0.refinery And Petrochemical Processes.pdf

Basic Refining & Petrochemical

University of Danang, University of Science and

Honeywell, 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

▪ Each molecule contains maximum amount of hydrogen ▪ No double bonds or impurities ▪ Stable ▪ Paraffinic / Waxy

iso-Butane C4H10

➢ 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: C4= for butene isomers

Butene C4H8

➢ 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) ▪ Formed in refinery processes that crack without the presence of hydrogen ▪ Saturate readily in hydrotreating reactors

Pentadiene C5H8

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—S— R’ Disulfide

R—S—H Mercaptan

S

S

Thiophene

S

Benzothiophene

CH3

CH3 Substituted Benzothiophene

S Dibenzothiophene 17

Nitrogen Compounds in Petroleum Basic Nitrogen – Nitrogen has extra lone pair of electrons to facilitate the reaction N

NH H C 3

2 N

Amine

N

Pyridine

NH

Indole

Quinoline

Phenanthridine

NH

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

Nitrogen, Wt%

1.2 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 API Gravity Specific Gravity Sulfur Pour Point Salt Content Neutralization No. Ramsbottom Carbon Metals Content

Measure API 15/15 C wt.% ºC PTB mg KOH/g wt.% PPM

Arab Light 33.4 0.8580 1.77 -54 6.0 0.01 4.7 17

BCF-17 16.4 0.9567 2.36 -25 7.4 2.44 9.5 145

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

1100

Boiling Temperature, F

1000 900 Residue

800 700 600

Gas Oils

500

Kerosene

400 300

Hvy Naphtha

200

Lt. Naphtha

100

Lt. Gasoline

0 0

10

20

30

40

50

60

70

80

90

600 550 500 450 400 350 300 250 200 150 100 50 0 100

Boiling Temperature, C

TBP Distillation Curves

Cumulative Percent Volume

24

Crude Quality

1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0

ARAB LT BCF-17

BONNY LIGHT

0

10

20

30

40

50

60

70

80

90

700 650 600 550 500 450 400 350 300 250 200 150 100 50 0 100

Boiling Temperature, C

Boiling Temperature, F

TBP Distillation Curves

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 --------- ------------ --------- ---------- ---------- ---------- ---------- ---------- ---------- ---------- ---------- ---------- ----------

PRODUCT PROPERTI ES --------- ------------ --------TBP Cut Poi nt s , degr ees F D Yi el d, LV pc t . D Yi el d, wt . pc t . D Gr av i t y , degr ees API C Spec i f i c Gr av i t y ( 60 F/ 60 F) D VABP, degr ees F C Char ac t er i z at i on Fac t or C Tot al Sul f ur , wt . pc t . D Mer c apt an Sul f ur , ppm wt D Tot al Ni t r ogen, wt . pc t . D Ani l i ne Poi nt , degr ees F D Napht henes , LV pc t . D Ar omat i c s , LV pc t . D Res ear c h Oc t ane No. Cl ear D Smok e Poi nt , mm D Cet ane I ndex C Fr eez e Poi nt , degr ees F D Pour Poi nt , degr ees F D Vi s c os i t y at 100 F, c St D Vi s c os i t y at 140 F, c St D Vi s c os i t y at 210 F, c St D Ni c k el , ppm wt . D Vanadi um, ppm wt . D Conr ads on Car bon, wt . pc t . D As phal t enes , wt . pc t . D n- Pent ane I ns ol ubl es , wt pc t D

