Basic Refining & Petrochemical

University of Danang,
Honeywell,
University of Science and
UOP, USA
 Supply and Demand – Driven by Price

• Multiple technologies are used to make the commodity product.

• Not every technology and every producer has the same cost structure.
• Means different producers will produce different amounts at different prices.
2
Energy: Sources and Uses

3
Competition for Resources

Should we make fuels, or make petrochemicals?

4
Refining

5
 Nature of Petroleum

➢ Petroleum is derived from the remains of macroscopic marine life which

existed in pre-historic oceans and seas.

Petroleum = Petra (Rock) + Oleum (Oil)

Synonyms = Crude Oil, Rock Oil

➢ Other sources of petroleum include: bitumen, tar sands, tar pits, shale, coal.

6
Nature of Petroleum

➢ Can vary from a white liquid to a

black, asphaltic, semi-solid form.

➢ Complex mixture of related organic

compounds called hydrocarbons.

➢ Some inorganic contaminates e.g.

sulfur, metals, oxygen, and nitrogen
occur in small quantities.

➢ Crude oils often arrive with free

water containing mineral salts.

7
Crude Oil Composition (wt%)

Atom Weight %

Carbon (C) 84 - 87

Hydrogen (H) 11 - 14

Sulfur (S) 0.1 - 2.0

Nitrogen (N) 0.01 - 0.2

Metals 0 - 0.1

8
Hydrocarbons

➢ Hydrocarbons are a class of compounds made up of hydrogen (H)

and carbon (C) atoms.

➢ Crude and crude products are mixtures of many hundreds of

hydrocarbons.

➢ H and C are chemically combined or bonded in different ways to

make hydrocarbons.

➢ As the number of carbon atoms increases, the boiling point

increases.

➢ Most refinery chemistry focuses on three hydrocarbon families:

paraffins, aromatics, and olefins.

9
Paraffins (Alkanes)

➢ Members of the paraffin family all have a single bond between each
carbon atom.

➢ Paraffins can have one of three different shapes

▪ Straight line, called normal or n-paraffins
▪ Branched, called iso-paraffins
▪ Ring shaped, called cycloparaffins or naphthenes

10
n-Paraffins

➢ Straight chained single bonded hydrocarbons

➢ Name ending in – ane

➢ Chemical Symbols
➢ CnH2n+2
Ethane C2H6
➢ Ranging from C1 to C50+
➢ Saturated
➢ Each molecule contains maximum amount of hydrogen
➢ No double bonds or impurities
➢ Stable
➢ Paraffinic / Waxy

n-Butane C4H10 CnH2n+2 11

iso-Paraffins

➢ Branched chained single bonded hydrocarbons

➢ Name ending in – ane

➢ Chemical Symbols
▪ CnH2n+2
▪ Ranging from C1 to C50+
➢ Saturated
iso-Butane C4H10
▪ Each molecule contains maximum amount of hydrogen
▪ No double bonds or impurities
▪ Stable
▪ Paraffinic / Waxy
➢ Higher octane than n-paraffins
▪ Important for gasoline blending

iso-pentane C5H12 12
Cyclo-Paraffins (Naphthenes)

➢ Ringed single bonded hydrocarbons

➢ Name ending in – ane

➢ Chemical Symbols
▪ CnH2n
▪ May contain several combined rings Cyclohexane C6H12

➢ Saturated
▪ Each molecule contains maximum amount
of hydrogen
▪ No double bonds
▪ May contain N or S impurities
▪ Stable
Methyl cyclopentane C6H12

13
Olefins (Alkenes)
➢ Double bonded hydrocarbons
➢ Name ending in – ene
➢ Chemical symbols
▪ CnH2n for 1 double bond
▪ Denoted by showing double bond as superscript: Butene C4H8
C4= for butene isomers

➢ Diolefins
▪ 2 double bonds
▪ Name ending in - diene
➢ Unsaturated
▪ Lacking some hydrogen due to double bonds
▪ Unstable – highly reactive
▪ Not normally found in nature (crude oil) Pentadiene C5H8
▪ Formed in refinery processes that crack without the
presence of hydrogen
▪ Saturate readily in hydrotreating reactors
14
Aromatics
➢ Ringed alternating double bonded hydrocarbons – benzene ring based

➢ Name ending in – ene

➢ Chemical symbols
Butene C4H8
▪ CnHn for base rings
▪ Can have sub groups - methyl, ethyl, etc
➢ Types
▪ Benzene, toluene, xylenes (BTX)
▪ Polynuclear aromatics (PNA) Toluene
➢ Two or more connected benzene rings

➢ Unsaturated
▪ Lacking hydrogen due to 3 double bonds per ring
▪ Double bonds very reactive
▪ High octane gasoline component
Polynuclearomatic PNA
15
Hydrocarbon Symbology
➢P = Paraffin

➢ P6 = Paraffin with 6 carbons

➢ P7 = Paraffin with 7 carbons

➢ P8 = Paraffin with 8 carbons . . . and so on

➢ Same numbering system for naphthenes (N) & aromatics (A)

➢ n-C6 = Normal Hexane (P6)

➢ CP = Cyclopentane (CP5)

