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Petrochemical Industry:

Role of Innovations and Feedstock Availability


Bipin Vora
Consultant, Former UOP Fellow
Lecture organised by PetroFed
and
Lovraj Kumar Memorial Trust

At
IndianOil Institute of Petroleum Management,
Gurgaon, India on March 6, 2008

Vora International Process (VIP) Corp

Outline
Introduction
Technology
Innovations and
Feedstocks
Coal & Natural Gas
Aromatics
Olefins

Summary
Vora International Process (VIP) Corp

Petrochemicals
There are three basic raw materials
that make up major part of
Petrochemical industry
1.

Synthesis Gas from Coal or Natural Gas


Hydrogen, Ammonia, Urea, Methanol,
GTL/CTL and derivatives

2. Aromatics
Benzene, Toluene and Xylenes (BTX) and
its derivatives
3. Olefins
Ethylene, Propylene and its derivatives

Outline
Introduction
Technology
Innovations and
Feedstocks
Coal & Natural Gas
Aromatics
Olefins

Summary

Petrochemicals:Methane Derivatives
GTL Fuel

FT

Coal
Coal Gasification

Fuel

DME

Steam
Electricity
LNG

Natural
Gas

Synthesis
Gas

Ethylene
Propylene
MTO

Reforming,
Partial Ox.

MTG
Methanol

Fuel

Hydrogen
Ammonia
Urea

Fuel

Vora International Process (VIP) Corp

Liquid
Fuel

Formaldehyde
Acetic acid
MTBE & Other
Chemicals

Coal & Natural Gas


New investments and
production for some
products shifting where
lower cost natural Gas is
available
With high crude oil prices
Coal is coming back

Alternative Feedstocks for petrochemicals and polymers


Vol. 2, Issue 2 January 28,2008, A weekly publication
1.

PT Bumi Resources interested coal liquification plant in


Indonesia
2. Reliance Industries interested in CTL plant in India
3. Gail planning coal project in China
4. Yankuang Groups CTL plant approved in China
5. China Coal to fund chemical projects from IPO
6. Sasol plans to build indirect CTL plant in China
7. Malaysia plans integrated gas-petrochemical project
8. Itera and Uralkhimpst to build 600 KTA methanol plant
in Rusiia
9. Shell proposes LNG/GTL project in Egypt
10. Mitsubishi gas Chemical kicks off 850 kta methanol
plant in China
11. Dow invests in direct methane utilization technology
There are 5 to 10 weekly news items on coal and natural gas upgrading

Synthesis Gas :- Key to Conversion of


Natural gas or Coal
Electricity

LNG

Natural
Natural Gas
Gas

Coal

Gasification

Steam
Reforming,
Partial Ox

Synthesis
Gas

For Coal or natural


gas to chemicals,
synthesis gas is the
key intermediate
With continuous
incremental
improvements, basic
technology is
unchanged

Synthesis Gas :- Key to Conversion of


Natural gas or Coal
Hydrogen
Ammonia
Urea
Acetic Acid
Formaldehyde
MTBE
Chemicals
MTG
Gasoline

Methanol

Fuel

MTO
Ethylene, Propylene

Linear
paraffins

Wax

FisherTropsch
GTL

Synthesis
Gas

Liquid Fuel
DME
Fuel

UOP 4628I-34

Coal & Natural gas (Methane)

Pre-1950s Coal based petrochemicals


In 1955 US Benzene production 70 %
from Coal and 30% from Petroleum

Late 1950s - With Refining capacity


increasing and development of
catalytic reforming technology,
naphtha becomes primary feedstock