LI GHT GASOLI NE -------C5/ 158 5. 10 3. 87 86. 4 0. 6493 0. 0116 77. 3 66. 4 -

LI GHT NAPHTHA -------158/ 212 4. 08 3. 35 69. 8 0. 7028 185. 0 12. 27 0. 0250 160. 0 14. 7 6. 5 51. 9 -

MEDI UM NAPHTHA -------212/ 302 8. 50 7. 37 59. 3 0. 7416 258. 4 12. 06 0. 0317 140. 0 18. 1 12. 9 39. 8 -

HEAVY NAPHTHA -------302/ 374 7. 94 7. 19 51. 4 0. 7737 338. 0 11. 97 0. 0620 50. 0 0. 00023 133. 0 18. 6 19. 0 26. 4 -

LI GHT KEROSENE -------374/ 455 8. 66 8. 11 45. 3 0. 8003 414. 5 11. 93 0. 2520 30. 9 0. 00089 142. 3 22. 2 22. 7 49. 6 - 45. 7 - 44. 3 1. 39 0. 69 -

HEAVY KEROSENE -------455/ 536 8. 45 8. 17 39. 8 0. 8261 495. 3 11. 91 0. 7394 9. 0 0. 00299 152. 3 21. 4 19. 8 53. 3 - 1. 1 - 5. 4 2. 35 1. 08 -

ATMOS. GAS OI L -------536/ 650 11. 04 11. 05 33. 9 0. 8556 592. 2 11. 87 1. 4305 0. 01043 161. 6 52. 3 30. 7 4. 97 1. 82 -

VACUUM GAS OI L -------650/ 1049 29. 74 31. 99 22. 4 0. 9196 841. 0 11. 85 2. 4408 0. 08262 178. 3 28. 4 83. 0 37. 53 6. 43 0. 05 0. 07 0. 24 -

VACUUM RESI DUE -------1049+ 14. 97 17. 89 7. 0 1. 0217 4. 1650 0. 34000 115. 0 3. 33E+04 1. 31E+03 18. 64 75. 62 16. 50 5. 20 9. 40

ATMOS. RESI DUE -------650+ 44. 71 49. 88 16. 9 0. 9538 3. 0592 0. 17493 35. 0 1. 03E+02 2. 47E+01 6. 72 27. 17 7. 80 2. 00 3. 10