➢ MCP = Methyl Cyclopentane

➢ CH = Cyclohexane (N6)

➢ BZ = Benzene (A6)

➢ R, R’ = Radicals or side chains attached to a ring

16
Sulfur Compounds in Petroleum

R—S—H R—S—S—
R’
Mercaptan Disulfide

S S
Thiophene Benzothiophene

S CH3
CH3 S
Substituted Benzothiophene Dibenzothiophene
17
Nitrogen Compounds in Petroleum

Basic Nitrogen – Nitrogen has extra lone pair of electrons to facilitate the
reaction

N
NH
H C 2
3 N N

Amine Pyridine Quinoline Phenanthridine

NH NH
Indole Carbazole

Non-Basic – The Nitrogen lone pair of electrons is delocalized in the ring

structure making the molecule less reactive. 19
Nitrogen Distribution

➢ Nitrogen rises as boiling range increases

➢ As boiling range increases, the complexity of the organic nitrogen

molecules also increase, making the nitrogen more difficult to remove

1.5

1.2
Nitrogen, Wt%

0.9

0.6

0.3

0
<315°C 315-370°C 370-425°C 425-480°C 480-535°C >535°C
Distillation Range
20
Metal Compounds

N N
V
N N
O

Porphyrin structures: organic salts

21
Inorganic Salts

➢ In suspension or dissolved in entrained water (brine)

▪ Calcium chloride – CaCl2
▪ Magnesium chloride – MgCl2
▪ Sodium chloride – NaCl

➢ Must be removed or neutralized before processing

▪ Corrosion
▪ Fouling
▪ Catalyst poisoning

22
Crude Properties

Properties Measure Arab Light BCF-17

API Gravity API 33.4 16.4
Specific Gravity 15/15 C 0.8580 0.9567
Sulfur wt.% 1.77 2.36
Pour Point ºC -54 -25
Salt Content PTB 6.0 7.4
Neutralization No. mg KOH/g 0.01 2.44
Ramsbottom Carbon wt.% 4.7 9.5
Metals Content PPM 17 145

API = American Petroleum Institute

PTB = pound of salt per ton barrel of crude
15/15 C = specific gravity measure at 15C respected to water at 15C

23
Crude Quality

TBP Distillation Curves

1100 600
1000 550
900 500
Boiling Temperature, F

Boiling Temperature, C
800
Residue 450
400
700
350
600 Gas Oils
300
500
Kerosene 250
400
200
300 Hvy Naphtha 150
200 Lt. Naphtha 100
100 Lt. Gasoline 50
0 0
0 10 20 30 40 50 60 70 80 90 100
Cumulative Percent Volume

24
Crude Quality

TBP Distillation Curves

1300 700
1200 650
1100 600
Boiling Temperature, F

550

Boiling Temperature, C
1000
900 500
ARAB LT
800 450
BCF-17
400
700
350
600
300
500 BONNY LIGHT
250
400 200
300 150
200 100
100 50
0 0
0 10 20 30 40 50 60 70 80 90 100
Cumulative Percent Volume

Note amount of atm. resid in BCF-17 as compared to Bonny Light 25

 Arabian Light
CRUDE PROPERTI ES CRUDE PROPERTI ES LI GHT HYDROCARBON YI ELDS
--------- ------------ --------- ---------- - - - - - -- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- -- -- -- -- -- -- -- - - - - - - - - - - - -
Gr av i t y , degr ees API 33. 4 Conr ads on Car bon, wt . pc t . 3. 580 Component LV PCT WT PCT
Spec i f i c Gr av i t y ( 60 F/ 60 F) 0. 8581 As phal t enes , wt . pc t . ND ----- ---------- ------ ------
Tot al Sul f ur , wt . pc t . 1. 7700 n- Pent ane I ns ol ubl es , wt pc t ND Met hane 0. 00 0. 00
Mer c apt an Sul f ur , ppm wt ND Rei d Vapor Pr es s ur e, ps i 3. 60 Et hane 0. 01 0. 00
Tot al Ni t r ogen, wt . pc t . 0. 0900 Fl as h Poi nt , degr ees F ND Pr opane 0. 26 0. 15
Pour Poi nt , degr ees F - 65. 0 Hy dr ogen Sul f i de, ppm wt 40. 0 I s obut ane 0. 20 0. 13
Vi s c os i t y at 70 deg. F, c s 11. 39 Neut r al i z at i on Number , mg KOH/ g 0. 000 Nor mal But ane 1. 05 0. 72
Vi s c os i t y at 100 deg. F, c s 8. 35 Bot t om Wat er & Sedi ment , LV pc t . ND I s opent ane 0. 92 0. 67
Vanadi um, ppm wt 13. 500 As h Cont ent , wt . pc t . 0. 004 Nor mal Pent ane 1. 81 1. 33
Ni c k el , ppm wt 3. 340 Sal t ( as NaCl ) , l bs / 1000 bbl s 6. 000
--------- ------------ --------- ---------- ---------- ---------- ---------- ---------- ---------- ---------- ---------- ---------- ----------

