in the second catalytic step
(see next section below). 2 H2 S + SO2 → 3 S + 2 H2 O (ΔH = −1165.6
The separation of the combustion processes ensures an kJ mol−1 )
accurate dosage of the required air volume needed as a
function of the feed gas composition. To reduce the pro- This sulfur can be S6 , S7 , S8 or S9 .
cess gas volume or obtain higher combustion tempera-
tures, the air requirement can also be covered by inject- The catalytic recovery of sulfur consists of three substeps:
ing pure oxygen. Several technologies utilizing high-level heating, catalytic reaction and cooling plus condensation.
and low-level oxygen enrichment are available in indus- These three steps are normally repeated a maximum of
try, which requires the use of a special burner in the re- three times. Where an incineration or tail-gas treatment
action furnace for this process option. unit (TGTU) is added downstream of the Claus plant,
only two catalytic stages are usually installed.
Usually, 60 to 70% of the total amount of elemental sul-
fur produced in the process are obtained in the thermal The first process step in the catalytic stage is the gas heat-
process step. ing process. It is necessary to prevent sulfur condensation
in the catalyst bed, which can lead to catalyst fouling. The
The main portion of the hot gas from the combustion required bed operating temperature in the individual cat-
chamber flows through the tube of the process gas cooler alytic stages is achieved by heating the process gas in a
and is cooled down such that the sulfur formed in the re- reheater until the desired operating bed temperature is
action step condenses. The heat given off by the process reached.
gas and the condensation heat evolved are utilized to pro-
duce medium or low-pressure steam. The condensed sul- Several methods of reheating are used in industry:
fur is removed at the liquid outlet section of the process
gas cooler. • Hot-gas bypass: which involves mixing the two pro-
cess gas streams from the process gas cooler (cold
The sulfur forms in the thermal phase as highly reac-
gas) and the bypass (hot gas) from the first pass of
tive S2 diradicals which combine exclusively to the S8
the waste-heat boiler.
allotrope:
• Indirect steam reheaters: the gas can also be heated
4 S 2 → S8 with high-pressure steam in a heat exchanger.
60 CHAPTER 15. CLAUS PROCESS

• Gas/gas exchangers: whereby the cooled gas from 15.3 Process performance
the process gas cooler is indirectly heated from the
hot gas coming out of an upstream catalytic reactor Using two catalytic stages, the process will typically yield
in a gas-to-gas exchanger. over 97% of the sulfur in the input stream. Over 2.6 tons
of steam will be generated for each ton of sulfur yield.
The physical properties of elemental sulfur obtained in
• Direct-fired heaters: fired reheaters utilizing acid the Claus process can differ from that obtained by other
gas or fuel gas, which is burned substoichiometri- processes.[5] Sulfur is usually transported as a liquid
cally to avoid oxygen breakthrough which can dam- (melting point 115 °C). In ordinary sulfur viscosity can
age Claus catalyst. increase rapidly at temperatures in excess of 160 °C due
to the formation of polymeric sulfur chains but not so in
Claus-sulfur. Another anomaly is found in the solubility
The typically recommended operating temperature of the of residual H2 S in liquid sulfur as a function of temper-
first catalyst stage is 315 °C to 330 °C (bottom bed tem- ature. Ordinarily the solubility of a gas decreases with
perature). The high temperature in the first stage also increasing temperature but now it is the opposite. This
helps to hydrolyze COS and CS2 , which is formed in means that toxic and explosive H2 S gas can build up in
the furnace and would not otherwise be converted in the the headspace of any cooling liquid sulfur reservoir. The
modified Claus process. explanation for this anomaly is the endothermic reaction
of sulfur with H2 S to polysulfane.
The catalytic conversion is maximized at lower temper-
atures, but care must be taken to ensure that each bed is
operated above the dew point of sulfur. The operating
temperatures of the subsequent catalytic stages are typi- 15.4 See also
cally 240 °C for the second stage and 200 °C for the third
stage (bottom bed temperatures). • Amine treating
In the sulfur condenser, the process gas coming from the • Hydro-desulfurization
catalytic reactor is cooled to between 150 and 130 °C.
The condensation heat is used to generate steam at the • Crystasulf
shell side of the condenser. • Hydrogenation
Before storage, liquid sulfur streams from the process gas
• Acid gas
cooler, the sulfur condensers and from the final sulfur sep-
arator are routed to the degassing unit, where the gases • Sour gas
(primarily H2 S) dissolved in the sulfur are removed.
The tail gas from the Claus process still containing com-
bustible components and sulfur compounds (H2 S, H2 and 15.5 References
CO) is either burned in an incineration unit or further
desulfurized in a downstream tail gas treatment unit. [1] Gas Processors Association Data Book, 10th Edition,
Volume II, Section 22

[2] Gary, J.H. and Handwerk, G.E. (1984). Petroleum Refin-


ing Technology and Economics (2nd Edition ed.). Marcel
Dekker, Inc. ISBN 0-8247-7150-8.
15.2.3 Sub dew point Claus process
[3] Sulfur production report by the United States Geological
The conventional Claus process described above is lim- Survey
ited in its conversion due to the reaction equilibrium be- [4] Discussion of recovered byproduct sulfur
ing reached. Like all exothermic reactions, greater con-
version can be achieved at lower temperatures, however [5] Der Claus-Prozess. Reich an Jahren und bedeutender denn
je, Bernhard Schreiner, Chemie in Unserer Zeit, Volume
as mentioned the Claus reactor must be operated above
42 Issue 6, Pages 378 - 392 2009
the sulfur dew point (120–150 °C) to avoid liquid sul-
fur physically deactivating the catalyst. To overcome this [6] Bibliographic Citation Sulfur Recovery Technology, B.G.
problem, the sub dew point Claus process operates with Goar, American Institute of Chemical Engineers Spring
reactors in parallel. When one reactor has become satu- National Meeting, New Orleans, Louisiana, April 6, 1986
rated with adsorbed sulfur, the process flow is diverted to
[7] Or between 950 and 1200 °C and even hotter near the
the standby reactor. The reactor is then regenerated by flame, as stated in Der Claus-Prozess. Reich an Jahren
sending process gas that has been heated to 300–350 °C und bedeutender denn je, Bernhard Schreiner, Chemie in
to vaporize the sulfur. This stream is sent to a condenser Unserer Zeit, Volume 42 Issue 6, 2009
to recover the sulfur.
Chapter 16

Hydrogen sulfide

Hydrogen sulfide is the chemical compound with the hydrogen sulfide in water, known as sulfhydric acid or
formula H hydrosulfuric acid, is initially clear but over time turns
2S. It is a colorless gas with the characteristic foul odor cloudy. This is due to the slow reaction of hydrogen sul-
of rotten eggs; it is heavier than air, very poisonous, cor-fide with the oxygen dissolved in water, yielding elemen-
rosive, flammable, and explosive. tal sulfur, which precipitates out. The sulfide dianion S2−
Hydrogen sulfide often results from the bacterial break- exists only in strongly alkaline aqueous solutions; it is ex-
ceptionally basic with a pKₐ > 14.
down of organic matter in the absence of oxygen gas,
such as in swamps and sewers; this process is commonly Hydrogen sulfide reacts with metal ions to form metal
known as anaerobic digestion. H sulfides, which may be considered the salts of hydrogen
2S also occurs in volcanic gases, natural gas, and in some sulfide. Some ores are sulfides. Metal sulfides often have
sources of well water. It is also present in natural halite a dark color. Lead(II) acetate paper is used to detect hy-
type rock salts, most notably in Himalayan Black Salt, drogen sulfide because it turns grey in the presence of the
which is mostly harvested from the mineral-rich “Salt gas as lead(II) sulfide is produced. Reacting metal sulfides
Range” mountains of Pakistan. The human body pro- with strong acid liberates hydrogen sulfide.
duces small amounts of H If gaseous hydrogen sulfide is put into contact with con-
2S and uses it as a signaling molecule. centrated nitric acid, it explodes.
Dissolved in water, hydrogen sulfide is known as hydro- Hydrogen sulfide reacts with alcohols to form thiols, an
sulfuric acid or sulfhydric acid, a weak acid.
important class of organosulfur compounds.
Swedish chemist Carl Wilhelm Scheele is credited with
having discovered hydrogen sulfide in 1777.
The British English spelling of this compound is hydro- 16.2 Production
gen sulphide, but this spelling is not recommended by the
International Union of Pure and Applied Chemistry nor Hydrogen sulfide is most commonly obtained by its sepa-
the Royal Society of Chemistry. ration from sour gas, which is natural gas with high con-
tent of H
2S. It can also be produced by reacting hydrogen gas with
16.1 Properties molten elemental sulfur at about 450 °C. Hydrocarbons
can replace hydrogen in this process.[7]

Hydrogen sulfide is slightly heavier than air; a mixture of Sulfate-reducing (resp. sulfur-reducing) bacteria gener-
H ate usable energy under low-oxygen conditions by using
2S and air is explosive. Hydrogen sulfide and oxygen burn sulfates (resp. elemental sulfur) to oxidize organic com-
with a blue flame to form sulfur dioxide (SO pounds or hydrogen; this produces hydrogen sulfide as a
2) and water. In general, hydrogen sulfide acts as a waste product.
reducing agent. The standard lab preparation is to react ferrous sulfide
At high temperature or in the presence of catalysts, sul- (FeS) with a strong acid in a Kipp generator:
fur dioxide can be made to react with hydrogen sulfide to
form elemental sulfur and water. This is exploited in the FeS + 2 HCl → FeCl2 + H2 S
Claus process, the main way to convert hydrogen sulfide
into elemental sulfur. A less well-known and more convenient alternative is to
[8]
Hydrogen sulfide is slightly soluble in water and acts as react aluminium sulfide with water:
a weak acid, giving the hydrosulfide ion HS− (pKₐ = 6.9
in 0.01-0.1 mol/litre solutions at 18 °C). A solution of 6 H2 O + Al2 S3 → 3 H2 S + 2 Al(OH)3

61
62 CHAPTER 16. HYDROGEN SULFIDE

This gas is also produced by heating sulfur with solid comes in contact with organic material, especially at high
organic compounds and by reducing sulfurated organic temperatures.
compounds with hydrogen. In 2011 it was reported that increased concentration of H
Hydrogen sulfide production can be costly because of the 2S, possibly due to oil field practices, was observed in
dangers involved in production. the Bakken formation crude and presented challenges
Water heaters can aid the conversion of sulfate in water to such as “health and environmental risks, corrosion of
wellbore, added expense with regard to materials han-
hydrogen sulfide gas. This is due to providing a warm en-
vironment sustainable for sulfur bacteria and maintaining dling and pipeline
[11]
equipment, and additional refinement
the reaction which interacts between sulfate in the water requirements”.
and the water heater anode, which is usually made from Besides living near a gas and oil drilling operations, ordi-
magnesium metal.[9] nary citizens can be exposed to hydrogen sulfide by being
near waste water treatment facilities, landfills and farms
with manure storage. Exposure occurs through breathing
16.3 Occurrence contaminated air or drinking contaminated water.[12]

16.4 Uses

16.4.1 Production of thioorganic com-


pounds
Several organosulfur compounds are produced using hy-
drogen sulfide. These include methanethiol, ethanethiol,
and thioglycolic acid.

16.4.2 Alkali metal sulfides


Upon combining with alkali metal bases, hydrogen sulfide
converts to alkali hydrosulfides such as sodium hydrosul-
Deposit of sulfur on a rock, caused by volcanic gases
fide and sodium sulfide, which are used in the degradation
of biopolymers. The depilation of hides and the deligni-
Small amounts of hydrogen sulfide occur in crude fication of pulp by the Kraft process both are effected by
petroleum, but natural gas can contain up to 90%. alkali sulfides.
Volcanoes and some hot springs (as well as cold springs)
emit some H
2S, where it probably arises via the hydrolysis of sulfide 16.4.3 Analytical chemistry
minerals, i.e. MS + H
2O → MO + H For well over a century, hydrogen sulfide was important
2S. Hydrogen sulfide can be present naturally in well wa- in analytical chemistry, in the qualitative inorganic anal-
ter, often as a result of the action of sulfate-reducing bac- ysis of metal ions. In these analyses, heavy metal (and
teria. Hydrogen Sulfide is created by the human body in nonmetal) ions (e.g., Pb(II), Cu(II), Hg(II), As(III)) are
small doses through bacterial breakdown of proteins con- precipitated from solution upon exposure to H
taining sulfur in the intestinal tract, it is also produced in 2S. The components of the resulting precipitate redis-
the mouth and is a cause for Halitosis.[10] solve with some selectivity.
A portion of global H For small-scale laboratory use in analytic chemistry, the
2S emissions are due to human activity. By far the largest use of thioacetamide has superseded H
industrial route to H 2S as a source of sulfide ions.
2S occurs in petroleum refineries: The
hydrodesulfurization process liberates sulfur from
petroleum by the action of hydrogen. The resulting H 16.4.4 Precursor to metal sulfides
2S is converted to elemental sulfur by partial combustion
via the Claus process, which is a major source of ele- As indicated above, many metal ions react with hydro-
mental sulfur. Other anthropogenic sources of hydrogen gen sulfide to give the corresponding metal sulfides. This
sulfide include coke ovens, paper mills (using the sulfate conversion is widely exploited. For example, gases or
method), and tanneries. H waters contaminated by hydrogen sulfide can be cleaned
2S arises from virtually anywhere where elemental sulfur with metal sulfides. In the purification of metal ores by
16.6. REMOVAL FROM WATER 63

flotation, mineral powders are often treated with hydro- 2O(l) → 2 Fe


gen sulfide to enhance the separation. Metal parts are 2O
sometimes passivated with hydrogen sulfide. Catalysts 3(s) + 2 H
used in hydrodesulfurization are routinely activated with 2O(l) + 6 S(s)
hydrogen sulfide, and the behavior of metallic catalysts
used in other parts of a refinery is also modified using On completion of the regeneration
hydrogen sulfide. reaction the container is drained of
water and can be returned to ser-
vice. The advantage of this system
16.4.5 Miscellaneous applications is that it is completely passive dur-
ing the extraction phase.[15]
Hydrogen sulfide is used to separate deuterium oxide, or
heavy water, from normal water via the Girdler Sulfide • Hydrodesulfurization
process.
Scientists from the University of Exeter discovered that Hydrodesulfurization is a more
cell exposure to small amounts of hydrogen sulfide gas complex method of removing sul-
have shown to prevent mitochondrial damage. When fur from fuels.
the cell is stressed with disease, enzymes are drawn into
the cell to produce small amounts of hydrogen sulfide • Filtration through impregnated activated carbon
This study could have further implications on preventing
strokes, heart disease and arthritis.[13] A gas stream containing hydrogen
sulfide can be purified by pass-
Hydrogen sulfide may have anti-aging properties by ing it through a suitably designed
blocking destructive chemicals within the cell, bearing filter containing an impregnated
similar properties to resveratrol, an antioxidant found in activated carbon. This method is
red wine.[14] typically used for odor abatement
at municipal sewage works and for
the purification of landfill biogas,
16.5 Removal from fuel gases prior to its use in combined heat and
power (CHP) engines, or injection
Hydrogen sulfide is commonly found in natural gas, into the gas grid.
biogas, and LPG. It can be removed in a number of ways.
• Treatment by plasma
• Reaction with iron oxide
Plasma dissociation of hydrogen
sulfide is a new method of treatment
Gas is pumped through a container which utilizes plasma to dissociate
of hydrated iron(III) oxide, which hydrogen sulfide into hydrogen gas
combines with hydrogen sulfide. and elemental sulfur.

Fe
2O 16.6 Removal from water
3(s) + H
2O(l) + 3 H
Hydrogen sulfide can be removed effectively from
2S(g) → Fe
drinking water and there are a number of processes de-
2S
signed for this purpose. However, the preferred method
3(s) + 4 H
can change according to the level of concentration in wa-
2O(l)
ter. Drinking water should be checked for hydrogen sul-
fide levels, especially if using ground water due to low
In order to regenerate iron(III) ox- dissolved oxygen levels.[16]
ide, the container must be taken out
of service, flooded with water and • Continuous Chlorination
aerated.
For levels up to 75 mg/L Chlorine is used in the pu-
2 Fe rification process as an oxidizing chemical to react with
2S hydrogen sulfide. This reaction yields insoluble solid
3(s) + 3 O sulfur. Usually the chlorine used is in the form of sodium
2(g) + 2 H hypochlorite.[17]
64 CHAPTER 16. HYDROGEN SULFIDE

• Aeration usually go away in a few weeks.


Long-term, low-level exposure may result in fatigue, loss
For concentrations of hydrogen sulfide less than 2mg/L of appetite, headaches, irritability, poor memory, and
aeration is an ideal treatment process. Oxygen is added dizziness. Chronic exposure to low level H
to a water and a reaction between oxygen and hydrogen 2S (around 2 ppm) has been implicated in increased mis-
sulfide react to produce odorless sulfate[18] carriage and reproductive health issues among Russian
and Finnish wood pulp workers,[26] but the reports have
not (as of circa 1995) been replicated.
16.7 Safety Short-term, high-level exposure can induce immediate
collapse, with loss of breathing and a high probability of
Hydrogen sulfide is a highly toxic and flammable gas death. If death does not occur, high exposure to hydro-
(flammable range: 4.3–46%). Being heavier than air, it gen sulfide can lead to cortical pseudolaminar necrosis,
tends to accumulate at the bottom of poorly ventilated degeneration of the basal ganglia and cerebral edema.[20]
spaces. Although very pungent at first, it quickly deadens Although respiratory paralysis may be immediate, it can
the sense of smell, so victims may be unaware of its pres- also be delayed up to 72 hours.[27]
ence until it is too late. For safe handling procedures,
a hydrogen sulfide material safety data sheet (MSDS) • 0.00047 ppm or 0.47 ppb is the odor threshold, the
should be consulted.[19] point at which 50% of a human panel can detect the
presence of an odor without being able to identify
it.[28]
16.7.1 Toxicity
• 0.0047 ppm is the recognition threshold, the con-
Hydrogen sulfide is considered a broad-spectrum poison, centration at which 50% of humans can detect the
meaning that it can poison several different systems in the characteristic odor of hydrogen sulfide,[28] normally
body, although the nervous system is most affected. The described as resembling “a rotten egg”.
toxicity of H
2S is comparable with that of hydrogen cyanide or carbon • 10 ppm is the OSHA permissible exposure limit
monoxide.[20] It forms a complex bond with iron in (PEL) (8 hour time-weighted average).[10]
the mitochondrial cytochrome enzymes, thus preventing
cellular respiration. • 10–20 ppm is the borderline concentration for eye
irritation.
Since hydrogen sulfide occurs naturally in the body, the
environment and the gut, enzymes exist in the body capa- • 20 ppm is the acceptable ceiling concentration es-
ble of detoxifying it by oxidation to (harmless) sulfate.[21] tablished by OSHA.[10]
Hence, low levels of hydrogen sulfide may be tolerated in-
definitely. • 50 ppm is the acceptable maximum peak above the
At some threshold level, believed to average around 300– ceiling concentration for an 8 hour shift, with a max-
350 ppm, the oxidative enzymes become overwhelmed. imum duration of 10 minutes.[10]
Many personal safety gas detectors, such as those used
by utility, sewage and petrochemical workers, are set to • 50–100 ppm leads to eye damage.
alarm at as low as 5 to 10 ppm and to go into high alarm
• At 100–150 ppm the olfactory nerve is para-
at 15 ppm.
lyzed after a few inhalations, and the sense of
A diagnostic clue of extreme poisoning by H smell disappears, often together with awareness of
2S is the discoloration of copper coins in the pock- danger.[29][30]
ets of the victim. Treatment involves immediate in-
halation of amyl nitrite, injections of sodium nitrite or • 320–530 ppm leads to pulmonary edema with the
administration of 4-dimethylaminophenol in combina- possibility of death.[20]
tion with inhalation of pure oxygen, administration of
bronchodilators to overcome eventual bronchospasm, and • 530–1000 ppm causes strong stimulation of the
in some cases hyperbaric oxygen therapy (HBOT).[20] central nervous system and rapid breathing, leading
HBOT has clinical and anecdotal support.[22][23][24] to loss of breathing.

