Olefins

Petrochemical
• Olefins
• Synthesis gas

University of Danang,
University of Science and Honeywell,
Technology, Vietnam
UOP, USA
Agenda

 The Global Petrochemical Context

▪ Impact of petrochemicals
▪ The 7 Key petrochemical materials
▪ Our 4 sources of petrochemicals
▪ A shift on the horizon – shale gas
 Ethylene
 Propylene
 Butenes
 Synthesis gas

2
Fractional Distillation of Crude Oil

(Gasoline)

Produced by UOP technology

▪ Transportation fuels 60 %
▪ Para-xylene 70 %
▪ Biodegradable detergents 90 %
▪ Natural gas 40 %

3
Products from Oil

4
What do petrochemicals make?

5
 The Global Petrochemical Industry

▪ Performance chemicals includes specialty chemicals, flavors and fragrances,

adhesives, explosives, etc.
▪ Life science chemicals includes pharmaceuticals, agrochemicals, fine chemicals and
nutritional products.

2011 Chemical Industry Sales: $3.4 trillion (estimated)

Source: Nexant Thinking, 2014 6

The 7 Cornerstone Petrochemicals

Olefins
• Ethylene
• Propylene
• C4 Olefins
▪ Butenes
▪ Butadiene

Synthesis Gas
• CO / H2

Aromatics
• Benzene
• Toluene
• Xylene

7
8
9

9
10
11
Sources of Our Petrochemical Building Blocks

Vacuum gas oil

ZSM-5 additive
Natural Gas Liquid for on-purpose
Light naphtha propylene

12
Shale Gas – The Case for Industry Change

For steam Cracker

Lighter feedstock producing less C3/C4 olefin, aromatic production

13
 Shale Gas – The Case for Industry Change

 Feedstock changes will have a profound impact on our industry in the

coming years
– Ethylene: low cost and highly efficient C2 cracker
• Little propylene, butadiene and aromatics
– On-purpose routes required to fill gaps
• Propylene/isobutylene: on-purpose C3/C4 dehydrogenation
• Ethylene/propylene: MTO and MTP
• On-purpose butadiene
– Demand imbalance for propylene, butadiene and aromatics versus ethylene

 Understanding how the petrochemical industry is interconnected will

give you insight into the current and coming challenges the industry
faces.

14
Refinery / Petrochemical Integration

95% (by mass) of all organic chemicals from these sources

15
Ethylene

Sources, Balance, Economics and Uses

16
 Ethylene: Sources, Economics and Uses

USES

Source: Nexant Thinking, UOP analysis, other industry sources 17

 Ethylene Supply & Demand (2014-2019)

Ethylene Production Primary Derivatives End Products

Technologies 28% ( 1.0%) Milk Jugs, Crates, Drums
HDPE Food Containers, Bottles,
Housewares, etc.
Steam 98% (1.%) 4.8%/yr
Crackers 14.5% ( 0.5%) Food Packaging, Film
60% LDPE Trash bags, Diapers, Toys
Polyethylene Housewares, etc.
3.1%/yr
1%
FCC LLDPE
17.5% ( 0.5%)

5.1%/yr

1% Ethylene 10% Siding, Windows, Frames

MTO EDC VCM PVC Pipe, Medical Tubing, etc.
139.6 million MTA
3.5%/yr Antifreeze
Others 4.2%/yr 61% 61%
15% EG PET Bottles, Film, etc.
EO
15%
Ethoxylates
Catalytic 4.4%/yr Insulation, Cups, etc.
Ethane 6%
Dehydro or EB Styrene Polystyrenes
Instrument Lenses,
Partial Ox 2.9%/yr Housewares, Tires
Other
Medical Gloves,
Carpeting, Coatings, etc.
Other
8%
2.3%/yr
Source: iHS Chemical World Analysis December, 2013
2014 Installed Capacity
2014 Forecasted Demand
Demand CAGR (2014-2019)
18
Uses of Ethylene

1. Polyethylene
▪ HDPE
▪ LDPE
▪ LLDPE
▪ SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Polyvinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

19
Ethylene to Polyethylene

Six Types of Polyethylene

1. High-Density Polyethylene (HDPE)

2. Low-Density Polyethylene (LDPE)
3. Linear-Low Density Polyethylene (LLDPE)
4. Very Low-Density Polyethylene (VLDPE)
5. Ultra Low-Density Polyethylene (ULDPE)
6. Single-Site Polyethylene (SSLLDPE)