LI GHT LI GHT MEDI UM HEAVY LI GHT HEAVY ATMOS. VACUUM VACUUM ATMOS.
PRODUCT PROPERTI ES GASOLI NE NAPHTHA NAPHTHA NAPHTHA KEROSENE KEROSENE GAS OI L GAS OI L RESI DUE RESI DUE
--------- ------------ --------- -------- -------- -------- -------- -------- -------- -------- -------- -------- --------
TBP Cut Poi nt s , degr ees F D C5/ 158 158/ 212 212/ 302 302/ 374 374/ 455 455/ 536 536/ 650 650/ 1049 1049+ 650+
Yi el d, LV pc t . D 5. 10 4. 08 8. 50 7. 94 8. 66 8. 45 11. 04 29. 74 14. 97 44. 71
Yi el d, wt . pc t . D 3. 87 3. 35 7. 37 7. 19 8. 11 8. 17 11. 05 31. 99 17. 89 49. 88
Gr av i t y , degr ees API C 86. 4 69. 8 59. 3 51. 4 45. 3 39. 8 33. 9 22. 4 7. 0 16. 9
Spec i f i c Gr av i t y ( 60 F/ 60 F) D 0. 6493 0. 7028 0. 7416 0. 7737 0. 8003 0. 8261 0. 8556 0. 9196 1. 0217 0. 9538
VABP, degr ees F C - 185. 0 258. 4 338. 0 414. 5 495. 3 592. 2 841. 0 - -
Char ac t er i z at i on Fac t or C - 12. 27 12. 06 11. 97 11. 93 11. 91 11. 87 11. 85 - -
Tot al Sul f ur , wt . pc t . D 0. 0116 0. 0250 0. 0317 0. 0620 0. 2520 0. 7394 1. 4305 2. 4408 4. 1650 3. 0592
Mer c apt an Sul f ur , ppm wt D 77. 3 160. 0 140. 0 50. 0 30. 9 9. 0 - - - -
Tot al Ni t r ogen, wt . pc t . D - - - 0. 00023 0. 00089 0. 00299 0. 01043 0. 08262 0. 34000 0. 17493
Ani l i ne Poi nt , degr ees F D - - - 133. 0 142. 3 152. 3 161. 6 178. 3 - -
Napht henes , LV pc t . D - 14. 7 18. 1 18. 6 - - - - - -
Ar omat i c s , LV pc t . D - 6. 5 12. 9 19. 0 22. 2 21. 4 - - - -
Res ear c h Oc t ane No. Cl ear D 66. 4 51. 9 39. 8 26. 4 - - - - - -
Smok e Poi nt , mm D - - - - 22. 7 19. 8 - - - -
Cet ane I ndex C - - - - 49. 6 53. 3 52. 3 28. 4 - -
Fr eez e Poi nt , degr ees F D - - - - - 45. 7 - 1. 1 - - - -
Pour Poi nt , degr ees F D - - - - - 44. 3 - 5. 4 30. 7 83. 0 115. 0 35. 0
Vi s c os i t y at 100 F, c St D - - - - 1. 39 2. 35 4. 97 37. 53 - -
Vi s c os i t y at 140 F, c St D - - - - - - - - 3. 33E+04 1. 03E+02
Vi s c os i t y at 210 F, c St D - - - - 0. 69 1. 08 1. 82 6. 43 1. 31E+03 2. 47E+01
Ni c k el , ppm wt . D - - - - - - - 0. 05 18. 64 6. 72
Vanadi um, ppm wt . D - - - - - - - 0. 07 75. 62 27. 17
Conr ads on Car bon, wt . pc t . D - - - - - - - 0. 24 16. 50 7. 80
As phal t enes , wt . pc t . D - - - - - - - - 5. 20 2. 00
n- Pent ane I ns ol ubl es , wt pc t D - - - - - - - - 9. 40 3. 10

26
Refinery Overview
Topping or Hydroskimming
Sulfur Plant Sulfur
Saturate Sulfur
Vapor Recovery Removal Fuel Gas

Liquefied Petroleum Gas

Light Straight-Run
Atmospheric Naphtha
Normal
Crude Paraffins
Distillation
Sulfur Removal Gasoline
Column Heavy
Naphtha Naphtha Catalytic
Hydrotreating Reformer

Kerosine Hydrotreating
Unit Kerosene/Jet Fuel

Diesel Hydrotreating
Unit Diesel

AGO Gas Oil

Desalter

Crude Oil
Fuel Oil
Atmospheric
Residue

Asphalt Asphalt
Oxidation

27
Refinery Overview
Medium Conversion
Sulfur Plant Sulfur
Saturate Sulfur
Vapor Recovery Removal Fuel Gas
Hydrogen Plant Hydrogen
Liquefied Petroleum Gas
Light Straight-Run
Atmospheric Naphtha Hydrotreatin C5/C6
Isomerization Normal
Crude g
Paraffins
Distillation
Sulfur Removal Gasoline
Column Heavy
Naphtha Naphtha Catalytic
Hydrotreating Reformer

Kerosine Hydrotreating
Unit Kerosene/Jet Fuel

Diesel Hydrotreating
Unit Diesel

Atmospheric Catalytic
Gas Oil Condensation
Fluid Catalytic Unsaturated Sulfur
Cracking Unit Vapor Recovery Removal