Exposure to lower concentrations can result in eye irrita- • 800 ppm is the lethal concentration for 50% of hu-
tion, a sore throat and cough, nausea, shortness of breath, mans for 5 minutes exposure (LC50).
and fluid in the lungs (pulmonary edema).[20] These ef-
fects are believed to be due to the fact that hydrogen sul- • Concentrations over 1000 ppm cause immediate
fide combines with alkali present in moist surface tissues collapse with loss of breathing, even after inhalation
to form sodium sulfide, a caustic.[25] These symptoms of a single breath.
16.9. INVOLVEMENT IN DISEASES 65

16.7.2 Incidents ical signaling functions. (Only two other such gases are
currently known: nitric oxide (NO) and carbon monoxide
Hydrogen sulfide was used by the British Army as a chem- (CO).)
ical weapon during World War I. It was not considered to
The gas is produced from cysteine by the enzymes
be an ideal war gas, but, while other gases were in short
cystathionine beta-synthase and cystathionine gamma-
supply, it was used on two occasions in 1916.[31]
lyase. It acts as a relaxant of smooth muscle and as a
In 1975, a hydrogen sulfide release from an oil drilling vasodilator[40] and is also active in the brain, where it in-
operation in Denver City, Texas, killed nine people and creases the response of the NMDA receptor and facili-
caused the state legislature to focus on the deadly hazards tates long term potentiation,[41] which is involved in the
of the gas. State Representative E L Short took the lead formation of memory.
in endorsing an investigation by the Texas Railroad Com-
Eventually the gas is converted to sulfite in the
mission and urged that residents be warned “by knocking
mitochondria by thiosulfate reductase, and the sulfite is
on doors if necessary” of the imminent danger stemming
further oxidized to thiosulfate and sulfate by sulfite oxi-
from the gas. One may die from the second inhalation of
dase. The sulfates are excreted in the urine.[42]
the gas, and a warning itself may be too late.[32]
Due to its effects similar to nitric oxide (without its po-
A dump of toxic waste containing hydrogen sulfide is be-
tential to form peroxides by interacting with superoxide),
lieved to have caused 17 deaths and thousands of illnesses
hydrogen sulfide is now recognized as potentially protect-
in Abidjan, on the West African coast, in the 2006 Côte
ing against cardiovascular disease.[40] The cardioprotec-
d'Ivoire toxic waste dump.
tive role effect of garlic is caused by catabolism of the
In 2014, Levels of Hydrogen Sulfide as high as 83 ppm polysulfide group in allicin to H
have been detected at a recently built mall in Thailand 2S, a reaction that could depend on reduction mediated
called Siam Square One at the Siam Square area. Shop by glutathione.[43]
tenants at the mall reported health complications such as
Though both nitric oxide (NO) and hydrogen sulfide have
sinus inflammation, breathing difficulties and eye irrita-
been shown to relax blood vessels, their mechanisms
tion. After investigation it was determined that the large
of action are different: while NO activates the enzyme
amount of gas originated from imperfect treatment and
guanylyl cyclase, H
disposal of waste water in the building.[33]
2S activates ATP-sensitive potassium channels in smooth
In November 2014, a substantial amount of hydrogen sul- muscle cells. Researchers are not clear how the vessel-
fide gas shrouded the central, eastern and south-eastern relaxing responsibilities are shared between nitric oxide
parts of Moscow. Residents living in the area were urged and hydrogen sulfide. However there exists some evi-
to stay indoors by the emergencies ministry. Although the dence to suggest that nitric oxide does most of the vessel-
exact source of the gas was not known, blame had been relaxing work in large vessels and hydrogen sulfide is re-
placed on a Moscow oil refinery.[34] sponsible for similar action in smaller blood vessels.[44]
Recent findings suggest strong cellular crosstalk of NO
and H
16.7.3 Suicides
2S,[45] demonstrating that the vasodilatatory effects of
these two gases are mutually dependent. Additionally, H
The gas, produced by mixing certain household ingredi-
2S reacts with intracellular S-nitrosothiols to form the
ents, was used in a suicide wave in 2008 in Japan.[35] The
smallest S-nitrosothiol (HSNO), and a role of hydrogen
wave prompted staff at Tokyo’s suicide prevention center
sulfide in controlling the intracellular S-nitrosothiol pool
to set up a special hot line during "Golden Week", as they
has been suggested.[46]
received an increase in calls from people wanting to kill
themselves during the annual May holiday.[36] Like nitric oxide, hydrogen sulfide is involved in the re-
laxation of smooth muscle that causes erection of the
As of 2010, this phenomenon has occurred in a num-
penis, presenting possible new therapy opportunities for
ber of US cities, prompting warnings to those arriving
[37] erectile dysfunction.[47][48]
at the site of the suicide. These first responders, such
as emergency services workers or family members are at
risk of death from inhaling lethal quantities of the gas, or
by fire.[38][39] Local governments have also initiated cam- 16.9 Involvement in diseases
paigns to prevent such suicides.
16.9.1 Hydrogen sulfide deficiency after
heart attack
16.8 Function in the body
A hydrogen sulfide (H2S) deficiency can be detrimen-
Hydrogen sulfide is produced in small amounts by some tal to the vascular function after an acute myocardial in-
cells of the mammalian body and has a number of biolog- farction (AMI).[49] AMIs can lead to cardiac dysfunc-
66 CHAPTER 16. HYDROGEN SULFIDE

tion through two distinct changes; increased oxidative centration was found to be reduced, and administering
stress via free radical accumulation and decreased NO hydrogen sulfide alleviated the condition.[55] In trisomy
bioavailability.[50] Free radical accumulation occurs due 21 (Down syndrome) the body produces an excess of hy-
to increased electron transport uncoupling at the active drogen sulfide.[42] Hydrogen sulfide is also involved in the
site of endothelial nitric oxide synthase (eNOS), an en- disease process of type 1 diabetes. The beta cells of the
zyme involved in converting L-arginine to NO.[49][50] pancreas in type 1 diabetes produce an excess of the gas,
During an AMI, oxidative degradation of tetrahydro- leading to the death of these cells and to a reduced pro-
biopterin (BH4), a cofactor in NO production, limits BH4 duction of insulin by those that remain.[44]
availability and limits NO productionby eNOS.[50] In-
stead, eNOS reacts with oxygen, another cosubstrates in-
volved in NO production. The products of eNOS are re-
duced to superoxides, increasing free radical production
and oxidative stress within the cells.[49] A H2S deficiency 16.10 Induced hypothermia and
impairs eNOS activity by limiting Akt activation and in- suspended animation
hibiting Akt phosphorylation of the eNOSS1177 activa-
tion site.[49][51] Instead, Akt activity is increased to phos-
phorylate the eNOST495 inhibition site, downregulating In 2005, it was shown that mice can be put into a state of
eNOS production of NO.[49][51] suspended animation-like hypothermia by applying a low
dosage of hydrogen sulfide (81 ppm H
H2S therapy uses a H2S donor, such as diallyl trisulfide
2S) in the air. The breathing rate of the animals sank
(DATS), to increase the supply of H2S to an AMI pa-
from 120 to 10 breaths per minute and their temperature
tient. H2S donors reduce myocardial injury and reper-
fell from 37 °C to just 2 °C above ambient temperature
fusion complications.[49] Increased H2S levels within the
(in effect, they had become cold-blooded). The mice sur-
body will react with oxygen to produce sulfane sulfur, a
vived this procedure for 6 hours and afterwards showed
storage intermediate for H2S.[49] H2S pools in the body
no negative health consequences.[56] In 2006 it was shown
attracts oxygen to react with excess H2S and eNOS to
that the blood pressure of mice treated in this fashion with
increase NO production.[49] With increased use of oxy-
hydrogen sulfide did not significantly decrease.[57]
gen to produce more NO, less oxygen is available to re-
act with eNOS to produce superoxides during an AMI, A similar process known as hibernation occurs naturally
ultimately lowering the accumulation of reactive oxygen in many mammals and also in toads, but not in mice.
species (ROS).[49] Furthermore, decreased accumulation (Mice can fall into a state called clinical torpor when food
of ROS lowers oxidative stress in vascular smooth muscle shortage occurs). If the H
cells, decreasing oxidative degeneration of BH4.[50] In- 2S-induced hibernation can be made to work in hu-
creased BH4 cofactor contributes to increased production mans, it could be useful in the emergency management
of NO within the body.[50] Higher concentrations of H2S of severely injured patients, and in the conservation of
directly increase eNOS activity through Akt activation donated organs. In 2008, hypothermia induced by hydro-
to increase phosphorylation of the eNOSS1177 activa- gen sulfide for 48 hours was shown to reduce the extent of
tion site, and decrease phosphorylation of the eNOST495 brain damage caused by experimental stroke in rats.[58]
inhibition site.[49][51] This phosphorylation process up- As mentioned above, hydrogen sulfide binds to
regulates eNOS activity, catalyzing more conversion of cytochrome oxidase and thereby prevents oxygen
L-arginine to NO.[49][51] Increased NO production en- from binding, which leads to the dramatic slowdown
ables soluble guanylyl cyclase (sGC) activity, leading to of metabolism. Animals and humans naturally produce
an increased conversion of guanosine triphosphate (GTP) some hydrogen sulfide in their body; researchers have
to 3’,5’-cyclic guanosine monophosphate (cGMP).[52] In proposed that the gas is used to regulate metabolic
H2S therapy immediately following an AMI, increased activity and body temperature, which would explain the
cGMP triggers an increase in protein kinase G (PKG) above findings.[59]
activity.[53] PKG reduces intracellular Ca2+ in vascular
smooth muscle to increase smooth muscle relaxation and Two recent studies cast doubt that the effect can be
promote blood flow.[53] PKG also limits smooth mus- achieved in larger mammals. A 2008 study failed to re-
cle cell proliferation, reducing intima thickening follow- produce the effect in pigs, concluding that the effects seen
ing AMI injury, ultimately decreasing myocardial infarct in mice were not present in larger mammals.[60] Likewise
size.[49][52] a paper by Haouzi et al. noted that there is no induction
of hypometabolism in sheep, either.[61]
At the February 2010 TED conference, Mark Roth an-
16.9.2 Other diseases nounced that hydrogen sulfide induced hypothermia in
humans had completed Phase I clinical trials.[62] The clin-
In Alzheimer’s disease the brain’s hydrogen sulfide con- ical trials commissioned by the company he helped found,
centration is severely decreased.[54] In a certain rat model Ikaria, were however withdrawn or terminated by August
of Parkinson’s disease, the brain’s hydrogen sulfide con- 2011.[63][64]
16.12. MASS EXTINCTIONS 67

16.11 Participant in the sulfur cy- 16.12 Mass extinctions


cle
Main article: Anoxic event
Hydrogen sulfide has been implicated in several mass
Main article: Sulfur cycle

Hydrogen sulfide is a central participant in the sulfur cy-


cle, the biogeochemical cycle of sulfur on Earth.
In the absence of oxygen, sulfur-reducing and sulfate-
reducing bacteria derive energy from oxidizing hydro-
gen or organic molecules by reducing elemental sulfur or
sulfate to hydrogen sulfide. Other bacteria liberate hydro-
gen sulfide from sulfur-containing amino acids; this gives
rise to the odor of rotten eggs and contributes to the odor
of flatulence.

A hydrogen sulfide bloom (green) stretching for about 150km


along the coast of Namibia. As oxygen-poor water reaches the
coast, bacteria in the organic-matter rich sediment produce hy-
drogen sulfide which is toxic to fish. (The image is taken from a
bird’s eye view)

extinctions that have occurred in the Earth’s past. In par-


ticular, a buildup of hydrogen sulfide in the atmosphere
may have caused the Permian-Triassic extinction event
252 million years ago.[66]
Organic residues from these extinction boundaries indi-
cate that the oceans were anoxic (oxygen-depleted) and
had species of shallow plankton that metabolized H
2S. The formation of H
2S may have been initiated by massive volcanic eruptions,
which emitted carbon dioxide and methane into the atmo-
Sludge from a pond; the black color is due to metal sulfides sphere, which warmed the oceans, lowering their capacity
to absorb oxygen that would otherwise oxidize H
2S. The increased levels of hydrogen sulfide could have
killed oxygen-generating plants as well as depleted the
ozone layer, causing further stress. Small H
As organic matter decays under low-oxygen (or hypoxic) 2S blooms have been detected in modern times in the
conditions (such as in swamps, eutrophic lakes or dead Dead Sea and in the Atlantic ocean off the coast of
zones of oceans), sulfate-reducing bacteria will use the Namibia.[66]
sulfates present in the water to oxidize the organic mat-
ter, producing hydrogen sulfide as waste. Some of the
hydrogen sulfide will react with metal ions in the water 16.13 See also
to produce metal sulfides, which are not water soluble.
These metal sulfides, such as ferrous sulfide FeS, are of- • Amine gas treating
ten black or brown, leading to the dark color of sludge.
• Sewer gas
Several groups of bacteria can use hydrogen sulfide as
fuel, oxidizing it to elemental sulfur or to sulfate by using • Induced hypothermia
dissolved oxygen, metal oxides (e.g., Fe oxyhydroxides
and Mn oxides) or nitrate as oxidant.[65] • Jenkem

The purple sulfur bacteria and the green sulfur bacteria • Gasotransmitters
use hydrogen sulfide as electron donor in photosynthesis,
thereby producing elemental sulfur. (In fact, this mode of
photosynthesis is older than the mode of cyanobacteria, 16.14 References
algae, and plants, which uses water as electron donor and
liberates oxygen.) [1] “Hydrogen Sulfide - PubChem Public Chemical
68 CHAPTER 16. HYDROGEN SULFIDE

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for Biotechnology Information. Komenda B, Maier A, Smolle-Juettner FM (December
2010). “Severe hydrogen sulphide poisoning treated with
[2] Perrin, D.D., Ionisation Constants of Inorganic Acids and 4-dimethylaminophenol and hyperbaric oxygen”. Diving
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ford, 1982. cific Underwater Medicine Society 40 (4): 213–7. PMID
23111938. Retrieved 2013-06-07.
[3] Bruckenstein, S.; Kolthoff, I.M., in Kolthoff, I.M.; Elving,
P.J. Treatise on Analytical Chemistry, Vol. 1, pt. 1; Wiley, [21] S. Ramasamy, S. Singh, P. Taniere, M. J. S. Langman, M.
NY, 1959, pp. 432-433. C. Eggo (2006). “Sulfide-detoxifying enzymes in the hu-
man colon are decreased in cancer and upregulated in dif-
[4] Pradyot Patnaik. Handbook of Inorganic Chemicals. ferentiation”. Am. J. Physiol. Gastrointest. Liver Physiol.
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[5] Zumdahl, Steven S. (2009). Chemical Principles 6th Ed.
Houghton Mifflin Company. p. A23. ISBN 0-618- [22] Gerasimon G, Bennett S, Musser J, Rinard J (May
94690-X. 2007). “Acute hydrogen sulfide poisoning in a
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[6] Hydrogen sulfide: Overview, National Pollutant Inven- doi:10.1080/15563650601118010. PMID 17486486.
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[7] Jacques Tournier-Lasserve “Hydrogen Sulfide” in Ull- [23] Belley R, Bernard N, Côté M, Paquet F, Poitras J (July
mann’s Encyclopedia of Chemical Industry 2005). “Hyperbaric oxygen therapy in the management
of two cases of hydrogen sulfide toxicity from liquid ma-
[8] McPherson, William (1913). Laboratory manual. nure”. CJEM 7 (4): 257–61. PMID 17355683. Retrieved
Boston: Ginn and Company. p. 445. 2008-07-22.

[9] “Why Does My Water Smell Like Rotten Eggs? Hydro- [24] Hsu P, Li H-W, Lin Y-T (1987). “Acute hydrogen sulfide
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Retrieved 1 December 2014. 07-22.

[10] Agency for Toxic Substances and Disease Registry (July [25] Lewis, R.J. Sax’s Dangerous Properties of Industrial Mate-
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[26] Hemminki K., Niemi M.L. (1982) Int. Arch. Occup. En-
[11] Holubnyak et al, SPE 141434-MS
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[14] Khan, Natasha. “Rotten Egg Gas Seen Offering Promise [29] USEPA; Health and Environmental Effects Profile for
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[30] Zenz, C., O.B. Dickerson, E.P. Horvath. Occupational
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[31] Foulkes, Charles Howard (2001) [First published Black-


[16] Lemley, Ann T.; Schwartz, John J.; Wagenet, Linda P.
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[50] Alp, Nicholas; Channon (2003). “Regulation
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[51] Coletta, Ciro; Papapetropoulos, Erdelyi, Olah, Modis,
[41] Kimura, Hideo (2002). “Hydrogen sulfide as a neu- Panopoulos, Asimakopoulou, Gero, Sharina, Martin, Sz-
romodulator”. Molecular Neurobiology 26 (1): 13–19. abo (April 2012). “Hydrogen sulfide and nitric oxide
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[42] Kamoun, Pierre (July 2004). “H2 S, a new neuro-
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Victor M Darley-Usmar, Jeannette E Doeller, David GMP-dependent protein kinase regulates vascular smooth
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doi:10.1073/pnas.0705710104. PMC 2084282. PMID dependent protein kinase mediates the reduction of Ca2+
17951430. by cAMP in vascular smooth muscle cells”. American
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[45] Coletta, C.; Papapetropoulos, A.; Erdelyi, K.; Olah, [54] Eto, Ko; Takashi Asada; Kunimasa Arima; Takao Maki-
G.; Modis, K.; Panopoulos, P.; Asimakopoulou, A.; fuchi; Hideo Kimura (2002-05-24). “Brain hydrogen sul-
Gero, D.; Sharina, I.; Martin, E.; Szabo, C. (2012). fide is severely decreased in Alzheimer’s disease”. Bio-
“Hydrogen sulfide and nitric oxide are mutually depen- chemical and Biophysical Research Communications 293
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dependent vasorelaxation”. Proceedings of the Na- PMID 12054683.
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doi:10.1073/pnas.1202916109. PMC 3384190. PMID [55] Hu, L. F.; Lu, M.; Tiong, C. X.; Dawe, G. S.; Hu, G.;
22570497. Bian, J. S. (2010). “Neuroprotective effects of hydrogen
sulfide on Parkinson’s disease rat models”. Aging cell 9
[46] Filipovic, M. R.; Miljkovic, J. L.; Nauser, T.; Royzen, (2): 135–146. doi:10.1111/j.1474-9726.2009.00543.x.
M.; Klos, K.; Shubina, T.; Koppenol, W. H.; Lippard, PMID 20041858.
S. J.; Ivanović-Burmazović, I. (2012). “Chemical Char-
acterization of the SmallestS-Nitrosothiol, HSNO; Cel- [56] Mice put in 'suspended animation', BBC News, 21 April
lular Cross-talk of H2S andS-Nitrosothiols”. Journal 2005
of the American Chemical Society 134 (29): 12016–
12027. doi:10.1021/ja3009693. PMC 3408084. PMID [57] Gas induces 'suspended animation', BBC News, 9 October
22741609. 2006
70 CHAPTER 16. HYDROGEN SULFIDE

[58] Florian B, Vintilescu R, Balseanu AT, Buga A-M, Grisk 16.16 External links
O, Walker LC, Kessler C, Popa-Wagner A (2008). “Long-
term hypothermia reduces infarct volume in aged rats after • International Chemical Safety Card 0165
focal ischemia”. Neuroscience Letters 438 (2): 180–185.
doi:10.1016/j.neulet.2008.04.020. PMID 18456407. • Concise International Chemical Assessment Docu-
ment 53
[59] Mark B. Roth and Todd Nystul. Buying Time in Sus-
pended Animation. Scientific American, 1 June 2005 • National Pollutant Inventory - Hydrogen sulfide fact
sheet
[60] Li, Jia; Zhang, Gencheng; Cai, Sally; Redington,
Andrew N (January 2008). “Effect of inhaled hydro- • NIOSH Pocket Guide to Chemical Hazards
gen sulfide on metabolic responses in anesthetized,
paralyzed, and mechanically ventilated piglets”. • NACE (National Association of Corrosion Epal)
Pediatric Critical Care Medicine 9 (1): 110–112.
doi:10.1097/01.PCC.0000298639.08519.0C. PMID
18477923. Retrieved 2008-02-07. H2 S does not appear
to have hypometabolic effects in ambiently cooled
large mammals and conversely appears to act as a
hemodynamic and metabolic stimulant.