Methanol Plant Construction


1980s

1990s

2000-2008

NA-USA & Canada

Venezuela

Trinidad & Tobago

Russia-Siberia

Norway

Chile

Saudi Arabia

Iran

Iran

Malaysia

Qatar,

Qatar

Ukraine

Saudi Arabia

Oman

Libya

Trinidad

China-Coal

New Zealand

Libya

Indonesia

Chile
Indonesia
Malaysia

Pre 1980 production mostly in NA, WE and Japan


Post 1980 new Construction mostly at advantaged natural gas sites

Methanol-Summary

Industry shifted to locations where cost


of natural gas is lower

Single train production capacity


increased from 2500 MTD to 5000
MTD, lowering cost of production per
ton of methanol

One or more new plants under design


construction with capacity of up to
10000 MTD

Outline
Introduction
Technology
Innovations and
Feedstocks
Coal & Natural Gas
Aromatics
Olefins

Summary

Aromatics (BTX): Raw Material &Technology

1950s: Development of liquid-liquid solvent


extraction technology accelerates production
and uses of BTX

1952 Extraction by EG; Dow Chemical


1960s Extraction by Sulfolane; Shell

1960s: Adsorptive separation of components,


employing molecular sieves, by class and
molecular shape developed
1964: separation of normal paraffins from
kerosene accelerated production of linear
alkylbenzene (LAB)

Until 1970 paraxylene produced via Crystallization


1971 Adsorptive Separation, UOP Parex
Commercialized for pX production

Petrochemicals:BTX Derivatives
Benzene
2007: 38 mm MTA

Toluene
2007: 36 mm MTA

Xylene
2007: 33 mm MTA

EB-Styrene

Toluene diisocynate

pX-PTA-Polyester

Cumene-PhenolPhenolic resins

Motor Fuel-Octane
Enhancement

oX-Phathalic anhydride

LAB

Solvent

mX-isophthalic acid

Cyclohexane

Conversion to Bz-pX

Cyclohexnol
Cyclohexanone
Caprolectum-Nylon
Adipicacid-Nylon

oX/mX Conversion to
pX

Aromatics (BTX)

Pre-1950s Coal based petrochemicals

In 1955 US Benzene production 70 % from


Coal and 30% from Petroleum

1950s - With Refining capacity


increasing and development of
catalytic reforming technology,
naphtha becomes primary feedstock

Two ways of deriving aromatics from


naphtha

Naphtha reforming
Pyrolysis of Naphtha

Capacity, MTA (millions)

Worldwide p-Xylene Production Capacity


24
22
20
18
16
14
12
10
Parex
8
6
Other
4
Crystallizer
Crystallization
2
Capacity
0
1970 1975 1980 1985 1990 1995 2000

Increasing market share by adsorptive


separation technology
.
Source: UOP

UOP ParexR Units


Increasing single train production Capacity
November 2006

1400

p-Xylene, KMTA

1200

Parex
Parex Units
Units On-Stream
On-Stream
Parex
Parex Units
Units Under
Under Construction
Construction

1000
800
600
400
200
0
1970

1975

1980

1985

1990

1995

2000

2005

y 77 Parex units had been brought on stream


y 14 Parex units under construction

2010

Source: UOP

Benzene- Paraxylene
Summary
Sulfolane continues to be preferred
solvent for aromatics extraction
Adsorptive separation is preferred
technology for paraxylene
No radical shift foreseen in use of raw
material or technology, Naphtha
remains dominant raw material

Linear Alkylbenzene (LAB)


3.3 mm MTA production in 2007
Kerosene

n-paraffins

n- paraffins

Adsorptive
separation

linear olefins + H2

Linear olefins + Benzene

LAB

Catalytic
dehydrogenation

HF Acid or
Solid acid Catalysis

Continuous Renewal of LAB Technologies


4,000
UOP Detal
UOP HF
Other AlCl3/HF
DDB

Capacity, KMTA

3,500
3,000
2,500
2,000
1,500
1,000
500
0
1965

1970

1975

1980

1985

1990

1995

2000

Year
Source: UOP

2005

Linear Alkylbenzene (LAB)