26

Refinery Overview Topping or Hydroskimming Sulfur

Sulfur Plant Saturate Vapor Recovery

Sulfur Removal

Fuel Gas Liquefied Petroleum Gas

Atmospheric Crude Distillation Column

Light Straight-Run Naphtha

Normal Paraffins Sulfur Removal

Heavy Naphtha

Naphtha Hydrotreating

Kerosine

Hydrotreating Unit

Diesel

Hydrotreating Unit

Gasoline

Catalytic Reformer

Kerosene/Jet Fuel Diesel

Gas Oil

AGO

Desalter

Crude Oil

Fuel Oil

Atmospheric Residue Asphalt Oxidation

Asphalt

27

Refinery Overview Medium Conversion Sulfur

Sulfur Plant Saturate Vapor Recovery

Sulfur Removal

Fuel Gas Hydrogen Plant

Atmospheric Crude Distillation Column

Light Straight-Run Naphtha

C5/C6 Isomerization

Hydrotreatin g

Normal Paraffins

Sulfur Removal

Heavy Naphtha

Naphtha Hydrotreating

Kerosine

Hydrotreating Unit

Diesel

Hydrotreating Unit

Hydrogen Liquefied Petroleum Gas

Gasoline

Catalytic Reformer

Kerosene/Jet Fuel Diesel

Atmospheric Gas Oil

Catalytic Condensation Fluid Catalytic Cracking Unit

Unsaturated Vapor Recovery

Sulfur Removal Alkylation

Sulfur Removal

Visbreaking Thermal Cracking Desalter

C4 Isomerization MTBE

Vacuum Distillation Column

Crude Oil

Residual Fuel Oil

Atmospheric Residue Asphalt Oxidation

Asphalt

28

Refinery Overview High Conversion Sulfur

Sulfur Plant Saturate Vapor Recovery

Sulfur Removal

Fuel Gas Hydrogen Plant

Atmospheric Crude Distillation Column

Light Straight-Run Naphtha

C5/C6 Isomerization

Hydrotreater

Isomer Separation

Catalytic Reformer

Naphtha Hydrotreater

Aromatics Separation

Benzene/Toluene/Xylen e Kerosene/Jet Fuel

Kerosine

Hydrotreating Unit

Diesel

Hydrotreating Unit

Atmospheric Gas Oil

Normal Paraffins Gasoline

Sulfur Removal

Heavy Naphtha

Hydrogen Liquefied Petroleum Gas

Diesel

Hydrocracking Unit

Catalytic Condensation

Fluid Catalytic Cracking Unit

Unsaturated Vapor Recovery

Sulfur Removal Alkylation

Visbreaking Thermal Cracking

Sulfur Removal

Desalter

MTBE Vacuum Distillation Column

Crude Oil Atmospheric Residue

C4 Isomerization

Coking

Residual Fuel Oil Coke

Demetallizing

Dewaxing Asphalt Oxidation

Lubricant Compounding

Lubricants 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 And crude units

Thermal C3/C4 Olefin Cracker

Propane n-Butane Alkylation Unit

Alkylate 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 Propylene

Primary Products 2,3-Dimethylpentane 2,4-Dimethylpentane

Research 91 83

Motor 89 84

Isobutylene

2,2,4-Trimethylpentane

100

100

Butene-2

2,2,3-Trimethylpentane 2,2,4-Trimethylpentane 2,3,3-Trimethylpentane 2,3,4-Trimethylpentane

109 100 106 103

100 100 99 96

Butene-1

2,2-Dimethylhexane 2,4-Dimethylhexane 2,3-Dimethylhexane

72 65 71

77 70 79

Pentenes

2,2,3,4-Tetramethylpentane 2,2,4-Trimethylhexane 2,2,5-Trimethylhexane 2,2,3-Trimethylhexane 2,3,4-Trimethylhexane 2,3-Dimethylheptane 2,4-Dimethylheptane

92

90

34

Isomerization to enhance gasoline octane number

35

Paraffin isomerization enhance gasoline octane number

n-Pentane

i-Pentane 93.5

61.7

OR

n-Hexane

2-MP

3-MP

31.0

74

76

OR

n-Hexane 31.0

2,2-DMB 94

2,3-DMB 105

36

A Bi-Functional Mechanism of Pt/Zeolite Catalyzed n-Hexane Isomerization + III II +

dialkyl PCP + proton jump

transport

I

+ H2

Pt

hydrogen transfer

Zeolite- OH

Zeolite - O-

IV V

+

branched olefins +

+

+

+ trialkyl PCP + proton jump

III-B

+

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

Major reaction

OH CH3

CH3 +

C CH2 CH3

CH3 CH3 O

C CH3 CH3

43

(Toluene + C9 aromatic -> 2 Xylenes)

Produce more p-X From o-, m-X

TATORAY & ISOMAR®

44

Petrochemical

46

Petrochemical Markets

120 100 Asia/Pacific Other 80

18% World Demand, 60 China MM MTA 40 11%

India

10% 20

LAB Latin America Acetic Acid 19% PX MeOH Benzene Propylene Ethylene

0

47

Petrochemical Landscape: Aromatics Gas Oil

Naphtha

Kerosene

Propane

Natural Gas Steam Reforming

Catalytic Reforming

PAREX

Benzene

Isomar

Steam Cracking

Tatoray

(T, o-X, m-X)

p-Xylene

Ethylbenzene

Cumene

PTA

Pacol

Styrene

Phenol

PET (SSP)

PS

LAB

Polystyrene

Detergents

Oleflex

Ethylene

Molex

Detal

Methanol

Aromatics Complex

EO/EG

MTO

Propylene

PE

PP

Vinyl Acetate

Capro /Nylon Polycarbonate Nylon

Polyester

Polyethylene

Acrylics Polypropylene

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

48

Aromatics Markets Annual Growth

30 Demand Increase over 1999 - MM MT

25

Other BZ BZ to Phenolics p-Xylene

BZ to Cyclohexane BZ to Styrenics

6.8%

20 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

Number of Complexes Commissioned

Commissioning of UOP Aromatics Complexes 8 7 6 5 4 3

Average 2-3 per Year

2 1 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

MX/OX

1.147

Number of Stages* 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

separation commercialized in 1971.

