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by
Peter R PujadConsultant, Kildeer, IL
Bipin V VoraConsultant, Naperville, IL
For presentation at the Midwest Regional AIChE meetingSeptember 2223, 2008UIC Campus, Chicago
September 22, 2008 1
Introduction to petrochemicals - 101
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Historical background
Modern petrochemical industry and processes
Summary
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coal derived chemicals
acetylene chemistry (Reppe chemistry)
steam crackers and the olefin industry
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The birth of petrochemicals goes back more than 150 years, when aniline and
dyestuffs were
first
produced
from
coal
The petrochemical industry was largely
developed in
Germany
and
was
based
on
coal
The first
large
scale
production
of
a
petrochemical was that of acetylene
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phenol F Raschig (Germany) 1901
Hoffmann LaRoche(Switzerland)
carbon tetrachloride Griesheim Elektro (Germany)
1903
trichloroethylene Wacker ( Germany) 1908
ethylene Griesheim Elektro (Germany
1913
ammonia BASF (Germany) 1913
acetic acid Wacker ( Germany) 1916
ethylene oxide BASF (Germany) 1916September 22, 2008 5source: Peter H Spitz
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acetaldehyde Hoechst (Germany) 1916
acetone Hoechst (Germany) 1917
Weitzman (UK)
Standard Oil of NJ (US)
vinyl acetate Shawinigan
Chemicals
(Canada)
1920
methanol BASF (Germany) 1923
butanol BASF (Germany) 1923
vinyl chloride Wacker ( Germany) 1930September 22, 2008 6source: Peter H Spitz
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Franz Fisher and Hans Tropsch in 1925 demonstrated that synthesis gas (a mixture of H2 and CO) can be converted into a mixture of
C2 to C30 carbon range oxygenates and hydrocarbons; later this came to be known as the Fischer Tropsch (FT) technology.
Development of FT technology led to the development of several downstream processes, among them Gas to Liquids (GTL), and
hydroformylation (OXO) processes for the production of alcohols.
Germany used GTL widely during WWII to support the demand for aviation fuels.
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Fischer Tropsch chain growth mechanism
0%
20%
40%
60%
80%
100%
0 0.2 0.4 0.6 0.8 1
W t - % s e l e c
t i v i
t y
Chain growth probability,
Fischer-Tropsch selectivity
C1
C2
C3
C4
C5-C11
C12-C18
C19-C25
C26-C35
C36-C120
September 22, 2008
C5-C11
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From these early developments, we arrive at todays petrochemical industry
There are roughly three basic types of raw materials for petrochemical derivatives
Synthesis gas (syn gas)
Aromatics: benzene, toluene, and xylenes (BTX) Olefins: ethylene, propylene, butenes
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For coal or natural gas to
chemicals or fuels, synthesis gas is the key intermediate
Although with continuous incremental improvements, the basic technology remains unchanged
Natural gasCoal
Steamreforming,Partial Ox
Synthesisgas
LNGElectricity
Gasification
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UOP 4628I-34
Synthesisgas
Methanol
Fisher-Tropsch,
GTL
DME
MTO: Ethylene,Propylene
MTG
Gasoline
Acetic acidFormaldehyde
MTBEChemicals
Fuel
Hydrogen, COAmmonia
Urea
Linearparaffins
Wax
Liquid fuels
Fuel
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iC4= + CH 3OH MTBE
CH 3OH + CO Acetic acid
CH 3OH Light olefins and gasoline
CH 3OH Light olefins
2 CH 3OH DME + water
Etherification
Carbonylation
ZSM-5 catalyst
SAPO-34 catalyst
Dehydration
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Before ~1950 petrochemicals were based on coal
In 1955,
the
US
benzene
production
was
70%
based on coal and 30% on petroleum
With the increase in refining capacity and the development of catalytic reforming technology, naphtha became the primary feedstock
There are two main ways of generating aromatics from naphtha:
naphtha reformingnaphtha pyrolysis
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1950s: The development of liquid liquid
solvent extraction
technology
accelerated the production and use of BTX
1952 extraction with ethylene glycols Dow Chemical (later also UnionCarbide)
1960s extraction with
sulfolaneShell
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1960s: the adsorptive separation of components was
developed, employing
molecular
sieves,
by
class
and
molecular shape
1964: the separation of normal paraffins from kerosene
was developed
using
molecular
sieves;
this
led
to
the
production of linear alkylbenzene (LAB) biodegradable detergent intermediates
1970s: until 1970
all
the
p
xylene
was
produced
via
crystallization; in 1971 the adsorptive separation of pxylene using molecular sieves was commercialized (UOP Parex TM process)
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02468
1012141618202224
1970 1975 1980 1985 1990 1995 2000
CrystallizerCapacity
ParexProcess
C a p a c i
t y , M
T A ( m i l l i o n s
)
.