Summary

Use of DDB began in 1940s, though superior in


detergency, it is phased out due to poor
biodegradability

All future growth of LAB is expected to use


alkylation technology employing solid acid
catalyst

Kerosene based paraffins may face


competition from GTL based paraffins in future

Outline
Introduction
Technology
Innovations and
Feedstocks
Coal & Natural Gas
Aromatics
Olefins

Summary

Petrochemicals:Olefins Derivatives
Ethylene
2007: 120 mm MTA

Propylene
2007: 70 mm MTA

Butadiene
2007: 10 mm MTA
Polymers and copolymers
with styrene and ACN

Polyethylene

Polypropylene

EB-Styrene

Acrylonitrile

Ethylene OxideEthylene glycols,

Cumene-Phenol

nButene-MEK

EDC, VCM

Propylene Oxide

Isobutene-TBA

Vinyl acetate

Epichlorohydrin,
Glycerol

Diisobutene, triisobutene
& polyisobutene

Ethyl alcohol
acetaldehyde

Nonylphenol
Tetramer

Isobutene-MTBE

ABS

Motor Fuel Alkylate

Ethylene: Raw Material &Technology


Raw Materials
Ethane
Propane, butane
Naphtha, gas oil

Technology
Thermal Pyrolysis

Incremental innovations in thermal


cracking and furnace design technology
have allowed single train ethylene capacity
to exceed 1 mm MT/Yr
Natural gas based or coal based Methanol to
Olefins technology is on horizon

Ethylene

Until 1980 primary production in NA, WE and Japan

Choice of feedstock depended on region


Feedstock
Year
C2-C4
Naphtha-GO

USA
79
65
35

91
75
25

WE
06
70
30

79
4
96

Japan
91
8
92

79
10
90

91
2
98

NA more ethane based


WE and Japan Naphtha based

Expansion of ethylene production in ME promotes


more ethane based crackers

Middle east Ethylene Capacity


Year
2000
2004
2008

MTA
7
11
18

2012

35

Source: CMAI- 2007 World Petroch. Conf.

Ethylene produced from Ethane


in ME has on average 250 to
400 $/MT production cost
advantage over NA/WE Europe
production

Ethylene Supply Global View


Incremental Supply

(Steam Crackers)

Others
Others
2%
2%
Ethane
Ethane
29%
29%

Naphtha
Naphtha
52%
52%

180
160

53%

140

47%

120

2012

2010

2008

2006

100

2014

Gas
Gas Oil
Oil
5%
5%

Non-ethane
Non-ethane
Ethane
Ethane
Current
Current Base
Base
Demand
Demand

million MTA

2006 Supply

Butane
Butane Propane
Propane
4%
8%
4%
8%

Source: CMAI 2007

Production
Production from
from ethane
ethane crackers
crackers will
will increase
increase
Non
-ethane sources
Non-ethane
sources of
of ethylene
ethylene are
are needed
needed to
to
meet
meet the
the demand
demand

UOP 4585F-04

Propylene Supply Global View


2006 Supply

Incremental Supply
100
43%

90

14%

80

42%

70

2014

2012

60

2010

Steam
Crackers
62%

2008

FCC
31%

Other
2%

2006

PDH
3%

Metath. OC
0.3%
2%

On-purpose propylene
FCC Refineries
Steam Crackers
Current Base
Demand

110

million MTA

(Polymer & Chemical Grades)


Grades

Source: CMAI 2007

Substantially
Substantiallymore
morepropylene
propylenewill
willcome
comefrom
from
on-purpose
on-purpose propylene
technologies
propylene
technologies
PDH = Propane Dehydrogenation, Metath. = Metathesis,
OC = Olefin Cracking, MTO = Methanol-to-Olefins
On-purpose propylene = PDH + Metath. + OC + MTO