xylene 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 ➢ Main demand is for pX to

Metal + H2

make polyester resin

EB

➢ EB, mX oX and pX can be

mX

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 Light Ends

Reactor Net Gas Product Separator

Charge Heater

Net Liquid Deheptanizer

Combined Feed Exchanger

Clay Treater

Product Condenser

Compressor Feed from Parex Unit

To Aromatic Fractionation Unit

Makeup H2 64

Increasing C8 Aromatics: Tatoray

65

Tatoray Process ➢ Main demand is for pX to make polyester resin

+

➢ Demand toluene

C9 aromatics

for

toluene

as

product is minimal. ➢ 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 Gas Oil

Naphtha

Kerosene

Propane

Natural Gas Steam Reforming

Catalytic Reforming

PAREX

Benzene

Isomar

Steam Cracking

Tatoray

(T, o-X, m-X)

p-Xylene

Ethylbenzene

Cumene

PTA

Pacol

Styrene

Phenol

PET (SSP)

PS

LAB

Polystyrene

Detergents

Oleflex

Ethylene

Molex

Detal

Methanol

Aromatics Complex

EO/EG

MTO

Propylene

PE

PP

Vinyl Acetate

Capro /Nylon Polycarbonate Nylon

Polyester

Polyethylene

Acrylics 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

(4%) Phenol

2.2

8.3

1.1

Cumene

Bonding/adhesives used in plywood, wood products, laminates, insulation, Phenolic Resins (3%) and abrasives

Nylon 6

1.4 3.6

Benzene

Propylene

Others

Used in PVC, ion exchange resins, and (4%) protective coatings.

Polycarbonate

Used in optical media, automotive, (8%) appliances, electronics, and glazing applications

Epoxy Resins

(3%) casting & molding, bonding &

BPA (7%)

Fibers used in carpeting, apparel, tire cord. Resins used in autos, power tools, (1%) industrial parts.

Used in surface coatings, composites, adhesive, floors and paving

Stronger growth possible if PC growth returns to double digits BPA = Bisphenol-A

69

Petrochemical Landscape: Olefins Gas Oil

Naphtha

Kerosene

Propane

Natural Gas Steam Reforming

Catalytic Reforming

PAREX

Benzene

Isomar

Steam Cracking

Tatoray

(T, o-X, m-X)

p-Xylene

Ethylbenzene

Cumene

PTA

Pacol

Styrene

Phenol

PET (SSP)

PS

LAB

Polystyrene

Detergents

Oleflex

Ethylene

Molex

Detal

Methanol

Aromatics Complex

EO/EG

MTO

Propylene

PE

PP

Vinyl Acetate

Capro /Nylon Polycarbonate Nylon

Polyester

Polyethylene

Acrylics 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 (Cooling Water)

(C3= Refrig)

(C2= Refrig) (C3= Refrig)

Compressed Vapor

C2H4

(C2= Refrig)

Demethanizer

CH4 & H2

(C3= Refrig)

(Quench Water) (C3= Refrig) c2-

(Cooling Water)

C3= Refrig C3= Refrig Condenser

c3+

Ethane c3-

(Steam, QW, Hot Oil)

(C3= Refrig)

Depropanizer

(C3= Refrig)

Deethanizer

c2+

C3 Splitter

C2 Splitter

Demethanizer Feed Chillers

C3H6

c4+

Propane

Excellent High Flux Tube Application Fair High Flux Tube Application (Steam, Hot Oil)

Excellent High 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 C3H8

-D oC

Propylene + H2 C3H6

Reactor By-Products

C1-C3 Paraffins 73

Oleflex Flow Scheme Reactor Section

R

R

R

Regeneration Section

R

Product Recovery Section

Turbo Expander

C C R

To Propylene Recovery H2 Recycle Propane

Net Separator Gas

74

Oleflex Process Heater CCR

Reactors

➢ C4 Oleflex unit reactor section ➢ AEF – Alberta Canada

Cold Box

75

Methanol to Olefins

Catalyst

Methanol +D oC CH3OH

Ethylene & Propylene 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=

Wt.% Yield (Carbon Basis)