Typically, VLDPE, ULDPE, and SSLLDPE are

combined with LLDPE

20
Brief Summary of Polyethylene Synthesis and Properties

LDPE HDPE LLDPE

Catalyst or Initiator Oxygen Ziegler Ziegler

Reaction Temp, C 200-300 As low as60 As low as 60

Reaction Pressure, 20-40,000 1-320 1-320

psi
Structure Branched Linear Linear with short
branches
App % Crystalline 55 85-95 55

Co-monomer None 1-Butene 1-Butene, 1-

Hexene, 1-Octene
Elongation @ Break, 500 10-100 500
%
Density, gm/cc 0.915-0.925 0.945-0.965 0.915-0.925
21
Terms Use in Polymers

22
Uses of Ethylene

1. Polyethylene
• HDPE
• LDPE
• LLDPE
• SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Poly vinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

23
Ethylene to Ethylene Oxide

Ethylene oxide to

1 Ethylene glycol
2 Polyester

24
U.S. Ethylene Oxide Demand

Demand % Demand
Ethylene Glycol 59

Nonionic Surfactants 12

Ethanolamine 11

Higher Glycols 7

Glycol Ethers 6

Poly(ethylene glycol) 3

Other 2

25
U.S. Ethylene Glycol Demand

Demand % Demand

Antifreeze 32

Pet Bottle and other resin 29

Polyester Fiber 28

Industrial & Other 11

26
Uses of Ethylene

1. Polyethylene
▪ HDPE
▪ LDPE
▪ LLDPE
▪ SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Poly vinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

27
Ethylene to Poly(vinyl chloride) - PVC

Main process: Oxychlorination

Combine process: Chlorination + Oxychlorination

1. Chlorination: CH2=CH2 + Cl2 CH2Cl-CH2Cl

2. Pyrolysis: 2 CH2Cl-CH2Cl 2 CH2=CHCl + 2 HCl

3. Oxy-chlorination: CH2=CH2 + 2HCl + 1/2O2 CH2Cl=CH2Cl + H2O

28
Combine process: Chlorination + Oxychlorination
QUIZ

Mix and match

1. Quench a. EDC to VCM + HCl

2. Pyrolysis b. Ethylene + Cl2 to EDC
3. Chlorination c. Cool EDC + hot VCM
4. Oxychlorination d. Ethylene + HCl + O2 to EDC

Write out the overall reaction.

U.S. Demands of PVC by End Use

End Use % End Use

Pipe 39
Siding 11
Calendaring 11
Exports 10
Film and Sheet 7
Molding 5
Wire and Cable 4
Coating 3
Other 10

31
Uses of Ethylene

1. Polyethylene
• HDPE
• LDPE
• LLDPE
• SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Poly vinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

32
Ethylene to Polystyrene

33
Uses of Ethylene

1. Polyethylene
• HDPE
• LDPE
• LLDPE
• SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Poly vinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

34
Ethylene to Oligomers to Linear α-Olefins

35
Shell’s SHOP Process to OXO Alcohol

36
Metathesis

37
Uses of Ethylene

1. Polyethylene
• HDPE
• LDPE
• LLDPE
• SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Poly vinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

38
Ethylene to Poly(Vinyl Acetate)

39
Uses of Ethylene

1. Polyethylene
• HDPE
• LDPE
• LLDPE
• SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Poly vinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

40
 Ethylene to Ethanol

Most of the world's ethanol is now produced by fermentation of crops (93%)

with synthetic ethanol (7%) being produced by direct hydration of ethylene.

SPA

Electrophilic attack by proton of solid phosphoric acid (SPA) catalyst 

carbonium ion  reacts with OH - from water. H+ from water returns to SPA

41
Uses of Ethylene

1. Polyethylene
• HDPE
• LDPE
• LLDPE
• SS-LLDPE
2. Ethylene Oxide
3. Ethylene Dichloride  Poly vinyl Chloride (PVC)
4. Ethylbenzene  Polystyrene
5. α-Olefins
6. Vinyl Acetate
7. Ethanol
8. Acetaldehyde

42
Ethylene to Acetaldehyde

The WACKER Process

43
Summary of Ethylene Technology

44
Ethylene Operating Rate Stays High…

Supply-Demand remain in reasonable balance

45
Global Net Trade of Ethylene
Source: Nexant Thinking, UOP analysis, other industry sources

This is a snapshot.
Supply/demand is
dynamic.

