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FLOW SHEET SYNTHESIS AND DEVELOPMENT

complexity Optimal
Flowsheet: + design
rational evaluation results

𝑚𝑜𝑠𝑡 𝑝𝑟𝑜𝑓𝑖𝑡𝑎𝑏𝑙𝑒
𝑚𝑜𝑠𝑡 𝑜𝑝𝑡𝑖𝑚𝑎𝑙 = 𝑠𝑎𝑓𝑒
𝑒𝑛𝑣𝑖𝑟𝑜𝑛𝑚𝑒𝑛𝑡𝑎𝑙𝑙𝑦 𝑠𝑜𝑢𝑛𝑑 𝑑𝑒𝑠𝑖𝑔𝑛
Procedures of constructing flow sheet
2

1. Hierarchical method based on heuristic rules


derived from past experience
Excellent for reasonably routine chemical plants and
less successful for complex plant

2. Algorithmic method
Utilizes mathematical programming procedures that
includes optimization technique
Hierarchical
Method

3
4
General Procedures in hierarchical methods
5

1. Process information
 Conduct a search of the technical and patent literature
 Study market condition and pricing

2. Input / Output (I/O) diagram


 Study all potential chemical reactions paths
 Do preliminary economic analysis of each path
 Eliminate those for which price of product < raw
material
 Eliminate those do not seem feasible
Benzene
Dodecene Water
AlCl3
Water Process
Sodium Dodecyl
H2SO4 Benzene Sulfonate
NaOH

I/O diagram for the production of sodium dodecylbenzene sulfonate

6
3. Function Diagram
7

 Indicate all the major functions of the process and


material in and out from these functions
 Show pre-process needed to meet the requirement
(pre-process box)
 Indicate flow rates (see Fig. 4-2-b)

 Suggest heat flow using the symbol “Q”


Function diagram for the production of sodium dodecylbenzene sulfonate

8
4. Operations diagram
9

 Select the technology suitable to achieve the


operation
 Choose the processing technology to accomplish the
temperature changes, phase change..etc.
 Determine type of the reactor

 Estimate range of T, P, x, selectivity

 Examine the technologies available to determine


whether phase separation should be used.
 Select finishing technology
Operations diagram for the production of sodium dodecylbenzene sulfonate

10
5. Flowsheet
11

Shows
Detailed separation steps
Detailed reaction sections
Detailed processes such as reaction, separation,
mixing….etc are shown
Final flowsheet
12
6. Base case design
13

 The above procedures may result in many


candidate flowsheets.
• Review each flowsheet
• Make detailed energy and material balance
• Make detailed economic analysis
• Check product satisfy the requirement
• Does it meet the health and safety rules
• Based on this some flowsheets may be eliminated!
Process Information
A. Back ground information
14

Basis to establish potential chemical processes:


 Use complete existing designs

 Modify an existing one

 Use part of an existing design

 Develop new design

 Extensive research is needed for all of the four


approaches.
Back ground information (continues)
15

 The search begins with:


 Handbooks
 Encyclopedia
 Textbooks
 More specifications are sought into
 Journals
 Patents
 Database
 Expert consultant
 Acquire specific information such as kinetic data,
thermodynamic data, prices…
 Note that laboratory measurements may be needed at
this stage.
Process Information
16
B. Molecular path synthesis
Molecules and its structure determine the nature of products. Steps might be
needed to go from the raw material to the final product (reaction train)

∗ 𝑦𝑖𝑒𝑙𝑑
𝑓𝑎𝑐𝑡𝑜𝑟𝑠 𝑡ℎ𝑎𝑡 𝑚𝑎𝑘𝑒𝑠 𝑎𝑠𝑠𝑒𝑠𝑠𝑚𝑒𝑛𝑡 𝑜𝑓
∗ 𝑏𝑦 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 𝑠𝑦𝑛𝑡ℎ𝑒𝑠𝑖𝑠 𝑑𝑖𝑓𝑓𝑖𝑐𝑢𝑙𝑡
∗ 𝑎𝑑𝑑𝑖𝑡𝑖𝑜𝑛𝑎𝑙 𝑝𝑟𝑜𝑐𝑒𝑠𝑠𝑖𝑛𝑔 𝑠𝑡𝑒𝑝𝑠

 In most cases it is difficult and very expensive to start with simple species.