[61] Haouzi P, Notet V, Chenuel B, Chalon B, Sponne I, Ogier


V et al. (2008). “H2 S induced hypometabolism in mice is
missing in sedated sheep”. Respir Physiol Neurobiol 160
(1): 109–15. doi:10.1016/j.resp.2007.09.001. PMID
17980679.

[62] “Mark Roth: Suspended animation is within our grasp”.

[63] “IK-1001 (Sodium Sulfide (Na2S) for Injection) in Sub-


jects With Acute ST-Segment Elevation Myocardial In-
farction”. ClinicalTrials.gov. 2010-11-04. This study has
been withdrawn prior to enrollment. ( Company decision.
Non-safety related )

[64] “Reduction of Ischemia-Reperfusion Mediated Cardiac


Injury in Subjects Undergoing Coronary Artery Bypass
Graft Surgery”. ClinicalTrials.gov. 2011-08-03. This
study has been terminated. ( Study Terminated - Com-
pany decision )

[65] Jørgensen, B. B. & D. C. Nelson (2004) Sulfide oxidation


in marine sediments: Geochemistry meets microbiology,
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Lyons (eds.) Sulfur Biogeochemistry - Past and Present.
Geological Society of America.

[66] “Impact From the Deep” in the October 2006 issue of Sci-
entific American.

16.15 Additional resources

• “Hydrogen Sulfide”, Committee on Medical and Bi-


ological Effects of Environmental Pollutants, Uni-
versity Park Press, 1979, Baltimore. ISBN 0-8391-
0127-9

• Siefers, Andrea (2010). A novel and cost-effective


hydrogen sulfide removal technology using tire de-
rived rubber particles (MS thesis). Iowa State Uni-
versity. Retrieved 8 February 2013.
Chapter 17

Cooling tower

See also: Evaporative cooler


A cooling tower is a heat rejection device which ex-

"Camouflaged" natural draft wet cooling tower near Dresden


(Germany)

Natural draft wet cooling hyperboloid towers at Didcot Power


Station (UK)

Cooling tower (forced draft) attached to a power station

water used in oil refineries, petrochemical and other


chemical plants, thermal power stations and HVAC sys-
tems for cooling buildings. The classification is based on
the type of air induction into the tower: the main types of
cooling towers are natural draft and induced draft cooling
towers.
Cooling towers vary in size from small roof-top units to
Forced draft wet cooling towers (height: 34 meters) and natural very large hyperboloid structures (as in the adjacent im-
draft wet cooling tower (height: 122 meters) age) that can be up to 200 metres (660 ft) tall and 100
metres (330 ft) in diameter, or rectangular structures that
tracts waste heat to the atmosphere through the cooling can be over 40 metres (130 ft) tall and 80 metres (260 ft)
of a water stream to a lower temperature. Cooling towers long. The hyperboloid cooling towers are often associ-
may either use the evaporation of water to remove pro- ated with nuclear power plants,[1] although they are also
cess heat and cool the working fluid to near the wet-bulb used to some extent in some large chemical and other
air temperature or, in the case of closed circuit dry cooling industrial plants. Although these large towers are very
towers, rely solely on air to cool the working fluid to near prominent, the vast majority of cooling towers are much
the dry-bulb air temperature. smaller, including many units installed on or near build-
Common applications include cooling the circulating ings to discharge heat from air conditioning.

71
72 CHAPTER 17. COOLING TOWER

17.1 History condenser must be pumped; from these it trickles down


over “mats” made of wooden slats or woven wire screens,
which fill the space within the tower.”[6]
A hyperboloid cooling tower was patented by the Dutch
engineers Frederik van Iterson and Gerard Kuypers
in 1918.[7] The first hyperboloid cooling towers were
built in 1918 near Heerlen. The first ones in the United
Kingdom were built in 1924 at Lister Drive power station
in Liverpool, England to cool water used at a coal-fired
electrical power station.[8]

17.2 Classification by use

17.2.1 Heating, ventilation and air condi-


tioning (HVAC)

A 1902 engraving of “Barnard’s fanless self-cooling tower”, an


early large evaporative cooling tower that relied on natural draft
and open sides rather than a fan; water to be cooled was sprayed
from the top onto the radial pattern of vertical wire-mesh mats.

Cooling towers originated out of the development in the


19th century of condensers for use with the steam en-
gine.[2] Condensers use relatively cool water, via various
means, to condense the steam coming out of the pistons or
turbines. This reduces the back pressure, which in turn Two HVAC cooling towers perched on the rooftop of a shopping
reduces the steam consumption, and thus the fuel con- center (Germany)
sumption, while at the same time increasing power and
recycling boiler-water.[3] However the condensers require See also: HVAC
an ample supply of cooling water, without which they are
impractical—the cost of the water exceeds the savings on
An HVAC (heating, ventilating, and air conditioning)
fuel.[4][5] While this was not an issue with marine engines, cooling tower is used to dispose of (“reject”) unwanted
it formed a significant limitation for many land-based sys-
heat from a chiller. Water-cooled chillers are normally
tems. more energy efficient than air-cooled chillers due to heat
By the turn of the 20th century, several evaporative meth- rejection to tower water at or near wet-bulb temperatures.
ods of recycling cooling water were in use in areas with- Air-cooled chillers must reject heat at the higher dry-
out a suitable water supply, such as urban locations rely- bulb temperature, and thus have a lower average reverse-
ing on municipal water mains.[2][5] In areas with available Carnot cycle effectiveness. Large office buildings, hospi-
land, the systems took the form of cooling ponds; in ar- tals, and schools typically use one or more cooling towers
eas with limited land, such as in cities, it took the form of as part of their air conditioning systems. Generally, in-
cooling towers.[4][6] dustrial cooling towers are much larger than HVAC tow-
These early towers were positioned either on the rooftops ers.
of buildings or as free-standing structures, supplied with HVAC use of a cooling tower pairs the cooling tower with
air by fans or relying on natural airflow.[4][6] An American a water-cooled chiller or water-cooled condenser. A ton
engineering textbook from 1911 described one design as of air-conditioning is defined as the removal of 12,000
“a circular or rectangular shell of light plate — in effect, BTU/hour (3500 W). The equivalent ton on the cooling
a chimney stack much shortened vertically (20 to 40 ft. tower side actually rejects about 15,000 BTU/hour (4400
high) and very much enlarged laterally. At the top is a W) due to the additional waste heat-equivalent of the en-
set of distributing troughs, to which the water from the ergy needed to drive the chiller’s compressor. This equiv-
17.3. CLASSIFICATION BY BUILD 73

alent ton is defined as the heat rejection in cooling 3 US supplied to the plant. Furthermore, discharging large
gallons/minute (1,500 pound/hour) of water 10 °F (6 °C), amounts of hot water may raise the temperature of the
which amounts to 15,000 BTU/hour, assuming a chiller receiving river or lake to an unacceptable level for the lo-
coefficient of performance (COP) of 4.0. This COP is cal ecosystem. Elevated water temperatures can kill fish
equivalent to an energy efficiency ratio (EER) of 14. and other aquatic organisms (see thermal pollution), or
Cooling towers are also used in HVAC systems that have can also cause an increase in undesirable organisms such
multiple water source heat pumps that share a common as invasive species of Zebra mussels or algae. A cooling
piping water loop. In this type of system, the water cir- tower serves to dissipate the heat into the atmosphere in-
stead and wind and air diffusion spreads the heat over a
culating inside the water loop removes heat from the con-
denser of the heat pumps whenever the heat pumps are much larger area than hot water can distribute heat in a
body of water. Some coal-fired and nuclear power plants
working in the cooling mode, then the externally mounted
cooling tower is used to remove heat from the water loop located in coastal areas do make use of once-through
ocean water. But even there, the offshore discharge water
and reject it to the atmosphere. By contrast, when the
heat pumps are working in heating mode, the condensers outlet requires very careful design to avoid environmental
problems.
draw heat out of the loop water and reject it into the space
to be heated. When the water loop is being used pri- Petroleum refineries also have very large cooling tower
marily to supply heat to the building, the cooling tower systems. A typical large refinery processing 40,000 met-
is normally shut down (and may be drained or winterized ric tonnes of crude oil per day (300,000 barrels (48,000
to prevent freeze damage), and heat is supplied by other m3 ) per day) circulates about 80,000 cubic metres of wa-
means, usually from separate boilers. ter per hour through its cooling tower system.
The world’s tallest cooling tower is the 202 metres (663
ft) tall cooling tower of Kalisindh Thermal Power Plant
17.2.2 Industrial cooling towers in Jhalawar, Rajasthan, India.[12]

Industrial cooling towers for a power plant


Package type cooling towers
Industrial cooling towers can be used to remove heat from
various sources such as machinery or heated process ma-
terial. The primary use of large, industrial cooling towers
is to remove the heat absorbed in the circulating cooling
water systems used in power plants, petroleum refineries,
petrochemical plants, natural gas processing plants, food
processing plants, semi-conductor plants, and for other
industrial facilities such as in condensers of distillation
columns, for cooling liquid in crystallization, etc.[9] The
circulation rate of cooling water in a typical 700 MW
coal-fired power plant with a cooling tower amounts to
about 71,600 cubic metres an hour (315,000 US gallons
per minute)[10] and the circulating water requires a sup-
ply water make-up rate of perhaps 5 percent (i.e., 3,600
cubic metres an hour). Field erected cooling towers
If that same plant had no cooling tower and used once-
through cooling water, it would require about 100,000
cubic metres an hour[11] and that amount of water would
have to be continuously returned to the ocean, lake or 17.3 Classification by build
river from which it was obtained and continuously re-
74 CHAPTER 17. COOLING TOWER

17.3.1 Package type is drawn past a flow of water, a small portion of the wa-
ter evaporates, and the energy required to evaporate that
This type of cooling towers are factory preassembled, and portion of the water is taken from the remaining mass of
can be simply transported on trucks as they are compact water, thus reducing its temperature. Approximately 970
machines. The capacity of package type towers is limited BTU of heat energy is absorbed for each pound of evap-
and for that reason, they are usually preferred by facilities orated water. Evaporation results in saturated air condi-
with low heat rejection requirements such as food pro- tions, lowering the temperature of the water processed by
cessing plants, textile plants, some chemical processing the tower to a value close to wet-bulb temperature, which
plants, or buildings like hospitals, hotels, malls, automo- is lower than the ambient dry-bulb temperature, the dif-
tive factories etc. ference determined by the initial humidity of the ambient
air.
Due to their frequent use in or near residential areas,
sound level control is a relatively more important issue To achieve better performance (more cooling), a medium
for package type cooling towers. called fill is used to increase the surface area and the time
of contact between the air and water flows. Splash fill
consists of material placed to interrupt the water flow
17.3.2 Field erected type causing splashing. Film fill is composed of thin sheets
of material (usually PVC) upon which the water flows.
Facilities such as power plants, steel processing plants, Both methods create increased surface area and time of
petroleum refineries, or petrochemical plants usually in- contact between the fluid (water) and the gas (air), to im-
stall field erected type cooling towers due to their greater prove heat transfer.
capacity for heat rejection. Field erected towers are usu-
ally much larger in size compared to the package type
cooling towers.
17.5 Air flow generation methods
A typical field erected cooling tower has a pultruded fiber-
reinforced plastic (FRP) structure, FRP cladding, a me-
chanical unit for air draft, drift eliminator, and fill.

17.4 Heat transfer methods


With respect to the heat transfer mechanism employed,
the main types are:

• dry cooling towers operate by heat transfer through


a surface that separates the working fluid from am-
bient air, such as in a tube to air heat exchanger,
utilizing convective heat transfer. They do not use
evaporation.

• wet cooling towers (or open circuit cooling tow- Access stairs at the base of a massive hyperboloid cooling tower
ers) operate on the principle of evaporative cooling. give a sense of its scale (UK)
The working fluid and the evaporated fluid (usually
water) are one and the same. With respect to drawing air through the tower, there are
three types of cooling towers:
• fluid coolers (or closed circuit cooling towers) are
hybrids that pass the working fluid through a tube • Natural draft — Utilizes buoyancy via a tall chim-
bundle, upon which clean water is sprayed and a fan- ney. Warm, moist air naturally rises due to the den-
induced draft applied. The resulting heat transfer sity differential compared to the dry, cooler outside
performance is much closer to that of a wet cooling air. Warm moist air is less dense than drier air at the
tower, with the advantage provided by a dry cooler same pressure. This moist air buoyancy produces an
of protecting the working fluid from environmental upwards current of air through the tower.
exposure and contamination.
• Mechanical draft — Uses power-driven fan motors
In a wet cooling tower (or open circuit cooling tower), the to force or draw air through the tower.
warm water can be cooled to a temperature lower than the
ambient air dry-bulb temperature, if the air is relatively • Induced draft — A mechanical draft tower
dry (see dew point and psychrometrics). As ambient air with a fan at the discharge (at the top) which
17.6. CATEGORIZATION BY AIR-TO-WATER FLOW 75

pulls air up through the tower. The fan in- Warm, moist
air out Fan
duces hot moist air out the discharge. This pro- Hot water in
duces low entering and high exiting air veloc-
ities, reducing the possibility of recirculation
Distribution basin
in which discharged air flows back into the air
Dry air in
intake. This fan/fin arrangement is also known
as draw-through.
• Forced draft — A mechanical draft tower Fill material

with a blower type fan at the intake. The fan Cold water out
Collection basin
forces air into the tower, creating high enter-
ing and low exiting air velocities. The low ex-
iting velocity is much more susceptible to re-
circulation. With the fan on the air intake, the
fan is more susceptible to complications due
to freezing conditions. Another disadvantage
is that a forced draft design typically requires
more motor horsepower than an equivalent in-
duced draft design. The benefit of the forced
draft design is its ability to work with high
static pressure. Such setups can be installed
in more-confined spaces and even in some in-
door situations. This fan/fill geometry is also
known as blow-through.

• Fan assisted natural draft — A hybrid type that


appears like a natural draft setup, though airflow is
assisted by a fan.

Hyperboloid (sometimes incorrectly known as Mechanical draft crossflow cooling tower used in an HVAC ap-
hyperbolic) cooling towers have become the design plication
standard for all natural-draft cooling towers because of
their structural strength and minimum usage of material. A distribution or hot water basin consisting of a deep pan
The hyperboloid shape also aids in accelerating the up- with holes or nozzles in its bottom is located near the
ward convective air flow, improving cooling efficiency. top of a crossflow tower. Gravity distributes the water
These designs are popularly associated with nuclear through the nozzles uniformly across the fill material.
power plants. However, this association is misleading,
as the same kind of cooling towers are often used at Advantages of the crossflow design:
large coal-fired power plants as well. Conversely, not
all nuclear power plants have cooling towers, and some • Gravity water distribution allows smaller pumps and
instead cool their heat exchangers with lake, river or maintenance while in use.
ocean water. • Non-pressurized spray simplifies variable flow.
• Typically lower initial and long-term cost, mostly
due to pump requirements.
17.6 Categorization by air-to-
water flow Disadvantages of the crossflow design:

• More prone to freezing than counterflow designs.


17.6.1 Crossflow
• Variable flow is useless in some conditions.
Crossflow is a design in which the air flow is directed per- • More prone to dirt buildup in the fill than counter-
pendicular to the water flow (see diagram at left). Air flow flow designs, especially in dusty or sandy areas.
enters one or more vertical faces of the cooling tower to
meet the fill material. Water flows (perpendicular to the
air) through the fill by gravity. The air continues through 17.6.2 Counterflow
the fill and thus past the water flow into an open plenum
volume. Lastly, a fan forces the air out into the atmo- In a counterflow design, the air flow is directly opposite to
sphere. the water flow (see diagram at left). Air flow first enters
76 CHAPTER 17. COOLING TOWER

Warm, moist • The air, now saturated with water vapor, is dis-
air out charged from the top of the cooling tower.
Fan

Hot water in
Distribution system • A collection or cold water basin is used to collect and
Spray nozzles contain the cooled water after its interaction with the
air flow.
Fill material

Both crossflow and counterflow designs can be used in


Dry air in
natural draft and in mechanical draft cooling towers.

Cold water out


Collection basin
17.7 Wet cooling tower material
balance
Quantitatively, the material balance around a wet, evapo-
rative cooling tower system is governed by the operational
variables of make-up flow rate, evaporation and windage
losses, draw-off rate, and the concentration cycles.[13][14]
In the adjacent diagram, water pumped from the tower
basin is the cooling water routed through the process cool-
ers and condensers in an industrial facility. The cool wa-
ter absorbs heat from the hot process streams which need
to be cooled or condensed, and the absorbed heat warms
the circulating water (C). The warm water returns to the
top of the cooling tower and trickles downward over the
Forced draft counter flow package type cooling towers fill material inside the tower. As it trickles down, it con-
tacts ambient air rising up through the tower either by nat-
an open area beneath the fill media, and is then drawn up ural draft or by forced draft using large fans in the tower.
vertically. The water is sprayed through pressurized noz- That contact causes a small amount of the water to be
zles near the top of the tower, and then flows downward lost as windage/drift (W) and some of the water (E) to
through the fill, opposite to the air flow. evaporate. The heat required to evaporate the water is
derived from the water itself, which cools the water back
Advantages of the counterflow design: to the original basin water temperature and the water is
then ready to recirculate. The evaporated water leaves its
• Spray water distribution makes the tower more dissolved salts behind in the bulk of the water which has
freeze-resistant. not been evaporated, thus raising the salt concentration in
• Breakup of water in spray makes heat transfer more the circulating cooling water. To prevent the salt concen-
efficient. tration of the water from becoming too high, a portion of
the water is drawn off/blown down (D) for disposal. Fresh
Disadvantages of the counterflow design: water make-up (M) is supplied to the tower basin to com-
pensate for the loss of evaporated water, the windage loss
• Typically higher initial and long-term cost, primarily water and the draw-off water.
due to pump requirements. Using these flow rates and concentration dimensional
• Difficult to use variable water flow, as spray charac- units:
teristics may be negatively affected. A water balance around the entire system is then:[14]
• Typically noisier, due to the greater water fall height
from the bottom of the fill into the cold water basin M=E+D+W

17.6.3 Common aspects Since the evaporated water (E) has no salts, a chloride
balance around the system is:[14]
Common aspects of both designs:

• The interactions of the air and water flow allow a M XM = DXC + W XC = XC (D + W )


partial equalization of temperature, and evaporation
of water. and, therefore:[14]
17.7. WET COOLING TOWER MATERIAL BALANCE 77

17.7.1 Cycles of concentration


Cycles of concentration represents the accumulation of
dissolved minerals in the recirculating cooling water.
Discharge of draw-off (or blowdown) is used principally
to control the buildup of these minerals.
The chemistry of the make-up water, including the
amount of dissolved minerals, can vary widely. Make-up
waters low in dissolved minerals such as those from sur-
face water supplies (lakes, rivers etc.) tend to be aggres-
sive to metals (corrosive). Make-up waters from ground
water supplies (such as wells) are usually higher in miner-
als, and tend to be scaling (deposit minerals). Increasing
the amount of minerals present in the water by cycling can
make water less aggressive to piping; however, excessive
levels of minerals can cause scaling problems.