Ethylene is a gas – difficult to move – limited trade

46
 Major World-Wide Producers of Ethylene

Modestly concentrated industry

Source: Nexant Thinking, UOP analysis, other industry sources 47

Ethylene From Steam Cracking Process
Steam cracking accounts for 98+% of the ethylene produced worldwide. The steam
cracking process can accept a variety of hydrocarbons, ranging from natural gas
(ethane, propane and butane) to petroleum liquids (naphtha and gas oils). There are 3
steps
1) Pyrolysis and Cooling
The feedstock is initially mixed with a dilution stream and heated to 815-900°C at 25-35
psia. The resulting products are immediately cooled to 340-510°C and further cooled to
37-43°C in a water quenching tower.
2) Compression and Acid gas Removal
The cracked gas stream is compressed from atmospheric pressure to 500-550 psia.
During the compression, acid gases (H2S and CO2) are removed by scrubbing the
stream. The resulting stream is dried over a solid absorbent.
3) Cryogenic Cooling and Production Separation
The dried gas is cooled to between –95°C and –130°C in a refrigeration train. The
resultant gas, consisting primarily of hydrogen, methane and carbon monoxide, is
purified to recover the hydrogen; the remainder is burned as plant fuel. Low-temperature
fractionation separates the desired products. Ethane and propane are generally
recycled, while hydrogenation of acetylene, propyne and propadiene yields ethylene and
propylene. 48
Steam Cracker Technology

49
Product dependence on Feedstock

Typical Product Stream Obtained From Cracking Various Feedstocks

In a 450 thousand metric tons/year ethylene plant
(thousands of metric tons)

Products Ethane Propane N-Butane Naphtha Vac Gas Oil

H2-Rich Gas 30 20 15 15 306

CH4-Rich Gas 40 300 250 220 200

Ethylene 450 450 450 450 450

Propylene 10 290 190 260 260

Butadiene 10 30 40 80 80

Butylenes/Butanes 5 20 80 130 80

Pyrolysis Gasoline 20 140 160 990 1200

+ BTX + others
Fuel Oil 0 10 30 300 610

Ethylene Yield (Wt%) 80.5 43 40 37 24

total 575 1260 1215 2445 3186

50
 Quiz

To make at least 500 million pounds of ethylene per year and at least 200
million pounds of propylene per year, how much propane or gas oil would you
have to crack in an olefins plant? How much butadiene would you make in
either case?

Ethane Propane Butane Naphtha Gas oil

Ethylene 0.80 0.40 0.36 0.23 0.18
Propylene 0.03 0.18 0.20 0.13 0.14
Butylene 0.02 0.02 0.05 0.15 0.06
Butadiene 0.01 0.01 0.03 0.04 0.04
Fuel gas 0.13 0.38 0.31 0.26 0.18
Gasoline 0.01 0.01 0.05 0.18 0.18
Gas oil -- -- -- 0.01 0.12
Pitch -- -- -- -- 0.10
Ethylene from Ethane or Naphtha?

Which is better – produce ethylene from ethane or from naphtha?

▪ It depends …

▪ Ethane technology, plant design simpler, cheaper

▪ You must have markets for all the products from naphtha

▪ But…

▪ Ethane must be available cost effectively

52
New Ethylene Capacity – 2014-2017

New plants take 4-6 years to bring to production

53
What do newest crackers look like?
2012 WW Ethylene Capacity 2013-2023 Capacity Additions (kMTA)

30,000
Only 26% of future capacity from naphtha
25,000
35.5% Ethane
20,000
Naphtha
15,000
Other
47.4% 10,000