 Selecting the appropriate reaction may be determined from the product


backwards.
Rules of thumb
17

 Divide molecules into subsections

sodium dodecylbenzene sulfonate


Rules of thump (continues)
18

 Divide molecules into repeating subsections

Polyacrylonitrile Polyethylene oxide


Rules of thump (continues)
19

 Divide subsections into functional groups

Benzyl acetate
Rules of thump (continues)
20

 Limit bond formation through steric hindrance either


permanent or temporarily

 Build more complex molecules

 Cut rings to make linear molecules

 Look for readily available inexpensive material


Process Information
21
C. Selecting a process path
 Use existing chemical process

 If a patent is involved then calculate the cost and


compare to different available process not covered
with patent

 Developing a new process is expensive and time


consuming but it may provide competitive
advantage.
Process Information
22
D. Selecting a process mode
Continuous Batch
Common Greater flexibility

𝑯𝒊𝒈𝒉 𝒂𝒗𝒆𝒓𝒂𝒈𝒆 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝒓𝒂𝒕𝒆 𝑳𝒐𝒘 𝒂𝒗𝒆𝒓𝒂𝒈𝒆 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝒓𝒂𝒕𝒆


𝒆𝒒𝒖𝒊𝒑𝒎𝒆𝒏𝒕 𝒔𝒊𝒛𝒆 𝒆𝒒𝒖𝒊𝒑𝒎𝒆𝒏𝒕 𝒔𝒊𝒛𝒆

Consistent product quality Lower quality

Consistent operating conditions Variable operating condition

Less labor Labor demand is large


Opportunity to choose the same
equipment for different product or
purpose
Rules of thumb for selecting Batch mode
23

 Production rate < 500 t/yr


 Expecting heavy fouling

 For biological processes

 For pharmaceutical processes

 Short (1 – 2 yr) life span

 Product value >> total product cost


Process Information
24
E. Recording decisions

At each branch point a decision must be made


to determine the path to be followed.
Example 4-1:
Production of Vinyl Chloride (VC) [C2H3Cl]
25

Required: develop information on potential reaction pathways and


physical and operational properties involved in VC production

Given:
 Capacity = 500000 t/yr

 VC and other chemicals involved in its production are toxic and


flammable
 It is corrosive material specially at high T and in the presence of
water
 HCl: corrosive, inhalation of the fumes causes coughing, choking,
inflammation of the nose, throat and upper respiratory system, burns
to the eye, skin irritation.
Production of VC (continues)
26

Answer
 Mode of operation = continuous (large production

> 5000 t/yr)


 Strict control = toxic material

 HCl: very corrosive in the presence of water then

must be dried < 10 ppm


 MOC: Industrial glass, carbon carbate, plastic,

Hastelloy B (see pp. 447), Inconel (see pp. 450|).


Production of VC (continues)
Reactions pathways
27

1. Acetylene hydrochlorination

C2H2 + HCl C2H3Cl

2. Ethylene direct chlorination

C2H4 + Cl2 C2H3Cl + HCl


Reactions pathways (continues)
28

3. Ethylene chlorination + 1,2-dichloethane pyrolysis

C2H4 + Cl2 C2H4Cl2


C2H4Cl2 C2H3Cl + HCl

C2H4 + Cl2 C2H3Cl + HCl (overall)


Reaction Pathways (continue)
29

4. Oxychlorination + 1,2-dichloroethane pyrolysis

C2H4 + 2HCl + ½ O2 C2H4Cl2 + H2O

C2H4Cl2 C2H3Cl + HCl

C2H4 + Cl2 + ½ O2 C2H3Cl + H2O (overall)


Reaction pathways (continue)
30

5. Chlorination + oxychlorination plus pyrolysis

C2H4 + Cl2 C2H4Cl2

C2H4 + 2HCl + ½ O2 C2H4 Cl2 + H2O

2 C2H4Cl2 2C2H3Cl + 2HCl

2C2H4 + Cl2 + ½ O2 2C2H3Cl + H2O (overall)


I/O structure diagram development.
Economic analysis to produce 1 kgmol of VC = 62 kg
(prices of 2002)
31