Fan-induced draft, counter-flow cooling tower

XC M M Relationship between
E cycles of concentration and flow rates in a
= concentration of Cycles = = = 1+
XM (D + W ) (M − E)
cooling tower
(D + W )

From a simplified heat balance around the cooling tower: As the cycles of concentration increase, the water may
not be able to hold the minerals in solution. When the
solubility of these minerals have been exceeded they can
C∆T cp precipitate out as mineral solids and cause fouling and
E= heat exchange problems in the cooling tower or the heat
HV
exchangers. The temperatures of the recirculating wa-
Windage (or drift) losses (W) is the amount of total tower ter, piping and heat exchange surfaces determine if and
water flow that is evaporated into the atmosphere. From where minerals will precipitate from the recirculating
large-scale industrial cooling towers, in the absence of water. Often a professional water treatment consultant
manufacturer’s data, it may be assumed to be: will evaluate the make-up water and the operating condi-
tions of the cooling tower and recommend an appropriate
range for the cycles of concentration. The use of water
W = 0.3 to 1.0 percent of C for a natural draft treatment chemicals, pretreatment such as water soften-
cooling tower without windage drift elimina- ing, pH adjustment, and other techniques can affect the
tors acceptable range of cycles of concentration.
W = 0.1 to 0.3 percent of C for an induced Concentration cycles in the majority of cooling towers
draft cooling tower without windage drift elim- usually range from 3 to 7. In the United States, many wa-
inators ter supplies use well water which has significant levels of
dissolved solids. On the other hand, one of the largest wa-
W = about 0.005 percent of C (or less) if the ter supplies, for New York City, has a surface rainwater
cooling tower has windage drift eliminators source quite low in minerals; thus cooling towers in that
W = about 0.0005 percent of C (or less) if city are often allowed to concentrate to 7 or more cycles
the cooling tower has windage drift eliminators of concentration.
and uses sea water as make-up water. Since higher cycles of concentration represent less make-
78 CHAPTER 17. COOLING TOWER

up water, water conservation efforts may focus on in- French researchers found that Legionella bacteria trav-
creasing cycles of concentration.[15] Highly treated recy- elled up to 6 kilometres (3.7 mi) through the air from a
cled water may be an effective means of reducing cool- large contaminated cooling tower at a petrochemical plant
ing tower consumption of potable water, in regions where in Pas-de-Calais, France. That outbreak killed 21 of the
potable water is scarce.[16] 86 people who had a laboratory-confirmed infection.[19]
Drift (or windage) is the term for water droplets of the
process flow allowed to escape in the cooling tower dis-
17.7.2 Water treatment charge. Drift eliminators are used in order to hold drift
rates typically to 0.001–0.005% of the circulating flow
See also: Industrial water treatment rate. A typical drift eliminator provides multiple direc-
tional changes of airflow to prevent the escape of water
Besides treating the circulating cooling water in large in- droplets. A well-designed and well-fitted drift eliminator
dustrial cooling tower systems to minimize scaling and can greatly reduce water loss and potential for Legionella
fouling, the water should be filtered to remove particu- or water treatment chemical exposure.
lates, and also be dosed with biocides and algaecides to Many governmental agencies, cooling tower manufactur-
prevent growths that could interfere with the continuous ers and industrial trade organizations have developed de-
flow of the water.[13] Under certain conditions, a biofilm sign and maintenance guidelines for preventing or con-
of micro-organisms such as bacteria, fungi and algae can trolling the growth of Legionella in cooling towers. Below
grow very rapidly in the cooling water, and can reduce is a list of sources for such guidelines:
the heat transfer efficiency of the cooling tower. Biofilm
can be reduced or prevented by using chlorine or other
• Centers for Disease Control and Prevention (CDC)
chemicals.
PDF (1.35 MB) - Procedure for Cleaning Cooling
Towers and Related Equipment (pages 225 and 226)
• Cooling Technology Institute PDF (240 KB) - Best
17.8 Legionnaires’ disease Practices for Control of Legionella, July, 2006
• Association of Water Technologies PDF (964 KB)
- Legionella 2003: An Update and Statement
• California Energy Commission PDF (194 KB) -
Cooling Water Management Program Guidelines
For Wet and Hybrid Cooling Towers at Power Plants
• SPX Cooling Technologies PDF (119 KB) - Cooling
Towers Maintenance Procedures
• SPX Cooling Technologies PDF (789 KB) -
ASHRAE Guideline 12-2000 - Minimizing the Risk
of Legionellosis
• SPX Cooling Technologies PDF (83.1 KB) - Cool-
Legionella pneumophila (5000x magnification) ing Tower Inspection Tips {especially page 3 of 7}
• Tower Tech Modular Cooling Towers PDF (109
Further information: Legionellosis and Legionella KB) - Legionella Control
• GE Infrastructure Water & Process Technologies
Another very important reason for using biocides in cool-
Betz Dearborn PDF (195 KB) - Chemical Wa-
ing towers is to prevent the growth of Legionella, includ-
ter Treatment Recommendations For Reduction of
ing species that cause legionellosis or Legionnaires’ dis-
Risks Associated with Legionella in Open Recircu-
ease, most notably L. pneumophila,[17] or Mycobacterium
lating Cooling Water Systems
avium.[18] The various Legionella species are the cause
of Legionnaires’ disease in humans and transmission is
via exposure to aerosols—the inhalation of mist droplets
containing the bacteria. Common sources of Legionella 17.9 Terminology
include cooling towers used in open recirculating evapo-
rative cooling water systems, domestic hot water systems, • Windage or Drift — Water droplets that are carried
fountains, and similar disseminators that tap into a public out of the cooling tower with the exhaust air. Drift
water supply. Natural sources include freshwater ponds droplets have the same concentration of impurities
and creeks. as the water entering the tower. The drift rate is
17.9. TERMINOLOGY 79

• Make-up — The water that must be added to the


circulating water system in order to compensate for
water losses such as evaporation, drift loss, blow-
out, blow-down, etc.
• Noise — Sound energy emitted by a cooling tower
and heard (recorded) at a given distance and direc-
tion. The sound is generated by the impact of falling
water, by the movement of air by fans, the fan blades
moving in the structure, vibration of the structure,
and the motors, gearboxes or drive belts.
• Approach — The approach is the difference in tem-
Fill plates at the bottom of the Iru Power Plant cooling tower
perature between the cooled-water temperature and
(Estonia). Tower is shut down, revealing numerous water spray the entering-air wet bulb temperature (twb). Since
heads. the cooling towers are based on the principles of
evaporative cooling, the maximum cooling tower ef-
ficiency depends on the wet bulb temperature of the
typically reduced by employing baffle-like devices, air. The wet-bulb temperature is a type of temper-
called drift eliminators, through which the air must ature measurement that reflects the physical proper-
travel after leaving the fill and spray zones of the ties of a system with a mixture of a gas and a vapor,
tower. Drift can also be reduced by using warmer usually air and water vapor
entering cooling tower temperatures.
• Range — The range is the temperature difference
• Blow-out — Water droplets blown out of the cool- between the warm water inlet and cooled water exit.
ing tower by wind, generally at the air inlet open-
• Fill — Inside the tower, fills are added to increase
ings. Water may also be lost, in the absence of wind,
contact surface as well as contact time between air
through splashing or misting. Devices such as wind
and water, to provide better heat transfer. The ef-
screens, louvers, splash deflectors and water divert-
ficiency of the tower depends on the selection and
ers are used to limit these losses.
amount of fill. There are two types of fills that may
• Plume — The stream of saturated exhaust air leav- be used:
ing the cooling tower. The plume is visible when wa- • Film type fill (causes water to spread into a
ter vapor it contains condenses in contact with cooler thin film)
ambient air, like the saturated air in one’s breath fogs
on a cold day. Under certain conditions, a cooling • Splash type fill (breaks up falling stream of
tower plume may present fogging or icing hazards water and interrupts its vertical progress)
to its surroundings. Note that the water evaporated • Full-Flow Filtration — Full-flow filtration contin-
in the cooling process is “pure” water, in contrast to uously strains particulates out of the entire system
the very small percentage of drift droplets or water flow. For example, in a 100-ton system, the flow
blown out of the air inlets. rate would be roughly 300 gal/min. A filter would
be selected to accommodate the entire 300 gal/min
• Draw-off or Blow-down — The portion of the cir- flow rate. In this case, the filter typically is installed
culating water flow that is removed (usually dis- after the cooling tower on the discharge side of the
charged to a drain) in order to maintain the amount pump. While this is the ideal method of filtration,
of Total Dissolved Solids (TDS) and other impuri- for higher flow systems it may be cost-prohibitive.
ties at an acceptably low level. Higher TDS con-
centration in solution may result from greater cool- • Side-Stream Filtration — Side-stream filtration,
ing tower efficiency. However the higher the TDS although popular and effective, does not provide
concentration, the greater the risk of scale, biolog- complete protection. With side-stream filtration, a
ical growth and corrosion. The amount of blow- portion of the water is filtered continuously. This
down is primarily designated by measuring by the method works on the principle that continuous par-
electrical conductivity of the circulating water. Bi- ticle removal will keep the system clean. Manufac-
ological growth, scaling and corrosion can be pre- turers typically package side-stream filters on a skid,
vented by chemicals (respectively, biocide, sulfuric complete with a pump and controls. For high flow
acid, corrosion inhibitor). On the other hand, the systems, this method is cost-effective. Properly siz-
only practical way to decrease the electrical conduc- ing a side-stream filtration system is critical to obtain
tivity is by increasing the amount of blow-down dis- satisfactory filter performance, but there is some de-
charge and subsequently increasing the amount of bate over how to properly size the side-stream sys-
clean make-up water. tem. Many engineers size the system to continuously
80 CHAPTER 17. COOLING TOWER

filter the cooling tower basin water at a rate equiva- adds more water to the air, saturated air with liquid wa-
lent to 10% of the total circulation flow rate. For ex- ter droplets can be discharged, which is seen as fog. This
ample, if the total flow of a system is 1,200 gal/min phenomenon typically occurs on cool, humid days, but is
(a 400-ton system), a 120 gal/min side-stream sys- rare in many climates.
tem is specified. This phenomenon can be prevented by decreasing the
• Cycle of concentration — Maximum allowed mul- relative humidity of the saturated discharge air. For
tiplier for the amount of miscellaneous substances in that purpose, in hybrid towers, saturated discharge air
circulating water compared to the amount of those is mixed with heated low relative humidity air. Some
substances in make-up water. air enters the tower above drift eliminator level, passing
through heat exchangers. The relative humidity of the
• Treated timber — A structural material for cooling dry air is even more decreased instantly as being heated
towers which was largely abandoned about 10 years while entering the tower. The discharged mixture has a
ago. It is still used occasionally due to its low initial relatively lower relative humidity and the fog is invisible.
costs, in spite of its short life expectancy. The life of
treated timber varies a lot, depending on the oper-
ating conditions of the tower, such as frequency of
shutdowns, treatment of the circulating water, etc. 17.11 Salt emission pollution
Under proper working conditions, the estimated life
of treated timber structural members is about 10 When wet cooling towers with seawater make-up are in-
years. stalled in various industries located in or near coastal ar-
eas, the drift of fine droplets emitted from the cooling
• Leaching — The loss of wood preservative chem- towers contain nearly 6% sodium chloride which deposits
icals by the washing action of the water flowing on the nearby land areas. This deposition of sodium
through a wood structure cooling tower. salts on the nearby agriculture/vegetative lands can con-
• Pultruded FRP — A common structural mate- vert them into sodic saline or sodic alkaline soils depend-
rial for smaller cooling towers, fibre-reinforced plas- ing on the nature of the soil. The salt deposition prob-
tic (FRP) is known for its high corrosion-resistance lem from such cooling towers aggravates where national
capabilities. Pultuded FRP is produced using pollution control standards are not imposed or not imple-
pultrusion technology, and has become the most mented to minimize the drift emissions from wet cooling
[20]
common structural material for small cooling tow- towers using seawater make-up.
ers. It offers lower costs and requires less main- Respirable suspended particulate matter, of less than 10
tenance compared to reinforced concrete, which is micrometers (µm) in size, can be present in the drift from
still in use for large structures. cooling towers. Larger particles above 10 µm in size are
generally filtered out in the nose and throat via cilia and
mucus but particulate matter smaller than 10 µm, referred
17.10 Fog production to as PM10 , can settle in the bronchi and lungs and cause
health problems. Similarly, particles smaller than 2.5
µm, (PM₂.₅), tend to penetrate into the gas exchange re-
gions of the lung, and very small particles (less than 100
nanometers) may pass through the lungs to affect other
organs. Though the total particulate emissions from wet
cooling towers with fresh water make-up is much less,
they contain more PM10 and PM₂.₅ than the total emis-
sions from wet cooling towers with sea water make-up.
This is due to lesser salt content in fresh water drift (be-
low 2,000 ppm) compared to the salt content of sea water
drift (60,000 ppm).[20]

17.12 Use as a flue-gas stack

Fog clouds produced by Eggborough Power Plant (UK) At some modern power stations equipped with flue
gas purification, such as the Power Station Staudinger
Under certain ambient conditions, plumes of water va- Grosskrotzenburg and the Power Station Rostock, the
por (fog) can be seen rising out of the discharge from a cooling tower is also used as a flue-gas stack (industrial
cooling tower, and can be mistaken as smoke from a fire. chimney), thus saving the cost of a separate chimney
If the outdoor air is at or near saturation, and the tower structure. At plants without flue gas purification, prob-
17.13. OPERATION IN FREEZING WEATHER 81

Large hyperboloid cooling towers made of structural steel for a


power plant in Kharkov (Ukraine)

17.13 Operation in freezing


weather
Some cooling towers (such as smaller building air condi-
tioning systems) are shut down seasonally, drained, and
winterized to prevent freeze damage.
During the winter, other sites continuously operate cool-
ing towers with 40 °F (4 °C) water leaving the tower.
Basin heaters, tower draindown, and other freeze protec-
Flue gas stack inside a natural draft wet cooling tower tion methods are often employed in cold climates. Oper-
ational cooling towers with malfunctions can freeze dur-
ing very cold weather. Typically, freezing starts at the
corners of a cooling tower with a reduced or absent heat
load. Severe freezing conditions can create growing vol-
umes of ice, resulting in increased structural loads which
can cause structural damage or collapse.
To prevent freezing, the following procedures are used:

• The use of water modulating by-pass systems is


not recommended during freezing weather. In
such situations, the control flexibility of variable
speed motors, two-speed motors, and/or two-speed
motors multi-cell towers should be considered a
requirement.[21]
Flue gas stack connection into a natural draft wet cooling tower
• Do not operate the tower unattended. Remote sen-
sors and alarms may be installed to monitor tower
conditions.

lems with corrosion may occur, due to reactions of raw • Do not operate the tower without a heat load. Basin
flue gas with water to form acids. heaters may be used to keep the water in the tower
pan at an above-freezing temperature. Heat trace
Sometimes, natural draft cooling towers are constructed
(“heating tape”) is a resistive heating element that
with structural steel in place of concrete (RCC) when the
is installed along water pipes to prevent freezing in
construction time of natural draft cooling tower is ex-
cold climates .
ceeding the construction time of the rest of the plant or
the local soil is of poor strength to bear the heavy weight • Maintain design water flow rate over the tower fill.
of RCC cooling towers or cement prices are higher at a
site to opt for cheaper natural draft cooling towers made • Manipulate or reduce airflow to maintain water tem-
of structural steel. perature above freezing point.[22]
82 CHAPTER 17. COOLING TOWER

17.14 Fire hazard • Power station

• Spray pond
Cooling towers constructed in whole or in part of com-
bustible materials can support internal fire propagation. • Water cooling
Such fires can become very intense, due to the high
surface-volume ratio of the towers, and fires can be • Willow Island disaster
further intensified by natural convection or fan-assisted
draft. The resulting damage can be sufficiently severe
to require the replacement of the entire cell or tower 17.17 References
structure. For this reason, some codes and standards[23]
recommend that combustible cooling towers be provided [1] CleanEnergy Footprints (cleanenergy.org). Identifying
with an automatic fire sprinkler system. Fires can prop- Nuclear Reactors in Google Earth Retrieved 5/19/2014
agate internally within the tower structure when the cell
is not in operation (such as for maintenance or construc- [2] International Correspondence Schools (1902). A Text-
tion), and even while the tower is in operation, especially book on Steam Engineering. Scranton, Pa.: International
those of the induced-draft type, because of the existence Textbook Co. 33-34 of Section 29:"Condensers”.
of relatively dry areas within the towers.[24] [3] Terrell Croft, ed. (1922). Steam-Engine Principles and
Practice. New York: McGraw-Hill. pp. 283–286.

17.15 Structural stability [4] Heck, Robert Culbertson Hays (1911). The Steam Engine
and Turbine: A Text-Book for Engineering Colleges. New
York: D. Van Nostrand. pp. 569–570.
Being very large structures, cooling towers are suscepti-
ble to wind damage, and several spectacular failures have [5] “Power plant and allied industries”. The Engineer (with
occurred in the past. At Ferrybridge power station on Which is Incorporated Steam Engineering) (Chicago: Tay-
1 November 1965, the station was the site of a major lor Publishing Co.) 43 (1): 69–72. 1 Jan 1906.
structural failure, when three of the cooling towers col- [6] Snow, Walter B. (1908). The Steam Engine: A Practical
lapsed owing to vibrations in 85 mph (137 km/h) winds. Guide to the Construction, Operation, and care of Steam
Although the structures had been built to withstand higher Engines, Steam Turbines, and Their Accessories. Chicago:
wind speeds, the shape of the cooling towers caused west- American School of Correspondence. pp. 43–46.
erly winds to be funnelled into the towers themselves, cre-
ating a vortex. Three out of the original eight cooling tow- [7] UK Patent No. 108,863
ers were destroyed, and the remaining five were severely [8] “Power Plant Cooling Towers Like Big Milk Bottle” Pop-
damaged. The towers were later rebuilt and all eight cool- ular Mechanics, February 1930 bottom-left of pg 201
ing towers were strengthened to tolerate adverse weather
conditions. Building codes were changed to include im- [9] U.S. Environmental Protection Agency (EPA).
proved structural support, and wind tunnel tests were in- (1997). Profile of the Fossil Fuel Electric Power
troduced to check tower structures and configuration. Generation Industry (Report). Washington, D.C.
http://www.epa.gov/compliance/resources/publications/
assistance/sectors/notebooks/fossil.html. Document No.
EPA/310-R-97-007. p. 79.
17.16 See also
[10] Cooling System Retrofit Costs EPA Workshop on Cooling
Water Intake Technologies, John Maulbetsch, Maulbetsch
• Alkali soils
Consulting, May 2003
• Architectural engineering [11] Thomas J. Feeley, III, Lindsay Green, James T. Mur-
phy, Jeffrey Hoffmann, and Barbara A. Carney (2005).
• Deep lake water cooling
“Department of Energy/Office of Fossil Energy’s Power
• Evaporative cooler Plant Water Management R&D Program.” U.S. Depart-
ment of Energy, July 2005.
• Evaporative cooling
[12] Comansa Jie builds the world’s highest cooling towers
• Fossil fuel power plant
[13] Beychok, Milton R. (1967). Aqueous Wastes from
• Heating, ventilating and air conditioning Petroleum and Petrochemical Plants (1st Edition ed.).
John Wiley and Sons. LCCN 67019834. (available in
• Hyperboloid structure many university libraries)

• Mechanical engineering [14] Milton R. Beychok (October 1952). “How To Calculate


Cooling Tower Control Variables”. Petroleum Processing:
• Nuclear power plant 1452–1456.
17.18. EXTERNAL LINKS 83

[15] “Best Management Practice Cooling Tower Manage-


ment”. Energy.gov. Department of Energy. 30 April
2005. Retrieved 16 June 2014.