5,000

-
Ethane Naphtha Other

54
Economics Helping Ethane Cracking

... but naphtha crackers will still be built 55

Propylene

Sources, Balance and Uses

56
Change in Propylene Demand over Time
2012 Propylene Demand

1970 Propylene Demand

57
 Propylene Chemistry

▪ Like ethylene, propylene has a reactive double bond, which allows lots
of useful chemistry
✓ Polypropylene, Oxo alcohols, cumene, Methyl methacrylate (MMA),
propylene oxide
▪ Unlike ethylene, it also has allylic hydrogens which allow different
chemical reactions to take place
✓ Acrylonitrile, acrylic acid, acrolein, acrylamide
▪ This leads to strong demand for propylene…

H2C H2C H2C

O
CH3 N O H2C
HO O
Propylene CH3
Acrylonitrile Acrylic acid
Methyl methacrylate

58
 However, Propylene is a Byproduct…

• Cracking of naphtha,
ethane and other materials
is driven by ethylene
demand

• This results in a gap

between demand for
propylene and the supply
of propylene from
traditional technologies 59
Product dependence on Feedstock
Typical Product Stream Obtained From Cracking Various Feedstocks
In a 450 thousand metric tons/year ethylene plant
(thousands of metric tons)

Products Ethane Propane N-Butane Naphtha Vac Gas Oil

H2-Rich Gas 30 20 15 15 306

CH4-Rich Gas 40 300 250 220 200

Ethylene 450 450 450 450 450

Propylene 10 290 190 260 260

Butadiene 10 30 40 80 80

Butylenes/Butanes 5 20 80 130 80

Pyrolysis Gasoline 20 140 160 990 1200

+ BTX + others
Fuel Oil 0 10 30 300 610

Ethylene Yield (Wt%) 80.5 43 40 37 24

total 575 1260 1215 2445 3186

60
 Propylene Supply - Global

140  “Propylene Gap” is growing

120 “Propylene Gap” – Steam Crackers shifting to lighter
feedstocks, which produce less
100 propylene
million MTA

80 – Refiners limited by flat gasoline growth

in some regions, which limits
60 propylene from FCCs
40  “On-Purpose Propylene” is filling
20
the gap
– Propane Dehydro (PDH)
0
– MTO (from gas & coal)
2001 2006 2011 2016 2021
– High Severity FCC
Supply from Refinery FCCs
Supply from Steam Crackers – Olefin Cracking
Demand (Polymer/Chemical Gr.) – Metathesis

On-Purpose Propylene will supply 25% of global propylene by 2021

Data Source: IHS Chemical 61

Propane Dehydro - Product Mix Comparison
P/E
0.03
0.14
0.40
0.43
0.53
0.58
0.69
0.63
---
3.76
---
1.00
1.47

Propane Dehydro provides the highest yield of propylene

62
Propane Dehydrogenation Technology

Pt-Sn catalyst

PDH Technology offered by: UOP, CB&I Lummus, Uhde

Additional ~20 PDH Units Licensed since 2012

63
Oleflex Process
C3 Oleflex = 4 Rxs
C4 & C3/C4 Oleflex = 3 Rxs
Reactor Regeneration
Section Section

Catalyst Flow

C
C >250 UOP CCR’s in
R Operation Today

Dryer
Rx Effluent
Compressor
Heater Cells

Cold Box
To Frac
Section
Process Features H2 Recycle
Fresh
 Positive Pressure / Pt Catalyst & Recycle Net Gas (H2)
 Lowest Energy Usage & Emissions Feed Product Recovery Section
 Fewest & Smallest Reactors
 Catalyst Change-Out without Shutdown 64
 65

Oleflex Reactions

Propane Dehydrogenation Iso-Butane Dehydrogenation

 Main Reaction ▪ Main Reaction
iC4 iC4= + H2
C3 C3= + H2
▪ Side reactions
 Side reactions iC4 nC4
C3 =C3= + 2H2 nC4 nC4= (1- or 2-butene) + H2
C3 C3+ 2H2
C3 C2= + CH4 =nC4=

C2

Process favored by high temperature and low pressure

Process run at equilibrium

65
 Artist’s impression of a Pt−Sn nanoparticle
within a Pt−Sn/Al2O3 catalyst

J.J.H.B. Sattler, J. Ruiz-Martinez, E. Santillan-Jimenez, and B.M. Weckhuysen, Chem. Rev. 2014, 114, 10613−10653 66
On-Purpose Production of Propylene