Alkylation

Visbreaking Sulfur
Thermal Cracking Removal C4 Isomerization

Desalter MTBE
Vacuum
Distillation
Crude Oil Column
Residual Fuel
Atmospheric
Oil
Residue

Asphalt
Oxidation Asphalt

28
Refinery Overview

High Conversion
Sulfur Plant Sulfur
Saturate Sulfur
Vapor Recovery Removal Fuel Gas
Hydrogen Plant Hydrogen
Liquefied Petroleum Gas
Light Straight-Run
Atmospheric Naphtha Hydrotreater C5/C6 Isomer
Isomerization Separation Normal
Crude
Paraffins
Distillation
Column Sulfur Removal Gasoline
Heavy
Naphtha Naphtha Catalytic Aromatics
Hydrotreater Reformer Separation
Benzene/Toluene/Xylen
Kerosine Hydrotreating e
Unit Kerosene/Jet Fuel

Diesel Hydrotreating
Unit Diesel

Hydrocracking
Unit Catalytic
Atmospheric Condensation
Gas Oil
Fluid Catalytic Unsaturated Sulfur
Cracking Unit Vapor Recovery Removal

Alkylation

Visbreaking Sulfur
Thermal Cracking Removal C4 Isomerization

Desalter MTBE
Coking
Vacuum
Distillation
Crude Oil Column
Demetallizing Residual Fuel
Atmospheric
Oil Coke
Residue
Dewaxing Lubricant
Compounding Lubricants
Asphalt
Oxidation Asphalt

29
30
What is Alkylation?

➢ Alkylation combines C3-C5 olefins with iso-butane to produce highly-branched,

high-octane C7-C9 isoparaffins

➢ Reaction is catalyzed by strong acids

➢ HF
➢ H2SO4
➢ Solid catalysts (UOP Inalk)
➢ Superacids
➢ BF3, HSO3F or HSO3CF3

31
Alkylation Feeds

Mixed butanes from

hydrocracking, reforming Propane
And crude units
n-Butane

Thermal C3/C4 Olefin Alkylation Alkylate

Cracker Unit Product
C3/C4 Olefin
Rich Stream

FCC Feed FCC Butamer

FCC Products
(Gasoline, etc.)

32
Alkylate Product

➢ Ideal RFG Blending Component

▪ High Octane (RON & MON)
✓ C3=/C4= Feed
• 91-94 RON / 90-93 MON
✓ C4= Feed
• 94-96 RON / 92-94 MON

▪ No Aromatics
▪ No Olefins
▪ Low RVP
✓ 3 - 6 psig
✓ Highly Dependent on Fractionation (nC4,iC5)

▪ Low Sulfur
➢ 10-15 % of Gasoline Pool
33
Primary Products and Octanes
Olefin Primary Products Research Motor
Propylene 2,3-Dimethylpentane 91 89
2,4-Dimethylpentane 83 84

Isobutylene 2,2,4-Trimethylpentane 100 100

Butene-2 2,2,3-Trimethylpentane 109 100

2,2,4-Trimethylpentane 100 100
2,3,3-Trimethylpentane 106 99
2,3,4-Trimethylpentane 103 96

Butene-1 2,2-Dimethylhexane 72 77
2,4-Dimethylhexane 65 70
2,3-Dimethylhexane 71 79

Pentenes 2,2,3,4-Tetramethylpentane
2,2,4-Trimethylhexane
2,2,5-Trimethylhexane 92 90
2,2,3-Trimethylhexane
2,3,4-Trimethylhexane
2,3-Dimethylheptane
2,4-Dimethylheptane
34
Isomerization to enhance gasoline octane number

35
Paraffin isomerization enhance gasoline
octane number

n-Pentane i-Pentane
61.7 93.5

OR

n-Hexane 2-MP 3-MP

31.0 74 76

OR

n-Hexane 2,2-DMB 2,3-DMB

31.0 94 105

36
A Bi-Functional Mechanism of Pt/Zeolite Catalyzed
n-Hexane Isomerization

+
III
dialkyl PCP
II + proton jump
+

I transport

+
+
Pt H2
hydrogen Zeolite- OH
transfer

IV Zeolite - O-
V branched
olefins

+ +
+

trialkyl PCP III-B

+ proton jump

37
Light Naphtha Isomerization

- To isomerize straight run naphtha into high octane

gasoline blend stock
- Typically Pt/AlCl3/Al2O3 catalyzed, but many zeolites
have been studied

Mechanism is dehydro / isom / hydro

38
Isomerization of C5/C7 to Increase Octane
Number
Compound RON MON (R + M) / 2
n-pentane 62 63 62
i-pentane (2-methylbutane) 92 90 91
neopentane (2,2-dimethylpropane) 85 80 83
n-hexane 25 26 25
methylcyclopentane (MCP) 91 80 86
2-methylpentane (2MC5) 73 73 73
3-methylpentane (3MC5) 74 74 74
2,2-dimethylbutane (22DMC4) 92 93 93
2,3-dimethylbutane (23DMC4) 101 94 98
n-heptane 0 0 0
2-methylhexane (2MC6) 42.4 46.4 44
2,3-dimethylpentane 91.1 88.5 90
2,2,3-trimethylbutane 112 101.3 106
39
Hydrotreating

- To “clean up” petroleum distillates by removal of S, O, N, trace metals, and

saturation of olefins.
- There are six basic types of reactions that occur in the hydrotreating unit.