[16] San Diego County Water Authority (July 2009).


“Technical Information for Cooling Towers Using
Recycled Water”. www.sdcwa.org (San Diego County
Water Authority). Retrieved 18 June 2014.

[17] Ryan K.J.; Ray C.G. (editors) (2004). Sherris Medical


Microbiology (4th Edition ed.). McGraw Hill. ISBN 0-
8385-8529-9.

[18] Centers for Disease Control and Prevention - Emerging


Infectious Diseases (page 495)

[19] Airborne Legionella May Travel Several Kilometres (ac-


cess requires free registration)

[20] Wet Cooling Tower Guidance For Particulate Matter, En-


vironment Canada, Retrieved on 2013-01-29

[21] http://spxcooling.com/library/detail/
cooling-tower-fundamentals SPX Cooling Tech-
nologies MARLEY, Cooling Tower Fundamentals Page
73 (75 of 119) Column 2, Last Paragraph

[22] SPX Cooling Technologies: Operating Cooling Towers in


Freezing Weather PDF (1.45 MB)

[23] National Fire Protection Association (NFPA). NFPA 214,


Standard on Water-Cooling Towers.

[24] NFPA 214, Standard on Water-Cooling Towers. Section


A1.1

17.18 External links


• What is a cooling tower? - Cooling Technology In-
stitute
• “Cooling Towers” - includes diagrams - Virtual Nu-
clear Tourist
• Wet cooling tower guidance for particulate matter,
Environment Canada.
• COP Metering for heat pumps and cooling towers
Chapter 18

Steam

For the software distribution platform, see Steam (soft- Superheated steam is steam at a temperature higher than
ware). For other uses, see Steam (disambiguation). its boiling point for the pressure, which only occurs where
all liquid water has evaporated or has been removed from
the system.[5]
Steam is the technical term for the gaseous phase of
water, which is formed when water boils. Technically Steam tables [6] contain thermodynamic data for wa-
speaking, in terms of the chemistry and physics, steam ter/steam and are often used by engineers and scientists
is invisible and cannot be seen; however, in common lan- in design and operation of equipment where thermody-
guage it is often used to refer to the visible mist or aerosol namic cycles involving steam are used. Additionally,
of water droplets formed as this water vapor condenses in thermodynamic phase diagrams for water/steam, such
the presence of (cooler) air. At lower pressures, such as in as a temperature-entropy diagram or a Mollier diagram
the upper atmosphere or at the top of high mountains wa- shown in this article, may be useful. Steam charts are
ter boils at a lower temperature than the nominal 100 °C also used for analysing thermodynamic cycles.
(212 °F) at standard temperature and pressure. If heated
further it becomes superheated steam.
The enthalpy of vaporization is the energy required to 18.2 Uses
turn water into the gaseous form when it increases in
volume by 1,700 times at standard temperature and 18.2.1 Agricultural
pressure; this change in volume can be converted into
mechanical work by steam engines such as reciprocating In agriculture, steam is used for soil sterilization to avoid
piston type engines and steam turbines, which are a sub- the use of harmful chemical agents and increase soil
group of steam engines. Piston type steam engines played health.
a central role to the Industrial Revolution and modern
steam turbines are used to generate more than 80% of
the world’s electricity. If liquid water comes in contact 18.2.2 Domestic
with a very hot substance (such as lava, or molten metal)
it can create a steam explosion. Steam explosions have Steam’s capacity to transfer heat is also used in the home:
been responsible for many foundry accidents, and may for cooking vegetables, steam cleaning of fabric and car-
also have been responsible for much of the damage to the pets, and heating buildings. In each case, water is heated
plant in the Chernobyl disaster. in a boiler, and the steam carries the energy to a target ob-
ject. "Steam showers" are actually low-temperature mist-
generators, and do not actually use steam.

18.1 Types of steam and conver- 18.2.3 Electricity generation (and cogener-
sion ation)

Steam is traditionally created by heating a boiler via burn- About 90% of all electricity is generated using steam as
ing coal and other fuels, but it is also possible to create the working fluid, nearly all by steam turbines.[7]
steam with solar energy.[1][2][3] Water vapor that includes In electric generation, steam is typically condensed at the
water droplets is described as wet steam. As wet steam end of its expansion cycle, and returned to the boiler for
is heated further, the droplets evaporate, and at a high re-use. However in cogeneration, steam is piped into
enough temperature (which depends on the pressure) all buildings through a district heating system to provide
of the water evaporates and the system is in vapor–liquid heat energy after its use in the electric generation cy-
equilibrium.[4] cle. The world’s biggest steam generation system is the

84
18.3. SEE ALSO 85

New York City steam system, which pumps steam into work. The ability to return condensed steam as water-
100,000 buildings in Manhattan from seven cogeneration liquid to the boiler at high pressure with relatively little ex-
plants.[8] penditure of pumping power is important. Condensation
of steam to water often occurs at the low-pressure end
of a steam turbine, since this maximizes the energy ef-
18.2.4 Energy storage ficiency, but such wet-steam conditions must be limited
to avoid excessive turbine blade erosion. Engineers use
an idealised thermodynamic cycle, the Rankine cycle, to
model the behavior of steam engines. Steam turbines are
often used in the production of electricity.

18.2.7 Sterilization
An autoclave, which uses steam under pressure, is used
in microbiology laboratories and similar environments for
sterilization.
Steam, especially dry (highly superheated) steam, may be
used for antimicrobial cleaning even to the levels of ster-
ilization. Steam is a non-toxic antimicrobial agent.[10] [11]

Fireless steam locomotive


Despite the resemblance to a boiler, note the lack of a chimney 18.2.8 Steam in piping
and also how the cylinders are at the cab end, not the chimney
end. Steam is used in piping for utility lines. It is also used in
jacketing and tracing of piping to maintain the uniform
In other industrial applications steam is used for energy temperature in pipelines and vessels.
storage, which is introduced and extracted by heat trans-
fer, usually through pipes. Steam is a capacious reservoir
for thermal energy because of water’s high heat of vapor- 18.2.9 Wood treatment
ization.
Fireless steam locomotives were steam locomotives that Steam is used in the process of wood bending, killing in-
operated from a supply of steam stored on board in a sects and increasing plasticity.
large tank resembling a conventional locomotive’s boiler.
This tank was filled by process steam, as is available in 18.2.10 Concrete treatment
many sorts of large factory, such as paper mills. The loco-
motive’s propulsion used pistons and connecting rods, as Steam is used to accentuate drying especially in prefabri-
for a typical steam locomotive. These locomotives were cates. Care should be taken since concrete produces heat
mostly used in places where there was a risk of fire from a during hydration and additional heat from the steam could
boiler’s firebox, but were also used in factories that simply be detrimental to hardening reaction processes of the con-
had a plentiful supply of steam to spare. crete.

18.2.5 Lifting gas 18.2.11 Cleaning


Owing to its low molecular mass, steam is an effective
Used in cleaning of fibers, sometimes prior to painting.
lifting gas, providing approximately 60% as much lift as
helium and twice as much as hot air. It is not flammable,
unlike hydrogen, and is cheap and abundant, unlike he-
lium. The required heat, however, leads to condensation 18.3 See also
problems and requires an insulated envelope. These fac-
tors have limited its use thus far to mostly demonstration • Electrification
[9]
projects.
• Food steamer or steam cooker
• Geyser—geothermally-generated steam
18.2.6 Mechanical effort
• IAPWS—an association that maintains
A steam engine and steam turbines use the expansion of international-standard correlations for the
steam to drive a piston or turbine to perform mechanical thermodynamic properties of steam, including
86 CHAPTER 18. STEAM

IAPWS-IF97 (for use in industrial simulation and 18.5 External links


modelling) and IAPWS-95 (a general purpose and
scientific correlation). • Steam Tables & Charts by National Institute of Stan-
• Industrial Revolution dards and Technology, NIST

• Live steam
• Mass production
• Nuclear power—and power plants use steam to gen-
erate electricity
• Oxyhydrogen
• Psychrometrics—moist air/vapor mixtures, humidity
and air conditioning
• Steam locomotive

18.4 References
[1] Taylor, Robert A.; Phelan, Patrick E.; Adrian, Ronald J.;
Gunawan, Andrey; Otanicar, Todd P. (2012). “Charac-
terization of light-induced, volumetric steam generation
in nanofluids”. International Journal of Thermal Sciences
56: 1–11. doi:10.1016/j.ijthermalsci.2012.01.012.

[2] Taylor, Robert A.; Phelan, Patrick E.; Otanicar, Todd


P.; Walker, Chad A.; Nguyen, Monica; Trimble, Steven;
Prasher, Ravi (2011). “Applicability of nanofluids in high
flux solar collectors”. Journal of Renewable and Sustain-
able Energy 3 (2): 023104. doi:10.1063/1.3571565.

[3] Taylor, Robert A.; Phelan, Patrick E.; Otanicar, Todd;


Adrian, Ronald J.; Prasher, Ravi S. (2009). “Va-
por generation in a nanoparticle liquid suspension us-
ing a focused, continuous laser”. Applied Physics Let-
ters 95 (16): 161907. Bibcode:2009ApPhL..95p1907T.
doi:10.1063/1.3250174.

[4] Singh, R Paul (2001). Introduction to Food Engineering.


Academic Press. ISBN 978-0-12-646384-2.

[5] “Superheated Steam”. Spirax-Sarco Engineering.

[6] Malhotra, Ashok (2012). Steam Property Tables: Ther-


modynamic and Transport Properties. ISBN 978-1-479-
23026-6.

[7] Wiser, Wendell H. (2000). “Energy Source Contributions


to Electric Power Generation”. Energy resources: occur-
rence, production, conversion, use. Birkhäuser. p. 190.
ISBN 978-0-387-98744-6.

[8] Bevelhymer, Carl (November 10, 2003). “Steam”.


Gotham Gazette.

[9] “Steam Balloon JBFA Article”.

[10] EP Patent Publication 2,091,572

[11] Song, Liyan; Wu, Jianfeng; Xi, Chuanwu (2012).


“Biofilms on environmental surfaces: Evaluation of the
disinfection efficacy of a novel steam vapor system”.
American Journal of Infection Control 40 (10): 926–30.
doi:10.1016/j.ajic.2011.11.013. PMID 22418602.
Chapter 19

Boiler

For other uses, see boiler (disambiguation). 19.1 Materials


A boiler is a closed vessel in which water or other fluid

The pressure vessel of a boiler is usually made of steel


(or alloy steel), or historically of wrought iron. Stainless
steel, especially of the austenitic types, is not used in
wetted parts of boilers due to corrosion and stress corro-
sion cracking.[3] However, ferritic stainless steel is often
used in superheater sections that will not be exposed to
boiling water, and electrically-heated stainless steel shell
boilers are allowed under the European “Pressure Equip-
ment Directive” for production of steam for sterilizers
and disinfectors.[4]
In live steam models, copper or brass is often used be-
cause it is more easily fabricated in smaller size boilers.
A portable boiler
(preserved, Poland). Historically, copper was often used for fireboxes (particu-
larly for steam locomotives), because of its better forma-
bility and higher thermal conductivity; however, in more
recent times, the high price of copper often makes this an
uneconomic choice and cheaper substitutes (such as steel)
are used instead.
For much of the Victorian “age of steam”, the only
material used for boilermaking was the highest grade
of wrought iron, with assembly by rivetting. This iron
was often obtained from specialist ironworks, such as at
Cleator Moor (UK), noted for the high quality of their
rolled plate and its suitability for high-reliability use in
critical applications, such as high-pressure boilers. In the
20th century, design practice instead moved towards the
use of steel, which is stronger and cheaper, with welded
construction, which is quicker and requires less labour. It
should be noted, however, that wrought iron boilers cor-
rode far slower than their modern-day steel counterparts,
A stationary boiler and are less susceptible to localized pitting and stress-
(United States). corrosion. This makes the longevity of older wrought-
iron boilers far superior to those of welded steel boilers.
is heated. The fluid does not necessarily boil. (In North Cast iron may be used for the heating vessel of domestic
America the term "furnace" is normally used if the pur- water heaters.[5] Although such heaters are usually termed
pose is not actually to boil the fluid.) The heated or va- “boilers” in some countries, their purpose is usually to
porized fluid exits the boiler for use in various processes produce hot water, not steam, and so they run at low pres-
or heating applications,[1][2] including central heating, sure and try to avoid actual boiling. The brittleness of cast
boiler-based power generation, cooking, and sanitation. iron makes it impractical for high-pressure steam boilers.

87
88 CHAPTER 19. BOILER

gas. Electric steam boilers use resistance- or immersion-


type heating elements. Nuclear fission is also used as a
heat source for generating steam, either directly (BWR)
or, in most cases, in specialized heat exchangers called
“steam generators” (PWR). Heat recovery steam genera-
tors (HRSGs) use the heat rejected from other processes
such as gas turbine.

19.3 Configurations
Boilers can be classified into the following configurations:

• “Pot boiler” or “Haycock boiler”: a primitive “kettle”


where a fire heats a partially filled water container
from below. 18th century Haycock boilers gener-
ally produced and stored large volumes of very low-
pressure steam, often hardly above that of the atmo-
sphere. These could burn wood or most often, coal.
Efficiency was very low.
Diagram of a fire-tube boiler • Fire-tube boiler: Here, water partially fills a boiler
barrel with a small volume left above to accommo-
date the steam (steam space). This is the type of
boiler used in nearly all steam locomotives. The heat
source is inside a furnace or firebox that has to be
kept permanently surrounded by the water in order
to maintain the temperature of the heating surface
below the boiling point. The furnace can be situated
at one end of a fire-tube which lengthens the path of
the hot gases, thus augmenting the heating surface
which can be further increased by making the gases
reverse direction through a second parallel tube or
a bundle of multiple tubes (two-pass or return flue
boiler); alternatively the gases may be taken along
the sides and then beneath the boiler through flues
(3-pass boiler). In case of a locomotive-type boiler,
a boiler barrel extends from the firebox and the hot
gases pass through a bundle of fire tubes inside the
barrel which greatly increases the heating surface
compared to a single tube and further improves heat
transfer. Fire-tube boilers usually have a compara-
tively low rate of steam production, but high steam
storage capacity. Fire-tube boilers mostly burn solid
fuels, but are readily adaptable to those of the liquid
or gas variety.

• Water-tube boiler: In this type, tubes filled with wa-


ter are arranged inside a furnace in a number of
possible configurations, often the water tubes con-
nect large drums, the lower ones containing water
Diagram of a water-tube boiler. and the upper ones, steam and water; in other cases,
such as a mono-tube boiler, water is circulated by a
pump through a succession of coils. This type gener-
19.2 Fuel ally gives high steam production rates, but less stor-
age capacity than the above. Water tube boilers can
The source of heat for a boiler is combustion of any be designed to exploit any heat source and are gen-
of several fuels, such as wood, coal, oil, or natural erally preferred in high-pressure applications since
19.4. SAFETY 89

the high-pressure water/steam is contained within • Oil Preheating System


small diameter pipes which can withstand the pres-
sure with a thinner wall. Salient Features of Package Boiler • Continuous supply
• Flash boiler: A flash boiler is a specialized type of of dry saturated steam • Generation of steam at constant
water-tube boiler in which tubes are too close to- pressure • Minimum site work: Lesser boiler house space
gether and water is pumped through them. A flash • Skid mounted, requires only a flat foundation • Fast
boiler differs from the type of mono-tube steam gen- steaming • Fully automatic, capable of adjusting steam
erator in which the tube is permanently filled with generation to varying loads • Often left unattended for op-
water. In a flash boiler, the tube is kept so hot that erations (wherever regulations permit) • Highly efficient,
the water feed is quickly flashed into steam and su- efficiencies range from 84-85% (GCV) depending on the
perheated. Flash boilers had some use in automo- fuel • Minimal operational costs
biles in the 19th century and this use continued into Burner -------is a device which converts energy from fuel
the early 20th century. . into heat energy which is transfeered to water through
Boiler which results in Steam. Essential Features of Good
Burners

• High combustion efficiency


• Part load performance
• Easy change over of fuels in case of dual fuel firing
• Ease of mounting
• Robust and compact design
• Noiseless operation
• Easy accessibility to all parts for inspection and
1950s design steam locomotive boiler, from a Victorian Railways maintenance
J class
• Reliable components for continuous service

• Fire-tube boiler with Water-tube firebox. Some- • Easy adjustment of air / fuel ratio
times the two above types have been combined • Suitability of components for specific fuel charac-
in the following manner: the firebox contains an teristics
assembly of water tubes, called thermic siphons.
The gases then pass through a conventional firetube • Low power consumption and preheating of air
boiler. Water-tube fireboxes were installed in many
Hungarian locomotives, but have met with little suc- • Provision for various safety interlocks
cess in other countries.
Types of burners Based on mode of atomisation 1. Pres-
• Sectional boiler. In a cast iron sectional boiler, sure jet 2. Rotary cup
sometimes called a “pork chop boiler” the water is
contained inside cast iron sections. These sections Type of modulation 1. High / low 2. 3 stage modulation
are assembled on site to create the finished boiler. 3. Stepless modulation
Based on fuel fired 1. Gas fired 2. Oil fired 3. Dual fired
Also Boilers can be classified as Package Boiler Based on construction 1. Monoblock 2. Dual block
• The package boiler is so called because it comes as a Based on Air to Fuel Ratio Control 1. Linkage Type/ Me-
complete package. Once delivered to site it requires only chanical Compound Regulation 2. Electronic Compound
the steam, water pipe work, fuel supply and electrical con- Regulation
nections to be made for it to become operational.
• What is not a Package Boiler - When work needs to be
done at site, which is classified under “erection”: 19.4 Safety