First Oleflex unit, 1992 - C3 Propane Dehydrogenation Plant, Rayong,

Thailand

2018: 30 Oleflex units (C3, iC4 and C3/iC4) + several in construction

67
Propylene Demand - 2013

Uses

68
 Propylene Supply & Demand (2014-2019)
Technologies Primary Derivatives End Products
67% (1%) Plastic Films,
Steam 53 % (1%) Polypropylene Fibers, Packaging, etc.
Crackers 4.9%/yr (0.1%)
Acrylic Fibers
7% Acrylonitrile ABS Resins, Nylon, etc.
2.3%/yr (0.1%)
FCC 33% (1%) 8% ( 1%) Antifreeze
(incl. HS FCC) Propylene Oxide Polyurethane Foams, etc.
4.5%/yr ( 1%)
4.5%/yr ( 1.1%)
7% ( 2%) Propylene
PDH 4% Epoxy Resins,
88 million MTA Cumene Phenol Polycarbonate, etc.

Metathesis 4% 3.6%/yr (1.1%)

4% Paints, Coatings
MTO/MTP 2% Acrylic Acid Hygienic Products
5.5%/yr (0.3%)
<1%
OCP
Plasticizers, Coatings,
Plastics, Solvents,
Others Others Acetone, Pharmaceuticals,
<1% 10%
3.6%/yr (1.1%) Gasoline, Detergents, etc.

Large, robust market with increasing share

Source: iHS Chemical World
Analysis December, 2013
2014 Installed Capacity
2014 Forecasted Demand
from on-purpose technologies
Demand CAGR (2014-2019) 69
Uses of Propylene
Chemical Uses
▪ Acrylic Acid and Esters
▪ Acrylonitrile
▪ Allyl Chloride/Epichlorohydrin
▪ Cumene
▪ Ethylene-Propylene Elastomers
▪ Isopropyl Alcohol
▪ Oxo Chemicals
▪ Polygas Chemicals (nonene, heptene, dodecene)
▪ Polypropylene
▪ Propylene Oxide

Non-chemical Uses
▪ Gasoline alkylate
▪ Polymer gasoline (polygas)
▪ Dimersol
▪ Fuels 70
Propylene to Acrylic Acid and Esters

About half of acrylic acid is converted to acrylate esters. Applications

are surface coatings, textiles, adhesives, and plastics.

The other half is converted to polyacrylic acid, which can be further

modified to produce superabsorbent polymers (disposable diapers)
and other polyacrylic acid copolymers.

71
 Propylene to Acrylonitrile

Catalytic ammoxidation of propylene

Acrylonitrile is used to prepare polyacrylonitrile, or several important

copolymers, such as:
▪ styrene-acrylonitrile (SAN)
▪ acrylonitrile butadiene styrene (ABS)
▪ acrylonitrile styrene acrylate (ASA)
▪ other synthetic rubbers such as acrylonitrile butadiene (NBR)

Acrylonitrile is also a precursor in the industrial manufacture of

acrylamide and acrylic acid.
72
Propylene to Phenol

Reaction to produce Cumene and to Phenol

Hock rearrangement

Phenol is an intermediate for production of: plastics, resins,

polycarbonates, nylon, drugs (aspirin), etc. 73
 Quiz
The Cutthroat Phenol Company is thinking about starting up and selling out
their 50 million pound per year phenol plant. The market for the various
feedstocks and products is as follows:
Benzene $ 1.60/gal
Propylene 0.25/lb
Oxygen 0.50/lb
Acetone 0.60/lb
By-products 0.10/lb
Their cumene plant operating cost are $0.20/lb. of feed; the fenol plant
operating costs are $0.25/lb. of fenol.
How much should Cutthroat charge for fenol if they want to make $0.02/lb.
Hint: specific gravity of benzene: 7.19 lbs./gal
Benzene + Propylene Cumene
681 lbs. 367 lbs. 1000 lbs.

Cumene + Oxygen Phenol + Acetone + by-products

20000 lbs. 6000 lbs. 14500 lbs. 8840 lbs. 1980 lbs.
ANSWER

FEED COST + 0.2(681+367) + 0.25(725)= X(725) + 0.02 (725)

X = 0.72 USD/lb
Phenol to Bisphenol A

BPA is a health concern, as it binds to estrogen receptors, thus

altering gene expression

76
Bisphenol A to Epoxy Resin

77
Bisphenol A to Polycarbonate

78
Global Polycarbonate Demand

NexantThinking – October 2015 79

 Industrial routes to Polycarbonate

GE Plastics first developed a

non-phosgene route in early
90’s. Various versions are
being developed by different
producers

Original “Interfacial”
process was developed in
the 50’s by Bayer and GE.