UOP 4585F-05

600

Installed Capacity
Size of New Units

4.0

500
400

3.0

300
2.0

200

1.0

100

0.0

0
1990

1994

1998 2002

2006

Unit Size, kMTA

Capacity, MM MTA

5.0

PDH Capacity Growth


600

2010
UOP 4824D-06

Zeolite-catalyzed MeOH conversion


1975 Mobil Oil discloses ZSM-5 catalyst for
conversion of methanol to gasoline (MTG)
2 CH3OH

-H2O
+H2O

CH3-O-CH3
-H2O

Isoparaffins
Aromatics
C6+ olefins

C2 - C5 olefins
Chang, Silvestri, and Smith,
US 3894103 and 3928483

Zeolite-catalyzed MeOH conversion


1977 Mobil Oil discloses the use of various
small pore zeolites for converting methanol to
olefins (MTO)
C2C4 olefin concentration < 60% at 100% conversion
Olefin fraction increases as conversion decreases

Chang, Lang, and Silvestri,


US 4062905

Zeolite-catalyzed MeOH conversion


1982 Edie Flanigen and her associates at
Union Carbide announce discovery of silico
aluminum phospate molecular sieves. Flanigen
and her group became part of UOP upon
merger of CAPS Division of UCC with UOP
SAPO-34 shows remarkable selectivity for
conversion of methanol to light olefins
C2C4 olefin concentration < 85% at 100%
conversion

Structures of SAPO-34 and ZSM-5


5.5

3.8

H
O
(Al-O)3Si

H
O

Al(O-P)3

Small Pore
Weak Acid Sites

(Si/Al-O)3Si

Al(O-Si)3

Medium Pore
Strong Acid Sites
Source: UOP

Product Yields from MeOH:


SAPO-34 and ZSM-5 Catalysts
50

% Yield

40

SAPO-34
ZSM-5

30
20
10
0

C2=

C3=

C4=

C5+

C1-C5
Paraffins

Coke +
COx

SAPO-34 Catalyst: Once through C2= + C3= yield of 80%


ZSM-5 Catalyst:
Once through C2= + C3= yield of 50%

Source: UOP

1400

Installed Capacity
Size of New Units

4.0

1200
1000

3.0

800

2.0

600
400

1.0

Unit Size, kMTA

Capacity, MM MTA

5.0

MTO Capacity Growth


1400

200
0

0.0
1996

2000

2004

2008

2012
UOP 4824D-06

Patent Activity in USA

100
90
80
70
60
50
40
30
20
10
0

Syngas to MeOH
Syngas to C2+ alcohol
Syngas to FT Liquid

Year

20
06

20
04

20
02

20
00

19
98

19
96

19
94

19
92

19
90

19
88

19
86

19
84

MTO + MTG

19
82

19
80

# US Patents

Syngas Conversion

Ethylene-Propylene
Summary

ME becomes a major player: China, India


growing as well
Advantaged ethane supply in ME is limited
Coal or natural gas based Methanol will be a new
raw material source for ethylene and propylene
Naphtha cracker and refinery FCC units will
continue to be major source for propylene
Advantaged propane feed stock will promote
PDH at selective locations
In future, natural gas based MTO projects at
advantaged NG locations (ME, USSR..) may give
tough competition to naphtha based projects.

Value of Products Produced from


1MM BTU of Natural Gas
12

Value of Products, $

10
8
6
4
2
0

Natural
Gas

LNG

Gasoline

Methanol

Olefins

Polymers

Minimum of $4 per mmBTU differential is needed


for NG to delivered LNG

Stranded Gas Monetization Options


(for world-scale capacities with $ 2 to 6 billion
investment)
Monetization
route

Worldscale
economic capacity

Gas needed
mm SCMD

30 Years
Consumption
billion SCM

LNG

5 MM MTA
LNG

22.2

222

GTL

100,000 BPD
F-T Liquids

26.8

268

GTP

1,000,000 MTA
PE + PP

7.5

75

LNG and GTL are suitable for only the largest gas fields
GTP can be implemented on many more gas fields

Worlds gas fields by size


% of world's gas fields

100%
90%

Large Fields
=13%

80%

50 - 500 Tcf
5-50 Tcf
1 - 5 Tcf
0.5 - 1 Tcf
0.25 - 0.5 Tcf
0.1 - 0.25 Tcf
0.01 - 0.1 Tcf
< 0.01 Tcf

70%
60%
50%
40%
30%
20%
10%
0%

Total = 4,448 Fields

Number of Fields
Source: Oil & Gas Journal

Why is Methanol Attractive?