Increasing market share by adsorptive
separation technologySource: UOP
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UOP Parex TM unitsIncreasing single train production capacity
0
200
400
600
800
1000
1200
1400
1970 1975 1980 1985 1990 1995 2000 2005
p - X y l e n e , k
M T A
2010
Parex units under construction
77 Parex units had been brought on stream14 Parex units were under construction
Parex units on-stream
November 2006
Source: UOP
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Toluene via disproportionation ortransalkylation with C 9-aromatics can
produce benzene and an equilibriummixture of xylenes
Ortho- and meta-xylene can beisomerized to give an equilibrium mixture ofxylenes
Thus one can maximize the production ofpara-xylene by adding isomerization anddisproportionation or transalkylation units
Maximizing para-xylene production
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Typical UOP aromatics complex
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ethylbenzene and styrenecumene, phenol and acetone
methacrolein, methacrylic acid, and methacrylatesketene and acetic anhydridebisphenol A and polycarbonates
anilinecyclohexanol and cyclohexanone, caprolactam, nylon 6
cyclohexane
cyclohexanol and
cyclohexanone,
caprolactam,
nylon
6
adipic acid, adiponitrile, 1,6 hexanediol, 6hydroxycaproic acid, etc .nitrobenzene and aniline (and isocyanates)
maleic anhydride, 1,4 butanediol, and derivativesSeptember 22, 2008 22
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benzoic acidnitrotoluenestolylene diamines and tolylene diisocyanates (TDI)
terephtahlic acid (via toluene carbonylation)
high octane gasoline component
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oxylene
phthalic anhydride, plasticizers, alkyd resins, unsaturated polyester resinsterephthalic acid (alternative scheme)
m xyleneisophthalic acid
pxyleneterephthalic acid and polyesters
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0
500
1,000
1,500
2,000
2,5003,000
3,500
4,000
1965 1970 1975 1980 1985 1990 1995 2000 2005
C a p a c i
t y , K
M T A
Year
UOP Detal ProcessUOP HF
Other AlCl3/HFDDB
Source: UOP
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September 22, 2008
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Olefins
The main raw materials for many petrochemical derivatives
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Raw materials Technology
ethanepropane, butane thermal pyrolysis
naphtha, gas
oil
Incremental innovations in thermal
cracking and furnace design technologyhave allowed single train ethylene capacityto exceed 1 mm MT/Yr
Natural gas based or coal based Methanolto Olefins (MTO) technology is on the
horizon
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ethane ethylene
LPG ethylene, propylene, etc.
naphtha ethylene, propylene, C4s (butadiene, etc.), py gas, BTX aromatics
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View of
a typical
steam
cracker
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View of a typical millisecond cracking coilsource: Lummus
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Main products (depending on feedstock, severity, and recovery scheme)
ethylene
propylene1,3 butadieneisobutylene
1butene (2butene)py gas (pyrolysis gasoline) and aromatics
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Choice of feedstock depends on region Feedstock USA WE Japan Year 79 91 06 79 91 79 91
C2C4 65 75 70 4 8 10 2Naphtha GO 35 25 30 96 92 90 98
NA more ethane based WE and Japan naphtha based
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Raw Material % in 2006 % New PlantsEthane 29 47Propane 8Butane 4Naphtha 52Gas Oil 5Other 2
Expected production in 2015: 160 mm MTUse of ethane feed is increasing due to the availability of low priced ethane in the Middle East
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Year MTA 2000 7
2004 11
2008 182012 35
Source: CMAI - 2007 World Petroch. Conf.