• Foundation See also: Boiler explosion

• Insulation and Cladding


To define and secure boilers safely, some professional
• Electrical Cabling specialized organizations such as the American Society
90 CHAPTER 19. BOILER

of Mechanical Engineers (ASME) develop standards and


regulation codes. For instance, the ASME Boiler and
Pressure Vessel Code is a standard providing a wide range
of rules and directives to ensure compliance of the boilers
and other pressure vessels with safety, security and design
standards.
Historically, boilers were a source of many serious in-
juries and property destruction due to poorly understood
engineering principles. Thin and brittle metal shells can
rupture, while poorly welded or riveted seams could open
up, leading to a violent eruption of the pressurized steam.
When water is converted to steam it expands to over
1,000 times its original volume and travels down steam A superheated boiler on a steam locomotive.
pipes at over 100 kilometres per hour. Because of this,
steam is a great way of moving energy and heat around a
site from a central boiler house to where it is needed, but
without the right boiler feed water treatment, a steam-
raising plant will suffer from scale formation and corro- Most boilers produce steam to be used at saturation tem-
sion. At best, this increases energy costs and can lead to perature; that is, saturated steam. Superheated steam
poor quality steam, reduced efficiency, shorter plant life boilers vaporize the water and then further heat the steam
and unreliable operation. At worst, it can lead to catas- in a superheater. This provides steam at much higher tem-
trophic failure and loss of life. Collapsed or dislodged perature, but can decrease the overall thermal efficiency
boiler tubes can also spray scalding-hot steam and smoke of the steam generating plant because the higher steam
out of the air intake and firing chute, injuring the firemen temperature requires a higher flue gas exhaust tempera-
who load the coal into the fire chamber. Extremely large ture. There are several ways to circumvent this problem,
boilers providing hundreds of horsepower to operate fac- typically by providing an economizer that heats the feed
tories can potentially demolish entire buildings. The Lo- water, a combustion air heater in the hot flue gas exhaust
comotive, by Hartford Steam Boiler Inspection and Insur- path, or both. There are advantages to superheated steam
ance Company, Published by Hartford Steam Boiler In- that may, and often will, increase overall efficiency of
spection and Insurance Co., 1911, Item notes: n.s.:v.28 both steam generation and its utilization: gains in input
(1910–11), Original from Harvard University, Digitized temperature to a turbine should outweigh any cost in ad-
December 11, 2007 by Google Books, Link to digitized ditional boiler complication and expense. There may also
document: an article on a massive Pabst Brewing Com- be practical limitations in using wet steam, as entrained
pany boiler explosion in 1909 that destroyed a building, condensation droplets will damage turbine blades.
and blew parts onto the roof of nearby buildings. This
documents also contains a list of day-by-day boiler acci- Superheated steam presents unique safety concerns be-
dents and accident summaries by year, and discussions of cause, if any system component fails and allows steam to
boiler damage claims. escape, the high pressure and temperature can cause se-
rious, instantaneous harm to anyone in its path. Since the
A boiler that has a loss of feed water and is permitted to escaping steam will initially be completely superheated
boil dry can be extremely dangerous. If feed water is then vapor, detection can be difficult, although the intense heat
sent into the empty boiler, the small cascade of incom- and sound from such a leak clearly indicates its presence.
ing water instantly boils on contact with the superheated
metal shell and leads to a violent explosion that cannot Superheater operation is similar to that of the coils on
be controlled even by safety steam valves. Draining of an air conditioning unit, although for a different purpose.
the boiler can also happen if a leak occurs in the steam The steam piping is directed through the flue gas path in
supply lines that is larger than the make-up water supply the boiler furnace. The temperature in this area is typi-
could replace. The Hartford Loop was invented in 1919 cally between 1,300 and 1,600 °C (2,372 and 2,912 °F).
by the Hartford Steam Boiler and Insurance Company as Some superheaters are radiant type; that is, they absorb
a method to help prevent this condition from occurring, heat by radiation. Others are convection type, absorb-
and thereby reduce their insurance claims. ing heat from a fluid. Some are a combination of the
two types. Through either method, the extreme heat in
the flue gas path will also heat the superheater steam pip-
ing and the steam within. While the temperature of the
steam in the superheater rises, the pressure of the steam
19.5 Superheated steam boilers does not and the pressure remains the same as that of the
boiler.[6] Almost all steam superheater system designs re-
Main article: Superheater move droplets entrained in the steam to prevent damage
to the turbine blading and associated piping.
19.6. HYDRONIC BOILERS 91

19.5.1 Supercritical steam generator ically by way of radiators, baseboard heaters or through
the floors. The fluid can be heated by any means...gas,
wood, fuel oil, etc., but in built-up areas where piped gas
is available, natural gas is currently the most economical
and therefore the usual choice. The fluid is in an enclosed
system and circulated throughout by means of a pump.
The name “boiler” can be a misnomer in that, except for
systems using steam radiators, the water in a properly
functioning hydronic boiler never actually boils. Some
new systems are fitted with condensing boilers for greater
efficiency. These boilers are referred to as condensing
boilers because they are designed to extract the heat of
vaporization of the flue gas water vapor. As a result of
the lower flue gas temperatures, flue gas water vapor con-
denses to liquid and with dissolved carbon dioxide forms
carbonic acid. The carbonic acid would damage a typi-
cal boiler by corroding the flue and fireside boiler heating
surfaces. Condensing boilers solve this problem by rout-
ing the carbonic acid down a drain and by making the
flue exposed to the corrosive flue gas of stainless steel or
PVC. Although condensing boilers are becoming more
Boiler for a power plant.
popular, they are still less common than other types of
hydronic boilers as they are more expensive.
Main article: Supercritical steam generator
Hydronic systems are being used more and more in
new construction in North America for several reasons.
Supercritical steam generators are frequently used for the
Among those are:
production of electric power. They operate at supercrit-
ical pressure. In contrast to a “subcritical boiler”, a su-
percritical steam generator operates at such a high pres- • They are more efficient and more economical than
sure (over 3,200 psi or 22 MPa) that the physical tur- forced-air systems (although initial installation can
bulence that characterizes boiling ceases to occur; the be more expensive, because of the cost of the copper
fluid is neither liquid nor gas but a super-critical fluid. and aluminum).
There is no generation of steam bubbles within the water,
• The baseboard copper pipes and aluminum fins take
because the pressure is above the critical pressure point
up less room and use less metal than the bulky steel
at which steam bubbles can form. As the fluid expands
ductwork required for forced-air systems.
through the turbine stages, its thermodynamic state drops
below the critical point as it does work turning the tur- • They provide more even, less fluctuating temper-
bine which turns electrical generator from which power atures than forced-air systems. The copper base-
is ultimately extracted. The fluid at that point may be board pipes hold and release heat over a longer pe-
a mix of steam and liquid droplets as it passes into the riod of time than air does, so the furnace does not
condenser. This results in slightly less fuel use and there- have to switch off and on as much. (Hydronic sys-
fore less greenhouse gas production. The term “boiler” tems heat mostly through conduction and radiation,
should not be used for a supercritical pressure steam gen- whereas forced-air heats mostly through forced con-
erator, as no “boiling” actually occurs in this device. vection. Air has much lower thermal conductivity
and volumetric heat capacity than copper, so the
conditioned space warms up and cools down more
19.6 Hydronic boilers quickly than with hydronic. See also thermal mass.)

• They tend to not dry out the interior air as much as


Hydronic boilers are used in generating heat for residen- forced air systems, but this is not always true. When
tial and industrial purposes. They are the typical power forced air duct systems are air-sealed properly, and
plant for central heating systems fitted to houses in north- have return-air paths back to the furnace (thus re-
ern Europe (where they are commonly combined with do- ducing pressure differentials and therefore air move-
mestic water heating), as opposed to the forced-air fur- ment between inside and outside the house), this is
naces or wood burning stoves more common in North not an issue.
America. The hydronic boiler operates by way of heat-
ing water/fluid to a preset temperature (or sometimes in • They do not introduce any dust, allergens, mold, or
the case of single pipe systems, until it boils and turns to (in the case of a faulty heat exchanger) combustion
steam) and circulating that fluid throughout the home typ- byproducts into the living space.
92 CHAPTER 19. BOILER

Forced-air heating does have some advantages, however. • Low- water cutoff: It is a mechanical means (usu-
See forced-air heating. ally a float switch) that is used to turn off the burner
or shut off fuel to the boiler to prevent it from run-
ning once the water goes below a certain point. If
19.7 Accessories a boiler is “dry-fired” (burned without water in it) it
can cause rupture or catastrophic failure.

19.7.1 Boiler fittings and accessories • Surface blowdown line: It provides a means for re-
moving foam or other lightweight non-condensible
• Pressuretrols to control the steam pressure in the substances that tend to float on top of the water in-
boiler. Boilers generally have 2 or 3 pressuretrols: side the boiler.
An manual-reset pressuretrol, which functions as a
safety by setting the upper limit of steam pressure, • Circulating pump: It is designed to circulate water
the Operating pressuretrol, which controls when the back to the boiler after it has expelled some of its
boiler fires to maintain pressure, and for boilers heat.
equipped with a modulating burner, a modulating • Feedwater check valve or clack valve: A non-
pressuretrol which controls the amount of fire. return stop valve in the feedwater line. This may be
• Safety valve: It is used to relieve pressure and pre- fitted to the side of the boiler, just below the water
vent possible explosion of a boiler. level, or to the top of the boiler.[7]

• Water level indicators: They show the operator the • Top feed: In this design for feedwater injection, the
level of fluid in the boiler, also known as a sight glass, water is fed to the top of the boiler. This can reduce
water gauge or water column is provided. boiler fatigue caused by thermal stress. By spray-
ing the feedwater over a series of trays the water is
• Bottom blowdown valves: They provide a means quickly heated and this can reduce limescale.
for removing solid particulates that condense and lie
• Desuperheater tubes or bundles: A series of tubes
on the bottom of a boiler. As the name implies, this
or bundles of tubes in the water drum or the steam
valve is usually located directly on the bottom of the
drum designed to cool superheated steam, in order
boiler, and is occasionally opened to use the pressure
to supply auxiliary equipment that does not need, or
in the boiler to push these particulates out.
may be damaged by, dry steam.
• Continuous blowdown valve: This allows a small
• Chemical injection line: A connection to add
quantity of water to escape continuously. Its pur-
chemicals for controlling feedwater pH.
pose is to prevent the water in the boiler becoming
saturated with dissolved salts. Saturation would lead
to foaming and cause water droplets to be carried 19.7.2 Steam accessories
over with the steam - a condition known as priming.
Blowdown is also often used to monitor the chem- • Main steam stop valve:
istry of the boiler water.
• Steam traps:
• Flash Tank: High-pressure blowdown enters this
vessel where the steam can 'flash' safely and be used • Main steam stop/Check valve: It is used on multi-
in a low-pressure system or be vented to atmosphere ple boiler installations.
while the ambient pressure blowdown flows to drain.

• Automatic Blowdown/Continuous Heat Recov- 19.7.3 Combustion accessories


ery System: This system allows the boiler to blow-
down only when makeup water is flowing to the • Fuel oil system:fuel oil heaters
boiler, thereby transferring the maximum amount of
heat possible from the blowdown to the makeup wa- • Gas system:
ter. No flash tank is generally needed as the blow- • Coal system:
down discharged is close to the temperature of the
makeup water. • Soot blower

• Hand holes: They are steel plates installed in open-


ings in “header” to allow for inspections & installa- 19.7.4 Other essential items
tion of tubes and inspection of internal surfaces.
• Pressure gauges:
• Steam drum internals, A series of screen, scrubber
& cans (cyclone separators). • Feed pumps:
19.9. SEE ALSO 93

• Fusible plug: 19.9 See also


• Inspectors test pressure gauge attachment:
• Aquastat
• Name plate:
• Boiler design
• Registration plate:
• British thermal unit (Btu)

19.8 Draught • Boiler feed water deaerator

A fuel-heated boiler must provide air to oxidize its fuel. • Dealkalization of water
Early boilers provided this stream of air, or draught,
through the natural action of convection in a chimney • Draft (boiler)
connected to the exhaust of the combustion chamber.
• Electric water boiler (for drinking water)
Since the heated flue gas is less dense than the ambient air
surrounding the boiler, the flue gas rises in the chimney,
• External combustion engine
pulling denser, fresh air into the combustion chamber.
Most modern boilers depend on mechanical draught • Firebox (used by railway locomotives)
rather than natural draught. This is because natural
draught is subject to outside air conditions and tempera- • Fossil fuel power plant
ture of flue gases leaving the furnace, as well as the chim-
ney height. All these factors make proper draught hard to • Furnace
attain and therefore make mechanical draught equipment
much more reliable and economical. • Geothermal power plant
Types of draught can also be divided into induced • Heating
draught, where exhaust gases are pulled out of the boiler;
forced draught, where fresh air is pushed into the boiler; • Heat-only boiler station
and balanced draught, where both effects are employed.
Natural draught through the use of a chimney is a type • Heat recovery steam generator
of induced draught; mechanical draught can be induced,
forced or balanced. • Hot water reset
There are two types of mechanical induced draught. The
first is through use of a steam jet. The steam jet oriented • Hydronics
in the direction of flue gas flow induces flue gasses into
• Internally rifled boiler tubes (also known as Serve
the stack and allows for a greater flue gas velocity increas-
tubes)
ing the overall draught in the furnace. This method was
common on steam driven locomotives which could not
• Lancashire boiler
have tall chimneys. The second method is by simply us-
ing an induced draught fan (ID fan) which removes flue
• Natural circulation boiler
gases from the furnace and forces the exhaust gas up the
stack. Almost all induced draught furnaces operate with • Power plant and Power station
a slightly negative pressure.
Mechanical forced draught is provided by means of a fan • Pulverized coal-fired boiler
forcing air into the combustion chamber. Air is often
passed through an air heater; which, as the name suggests, • Radiator
heats the air going into the furnace in order to increase the
overall efficiency of the boiler. Dampers are used to con- • Recovery boiler
trol the quantity of air admitted to the furnace. Forced
draught furnaces usually have a positive pressure. • Steam generator (nuclear power)

Balanced draught is obtained through use of both induced • Thermal power station
and forced draught. This is more common with larger
boilers where the flue gases have to travel a long distance • Thermoelectric
through many boiler passes. The induced draught fan
works in conjunction with the forced draught fan allow- • Thermostat
ing the furnace pressure to be maintained slightly below
atmospheric. • Water heater
94 CHAPTER 19. BOILER

19.10 References
[1] Frederick M. Steingress (2001). Low Pressure Boilers (4th
Edition ed.). American Technical Publishers. ISBN 0-
8269-4417-5.

[2] Frederick M. Steingress, Harold J. Frost and Darryl R.


Walker (2003). High Pressure Boilers (3rd Edition ed.).
American Technical Publishers. ISBN 0-8269-4300-4.

[3] ASME Boiler and Pressure Vessel Code, Section I, PG-


5.5, American Society of Mechanical Engineers (2010)

[4] BS EN 14222: “Stainless steel shell boilers”

[5] “The evolution of domestic gas central heating systems”.

[6] Bell, A.M. (1952) Locomotives 1 p 46. Virtue and Com-


pany Ltd, London

[7] Bell (1952: 1 35)

19.11 Further reading


• American Society of Mechanical Engineers: ASME
Boiler and Pressure Vessel Code, Section I. Updated
every 3 years.

• Association of Water Technologies: Association of


Water Technologies (AWT).

• The Babcock & Wilcox Co. (1902): “Steam,


its generation and use”, New York-London, re-
published by Nabu Press, ISBN 978-1147-61244-8
(2010)
Chapter 20

API oil-water separator

An API oil-water separator is a device designed to sep- to the bottom of the separator as a sediment layer, the oil
arate gross amounts of oil and suspended solids from will rise to top of the separator, and the wastewater will
the wastewater effluents of oil refineries, petrochemical be the middle layer between the oil on top and the solids
plants, chemical plants, natural gas processing plants on the bottom.[2]
and other industrial sources. The name is derived from Typically, the oil layer is skimmed off and subsequently
the fact that such separators are designed according to
re-processed or disposed of, and the bottom sediment
standards published by the American Petroleum Institute layer is removed by a chain and flight scraper (or simi-
(API). [1][2]
lar device) and a sludge pump. The water layer is sent
to further treatment consisting usually of a dissolved air
flotation (DAF) unit for further removal of any residual
20.1 Description of the design and oil and then to some type of biological treatment unit for
removal of undesirable dissolved chemical compounds.
operation

A typical parallel plate separator

Parallel plate separators are similar to API separators but


they include tilted parallel plate assemblies (also known
A typical gravimetric API separator as parallel packs).[2] The underside of each parallel plate
provides more surface for suspended oil droplets to coa-
The API separator is a gravity separation device designed lesce into larger globules. Any sediment slides down the
by using Stokes Law to define the rise velocity of oil topside of each parallel plate. Such separators still de-
droplets based on their density and size. The design of pend upon the specific gravity between the suspended oil
the separator is based on the specific gravity difference and the water. However, the parallel plates enhance the
between the oil and the wastewater because that differ- degree of oil-water separation. The result is that a par-
ence is much smaller than the specific gravity difference allel plate separator requires significantly less space than
between the suspended solids and water. Based on that a conventional API separator to achieve the same degree
design criterion, most of the suspended solids will settle of separation.

95
96 CHAPTER 20. API OIL-WATER SEPARATOR

20.2 History [3] International Convention for the Prevention of Pollution


from Ships, 1973 (and later amendments)
The API separator was developed by the API and the Rex [4] Oily water separator
Chain Belt Company (now Siemens Water). The first
API separator was installed in 1933 at the Atlantic Re- [5] Leonard L.Grigsby (2001). The Electrical Power Engi-
fining Company (ARCO) refinery in Philadelphia. Since neering Handbook. CRC Press. ISBN 0-8493-8578-4.
that time, virtually all of the refineries worldwide have
installed API separators in their wastewater treatment
plants. The majority of those refineries installed the API 20.6 External links
separators using the original design based on the specific
gravity difference between oil and water. However, many • Photographs, drawings and design discussion of
refineries now use plastic parallel plate packing to en- gravimetric API Separators
hance the gravity separation.[1][2]
• Oil/Water Separators Diagrams and description of
separators using plastic parallel plate packing.
20.3 Other oil-water separation ap- • Oil-in-water Separation Good discussion and expla-
plications nation of wastewater treatment processes.

• Monroe Environmental Clarifiers Manufacturer,


There are other applications requiring oil-water separa- drawings, photographs, diagrams and descriptions.
tion. For example:
• Oil Water Separators Features, Case Studies, Tech-
nology, Photos
• Oily water separators (OWS) for separating oil from
the bilge water accumulated in ships as required by
the international MARPOL Convention.[3][4]

• Oil and water separators are commonly used in


electrical substations. The transformers found in
substations use a large amount of oil for cooling
purposes. Moats are constructed surrounding unen-
closed substations to catch any leaked oil, but these
will also catch rainwater. Oil and water separators
therefore provide a quicker and easier cleanup of an
oil leak.[5]

20.4 See also


• Pollution

• Wastewater

• Industrial wastewater treatment

• Industrial water treatment

• Centrifugal oil-water separator

20.5 References
[1] American Petroleum Institute (API) (February 1990).
Management of Water Discharges: Design and Opera-
tions of Oil-Water Separators (1st Edition ed.). American
Petroleum Institute.

[2] Beychok, Milton R. (1967). Aqueous Wastes from


Petroleum and Petrochemical Plants (1st Edition ed.).
John Wiley & Sons. LCCN 67019834.
Chapter 21

Dissolved air flotation

Dissolved air flotation (DAF) is a water treatment pro-


cess that clarifies wastewaters (or other waters) by the
removal of suspended matter such as oil or solids. The
removal is achieved by dissolving air in the water or
wastewater under pressure and then releasing the air at
atmospheric pressure in a flotation tank or basin. The
released air forms tiny bubbles which adhere to the sus-
pended matter causing the suspended matter to float to
the surface of the water where it may then be removed by
a skimming device.[1][2][3]
Dissolved air flotation is very widely used in treating
the industrial wastewater effluents from oil refineries,
petrochemical and chemical plants, natural gas process-
ing plants, paper mills, general water treatment and sim-
ilar industrial facilities. A very similar process known DAF unit with a capacity of 20 m³/h, visible also: flocculant
as induced gas flotation is also used for wastewater treat- preparation station and pipe flocculator
ment. Froth flotation is commonly used in the processing
of mineral ores.
In the oil industry, dissolved gas flotation (DGF) units do
not use air as the flotation medium due to the explosion
risk. Nitrogen gas is used instead to create the bubbles.

21.1 Process description

Modern DAF units using parallel plate technology are quite com-
pact.
Picture shows a 225 m³/h DAF.

A portion of the clarified effluent water leaving the DAF


tank is pumped into a small pressure vessel (called the
air drum) into which compressed air is also introduced.
This results in saturating the pressurized effluent water
with air. The air-saturated water stream is recycled to
the front of the float tank and flows through a pressure
reduction valve just as it enters the front of the float tank,
which results in the air being released in the form of tiny
A typical dissolved air flotation unit (DAF) bubbles. The bubbles adhere to the suspended matter,
causing the suspended matter to float to the surface and
The feed water to the DAF float tank is often (but not form a froth layer which is then removed by a skimmer.
always) dosed with a coagulant (such as ferric chloride or The froth-free water exits the float tank as the clarified
aluminum sulfate) to flocculate the suspended matter. effluent from the DAF unit.[1]

97
98 CHAPTER 21. DISSOLVED AIR FLOTATION

Some DAF unit designs utilize parallel plate packing ma- 21.5 External links
terial, lamellas, to provide more separation surface and
therefore to enhance the separation efficiency of the unit. • Treatment and Disposal of Ship-Generated Solid
DAF systems can be categorized as circular (more effi- and Liquid Wastes (REMPEC Regional Marine Pol-
cient) and rectangular (more residence time). The former lution Emergency Response Centre for the Mediter-
type requires just 3 minutes; an example is a Wockoliver ranean Sea, Project MED.B4.4100.97.0415.8,
DAF system. The rectangular type requires 20 to 30 min- April 2004)
utes; a typical example is a Syskill DAF system. One
of the bigger advantages of the circular type is its spiral
scoop.