Readily synthesized on a large
scale (current largest unit is 5000
MTD, 10,000 MTD under design)
Transportable liquid fuel
Has high energy density

Kcal/M3
@ 1 atm.
25C

H2
gas

Methane
gas

DME
gas

Methanol
liquid

Naphtha
liquid

2400

8600

14200

3.97x106

8.2x106

LNG Transportation Cost about $150-200MT


Methanol Transportation Cost $10-20/MT

Advances in Methanol Technology


Significant advances
have taken place in
mega methanol
projects
First 5000 MTD
methanol plant in
operation in Trinidad
since July 2004
7500 MTD plant for
Nigeria in design
10 to 15000 MTD
plants for Qatar in
planning

300

C o st, $ /M T m etha no l

269

250
200
150

121

100

Shipping
15% ROC
Depreciation
Fixed costs
Consumables
Nat. gas

136

85

50
0

Industrial
location

Nat. gas Price,


Cost of methanol
production has come $/MM Btu
Capacity, MT/D
down significantly

$5.00
1500

Stranded
gas location

$0.75
3000

Mega-scale
methanol

Mega-scale
Methanol

$0.50
7500

100 $/MT MeOH = 229 $/MT HC Equiv.


150 $/MT MeOH = 343 $/MT HC Equiv.

$2.00
7500

Methanol Plant Closure


1990-2004

2005-2007 Closure

Japan 100%
Norway 100%

Beaumont, USA

850

Celanese, Bishop, USA

500

Korea 100%

Celanese, Clear Lake, USA 600

Italy 100%

Methanex, Kitimat, Canada 520

Spain 100%

Edmonton, Canada

France 100%
USA

Pemex, Mexico

Part of it

Methanor, Netherland

Canada Part of it

Methanex, New Zealand


Total

800
180
1000
700
5150

Source: 2007 CMAI World Methanol Conf.

Why is Methanol Attractive?

NG to LNG Delivered C efficiency about 85-90%

NG to Methanol C efficiency about 70-80%

LNG Transportation Cost about $150-200MT

Methanol Transportation Cost $10-20/MT

Gas to Polymer/Olefin Scenarios


Remote Gas Production
Segregated GTP
Integrated GTP
Methanol Plant
MTO Plant
Polyolefin Plant

Methanol Plant

MTO Plant
Polyolefin Plant

Polyolefin Markets

Patent Activity in USA

100
90
80
70
60
50
40
30
20
10
0

Syngas to MeOH
Syngas to C2+ alcohol
Syngas to FT Liquid

Year

20
06

20
04

20
02

20
00

19
98

19
96

19
94

19
92

19
90

19
88

19
86

19
84

MTO + MTG

19
82

19
80

# US Patents

Syngas Conversion

Overall Summary

New application for production of light


olefins will accelerate growth

Significant Patent activity for Methanol to


Olefins

Though research continues in direct


conversion of methane, no breakthrough
on horizon

Overall Summary

Time and time again, technology breakthrough has made


major impact on industry.

Industry always looks at availability of lower cost raw


material or shifts to where they are

No major changes expected in BTX or LAB production


technologies

As happened to the methanol industry, Olefins industry is


poised for another change to come

Natural gas based ethylene and propylene via MTO will


dominate future new capacity

Methanol will become a bigger and more important


industry

Acknowledgement
My thanks to UOP and UOP
colleagues for providing me
updates on UOP processes