Species MM Price Reaction Path


Kg/km $/kg 1 2 3 4 5
ol
Cl2 70 0.03 0.0 -2.1 -2.1 0.0 -1.05
HCl 36 0.22 -7.92 7.92 7.92 -7.92 0.0
C2H2 26 1.39 -36.14 0.0 0.0 0.0 0.0

C2H4 28 0.45 0.0 -12.6 -12.6 -12.6 -12.6


C2H3Cl 62 0.45 27.9 27.9 27.9 27.9 27.9

O2 32 0.04 0.0 0.0 0.0 -0.64 -0.32


Net -16.16 21.12 21.12 6.74 13.93
value
Decisions #1: Pathway 1 is not suitable and should be
eliminated since the process is not feasible economically.
32

Species MM Price Reaction Path


Kg/km $/kg 1 2 3 4 5
ol
Cl2 70 0.03 0.0 -2.1 -2.1 0.0 -1.05
HCl 36 0.22 -7.92 7.92 7.92 -7.92 0.0
C2H2 26 1.39 -36.14 0.0 0.0 0.0 0.0

C2H4 28 0.45 0.0 -12.6 -12.6 -12.6 -12.6


C2H3Cl 62 0.45 27.9 27.9 27.9 27.9 27.9

O2 32 0.04 0.0 0.0 0.0 -0.64 -0.32


Net -16.16 21.12 21.12 6.74 13.93
value
Decisions #2: Path 2 can be eliminated.
33

Path 2 and 3 are similar. Literature indicates that when


ethane reacts with chlorine the result is mainly ethylene
dichloride and not VC

See Allen, D. T. "Chapter 4 - Industrial Ecology". Green


Engineering. United States Environmental Protection
Agency
34

Species MM Price Reaction Path


Kg/kmol $/kg 3 4 5

Cl2 70 0.03 -2.1 0.0 -1.05


HCl 36 0.22 7.92 -7.92 0.0
C2H2 26 1.39 0.0 0.0 0.0
C2H4 28 0.45 -12.6 -12.6 -12.6
C2H3Cl 62 0.45 27.9 27.9 27.9
O2 32 0.04 0.0 -0.64 -0.32
Net 21.12 6.74 13.93
value
Decisions (continue)
35

Comparing 3, 4 and 5 it seems that path 3 is the best.


Now to come up with solid conclusion check the
average price over past years (say 10 years). Notice
that Cl2 price is very small and an increase in its price
may flip the decision. So assume the followings prices
are the prices averaged over 8 years then the picture
becomes:
Calculation to produce 1 kgmol of VC =
62 kg (8 years average prices)
36

MM Price Reaction Path


Species
Kg/kmol $/kg 3 4 5
Cl2 70 0.21 -14.7 0.0 -7.35
HCl 36 0.27 9.72 -9.72 0.0
C2H4 28 0.53 -14.84 -14.84 -14.84
C2H3Cl 62 0.41 25.42 25.42 25.42
O2 32 0.04 0.0 -0.64 -0.32
Net
5.6 0.22 2.91
value
37

Reaction Path Reaction Path


MM
Price Price
Species Kg/kmo
$/kg 3 4 5 $/kg 3 4 5
l

Cl2 70 0.03 -2.1 0.0 -1.05 0.21 -14.7 0.0 -7.35


HCl 36 0.22 7.92 -7.92 0.0 0.27 9.72 -9.72 0.0
C2H2 26 1.39 0.0 0.0 0.0 - - -
C2H4 28 0.45 -12.6 -12.6 -12.6 0.53 -14.84 -14.84 -14.84
C2H3Cl 62 0.45 27.9 27.9 27.9 0.41 25.42 25.42 25.42
O2 32 0.04 0.0 -0.64 -0.32 0.04 0.0 -0.64 -0.32
Net
21.12 6.74 13.93 5.6 0.22 2.91
value
Decision: Path 4 cannot compete with 3 and 5 hence it is
eliminated and we are left with path 3 and 5.
38