Reactions
1. Conversion of organic sulfur compounds to hydrogen sulfide
2. Conversion of organic nitrogen compounds to ammonia
3. Conversion of organic oxygen compounds to water
4. Saturation of olefins
5. Conversion of organic halides to hydrogen halides
6. Removal of organo-metallic compounds

40
Hydrocracking

The hydrocracking process is carried out at elevated temperature and

pressure over a fixed catalyst system where the fresh feed is cracked in a
hydrogen atmosphere.

The reaction involved in hydrocracking can be classified as follows

1) Contaminant removal by hydrogenation of S, N, and O compounds
2) Hydrogenation of olefins to paraffins and of polycyclic aromatics to
monocyclic aromatics: middle distillates to BTX or vacuum gas oil to
high-quality lubricants.
3) Hydrocracking C-C bonds to form lower molecular weight hydrocarbons:
naphtha to LPG

41
Fluid Catalytic Cracking (FCC)

➢ A process for conversion of straight-run

atmospheric gas oil, vacuum gas oil, and
others into high octane gasoline, light
fuel oils and olefin-rich light gases.
➢ It is operated at high temperature but
low pressure
➢ The name FCC – use of a small particles
of catalyst (acid) which, when aerated,
will behave as a fluid. This fluidized
catalyst will flow and is circulated.

42
Oxygenated Motor Fuels
(Methyl tertiary butyl ether – MTBE)
MTBE process uses a catalyst at relatively low temperature and
pressure to react methanol and isobutene

OH CH3 CH3
Major reaction
CH3 + C CH2 CH3 O C CH3
CH3 CH3

43
(Toluene + C9 aromatic -> 2 Xylenes)

TATORAY
Produce more p-X &
From o-, m-X
ISOMAR®

44
Petrochemical

46
Petrochemical Markets

120

100
Asia/Pacific LAB
Latin
Other America
Acetic Acid
80
World 18% 19%
PX
Demand, 60 MeOH
China
MM MTA Benzene
40 11% India Propylene
10% Ethylene
20

47
Petrochemical Landscape: Aromatics
Kerosene Naphtha Gas Oil Propane Natural Gas

Steam
Reforming
Catalytic
Reforming Aromatics Methanol
Complex
Steam
PAREX Isomar Tatoray Oleflex MTO
Cracking

Benzene (T, o-X, m-X) p-Xylene Ethylene Propylene

Molex Ethyl- Vinyl

Cumene PTA EO/EG PE PP
benzene Acetate

Pacol Styrene Phenol PET (SSP)

Capro
Detal PS
/Nylon

LAB Polystyrene Polycarbonate Polyethylene Acrylics

Detergents Nylon Polyester Polypropylene

Key
Process, Catalyst/Adsorbent, Equipment & Services
Process Technology and Services
Catalyst/Adsorbent, Equipment & Services
Alliance 48
Aromatics Markets

Annual Growth

30
Other BZ BZ to Cyclohexane
25 BZ to Phenolics BZ to Styrenics
over 1999 - MM MT

p-Xylene
Demand Increase

20 6.8%

15

10
3.6%
5

0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Strong Aromatics & Derivatives Growth

Sources: CMAI & UOP 49
Aromatics Complex Flowsheet

50
Units in the aromatics complex
Process Unit Licensed Operating
CCR Platforming 258 208
Sulfolane 150 129
Tatoray 51 42
Parex 91 76
Isomar 72 58

51
 Commissioning of UOP Aromatics Complexes

8
Number of Complexes Commissioned

3
Average 2-3 per Year
2

0
‘71 ‘73 ‘75 ‘77 ‘79 ‘81 ‘83 ‘85 ‘87 ‘89 ‘91 ‘93 ‘95 ‘97 ‘99 ‘01 ‘03 ‘05 ‘07 ‘09

The latest wave of complexes represent a much larger

capacity increase than the previous wave
52
Benzene Recovery: Sulfolane

53
Sulfolane Process
Extraction of aromatics from non-aromatics

54
P-Xylene Recovery: Parex

55
 Separating the C8 Isomers

• C8 aromatics boil too close to separate by distillation.

Mixture Relative Volatility Number of

Stages*
MX/OX 1.147 150

EB/PX 1.058 350

PX/MX 1.019 800

• Phillips developed fractional crystallization in 1962.

• Esso first demonstrated chromatography using molecular sieves in 1964,

but productivity was too low.

* To 99% pure products 56

Counter current adsorption was developed for
p-Xylene separation

➢ Clarence Gerhold and Don Broughton’s

SORBEX SMB process switched net
flows through a sequence of packed beds
to simulate solid flow.

➢ Originally invented for separating

paraffin isomers to raise gasoline octane
number and first commercialized as
MOLEX.

➢ Allowed continuous adsorption using

mol sieves that couldn’t withstand
flowing.