80%

C2=

C3= 40%

The unique pore size allows the selective conversion to olefins and excludes heavier compounds 0% 0.75

1.00

1.25

Ethylene / Propylene Ratio

1.50 77

Olefin Cracking Process (OCP)

Ethylene

C4 – C8 Olefins

C2H4

Catalyst

Propylene Endothermic

C3H6

C4 Raffinate & Light Gasoline 78

Olefin Cracking Flow Scheme ATOFINA/UOP Olefin Cracking Process

Olefinic C 4 - C8

Light Olefin Product

OCP Reactor Section

C4 By-product

Depropanizer Debutanizer

C5+ By-products

79

Petrochemical Landscape: Detergents Gas Oil

Naphtha

Kerosene

Propane

Natural Gas Steam Reforming

Catalytic Reforming

PAREX

Benzene

Isomar

Steam Cracking

Tatoray

(T, o-X, m-X)

p-Xylene

Ethylbenzene

Cumene

PTA

Pacol

Styrene

Phenol

PET (SSP)

PS

LAB

Polystyrene

Detergents

Oleflex

Ethylene

Molex

Detal

Methanol

Aromatics Complex

EO/EG

MTO

Propylene

PE

PP

Vinyl Acetate

Capro /Nylon Polycarbonate Nylon

Polyester

Polyethylene

Acrylics 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

18%

•Linear Alkylbenzene Sulfonate

2% 1%9%

•Alcohol Sulfate •Alcohol Ether Sulfate

20%

•Alcohol Ethoxylate

50% Surfactant Bleach Enzymes

Builders Antiredeposition agent Fillers 82

UOP Integrated LAB Complex

Kerosene Prefractionation Hydrotreating

Molex

Raffinate return to refinery

Normal Paraffin

Benzene Light Hydrogen Ends Aromatics

Pacol DeFine

PEP

Heavy Alkylate

Detal or Detergent Alkylate

LAB

Recycle Paraffin

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 Recycle Paraffins

DETAL UNIT

Alkylation of olefins with benzene

Process Conditions

Linear Alkylbenzene (LAB)

  

Heavy Alkylate



Liquid Phase Rxn. 120-160 ºC, 170 psig 30 Bz:Olefin Ratio 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 Acid gas CO2 H2S H2O

Gas Composition

Pipeline Spec • CO2 < 2 – 8% N2

Hg

C2+

• H2S < 4 ppm • Hg < 0.01 ppb • H2O < 2 – 8%

?

CH4, C2+, H2O, H2S, CO2, N2, Hg

Pipeline Gas

LNG

? Acid gas H2O CO2 H2S

N2

Hg

C2+

LNG Spec • CO2 < 50 ppm

• H2S < 2 - 4 ppm • 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)  Glycol dehydration

XX XXXX

Absorber

Stripper Feed Gas xxxx

98

Amine Guard for Gas Sweetening (Absorption) Treated Gas Water

Acid Gas

Cooler

Knock-Out Drum

Amine Stripper

Amine Absorber

Filter

Lean Amine Cooler Feed Gas

Flash Gas Water

Lean/Rich Exchanger

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 (High CO2)

One-Stage Membrane System

Permeate Stg. 1

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  MolSiv dehydration

UOP MOLSIVTM 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

Partial pressure of acid gas in feed, psia

Natural Gas Treating Portfolio BenfieldTM Process

SelexolTM Process

Amine GuardTM FS Process

SeparexTM Membrane Systems

PolybedTM PSA

UOP Molecular Sieves Scavengers

0.001 0.01 1.0 10 100 0.1 Partial pressure of acid gas in product, psia

Overlapping Technology Options; Complex Integration and Competition 105