Ethylene produced from ethane inthe Middle East has on average 250to 400 $/MT production costadvantage over NA/WE Europe
production
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polyethylene (LDPE, HDPE, LLDPE, etc.)ethylene oxideethylene glycolethylene dichloride, vinyl chlorideacetaldehyde
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LDPE high pressure, non catalyticHDPE catalyticLLDPE various catalysts, including metallocenes, single site catalystsethylene oxide silver on (typically) alumina, with oxygenethylene glycol noncatalytic hydration of ethylene oxideethylene dichloride ethylene chlorination (with FeCl3 catalyst)
in the liquid phase (also CaCl2 in vapor phase processes)vinyl chloride thermal pyrolysis of ethylene dichloridevinyl chloride ethylene oxychlorination with CuCl
2catalysts in
fixed or fluidized bed processes with either air or oxygenacetaldehyde various processes: typically (Wacker Hoechst) by
liquid phase oxidation of ethylene over a PdCl2 catalyst (one or two step process)
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Until 1990 propylene was produced from the following two sources:
Steam cracking provided about 2/3 of the propylene demand: Propylene is a byproduct when propane and heavier feed stocks are used for ethylene production
The remaining 1/3 came from refinery FCC: Propylene is a byproduct of refinery FCC
operation for
the
production
of
gasoline
and
diesel
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Source % in 2006 Future New Plants
FCC 31 14Steam cracking 62 42PDH 3Metathesis 2Other 2
Expected production in 2015: 95 mm MT
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Due to increasing use of lighter ethane feedstock for ethylene production, a gap developed between propylene supply and demand promoting on purpose propylene production
Catalytic dehydrogenation of propane to propylene (PDH) began in1990
Metathesis (C 2= + C 4= to 2 C 3=)
Higher olefins ( C 4-C8 olefins)cracking technology came on streamduring the late 1990s
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polypropylene and ethylene/propylene copolymerspropylene oxidepropylene glycol
acrylonitrile (acetonitrile, HCN), ABS, SANadiponitrileacrolein and acrylic acid (methionine)
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polypropylene and ethylene/propylene copolymers using Ziegler Natta or single site catalysts
propylene oxide either via the chlorohydrin process or by the oxidation of propylene with peroxide compounds
propylene glycol usually by the hydration of propylene oxide
acrylonitrile (acetonitrile, HCN)
by
the
ammoxidation of
propylene
in a fluid bed reactor
adiponitrile various schemes: dimerization of acrylonitrrile, hydrocyanation of butadiene, from adipic acid, etc.
acrolein and acrylic acid usually by air or oxygen oxidation over mixed metal oxides
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tert butanol and MTBE (methyl tert butyl ether)
methacrylatessec butanol and MEK (methyl ethyl ketone)maleic anhydride and 1,4 butanediolhigh octane motor fuel gasoline (alkylation or condensation)1,3 butadiene (polybutadiene, ABS, etc.)
adiponitrile and
HMDA
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1977 Mobil Oil disclosed the use of various small pore zeolites for converting methanol to olefins (MTO)
C2C3 olefin concentration ~ 50% at 100% conversion
Chang, Lang, and Silvestri, US 4062905
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Small pore
Weak acid sites
Medium pore
Strong acid sites
3.8 5.5
Source: UOP
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0
10
20
3040
50
C2= C3= C4= C5+ C1-C5Paraffins
Coke +COx
%
Y i e l d
SAPO-34ZSM-5
SAPO-34 catalyst: Once through C2= + C3= yield of 80%
ZSM-5 catalyst: Once through C2= + C3= yield of 50%Source: UOP
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The Middle East has become a major player; China, India are growing as well
Coal or natural gas based methanol will be a new
raw material source for ethylene and propylene
Naphtha crackers and refinery FCC units will
continue to be a major source of propylene
Advantaged propane feed stock will promote PDH
at selective
locations
In the future, natural gas based MTO projects at advantaged NG locations (ME, FSU) may give tough competition to naphtha based projects.
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Time and time again, technology breakthroughs make major impacts on
industry.Industry always looks at the availability of lower cost raw materials or relocates to where they are
No near term major changes are
expected in BTX or LAB production technologies
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New technologies for the production of light olefins will accelerate growth
ME is becoming a key player due to low cost ethane feed stock
As happened to the methanol industry, the olefins industry is poised for another change to come
Methanol will
become
a
bigger
and
more
important industry
Natural gas or coal based methanol will promote MTO
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We have only covered aromatics and
olefins as
main
petrochemical
ntermediates
The downstream industry of polymers, plastics, fibers, resins is vast, continuously innovating, and coming
up with new engineered materials
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We would like thank UOP for giving us permission to use some of the flow schemes and other material.
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