➢ PAREX application to xylene

separation commercialized in 1971. 57
SORBEX™ Process

58
P-Xylene separation by SORBEX Technology

59
PAREX Unit

➢ 93 units now
licensed

➢ Largest single
train designed for
1 MMTA

➢ Total capacity
over 18 million
MTA of PX

60
para-Xylene Production Technologies

34

UOP Parex

UOP Parex accounts for ~ 68% of world p-X production

61
Increasing p-X yields: Isomar

62
Isomar Process

Metal ➢ Main demand is for pX to

+ H2
EB make polyester resin

mX ➢ EB, mX oX and pX can be

brought back to equilibrium
oX
Acid over a suitable catalyst

➢ EB is harder to isomerize so
two types of Isomar

Metal ▪ EB dealkylation (to Bz)

▪ EB isom (to C8 mix)

+ paraffins due to cracking

pX

~24 mol% pX eqbm yield

63
Isomar Flowscheme

Reactor Light Ends

Net Gas

Product Net
Separator Liquid
Charge
Heater
Deheptanizer

Combined Feed
Exchanger Clay
Treater
Product
Condenser
To Aromatic
Compressor Fractionation Unit

Feed from Makeup H2

Parex Unit
64
Increasing C8 Aromatics: Tatoray

65
Tatoray Process

➢ Main demand is for pX to

make polyester resin
+
➢ Demand for toluene as
toluene product is minimal.
C9 aromatics

➢ Toluene and C9 aromatics

zeolite are only worth gasoline
blending value (high octane)

➢ Transalkylation shifts
methyl group to increase
C8 aromatics yield of higher value C8
aromatics

New TA-30 Catalyst based on UZM-14

66
Where are product Xylenes made?

The majority of A8 products are created through transalkylation of

A7, A9, and A10 feed compounds

Reformer
32%

Transalkylation
65%
Isomerization
3%

67
Aromatics Derivatives
Kerosene Naphtha Gas Oil Propane Natural Gas

Steam
Reforming
Catalytic
Reforming Aromatics Methanol
Complex
Steam
PAREX Isomar Tatoray Oleflex MTO
Cracking

Benzene (T, o-X, m-X) p-Xylene Ethylene Propylene

Molex Ethyl- Vinyl

Cumene PTA EO/EG PE PP
benzene Acetate

Pacol Styrene Phenol PET (SSP)

Capro
Detal PS
/Nylon

LAB Polystyrene Polycarbonate Polyethylene Acrylics

Detergents Nylon Polyester Polypropylene

Key
Process, Catalyst/Adsorbent, Equipment & Services
Process Technology and Services
Catalyst/Adsorbent, Equipment & Services
Alliance 68
Phenolics Value Chain
(2005-2010 % Annual Growth)
2005 Production in Million MTA

Consumer Products
Bonding/adhesives used in plywood,
8.3 2.2 wood products, laminates, insulation,
(4%) Phenol Phenolic Resins (3%)
and abrasives
Fibers used in carpeting, apparel, tire
1.1 cord. Resins used in autos, power tools,
Nylon 6 (1%) industrial parts.
Cumene Used in PVC, ion exchange resins, and
1.4
Others (4%) protective coatings.

3.6 Used in optical media, automotive,

Propylene

Polycarbonate (8%) appliances, electronics, and glazing

Benzene

applications
BPA
Used in surface coatings, composites,
Epoxy Resins (3%) casting & molding, bonding &
(7%)
adhesive, floors and paving

Stronger growth possible if PC growth returns to double digits

BPA = Bisphenol-A 69
Petrochemical Landscape: Olefins
Kerosene Naphtha Gas Oil Propane Natural Gas

Steam
Reforming
Catalytic
Reforming Aromatics Methanol
Complex
Steam
PAREX Isomar Tatoray Oleflex MTO
Cracking

Benzene (T, o-X, m-X) p-Xylene Ethylene Propylene

Molex Ethyl- Vinyl

Cumene PTA EO/EG PE PP
benzene Acetate

Pacol Styrene Phenol PET (SSP)

Capro
Detal PS
/Nylon

LAB Polystyrene Polycarbonate Polyethylene Acrylics

Detergents Nylon Polyester Polypropylene

Key
Process, Catalyst/Adsorbent, Equipment & Services
Process Technology and Services
Catalyst/Adsorbent, Equipment & Services
Alliance 70
UOP Position in Olefins

➢ Steam cracking
▪ Feeds: ethane, propane, naphtha, gas oil
▪ Cracking is thermal with steam as diluent
▪ UOP products: adsorbents, selective hydrogenation (SHP), trays & tubes
➢ On-purpose propylene
▪ Dehydrogenation of propane
▪ UOP Oleflex process (+ catalysts, SHP, reactor, CCR, trays)
➢ Propylene from FCC
▪ PetroFCC process
➢ Alternative feedstocks
▪ Olefins from stranded natural gas: UOP Methanol to Olefins (MTO) process

71
Ethylene Plant Separation Section

(C2= Refrig) (C3= Refrig) (C3= Refrig) (Cooling Water)

