101 Petchem 2008 Midwest Regional Pujado Introduction Petrochemical Industry

7/31/2019 101 Petchem 2008 Midwest Regional Pujado Introduction Petrochemical Industry

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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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Documents

101 Petchem 2008 Midwest Regional Pujado Introduction Petrochemical Industry