Still the predominant

process today.

NexantThinking – October 2015 80

 Asahi Kasei’s non-phosgene routes

NexantThinking – October 2015 81

Propylene & Cumene End-Products

82
 Propylene to Polypropylene
Polypropylenes are Tacticity
produced either by
slurry or gas phase
polymerization of
propylene using
Ziegler-Natta-type or
metallocene
catalysts.

In 2013, the global market

for polypropylene was
about 55 million tons.

Polypropylene is the
world's second-most widely
produced synthetic plastic,
after polyethylene.
 Propylene to Propylene Oxide

Hydrochlorination route

Oxidation route
CH3CH=CH2 + RO2H → CH3CHCH2O + ROH
(In 2009 BASF and DOW started up their HPPO plant using H2O2)

The two largest markets for propylene oxide

▪ polyether polyols (60-70%) for the production of polyurethane plastics
▪ propylene glycols (20%)
84
Non-chemical Uses of Propylene

▪ Gasoline alkylate
▪ Polymer gasoline (polygas)
▪ Dimersol
▪ Fuels

85
The Competition for Propylene Consumption

Fuels is a perfectly good use of propylene….

Fuels use sets a “floor” price for the value of propylene 86

Propylene to Gasoline Alkylate

▪ Alkylate is a refinery product made by catalytically reacting

propylene and/or butylenes with isobutane to yield C7-C8
hydrocarbons with octane ratings suitable for use in gasoline.
▪ Alkylation can be done by 2 processes as
• Hydrofluoric acid (HF) catalyst
• Sulfuric acid catalyst
▪ Both sulfuric and HF processes yield about the same quantity and
quality of product, but the HF process is less energy-intensive.

87
Propylene (+ C4 olefins) to Polymer Gasoline (Polygas)

▪ Catalytic polymerization (dimerization, oligomerization) uses C3-C4 olefins

from catalytic cracking off-gases to produce hydrocarbon mixtures in the C6-
C12 range.

▪ The UOP process, employing a phosphoric acid catalyst supported on

diatomaceous earth (SPA) in either a chamber or a tubular reactor, is most
commonly used for catalytic polymerization.

88
 89
The development of 100 octane gasoline -
oligomerization
 Ipatieff and coworkers investigated
methods of utilizing cracked gasses
containing C3= and C4=
 Discovered that acids catalyze
oligomerization of olefins to longer,
branched olefins
 Good octane value gasoline
– Gasoline production 1934 was
18 billion gallons of 65 octane

100 octane gasoline:

dimerization of isobutene
From UOP archives and Ipatieff, V.N.; Corson, B.B.;
Egloff, G. Ind. Eng. Chem. 1935, 27, 1077-81.

followed by hydrogenation

Ipatieff and Pines commercialize a new reaction at UOP 89

The development of 100 octane gasoline –
paraffin alkylation
Ipatieff, V.N.; Corson, B.B.; Egloff, G. Ind. Eng.
▪ During development of Chem. 1935, 27, 1077-81.
oligomerization, Pines notes an
increase in gasoline liquids during
routine analytical testing
▪ Many acids investigated
• HF and H2SO4 found to be the most
effective
▪ Shell leads war efforts to
commercialize initial results

Isooctane from
paraffin

Ipatieff, V.N.; Schmerling, L. Adv. Catal. 1948, 1, 27-64. 90

 91
100 Octane Fuel and the Battle of Britain (1940)

Supermarine Spitfire
photograph A 9534 from the collections of the Imperial War Museums.
P-38 Lightning Six Fleet Air Arm Hawker Sea Hurricanes operating from Yeovilton, flying in formation.

P-40 Lightning

P-51 Mustang
Ipatieff, V.N. Chem. Eng. News 1942, 20, 1367-8.