Compressed C2H4 C3H6
Vapor
Demethanizer Feed Chillers

C3 Splitter
C2 Splitter
(C2= Refrig)
CH4 & H2
(C3= Refrig)
Demethanizer

(Quench
Water)

(C3= Refrig) Ethane

(C3= Refrig) Propane
c2- c3-

c2+ Excellent High Flux

(C3= Refrig) Depropanizer
Deethanizer

Tube Application

Fair High Flux

(Cooling Water) Tube Application
(Steam,
C3= Refrig QW,
Hot Oil) (Steam, Excellent High
C3= Refrig Condenser c3+ c4+ Hot Oil) Cond Tube
Application 72
Oleflex Process

➢ Catalytic Dehydrogenation of Light Paraffins to Olefins and Hydrogen

- C3 to C3= (Petrochemicals)
- i-C4 to i-C4= (MTBE)

- n-C4 to n-C4= (Petrochemicals)

- i-C5 to i-C5= (TAME)

➢ Highly selective process – produces limited byproducts

Catalyst
Propane Propylene + H2
C3H8 -D oC C3H6

Reactor By-Products
C1-C3 Paraffins
73
Oleflex Flow Scheme
Regeneration
Reactor Section Section Product Recovery
Section

C Turbo
R R R R C Expander
R

To
Propylene
Recovery
H2 Recycle

Net
Propane Separator
Gas

74
Oleflex Process

➢ C4 Oleflex unit reactor section

Heater
CCR ➢ AEF – Alberta Canada
Reactors

Cold Box

75
Methanol to Olefins

Catalyst
Methanol Ethylene &
+D oC Propylene
CH3OH C2H4 & C3H6

Reactor By-Products
Mixed Butenes,
C5+ Hydrocarbons,
C1-C4 Paraffins, Water,
Oxygenates, Coke, H2 & COX

76
MTO Catalyst and Yields

3.8 Angstroms

C2= + C3=
80%

Wt.% Yield (Carbon Basis)

C2=
C3=

40%

The unique pore size allows the

selective conversion to olefins and
excludes heavier compounds
0%
0.75 1.00 1.25 1.50
Ethylene / Propylene Ratio 77
Olefin Cracking Process (OCP)

Ethylene C2H4

Catalyst
C4 – C8
Propylene
Olefins C3H6
Endothermic

C4 Raffinate &
Light Gasoline

78
Olefin Cracking Flow Scheme
ATOFINA/UOP Olefin Cracking Process

Light
Olefin
Olefinic Product
C 4 - C8
OCP
Reactor Section

C4
Depropanizer
By-product
Debutanizer
C5+
By-products

79
Petrochemical Landscape: Detergents
Kerosene Naphtha Gas Oil Propane Natural Gas

Steam
Reforming
Catalytic
Reforming Aromatics Methanol
Complex
Steam
PAREX Isomar Tatoray Oleflex MTO
Cracking

Benzene (T, o-X, m-X) p-Xylene Ethylene Propylene

Molex Ethyl- Vinyl

Cumene PTA EO/EG PE PP
benzene Acetate

Pacol Styrene Phenol PET (SSP)

Capro
Detal PS
/Nylon

LAB Polystyrene Polycarbonate Polyethylene Acrylics

Detergents Nylon Polyester Polypropylene

Key
Process, Catalyst/Adsorbent, Equipment & Services
Process Technology and Services
Catalyst/Adsorbent, Equipment & Services
Alliance 80
LAB: Linear Alkylbenzenes

Raw material for Linear Alkylbenzene Sulfonate (LAS)

- The lowest cost detergent surfactant

- The most widely used detergent surfactant
- Has withstood environmental pressures
- 90% is used in household laundry detergents
81
Detergent Components
Typical European Heavy Duty Laundry Powder

Surfactants
•Linear Alkylbenzene Sulfonate
18% 2% 1%9%
•Alcohol Sulfate
•Alcohol Ether Sulfate
20% •Alcohol Ethoxylate

50%
Surfactant Builders
Bleach Antiredeposition agent
Enzymes Fillers

82
UOP Integrated LAB Complex

Kerosene
Benzene

Prefractionation Light Heavy

Hydrogen Ends Aromatics Alkylate
Hydrotreating

Normal
Paraffin Pacol Detal or
Molex PEP LAB
DeFine Detergent
Alkylate
Raffinate
return to Recycle Paraffin
refinery

83
Producing LAB

Raw materials – Kerosene and Benzene

LAB Production Steps

➢ Hydrotreating
▪ Kerosene desulfurization and aromatics reduction (reaction)
➢ Molex
▪ Removal normal paraffins from kerosene (adsorption)
➢ Pacol
▪ Dehydrogenate normal paraffins (reaction)
➢ Define
▪ Saturate diolefins (produced in Pacol) to mono-olefins (reaction)
➢ PEP
▪ Remove aromatics formed in Pacol (adsorption)
➢ Detal
▪ Alkylation – combine benzene and normal olefins to make LAB (reaction)

84
Detal Process

Objectives
Benzene  Alkylation of olefins with benzene
Recycle
Paraffins
Process Conditions
Linear
Alkylbenzene  Liquid Phase Rxn.
DETAL (LAB)
UNIT  120-160 ºC, 170 psig
Heavy  30 Bz:Olefin Ratio
Alkylate
 24 hr. process cycle followed by 24 hr.
benzene regeneration cycle.