21.2 Drinking water treatment


Drinking water supplies that are particularly vulnerable to
unicellular algal blooms, and supplies with low turbidity
and high colour often employ DAF. After coagulation and
flocculation processes, water flows to DAF tanks where
air diffusers on the tank bottom create fine bubbles that
attach to floc resulting in a floating mass of concentrated
floc. The floating floc blanket is removed from the surface
and clarified water is withdrawn from the bottom of the
DAF tank.[4]

21.3 See also


• API oil-water separator

• Flotation process

• Industrial wastewater treatment

• Industrial water treatment

• List of waste-water treatment technologies

21.4 References
[1] Beychok, Milton R. (1967). Aqueous Wastes from
Petroleum and Petrochemical Plants (1st ed.). John Wi-
ley & Sons. LCCN 67019834.

[2] Lawrence K. Wang, Yung-Tse Hung, Howard H. Lo and


Constantine Yapijakis (2004). Handbook of Industrial
and Hazardous Wastes Treatment (2nd ed.). CRC Press.
ISBN 0-8247-4114-5.

[3] Kiuru, H.; Vahala, R., eds. (2000). “International con-


ference on DAF in water and waste water treatment No.
4, Helsinki, Finland”. IWA Publishing, London. ISBN
1-900222-81-7. |chapter= ignored (help)

[4] Edzwald, James K., ed. (2011). Water Quality and Treat-
ment. 6th Edition. New York:McGraw-Hill. pp. 9.46.
ISBN 978-0-07-163011-5
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21.6 Text and image sources, contributors, and licenses


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Arnett, RedWolf, Hemanshu, Pretzelpaws, BenFrantzDale, Tom harrison, Lupin, Leonard G., Unconcerned, Jorge Stolfi, H Padleckas,
AndrewKeenanRichardson, Scott Burley, Neutrality, Mike Rosoft, Yueni, Discospinster, Wk muriithi, Mani1, ESkog, *drew, Edward Z.
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inWiki, Wiki alf, AdiJapan, Stevenwmccrary58, 21655, Ageekgal, Wsiegmund, Stuhacking, Katieh5584, robot, Luk, SmackBot,
Saravask, KnowledgeOfSelf, Cdcon, Hardyplants, Knuto, Edgar181, Steam5, Gilliam, Hmains, Skizzik, Bluebot, Sbharris, Colonies Chris,
Antonrojo, Zsinj, Rogermw, Can't sleep, clown will eat me, Addshore, Kcordina, Markrobi, Falconeer, Gbinal, DMacks, Nathanael Bar-
Aur L., Anlace, John, CorvetteZ51, Aleator, Mbeychok, Boswell, Euphonisten, SimonD, Igoldste, Woodshed, Tawkerbot2, GBuilder,
CmdrObot, Rorshacma, Dycedarg, Tex, Rdaveh, LouisBB, Rifleman 82, Lowellt, Nikopoley, M karzarj, Hubba, MayaSimFan, Calvero JP,
Aldis90, Richhoncho, Thijs!bot, Epbr123, Hazmat2, RobDe68, AntiVandalBot, Crentsch, Tillman, Yellowdesk, David Shankbone, JAnD-
bot, Bongwarrior, VoABot II, Flavus Ahenobarbus, Dbushong, Kosm, Avicennasis, 28421u2232nfenfcenc, Beagel, JaGa, JRWalko, Anony-
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tional, WilfriedC, Cometstyles, Useight, KGV, Idioma-bot, Funandtrvl, Spongessuck, VolkovBot, Lear’s Fool, XterraGuy, Philip Trueman,
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mutator, Alex.muller, Fratrep, Hatster301, OKBot, JL-Bot, Arinnian, ClueBot, Waynems, The Thing That Should Not Be, Thehelpfulone,
Thingg, Aitias, Putje81, DumZiBoT, Duckrob47, Lollypopcandygum1, XLinkBot, Thiswebsitesuckssomuch, BodhisattvaBot, Dthomsen8,
WikHead, Sicvolo, Thatguyflint, Elader, Addbot, Annwhent, Betterusername, Ronhjones, Brandonlighty, MrOllie, Glane23, Lakshmix,
Txag99, Tide rolls, Lightbot, Kahar13, Gail, JonathanBentz, Luckas-bot, 2D, Mauler90, Fatal!ty, Daniele Pugliesi, Darolew, Flewis, Ma-
terialscientist, The High Fin Sperm Whale, Citation bot, Poofacejim, Sozchick101, ArthurBot, BritishWatcher, J04n, Chubbz1995, Troys-
ter87, Doulos Christos, Tech408, BNSDRX09, Insomnia64, Helloaday, FrescoBot, Peterbmoorman, Aleksa Lukic, Pinethicket, Explocon-
trol, Utain, Allen Mesch, Aboriginal Noise, Hyd12, Sameeraemail, Thecoolmusic, JimmyCraig, Vrenator, Minimac, Onel5969, Rjwilm-
siBot, TjBot, Ripchip Bot, Kiko4564, EmausBot, Francophile124, Desertroad, Tommy2010, TeleComNasSprVen, Dh m83, Kittylionel,
UrbanNerd, IGeMiNix, Donner60, Uthican, Scientific29, ChuispastonBot, DASHBotAV, CharlieEchoTango, 28bot, Aaronw08, Zip822,
ClueBot NG, Corusant, HISTMichelleS253, Widr, JohnSRoberts99, Cccefalon, Arnavchaudhary, Mohamed CJ, M0rphzone, Northamer-
ica1000, Mur61j, Silvio1973, Zujua, Grand Armor, Fozia nasir, ChrisGualtieri, YFdyh-bot, Asoleimanif, Geremy.Hebert, Makecat-bot,
Frosty, Sfgiants1995, Arham pincha, Басилей, Robo4321, Adbar, JaconaFrere, Ryanwilliams98, Amp121212, Michaelraymond40170,
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NielsenGW, Edgar181, Colonies Chris, Mbeychok, Beetstra, RHB, LouisBB, Rifleman 82, Kozuch, Malleus Fatuorum, Thijs!bot,
TimVickers, Ccrrccrr, Magioladitis, Rich257, WilfriedC, VolkovBot, TreasuryTag, Suprcel, Anonymous Dissident, Lightmouse,
Fri117336, MystBot, Addbot, MrOllie, Daniele Pugliesi, Citation bot, Fti74, Mnmngb, FrescoBot, Gire 3pich2005, Citation bot 1, Hyd12,
ChemE50, Wagino 20100516, ClueBot NG, BarrelProof, MusikAnimal, Dave Bowman - Discovery Won, Tentinator and Anonymous: 16
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Roboto de Ajvol, Wiki alf, BOT-Superzerocool, SmackBot, Edgar181, Colonies Chris, Hgrosser, Cybercobra, AstroChemist, Mbeychok,
Swotboy2000, BoH, Rifleman 82, Christian75, WinBot, Quantockgoblin, Jeepday, Emonkey, WilfriedC, VolkovBot, Dogsgomoo, Elson-
huge, SieBot, Izmaelt, Kkolmetz, Pointillist, Addbot, JohnPaulGeorge, Bunnyhop11, Julia W, Daniele Pugliesi, Dinesh smita, Citation
bot, Elvim, ‫قلی زادگان‬, Mnmngb, Inhwiki, Pinethicket, Mys 721tx, Crimmm5, RjwilmsiBot, EmausBot, ZéroBot, ClueBot NG, VUGD,
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Sixtyseven, R. S. Shaw, Polyparadigm, Rjwilmsi, Czar, Wavelength, RussBot, Hellbus, Light current, Bluebot, Cadmium, Smokefoot,
Heteren, Mion, Mbeychok, Beetstra, CmdrObot, Thijs!bot, OrenBochman, JAnDbot, Flavus Ahenobarbus, Beagel, User A1, DadaNeem,
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100 CHAPTER 21. DISSOLVED AIR FLOTATION

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abazooka, Rob Hooft, Gentgeen, Rfc1394, Jeremiah, Giftlite, Eequor, Cacycle, Michall, Luxdormiens, Kwamikagami, Bobo192, Maur-
reen, Goatboy, Vuo, Freyr, Sburke, V8rik, R.e.b., FlaBot, Chobot, Mahahahaneapneap, RussBot, RazorICE, Mysid, Dextery, Silverchemist,
Ninly, Lunch, ChemGardener, Itub, FloNight, Edgar181, Bluebot, Shalom Yechiel, SundarBot, Ctalmageblack, Smokefoot, Qmwne235,
Wizard191, Jaeger5432, Meodipt, MrFish, Cydebot, Rifleman 82, Gogo Dodo, Alaibot, Calvero JP, Thijs!bot, Jmille01, HForN, TuvicBot,
JAnDbot, Deflective, Pi.1415926535, Ph.eyes, Quantockgoblin, Su-no-G, Andre.holzner, ChemNerd, Nono64, Layraud, NewEnglandYan-
kee, STBotD, VolkovBot, Levg, Hersfold, LokiClock, TXiKiBoT, Captain Wikify, Strangerer, TheLastNinja, ToePeu.bot, Reinderien,
ClueBot, Muhandes, TAKEN00, Good Olfactory, Addbot, Sergei, Quercus solaris, Oxen64, Luckas-bot, Daniele Pugliesi, Thehelpfulbot,
Citation bot 1, Mikespedia, EmausBot, Jorge c2010, Dcirovic, GianniG46, Nikos 1993, NotWith and Anonymous: 53
• Isomerization Source: http://en.wikipedia.org/wiki/Isomerization?oldid=635903432 Contributors: Tarquin, 168..., Astronautics, Vsmith,
Snowolf, Melaen, Gene Nygaard, V8rik, Bruce1ee, Gurch, Jrtayloriv, Physchim62, Jared Preston, JDnCoke, KnowledgeOfSelf, Smokefoot,
SilkTork, Mbeychok, CmdrObot, Rifleman 82, Thijs!bot, Nonagonal Spider, Quantockgoblin, Pharaoh of the Wizards, LordAnubisBOT,
Snowbot, EdChem, Addbot, Yobot, Citation bot, Elvim, GrouchoBot, BenzolBot, DrilBot, Île flottante, Reallynca, RjwilmsiBot, ClueBot
NG, BG19bot, Wikitrolol, Epicgenius, Tentinator, Bigfoottoecheese, Tu178 and Anonymous: 29
• Amine gas treating Source: http://en.wikipedia.org/wiki/Amine%20gas%20treating?oldid=636569656 Contributors: H Padleckas, Rich
Farmbrough, Cacycle, Spalding, R. S. Shaw, Hooperbloob, Allen3, Fivemack, RussBot, SmackBot, Smokefoot, Goatchze, Mbeychok,
Magioladitis, JamesBWatson, Beagel, R'n'B, WilfriedC, Funkysapien, Outpostn, SieBot, ClueBot, Kuikentje, Jdavis41759, Thebearix,
Vianello, Addbot, Naudefjbot, Borvan53, AnomieBOT, Daniele Pugliesi, Citation bot, Riventree, Zrhodes, Amse12, RjwilmsiBot, New-
pointgas, GoingBatty, K6ka, Gertdam, ZéroBot, Crbn2020, Widr, Testem, Syzygy32, Blockyblock567 and Anonymous: 24
• Claus process Source: http://en.wikipedia.org/wiki/Claus%20process?oldid=621186474 Contributors: Charles Matthews, R. S. Shaw,
Pearle, Japanese Searobin, Boothy443, Woohookitty, Mindmatrix, Firien, V8rik, Bosquewiki, SmackBot, Chris the speller, Goatchze, Mb-
eychok, Rifleman 82, Storm63640, Faigl.ladislav, MisterWeatherbee, Beagel, MartinBot, WilfriedC, STBotD, VolkovBot, Funkysapien,
Otispa, Pjoef, SieBot, Arnobarnard, Correogsk, Shinkolobwe, UrsoBR, MystBot, Addbot, Yobot, Daniele Pugliesi, Citation bot, Asuter-
isuku, Webmina, EmausBot, Joshramsey, Helpful Pixie Bot, BG19bot and Anonymous: 23
• Hydrogen sulfide Source: http://en.wikipedia.org/wiki/Hydrogen%20sulfide?oldid=638717662 Contributors: AxelBoldt, Mav, Bryan
Derksen, Zundark, Tarquin, Roadrunner, Ktsquare, Tim Starling, Pit, David Martland, Wapcaplet, Ahoerstemeier, Darkwind, Julesd,
Jschwa1, Andrewman327, Timc, Haukurth, Grendelkhan, Francs2000, Denelson83, Gentgeen, Robbot, Pigsonthewing, RedWolf,
Ee00224, Antonin, Cutler, Clementi, Giftlite, Graeme Bartlett, Unconcerned, Duncharris, Mboverload, Pne, OldakQuill, Keith Edkins,
Sonjaaa, Edsanville, Sonett72, Mike Rosoft, Spiffy sperry, Noisy, Vsmith, Aardark, DcoetzeeBot, Geoking66, Odalcet, CanisRufus, Art
LaPella, Spoon!, Marco Polo, Robotje, Vortexrealm, Foobaz, Sam Korn, A Karley, Alansohn, Free Bear, Quatermass, Keenan Pep-
per, Moanzhu, Benjah-bmm27, Ahruman, MarkRose, RainbowOfLight, Dirac1933, Shigernafy, Skatebiker, Versageek, Gene Nygaard,
Capecodeph, LukeSurl, Walshga, BerserkerBen, Dandv, Benbest, GregorB, SCEhardt, Palica, V8rik, BD2412, Davion, DePiep, Drbog-
dan, Rjwilmsi, WCFrancis, Vuong Ngan Ha, FlaBot, Margosbot, RexNL, Parutakupiu, Physchim62, Imnotminkus, Chobot, Dj Capricorn,
WriterHound, Quicksilvre, YurikBot, Wavelength, NTBot, WO2, Hellbus, Gaius Cornelius, Shaddack, Member, NawlinWiki, RyanJones,
Brianfedirko, FF2010, Zzuuzz, Chase me ladies, I'm the Cavalry, Sbyrnes321, MacsBug, SmackBot, Snowmobile, Edgar181, Hmains,
Chris the speller, Bluebot, Ottawakismet, M m hawk, Thumperward, Salvor, Baa, Kbailey1, Laslovarga, Onorem, Addshore, RandomP,
21.6. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 101