Species MM Price Reaction Path


Kg/kmol $/kg 3 5
Cl2 70 0.21 -14.7 -7.35
HCl 36 0.27 9.72 0.0
C 2 H4 28 0.53 -14.84 -14.84
C2H3Cl 62 0.41 25.42 25.42
O2 32 0.04 0.0 -0.32
Net value 5.6 2.91
Decision: The only feasible pathway is path # 5.
39

 Comparing 3 and 5, the economy depends strongly on


HCl which is a product and it is assumed that it will be
sold. Now for a weak market of HCl no profit is made
and hence the value 9.7 should be replaced. Hence
the sum becomes 5.6 - 9.72 = -4.12.
 Note: references say that 95% of VC is produced via
path 5. See
 http://www.thyssenkrupp-
uhde.de/fileadmin/documents/brochures/uhde_brochu
res_pdf_en_8.pdf
Conclusion
40

5. Chlorination + oxychlorination plus pyrolysis

C2H4 + Cl2 C2H4Cl2

C2H4 + 2HCl + ½ O2 C2H4 Cl2 + H2O

2 C2H4Cl2 2C2H3Cl + 2HCl

2C2H4 + Cl2 + ½ O2 2C2H3Cl + H2O (overall)


I/O diagram for the Production of VC by
Chlorination + oxychlorination plus pyrolysis
41

C2H4 + Cl2 ==== C2H4Cl2


2C2H4
2C2H3Cl
C2H4 + 2HCl + ½ O2 ==== C2H4Cl2 + H2O
Cl2
H2O
2 C2H4Cl2 ==== 2C2H3Cl + 2HCl
½ O2

2 C2H4 + Cl2 + ½ O2 ==== 2C2H3Cl + H2O


Functions Diagram
42

It is the identification of the major units and its function


in the plant. It is represented by a block showing the
feed and the exit from these units. The quantities
should be shown as well. Any subsequent unit or
processing unit should be shown. Recycle streams
should also be shown. Details
Functions Diagram (continues)
43

Preprocessing
 Heating or cooling the raw material
 Reduce impurities to acceptable levels.
 Remove harmful materials as complete as possible
 Remove (reduce) impurities if they affect the
economics of the plant
 Do not separate inert if they are not harmful to the
plant
Functions Diagram (continues)
44

Reactions
 Show data needed for each main reactor

 Information needed to specify type of the catalyst,

type of the reactor, kinetic data, operating


conditions, phase, conversion, yield,

Recycle
Functions Diagram (continues)
45

Rules:
 Recycle raw material that appears in the product

(output streams)
 Mixtures of components that need to be recycled
should not be separated (do not separate mixtures
that will be mixed again)
 Generally there is an optimum recycle/purge ratio

 Whenever possible, recycle material as liquid

rather than gases


Functions Diagram (continues)
46

 By products, Intermediate and Wastes


co-product: C2H4 + Cl2 C2H3Cl + HCl

by-product: C2H4 + 2HCl + ½ O2 C2H4Cl2 + H2O

C2H4Cl2 C2H3Cl + HCl

C2H4 + HCl + ½ O2 C2H3Cl + H2O (overall)


Functions Diagram (continues)
47

Intermediate:

Intermediate
C2H4 + Cl2 ==== C2H4Cl2

C2H4 + 2HCl + ½ O2 ==== C2H4Cl2 + H2O

2 C2H4Cl2 ==== 2C2H3Cl + 2HCl

2 C2H4 + Cl2 + ½ O2 ==== 2C2H3Cl + H2O

Waste
Functions Diagram (continues)
48

Separations
Guidelines:
 Reactor products (product, co-product, by-product,

intermediate) need to be separated. Reactants are


recycled
 Separation involves energy are indicated by arrows

with Q
Functions Diagram (continues)
49

Example: Function diagram for VC production

Chlorination + oxychlorination plus pyrolysis

C2H4 + Cl2 C2H4Cl2

C2H4 + 2HCl + ½ O2 C2H4 Cl2 + H2O

2 C2H4Cl2 2C2H3Cl + 2HCl

2C2H4 + Cl2 + ½ O2 2C2H3Cl + H2O (overall)