Pacolate
from PEP

R-C-C-C-C-R’
R-C-C=C-C-R’ +

85
LAB Complex

LAB Complex in Canada

86
Gas Processing

87
Natural Gas Impurity and Treating Requirements
Pipeline Spec
Acid gas • CO2 < 2 – 8%
CO2 • H2S < 4 ppm
H2S H2O N2 Hg C2+ • Hg < 0.01 ppb
• H2O < 2 – 8%
?
Gas Composition CH4, C2+, Pipeline Gas
H2O, H2S,
CO2, N2, Hg

LNG
?
LNG Spec
Acid gas H2O N2 Hg C2+
• CO2 < 50 ppm
CO2 • H2S < 2 - 4 ppm
H2S • Hg < 0.01 ppb
• H2O < 0.1 ppmv

Treating technologies are selected based on feed composition and

product specs 88
Shale Gas vs Traditional Gas

89
Sources of Gas and Oil

90
Shale Gas: Plate-Form

91
Shale Gas: Cross Section

92
Shale Gas: Cross-Section

93
Shale Gas: Fracking

94
Barnett Shale gas composition

Well C1 C2 C3 CO2 N2
1 80.3 8.1 2.3 1.4 7.9
2 81.2 11.8 5.2 0.3 1.5
3 91.8 4.4 0.4 2.3 1.1
4 93.7 2.6 0.0 2.7 1.0

95
Shale Gas: Reserve & Resource

96
 UOP Separation Technologies

➢Adsorption
▪ Sorbex Simulated Moving Bed Process & Adsorbents
▪ Polybed Pressure Swing Adsorption Units
▪ Thermal Swing Adsorption Units
▪ TSA / PSA / VSA Adsorbents
▪ Non-regenerative Adsorbents
➢Absorption
▪ Selexol
▪ Amine Guard
▪ Benfield
➢Membranes
▪ Separex (CO2)
▪ Polysep (H2)
➢Distillation
▪ MD Trays
97
Absorption
▪ Transfer of a component or multi-components of natural gas to a
liquid phase in which they are soluble.

▪ Transfer of a component or multi-components from a liquid phase to

a gas phase, is usually applied to regenerate the liquid (solvent)

▪ Examples of absorption
 Amine process
 Physical solvent Treated
Gas Acid
Gas
(Selexol process) XX

 Glycol dehydration XXXX

Absorber

Stripper

Feed
Gas

xxxx

98
Amine Guard for Gas Sweetening (Absorption)
Treated Gas
Cooler Acid Gas
Water

Knock-Out
Amine
Drum
Amine Stripper
Absorber Filter

Lean Amine
Cooler
Flash Gas
Feed Gas
Lean/Rich
Exchanger
Water

Rich Flash Drum

Reboiler

▪ For removal of H2S &/or CO2 from gases using solvents such as
methyldiethanolamine (MDEA)
▪ Other UOP solvents processes: Selexol; Benfield 99
Membrane Separation
Components in natural gas permeates through a polymeric membrane. The separation is
realized by selectively permeating components. The components with high sorption and
high diffusivity in the polymer membrane will preferably pemeate through the membrane
while other components will be kept at the feed side of the membrane.
Example
Membranes for CO2 and H2S removal from natural gas

Residue
Residue
(Low CO2) Feed
Permeate
Feed
Permeate
Permeate Stg. 1
(High CO2)

One-Stage Membrane System Two-Stage Membrane System

100
UOP Separex Membranes

Cellulose acetate
membranes for CO2
rejection from natural gas

101
Membrane
Plants
For CO2
Removal
Adsorption
▪ Selectively concentrating one or more components of the
natural gas at the surface of a microporous solid. The
mixture of adsorbed components is called the adsobate,
and the microporous solid is the adsorbent.
▪ Two types of adsorption: chemisorption and physisorption.
Chemisorption takes place when an adsorbed component
reacts chemically with the adsorbent. Desorption is
generally not possible. Physisorption, also called physical
sorption, does not involve chemical reaction. In
physisorption, a component is adsorbed through
interacting with asorbent by van der waals force. The
interaction energy for physisorption is weak, and the
adsorbate can generally be released (desorbed) by raising
temperature or reducing partial pressure of component in
gas phase.

▪ Examples UOP MOLSIVTM

Dehydration
 MolSiv dehydration
 Natural gas dew-pointing by adsorption
 Contaminant removal by adsorption
Water 103
 Hydrogen Recovery: 12-Bed PSA Unit

Surge Tank Adsorber Vessels

Valve Skid

Source: UOP 104

Natural Gas Treating Portfolio

Partial pressure of acid gas in feed, psia

SelexolTM SeparexTM
BenfieldTM Process Membrane
Process Systems

PolybedTM
PSA
Amine GuardTM FS
Process

UOP Molecular Sieves

Scavengers

0.001 0.01 0.1 1.0 10 100

Partial pressure of acid gas in product, psia

Overlapping Technology Options; Complex Integration and Competition

105