Smokefoot, Agentmoose, Drphilharmonic, Gump Stump, Chymicus, Dgfduck, Aussie Alchemist, Gobonobo, Jaganath, Mbeychok, Stwalk-
erster, Beetstra, Kyoko, Vie charlie, InedibleHulk, Gegnome, Iridescent, Shoeofdeath, IvanLanin, Twas Now, Courcelles, Thricecube, Billy
Hathorn, Andrhyo, Mellery, Nova325, Van helsing, Zureks, Cybernetic, Infodek, Stephend01, Icek, A876, Zgystardst, Mtpaley, Ufwuct,
James086, Sean2074, Amlz, Escarbot, Luna Santin, Paul from Michigan, Spencer, Mikenorton, Pi.1415926535, Fetchcomms, BeeArkKey,
Probios, Extropian314, Antelan, Nyq, Whisk3rs, Emilyjem, Ahecht, David Eppstein, Nevit, Hdt83, MartinBot, ChemNerd, Yasingam,
RiddG07, Nono64, Leyo, Wikiman232, RockMFR, J.delanoy, MITBeaverRocks, AstroHurricane001, Nwbeeson, KylieTastic, Tigger-
jay, MartinBotIII, Deor, VolkovBot, Gene Hobbs, Vlmastra, WOSlinker, Philip Trueman, TXiKiBoT, Michi zh, Crockki, Someguy1221,
Piperh, Kalothira, Broadbot, CanOfWorms, BotKung, Xhandar, Lamro, Ducky3.14, Andrewmcgibbon, SieBot, Mycomp, Da Joe, A.
Carty, Darrylzero, Oxymoron83, Hobartimus, Alex.muller, Quisquillian, Wikiwayman, Maderibeyza, Movalley, Chem-awb, ClueBot, Yel-
lier, Drmies, NovaDog, Jacco Huisman, Ktr101, AssegaiAli, Eeekster, Shinkolobwe, Sun Creator, Garing, Henrylesliegrahamlong, Heffner,
Plasmic Physics, Dana boomer, Norum370, Arniepie1990, Rror, Vanished 45kd09la13, Alexius08, MystBot, Airplaneman, Arturo57,
Prowikipedians, Addbot, Danielaustinhall12, DOI bot, Element16, NjardarBot, Rickydrunk, CarsracBot, Jamie Wade, FiriBot, Baffle
gab1978, Nyc445, Rickjames112, OlEnglish, ScAvenger, Վազգեն, Peatswift, Luckas-bot, Yobot, CheMoBot, Kilom691, Plasticbot,
AnomieBOT, Casforty, Jim1138, Μυρμηγκάκι, Materialscientist, The High Fin Sperm Whale, Citation bot, Xqbot, Sionus, TechBot,
Sylwia Ufnalska, Anna Frodesiak, GrouchoBot, Amaury, FrescoBot, ShelbyBell, Riventree, Orthonto, Pigcatapult, Citation bot 1, Dig-
byDalton, Nirmos, Pinethicket, Bluescolor234, RedBot, Dinamik-bot, Clarkcj12, DARTH SIDIOUS 2, RjwilmsiBot, Bento00, ElPeste,
Mordekai wiki, WikitanvirBot, Ramones74, Lhutchinson, Scr999, NotAnonymous0, Wikipelli, Kp grewal, JSquish, Hitokui Pineapple,
Consciouslee, H3llBot, J1812, CameronTylar, Wayne Slam, Seattle, TyA, Mayur, Ego White Tray, YOSF0113, ChuispastonBot, Zabacad,
Laveshtyagi, Sven Manguard, DASHBotAV, Whoop whoop pull up, GrindItOut, Kabhi1995, ClueBot NG, Bjohns86, Satellizer, Hon-
3s-T, Rycecube57, Vacation9, O.Koslowski, Rezabot, Nao1958, Platonicmaria, Helpful Pixie Bot, Brad5001, JohnSRoberts99, Bibcode
Bot, Gauravjuvekar, BG19bot, Jay8g, Suicide Prevention, Dan653, Nsda, MrBill3, Chip123456, BattyBot, LegacyOfValor, Bleistift2,
Lesbolover, EuroCarGT, Amysawiki, ThunderSkunk, MilosF, Osmoregulator, Howicus, BlackDragon2712, Harlem Baker Hughes, Si-
mon150999, David Reay, Meteor sandwich yum, Monkbot, Bunnyluvur11, Johnsonman1234, Amandas2780, NewsOrgNet, Pavel989,
Valeg96, Goku778777877, Ananasanana, Cavalierhld and Anonymous: 354
• Cooling tower Source: http://en.wikipedia.org/wiki/Cooling%20tower?oldid=639094087 Contributors: Edward, Kku, Ronz, Bogdan-
giusca, Samw, Dfeuer, Blainster, Buster2058, Tom harrison, Foot, Rchandra, Blue387, DanielCD, Vsmith, Goochelaar, Jnestorius, Re-
muel, BarkingFish, Barbirossa, Velella, Stephan Leeds, Dragunova, Pauli133, Oleg Alexandrov, Crosbiesmith, Linas, MGTom, MONGO,
CharlesC, MarcoTolo, Magister Mathematicae, BD2412, Grammarbot, Rjwilmsi, Hazel75, Strait, NewGuy4, The wub, Old Moonraker,
Sean Tevis, Godal, Foolishgrunt, Trublu, BjKa, Kolbasz, Lmatt, SteveBaker, Chobot, YurikBot, Wavelength, Hairy Dude, Deeptrivia,
Limulus, Ikar.us, Hydrargyrum, Alynna Kasmira, DragonHawk, ErkDemon, Squeed, Zerodamage, Asterion, Nekura, Mach10, Smack-
Bot, Ratarsed, KnowledgeOfSelf, Hydrogen Iodide, Markus Schweiss, Hmains, Chris the speller, Bluebot, Neo-Jay, Kostmo, H Bruth-
zoo, Scwlong, Racklever, Theanphibian, Fuhghettaboutit, Zonk43, Daniel.Cardenas, Mion, CopelandJim, SashatoBot, Microchip08, Ji-
danni, Copeland.James.H, Mbeychok, Peterlewis, EdC, MikeWazowski, Chanbc, JoeBot, Tony Fox, IanOfNorwich, Mr3641, Com-
pRhetoric, Tonydevito, Gogo Dodo, PKT, Gralo, AgentPeppermint, RobotG, Farosdaughter, Klow, Ritabest, MER-C, Edreher, John-
Jardine, PhilKnight, TJBlackwell, Nyq, Jéské Couriano, Slov01, Beagel, Black Stripe, Sych, Anonymous 57, Pomte, CDM2, Jon seah,
AlphaEta, Cherrypj, Mattnad, Nfette, Carlos1873, Geekdiva, Bwnichols, Inwind, Deor, MilestonebyMilestone, TXiKiBoT, Technopat,
A4bot, Jcthunder1, Serknap, PDFbot, Maxim, Auvi82, Kilmer-san, Koysmile, Lightmouse, Hobartimus, Xnatedawgx, ClueBot, PipepBot,
Anwarulmaruf, Snigbrook, Kkolmetz, The Thing That Should Not Be, VQuakr, Websites, DragonBot, Moreau1, Sun Creator, Stefano Schi-
avon, Thewellman, DJ Creamity, Abhijit033, DumZiBoT, Duncan, Kbdankbot, Addbot, AkhtaBot, Sunny7218214, Plerlmoc, OlEnglish,
Robinashby, Vizu, Luckas-bot, Yobot, Themfromspace, MinorProphet, AnomieBOT, KDS4444, Daniele Pugliesi, Materialscientist, Ci-
tation bot, Dirk Schlichting, Sionus, Mononomic, DSisyphBot, J JMesserly, GrouchoBot, FrescoBot, Part Time Security, Rahul.dixit101,
DanTheSeeker, TreeBread, MacBuzz, Tinton5, Herogamer, RedBot, Gamewizard71, Intelshwets, Vrenator, Reaper Eternal, Ondertitel,
Ana.socev, RjwilmsiBot, Jackehammond, Beyond My Ken, EmausBot, Orphan Wiki, Alexabbrevoir, Mmeijeri, Cathodic, Hair2leern,
ClueBot NG, Eotterman, Eurovent, Braincricket, LightRobb, Morgan Riley, Reify-tech, Kwdt2, Krevonims, Helpful Pixie Bot, Cenk En-
dustri, Jeyakumarjohn, Wiki13, Yannick Lu-Cotrelle, Emmanuelxp, Webmasterpct, BattyBot, GinGin-1995, HzimmermanMSP, Chris-
Gualtieri, Keesvliet, Schilzm, Hmainsbot1, Expertseeker90, Rafa3040, Frosty, Marcionist, Dan Coday, Regional planner, Laluthoms, Re-
gionalplaner, Birhanb, Kdwhelpton, Manupaul123, CarbonWHO, Monkbot, Dutchydylan10, Cappmt41, Taniamcintosh, CapabilityCounts
and Anonymous: 254
• Steam Source: http://en.wikipedia.org/wiki/Steam?oldid=638670088 Contributors: The Anome, Tarquin, Malcolm Farmer, Drj, Rjs-
tott, Dave McKee, Vignaux, Jdpipe, Topory, Edward, Patrick, Ixfd64, Zanimum, Tregoweth, 168..., Ahoerstemeier, Aarchiba, Ugen64,
Mulad, Dysprosia, Piolinfax, Jgm, SEWilco, Omegatron, Morven, Archivist, Jeffq, Fredrik, Chris 73, Matt me, Chris Roy, HaeB,
DocWatson42, Karn, Foobar, H Padleckas, Icairns, Vsmith, Adam850, Roybb95, Alistair1978, *drew, Art LaPella, RoyBoy, Robotje,
QTxVi4bEMRbrNqOorWBV, Nk, Pearle, Linuxlad, Ranveig, Velella, HenkvD, Randy Johnston, Gene Nygaard, Redvers, Isfisk, Tiger-
Shark, BeebleBrox6, Keydel, Graham87, Kbdank71, Old Moonraker, Nihiltres, RexNL, KFP, Kummi, The Rambling Man, Wolfmankurd,
Milena Popovic, Chris Capoccia, Chaser, Manop, Wimt, NawlinWiki, Janke, Sangwine, Brandon, Number 57, Wknight94, Thorney¿?,
DVD R W, Luk, Shoy, Markus Schweiss, Bmearns, Kopaka649, Edgar181, Ohnoitsjamie, Bluebot, Persian Poet Gal, Ce1984, MK8,
Thumperward, Akanemoto, Colonies Chris, Nick Levine, Rrburke, SundarBot, Nakon, John of Paris, Kukini, Rklawton, Beetstra, Hogyn
Lleol, BranStark, BananaFiend, TwistOfCain, Roswell native, RekishiEJ, Daniel5127, Americasroof, Iokseng, Lee Bailey, Flowerpotman,
CNMIN, Christian75, Bomzhik, Tunheim, Epbr123, Kablammo, Davidhorman, Roger S Johnson, Jonny-mt, Raditzu, Escarbot, EdJogg,
Rees11, AntiVandalBot, DJKingpin, Opelio, Jayron32, Myanw, JAnDbot, Instinct, Arch dude, ProjectPlatinum, Knowledgesmith, Bong-
warrior, CTF83!, Email4mobile, Allstarecho, DerHexer, MartinBot, Fredrosse, R'n'B, AlexiusHoratius, J.delanoy, Ian.thomson, McSly,
M-le-mot-dit, Jrcla2, Juliancolton, Treisijs, Steel1943, Valugi, Pirate King Tye, Wikieditor06, VolkovBot, Macedonian, Hqb, Ask123,
Qxz, Tiger1948, Andy Dingley, Meters, Joejack1029, Fanofranz, Ryetrustband, HybridBoy, Neparis, Kbrose, Biscuittin, SieBot, Yuweh,
Euryalus, Hertz1888, Mbz1, Caltas, Stevejobsforilife, Oda Mari, OKBot, Ronaldaroo, ClueBot, Hemalsj, The Thing That Should Not
Be, Drmies, Turbojet, Liempt, Alex0956, DragonBot, Excirial, Spoondoodle, DumZiBoT, XLinkBot, Martin Chaplin, Frood, The Tu-
tor, Kelly, Emok, Ronhjones, KorinoChikara, Couposanto, MrOllie, Jasper Deng, Tide rolls, Tressor, Teles, Senator Palpatine, Fraggle81,
, AnomieBOT, Jim1138, Galoubet, Accuruss, Trotnixon777, Celtis123, The High Fin Sperm Whale, Citation bot, Wikivendett,
Mike Dill, Muion, PeterEastern, Krish Dulal, I dream of horses, Calmer Waters, Full-date unlinking bot, Thrissel, ‫کاشف عقیل‬, Yunshui,
The goatlama, சதீஷ், JeepdaySock, Vaypertrail, Woolly wombat, Карма2, Wikipelli, K6ka, Ipwnedx, Macempty, Quondum, Erianna,
Cedric88, Somewhere12, ClueBot NG, Astatine211, Jack Greenmaven, Satellizer, O.Koslowski, Boblehest, Widr, MerlIwBot, Helpful
Pixie Bot, SchroCat, TheRealSteveJ, KillzHuman, Achowat, Raccoon5r, Urmom5r, Tutelary, Jonnyz007, Boblonam, Ks.magi, Rhys-
Lowe, Farhan911, Jcbmack, Bps633, Drluigi4212, Piercedvk, Wikisekharja, RustyOldShip, Ginsuloft, Bobbyeatschildren, Ratdz70095,
TheNorlo, Steviey1, Kingkingsorgs, Unbakedcake, Trackteur, The Expedia, Marsden107, Trollderpes, Falcondude123, Rumha Nexus,
102 CHAPTER 21. DISSOLVED AIR FLOTATION

Jerrodlack, Tinn36, Donaldmarfsion and Anonymous: 265


• Boiler Source: http://en.wikipedia.org/wiki/Boiler?oldid=635652482 Contributors: The Anome, Rjstott, Heron, Topory, Edward, Michael
Hardy, Stoddard, Mac, Ronz, Kragen, Jll, Jschwa1, Andrewman327, UninvitedCompany, Robbot, Seglea, ClemRutter, Buster2058,
Stroback, Giftlite, DocWatson42, Mintleaf, TDC, Mark.murphy, Solipsist, Khalid hassani, Bodnotbod, Beginning, Mormegil, Guanabot,
Quistnix, Surachit, Elipongo, Toh, Haham hanuka, Hooperbloob, Anthony Appleyard, Eric Kvaalen, InShaneee, Phreq, DV8 2XL, Tiger-
Shark, Camw, MONGO, Rtdrury, Tabletop, Oldie, Male1979, BD2412, Mendaliv, Josiah Rowe, Smithfarm, Crazynas, Bhadani, FlaBot,
Old Moonraker, Jared Preston, Bgwhite, Roboto de Ajvol, YurikBot, Wavelength, Retaggio, Huw Powell, Jimp, DMahalko, Mgway,
Peterkingiron, Epolk, Stephenb, Gaius Cornelius, Albedo, Syrthiss, DeadEyeArrow, Cinik, AjaxSmack, WAS 4.250, E Wing, N3362,
SmackBot, Jab843, Collieman, MerlinMM, Gilliam, Chris the speller, NCurse, Darth Panda, Addshore, Mini-Geek, Kellyprice, Mion,
John of Paris, Rg stephens, Tomhubbard, Mbeychok, 16@r, Peter Horn, Sgstarling, Hu12, DabMachine, Chanbc, Tomia, Barinmich,
Ollie, Mapsax, CmdrObot, MessedRobot, TheTito, Fletcher, Rifleman 82, Wordbuilder, Optimist on the run, VPliousnine, Wikid77,
Ning-ning, Dtgriscom, Miller17CU94, Northumbrian, Escarbot, EdJogg, BobbyDooley, Jim whitson, Lumbercutter, JAnDbot, Billy90210,
MER-C, Bahar101, Jrennie, Acroterion, Magioladitis, Bongwarrior, WikiSwami, Calltech, Pikolas, STBot, StaraBlazkova, Fredrosse,
Em Mitchell, CDM2, Bogey97, Stan J Klimas, Dreamer88, Warut, SriMesh, KylieTastic, DorganBot, KudzuVine, Earfetish1, Idioma-
bot, Tetris L, Freedml, Thomas.W, TXiKiBoT, Caster23, Piperh, BotKung, Andy Dingley, Riversong, Skipweasel, Biscuittin, SieBot,
Kazanrao, This, that and the other, Yintan, Johntindale, Sphilbrick, Roland Goossens, ClueBot, Flominator, Shinpah1, SuperHamster,
LizardJr8, Neverquick, Sv1xv, Mumiemonstret, Lasta, Maniago, Alexknight12, Thewellman, Vilkapi, XLinkBot, Dthomsen8, Silvonen-
Bot, Pravin chhaukar, Kbdankbot, Addbot, Betterusername, Mr. Wheely Guy, Chzz, Ginosbot, Farmercarlos, Tide rolls, Anyname21,
Zorrobot, V.chen96, Luckas-bot, Yobot, Jdonohue41, Stelterbrinck, Daniele Pugliesi, Jim1138, RadioBroadcast, Citation bot, ‫رضا‬.‫محمد‬,
TheAMmollusc, TechBot, Mononomic, Al-Zayani, Ιων, Uhhhhhh, Erik9, Thehelpfulbot, Odney, FrescoBot, Sankararkv, Muion, Can-
nolis, Pinethicket, Subhendumishra29, GeeZ, Vrenator, Diannaa, ThinkEnemies, Jesse V., Benzy16, GoingBatty, Erpert, Cathodic, Ego
White Tray, Munay09, X sprainpraxisL, Xanchester, Mark886, ClueBot NG, AnswerManDan, Widr, Electriccatfish2, Ringedslink, Sid-
dhu.iam, Northamerica1000, Sarahliaoye, Mark Arsten, Zedshort, Khazar2, SreejanAlapati, Jiru27, Ghorpaapi, Schmetterling5, Ab-
hishek20061994, JaconaFrere, Mansoor bhutta, Trackteur, Nimrainayat6290, Sakko303, Blazebtw and Anonymous: 295
• API oil-water separator Source: http://en.wikipedia.org/wiki/API%20oil-water%20separator?oldid=627606251 Contributors: Wt-
mitchell, Rjwilmsi, AndreasJS, Mbeychok, Snezzy, Zuluct, CZmarlin, Max736, Beagel, User A1, Andy Dingley, ClueBot, Addbot, Hy-
droflo, Dceron, Luckas-bot, Jimenvironmental, Daniele Pugliesi, Xqbot, ‫عبد المؤمن‬, Micasta, I dream of horses, HRoestBot, Gamewiz-
ard71, Trappist the monk, Lv58, Robinwizard and Anonymous: 12
• Dissolved air flotation Source: http://en.wikipedia.org/wiki/Dissolved%20air%20flotation?oldid=622055757 Contributors: Xezbeth,
Longhair, Shenme, Maurreen, Pearle, Versageek, Grafen, Chrishmt0423, SmackBot, Bluebot, Langbein Rise, BWKA, James084,
ILike2BeAnonymous, Mbeychok, IronGargoyle, Amalas, Bharatdandekar, Mattisse, MarshBot, Karlhahn, Beagel, User A1, SmileJohn,
Lavenircestlautre, Moreau1, Shinkolobwe, Cleanwatertech, Addbot, Hydroflo, Splodgeness, Enysjg, Dceron, Daniele Pugliesi, Citation bot,
FrescoBot, Citation bot 1, Gamewizard71, John Cline, Sophie VIS, ChuispastonBot, EdoBot, ClueBot NG, LukaszKatlewa, Stefan.p21,
Mark Arsten, BluesLewis, Vardenafil and Anonymous: 21

21.6.2 Images
• File:API_Separator.png Source: http://upload.wikimedia.org/wikipedia/commons/9/9c/API_Separator.png License: CC-BY-SA-3.0
Contributors: Originally from en.wikipedia; description page is/was here. Original artist: Original uploader was Mbeychok at en.wikipedia
• File:AlbertaSulfurAtVancouverBC.jpg Source: http://upload.wikimedia.org/wikipedia/commons/f/fa/AlbertaSulfurAtVancouverBC.
jpg License: CC SA 1.0 Contributors: English Wikipedia, original upload 10 July 2005 by Leonard G. Original artist: Leonard G.
• File:AmineTreating.png Source: http://upload.wikimedia.org/wikipedia/commons/f/f9/AmineTreating.png License: CC-BY-SA-3.0
Contributors: ? Original artist: ?
• File:Anacortes_Refinery_31911.JPG Source: http://upload.wikimedia.org/wikipedia/commons/5/51/Anacortes_Refinery_31911.JPG
License: CC-BY-SA-3.0 Contributors: Own work Original artist: Walter Siegmund (talk)
• File:Anacortes_Refinery_32017.JPG Source: http://upload.wikimedia.org/wikipedia/commons/2/2c/Anacortes_Refinery_32017.JPG
License: CC-BY-SA-3.0 Contributors: Own work Original artist: Walter Siegmund (talk)
• File:BP_PLANT_EXPLOSION-1_lowres2.jpg Source: http://upload.wikimedia.org/wikipedia/commons/7/71/BP_PLANT_
EXPLOSION-1_lowres2.jpg License: Public domain Contributors: http://www.csb.gov/assets/news/image/BP_PLANT_
EXPLOSION-1_lowres2.jpg Original artist: Chemical safety and hazards investigation board
• File:Barnard’{}s_fanless_self-cooling_tower.jpg Source: http://upload.wikimedia.org/wikipedia/commons/8/86/Barnard%27s_
fanless_self-cooling_tower.jpg License: Public domain Contributors: Illustration from A Textbook on Steam Engineering. Scranton, PA:
International Textbook Company. Sectionb 29: p. 39. Digital scan at http://archive.org/details/textbookonsteame04inteiala Original artist:
Unsigned engraving; book by International Textbook Company
• File:Benzene_Friedel-Crafts_alkylation-diagram.svg Source: http://upload.wikimedia.org/wikipedia/commons/f/f4/Benzene_
Friedel-Crafts_alkylation-diagram.svg License: CC BY 3.0 Contributors: Own work Original artist: Pen1234567
• File:Buckminsterfullerene-perspective-3D-balls.png Source: http://upload.wikimedia.org/wikipedia/commons/0/0f/
Buckminsterfullerene-perspective-3D-balls.png License: Public domain Contributors: ? Original artist: ?
• File:Carboxylic_acid_dimers.png Source: http://upload.wikimedia.org/wikipedia/commons/c/c9/Carboxylic_acid_dimers.png License:
Public domain Contributors: ? Original artist: ?
• File:CatReformer.png Source: http://upload.wikimedia.org/wikipedia/commons/2/21/CatReformer.png License: CC-BY-SA-3.0 Con-
tributors: I drew this flow diagram myself and currently I own all rights to it. I used Microsoft’s Paint program to draw it. I am User:mbeychok
and the date is December 5, 2006. Original artist: User:mbeychok
• File:CatReformerEq4.png Source: http://upload.wikimedia.org/wikipedia/commons/6/63/CatReformerEq4.png License: CC-BY-SA-
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tors: Originally from en.wikipedia; description page is/was here. Original artist: Original uploader was Mbeychok at en.wikipedia
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Lück alias Schreibschaf
104 CHAPTER 21. DISSOLVED AIR FLOTATION

• File:Dehydrocyclization_reaction_of_heptane_to_toluene.svg Source: http://upload.wikimedia.org/wikipedia/commons/9/95/


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• File:Delayed_Coker.png Source: http://upload.wikimedia.org/wikipedia/commons/c/c1/Delayed_Coker.png License: Public domain
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sulphide.jpg License: CC-BY-SA-3.0 Contributors: Own work Original artist: Stan Zurek
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%28SEM%29_2.jpg License: Public domain Contributors: This media comes from the Centers for Disease Control and Prevention's Public
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106 CHAPTER 21. DISSOLVED AIR FLOTATION

• File:Steam_Boiler_2_English_version.png Source: http://upload.wikimedia.org/wikipedia/commons/1/18/Steam_Boiler_2_English_


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MD, 20899, http://webbook.nist.gov, (retrieved November 2, 2010).) Original artist: Emok
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3.0 Contributors: The photograph was obtained from http://resources.schoolscience.co.uk/SPE/knowl/4/2index.htm?vacuum.html which
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• File:Water_droplet.jpg Source: http://upload.wikimedia.org/wikipedia/commons/e/ec/Water_droplet.jpg License: CC-BY-SA-3.0 Con-
tributors: ? Original artist: ?
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