Functions Diagram (continues)
50

C2H4 + Cl2 ↔C2H4Cl2


o It occurs rapidly at 65oC < C2H4, Cl2
200oC C2H4 Cl2

o The reaction media is liquid


EDC Reactor # 1 (R-1) Separator C2H4Cl2
Chlorination reactor C2H4Cl2
o ALCl3 is used as a catalyst S-1
T=65 – 200oC
P=150 – 1200 kPa
o Preactor ≥ Pv of EDC exothermic
Q
o Conversion is ~ 100% Q

o Conversion to EDC is > 99.5%


Impurities
o Reactants are provided nearly
pure

o Reactants are in gaseous form

o The reaction is exothermic


Functions Diagram (continues)
51

2 C2H4Cl2↔2C2H3Cl + 2HCl
C2H4Cl2
EDC is pure
C2H4Cl2
The reaction occurs at 475oC < T <
525oC
C2H3Cl
Reactor # 2 (R-2) C2H4Cl2 Separator C2H3Cl
The reaction is endothermic
Pyrolysis reactor HCL
Reaction pressure ranges from 1.5-3 S-2
T=475 – 525oC
Mpa P=1.5 – 3 MPa
Endothermic
Conversion is 53 to 63% Q
Q HCL
Residence time 2 – 30 s to prevent
VC from decaying

Conversion of EDC to VC > 99% Impurities

Rapid cooling is a must to avoid


product loss
Functions Diagram (continues)
52

C2H4 + 2HCl + ½ O2 ↔
C2H4 Cl2 + H2O

CuCl2 is used as a catalyst C2H4, HCl, O2


C2H4 HCl O2
20oC < T <300oC

0.25 < P < 1.5MPa Separator C2H4Cl2


Reactor # 3 (R-3)
The reaction is highly exothermic Oxychlorination reactor
C2H4Cl2 S-3
T=220 – 300oC
Conversion is 94 to 99% for Eth. P=0.25 – 1.5 MPa H2O
exothermic HCl
Conversion is 98 to 99.5% for HCl O2 Q
Q C2H4
Conversion of O2 is 100%

EDC yield is 94 – 97%


Impurities, H2O
EDC must be purified to at least
99.5%

Water content must be < 10 ppm


Functions Diagram (continues)
53

2 C2H4Cl2↔2C2H3Cl + 2HCl
C2H4Cl2
EDC is pure
C2H4Cl2
The reaction occurs at 475oC < T <
525oC
C2H3Cl
Reactor # 2 (R-2) C2H4Cl2 Separator C2H3Cl
The reaction is endothermic
Pyrolysis reactor HCL
Reaction pressure ranges from 1.5-3 S-2
T=475 – 525oC
Mpa P=1.5 – 3 MPa
Endothermic
Conversion is 53 to 63% Q
Q HCL
Residence time 2 – 30 s to prevent
VC from decaying

Conversion of EDC to VC > 99% Impurities

Rapid cooling is a must to avoid


product loss
54
Operations Diagram
55

The aim is to determine the type of the process


equipment necessary to accomplish the function
previously identified. Key conditions are specified (T,
P). The operations are:

Preprocessing:
 Heating, cooling, purification, conditioning,
Operations Diagram (Reactors)
56

 Type of reactor, operating T and P, residence time,


catalyst, space velocity, how to achieve good
contact between catalyst and reactants, T control,
kinetics, conversion….

 Note if a range of T and/or P is involved choose


the average.
Operations Diagram (Separation Method)
57

 Select the physicochemical properties to choose the


suitable separation method.
Operations Diagram (Separation Method)
58

Property Separation method Volatility Flash


Size Screening vaporization
Filtration Distillation
Molecular sieve Drying
Filtration Evaporation
Settling
Solubility Absorption
Centrifugal settling
Cyclone Adsorption
Flotation Extraction
Leaching
Charge Ion exchange Permeability Membrane
Electrostatic precipitator Phase change Crystallization
Melting
Solidification
Operations Diagram (Rules)
59

 List possible (potential) separation techniques


 Choose the easiest, cheaper, lead to high
purity…etc.
 Use distillation if the relevant volatility of key
component > 1.2
 Go with known techniques
 Avoid introducing foreign species
 Energy based technologies are favored over mass
based technologies
Operations Diagram (Heating and Cooling)
60