Development of 100 octane fuel allows Allies to win air war 91

Global Propylene Supply-Demand Balance

Operating rates remain high – strong market dynamics

92
Net Trade of Propylene Monomer

93
Major Global Producers of Propylene

Minimal Trade – expensive & difficult to move

94
New Propylene Capacity Additions (2014-17)

95
Emerging Trend – Methanol to Olefins (MTO)

96
SAPO-34 vs. ZSM-5 for MTO

 ZSM-5 used for MTG by Mobil in

1970s
 SAPO-34 discovered and used
for MTO by Union Carbide in
early 1980’s
 MTO development shifted to
UOP in 1988

 SAPO-34 has a smaller pore

size (about 4 Å) compared to
that of ZSM-5 (about 5.5 Å)
 The pore size and acidity of
SAPO-34 favors light olefin
production

97
 98
98

UOP/HYDRO MTO Process

Reactor/Regenerator System
Fluidized Catalyst System Fast
Fluidized Bed Regenerator
▪ Catalyst circulation to/from reactor
• Provides continuous steady-state
operation
• Maintains high catalyst activity

▪ Catalyst circulation within reactor

results in uniform temperature in the
reaction zone

▪ Robust regenerator design provides

operating flexibility

▪ Large single reactor capacities

with proven equipment sizes 98
C4 Olefins

99
Product dependence on Feedstock
Typical Product Stream Obtained From Cracking Various Feedstocks
In a 450 thousand metric tons/year ethylene plant
(thousands of metric tons)

Products Ethane Propane N-Butane Naphtha Vac Gas Oil

H2-Rich Gas 30 20 15 15 306

CH4-Rich Gas 40 300 250 220 200

Ethylene 450 450 450 450 450

Propylene 10 290 190 260 260

Butadiene 10 30 40 80 80

Butylenes/Butanes 5 20 80 130 80

Pyrolysis Gasoline 20 140 160 990 1200

+ BTX + others
Fuel Oil 0 10 30 300 610

Ethylene Yield (Wt%) 80.5 43 40 37 24

total 575 1260 1215 2445 3186

10
0
Typical Distribution of C4’s From Steam Cracking

Remember – about 320 tons of C4’s per 1,000 tons of ethylene

10
1
Many Process Steps in C4 Separation…

Being in the C4 Olefins Business is Expensive 10

2
Uses of Butenes

Fuels Uses
▪ Dimersol
▪ Gasoline Alkylate
▪ MTBE/ETBE
▪ Polymer Gasoline
▪ Direct Blending

Chemical Uses
▪ N-butenes
▪ Isobutene
▪ Butadiene

103
Uses of Butenes

104
Fuel Uses of Butenes

1. Dimersol

2. Gasoline Alkylate

3. MTBE/ETBE

4. Polymer Gasoline

5. Direct Blending

Chemistry and production of Gasoline Alkylates and Polymer Gasoline

are similar as with propylene

105
Chemical Uses of Butenes

1. N-butene

2. Isobutene

3. Butadiene

106
Butadiene Major Uses

11.2 million metric tons (2014 est.)

107
Butadiene Production less concentrated…

Top Ten account for only 39% of World Butadiene Production

108
Butadiene is a story of auto tires…

▪ Names you recognize?

▪ How are they different

from earlier companies
named?

109
Uses of Butadiene

110
Uses of Butadiene

Both of these are intermediates in the synthesis of Nylon 66

111
Uses of Butenes

▪ Largest is isobutene – used to

make MTBE (fuel additive) –
approximately 8 million metric
tons per year

▪ Other butenes have demand of

about 2 million metric tons per
year

▪ Similarly, maleic anhydride

demand is about 2 million metric
tons per year

112
Uses of 2-Butene

Vapor-phase oxidation, VOPO4

113
Chemical Uses of Isobutene

114
Synthesis Gas

The most versatile building block?

115
Many Possible Sources of Syngas

116
…And Many Potential End-Products

117
But Today, an Ammonia / Methanol Story

118
Fertilizers Dominates Ammonia Uses

119
And Methanol has become an Asia Story
▪ Driven mostly by coal monetization in
Methanol WW Production Capacity China
▪ Today, 91% of MeOH capacity in Asia is
based in China
▪ About 90% of China MeOH based on
coal gasification
▪ Operating rates remain very low – coal
not near markets

120
Regional Trade Flows of Methanol

Despite Asia Build-up, Still a Net Importer

121
The Building Blocks and Major Petrochem
Products

122