 Specify source of heating and cooling


 Cooling to 20oC can be achieved by cooling water.
For lower temperatures use refrigeration.
 Use combustion to heat to above 400oC .
 Use steam or hot streams for T < 400oC
 Minimize energy consumption
Operations Diagram
(Minimization of Processing)
61

When possible combine processes in one equipment


(reactive distillation, absorption..etc.)
Operations Diagram
62

Example Select equipment type of VC


production process
Reactor #1
63

Q = -90 kJ
Reactor # 1 (R-1)
Chlorination reactor C2H4Cl2
T=65 – 200oC 183oC
P=.15 – 12 MPa 1MPa
exothermic

Cooling
1. Coil
2. Jacket
3. External
C2H4 + Cl2
Separator
64

Conversion > 99.5% C2H4 Cl2


C2H4, Cl2

Hence the product is


Separator C2H4Cl2
Almost pure and hence Reactor # 1 (R-1)
Chlorination reactor C2H4Cl2
S-1
no need For a T=65 – 200oC
P=150 – 1200 kPa
exothermic
separator after R1 Q
Q

Impurities
Reactor #2
65

 The reaction is endothermic


 No catalyst is required Exhaust gas
 T > (500oC)
Heat
 Immediate cooling of VC
exchanger
VC
The heat exchanger HCl
* Spraying cold vapor EDC
Flame
* Heat exchanger

Fuel + air
Separator
66

HCl to R3
Chemical Boiling point
HCl -32oC
VC 58oC Q

Separator#1
VC
EDC 183oC
EDC
Q
HCl EDC to the
VC Pyrolysis
250oC

Separator#2
reactor

EDC
Q
Impurities
Reactor #3
67

Highly exothermic
CuCl2 pellets
220<T<300 260oC
0.25<P<1.5 1MPa
Exothermic HCl
Catalyst: CUCl2 O2C2H4

Possible reactors
Fluidized bed EDC
Water
Packed as HE
Cooling Media C2H4
HCl
O2
Reactor#3 product treatment
68

Conversion is 94 to 99% for


Eth. CuCl2 pellets

Conversion is 98 to 99.5%
for HCl
HCl
Conversion of O2 is 100% O2
C2H4
EDC yield is 94 – 97%

EDC must be purified to at


least 99.5%
EDC
Water
Water content must be < 10
ppm Cooling Media C2H4
HCl
O2
Reactor#3 product treatment (continues)
69

C2H4, HCl to separation

Reactor#3
output
EDC
Water
Cooling
HCl
EDC should C2H4

Not have
EDC+Water
More than To
10 ppm water separation
70
Operation diagram of VC production
Process Flow Sheet
71

It is the final step where key equipment performance,


mass balance, energy balance, define separation units,
develop heat integration…is performed.

Reactor
A given conversion, yield is assumed. This will improve
mass and energy balance. Appropriate equilibrium, mass
transfer and kinetic models are used to size the reactor to
achieve the selected conversion. The assumed variables (x,
T, P are then optimized to achieve final design.
Mass and Energy Balance
72

Approximate mass and energy balances must be


conducted. Convenient basis are chosen (100 kmol or 100
kg of the desired product). Separation processes should
be well defined to determine its energy needs. Example:
reflux ratio, operating pressure. The pressure is
established from the neighboring unit.

Separation Train
 To separate a mixture containing m component you
need m-1 separation unit
 Need not to be of the same technology
Rules of Thumb
73

 Reduce the separation load by splitting or blending streams


 Difficult separations are left for last
 Remove high concentration component early in the sequence
 Remove component not normally present in the process soon
after using
 Avoid wide excursion in T and P
 Cooling at T above ambient is cheap, heating is expensive
 Cooling at T below ambient is expensive heating is cheap
Rules of thumb for distillation
74

 Remove thermally unstable, corrosive and reactive


components early.
 Remove final product one by one starting with the most
volatile.
 Remove components present in large amounts first
 Leave most difficult components to separate to the last
 Sequence of separation is in order of increasing product
quality
 Sequence so that the top and bottom product are of same
flow rates
 If not possible to apply all of the above rules, apply them in
the sequence they appear.
Heat exchange
75

Search for opportunities to save energy


Flow Sheet for PVC

76

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