1

RECENT ADVANCES IN PETROCHEMICAL PROCESSES-AN

OVERVIEW

DR. R.P. VERMACONSULTANT - R&D, HPCL

Formerly : Petrotech Chair Professor, IIT Delhi;Executive Director & Head-R&D, IOCL

KEY NOTE LECTURE FOR PRI KACST, Riyadh

JUNE 2011

2

CONTENTS

• Petroleum Refining - Petrochemicals

• The Value Chain

• Basic/Primary Petrochemicals

• Petrochemicals - Polymers

• Polyolefins Catalysts, Process Technologies

and Latest Challenges

• Conclusions

3

4

PETROLEUM REFINING - THE

MOTHER INDUSTRY

TRANSPORT

PETROLEUM REFINING

ENERGY

CHEMICALS & FERTILIZERS

PETROCHEMICALS

5

PETROLEUM REFINING/PETROCHEMICALS

CHEMICAL PROCESS TECHNOLOGY HAVING VARIOUS INTEGRAT ED DISCIPLINES�Scale independent

• Chemistry, Biology, Physics, Mathematics• Thermodynamics• Physical Transport Phenomena

�Micro Level• Kinetics• Catalysis on molecular level• Interface Chemistry• Microbiology• Particle Technology

�Meso Level• Reactor Technology• Unit Operations• Scale-up

�Macro Level• Process and Technology Development (including Cost Engineering)• Process Integration and Design (including Materials Science)• Process Control and Operation (including Informatio n Science)

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PETROCHEMICALS

PETROCHEMICALSINDUSTRY

PETROCHEMICALS –PRODUCTS / INTERMEDIATES

[PE,PP,PVC,PS,PBR, MEG, LAB,ACN, AF,

PTA, PHA, MA,CPL]

BASIC PETRO CHEMICALS[Ethylene, Propylene,

Butadiene/s & BTX]

FEEDSTOCKS[NG, Naphtha,

Gas Oil, Kerosene]

Petrochemicals IndustryPetrochemicals Industry

• One of the most rapidly growing industries worldwide

• Broad spectrum of the products

• Large scale industry - high investment cost but generates high profits

• The industry is cost driven and the feed stock price largely affect the product price.

• Important factors governing the consumption markets include the geographic location and demographics.

• One of the most rapidly growing industries worldwide

• Broad spectrum of the products

• Large scale industry - high investment cost but generates high profits

• The industry is cost driven and the feed stock price largely affect the product price.

• Important factors governing the consumption markets include the geographic location and demographics.

Source: Exxon-Mobil

Technological Changes - Key Drivers

Social Challenges

Technological Changes - Key Drivers

Social Challenges

• Increasing consumption• Rising standards of living• Urbanization• Growing population• Longer life span• Demand for better performing materials by consumer

• Fewer closed borders and more trade – more connected world

• Emerging economies (GDP growth) with growing middle classes and disposable income

• Increasing consumption• Rising standards of living• Urbanization• Growing population• Longer life span• Demand for better performing materials by consumer

• Fewer closed borders and more trade – more connected world

• Emerging economies (GDP growth) with growing middle classes and disposable income

• Cyclic nature of the petrochemical industry

• Unforeseen and unexpected frequent changes in the crude price and economy e.g. Recession

• Variation in demand-supply scenario

• Establishment of new capacities

• This has put the industry in a situation where Technical Innovations and Advancementsare highly required.

• Cyclic nature of the petrochemical industry

• Unforeseen and unexpected frequent changes in the crude price and economy e.g. Recession

• Variation in demand-supply scenario

• Establishment of new capacities

• This has put the industry in a situation where Technical Innovations and Advancementsare highly required.

Technological Changes - Key Drivers

Cyclic Nature of Industry

Technological Changes - Key Drivers

Cyclic Nature of Industry

Technology Innovations – Key to SuccessTechnology Innovations – Key to Success

11

Nexant -2009

Profitability will reach the trough in 2011 and climb to a new peak in 2015 with return matching those of 2004

Profitability will reach the trough in 2011 and climb to a new peak in 2015 with return matching those of 2004

Adding Value to the Crude

Petrochemical add significant Value

Refinery Streams for Petrochemicals/Chemicals

REFINERY

CRACKED LPGPROPYLENE

BUTENE, BUTANE

PETROCHEMICALS

/CHEMICALS

AROMATICS

PETROL

FERTILIZERS

POWER PLANTS

NAPHTHA CRACKER

ETHYLENE

PROPYLENE

C4s

N-PARAFFINS

FUEL

NAPHTHA

KEROSENE

PETROCHEMICALS/ CHEMICALS

PETROCHEMICALS/ CHEMICALS

PETROCHEMICALS/ CHEMICALS

HAN

LAN

HAN PX PTA

PSF

PFY

PET

TEXTILES

FILMS, BOTTLES

Products from High Aromatic Naphtha

SK N-PARAFFINS LAB DETERGENTS

Products from Kerosene

HAN : High aromatic naphtha, PX: Pata-Xylene, PTA: Purified Terephthalic Acid, PSF: Polyester Staple Fibre, PFY: Polyester Fibre Yarn, PET: Poly Ethylene Terephthalate

LAB : Linear Alkyl Benzene

Value Chain from Refinery Streams

LAN

ETHYLENE

PROPYLENE

LDPE/LLDPE

HDPE

PP

POLYMERS- BOTTLES, FILM,

PIPE, PLASTICS

POLYMERS-LUGGAGE, FURNITURE,

FILMS, RAFFIA, CONTAINERS, ETC.

Products from Low Aromatic Naphtha

PVC, MEG, Styrene

CABLES, FILM, PIPE, FIBRES,

POLYSTYRENE, ABS, SBR

PO/PG,ACN,Acrylic

Acid/ Acrylate, Cumene/ Phenol

SPECIALTIES- ACRYLIC FIBRES, PAINTS,

SUPER ADSORBENT POLYMERS, WATER

TREATMENT CHEMICALS , BISPHENOL,

POLYCARBONATES

LAN: Low Aromatic Naphtha, PVC : Poly-Vinyl Chloride, MEG: Mono Ethylene Glycol, LDPE : Low density Poly Ethylene, LLDPE : Linear Low Density Poly Ethylene,

HDPE : High Density Poly Ethylene, PP : Poly Propylene, PO: Propylene Oxide, PG : Propylene Glycol, ACN :

Acrylonitrile, ABS : Acrylonitrile Butadiene Styrene, SBR: Styrene Butadiene Rubber

Polyethylene (LDPE, LLDPE, HDPE), Polypropylene and PVC are classified

as Polymers

Value Chain from Refinery Streams

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REFINERY AS THE SOURCE OF PRTROCHEMICAL FEEDSTOCKS

Olefins Aromatics

Ethylene BenzenePropylene TolueneIsobutylene Xylene

FCC - C3/C4,s REFORMING

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Olefins & Aromatics feedstock sources

Source: Total Petrochemicals

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Ethylene & Propylene Yields from Various Feedstocks

0.01 0.40 0.43 0.53 0.58 P/E

Advantaged Regions

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Investments flow to:- Where market exists

And /or- Where there is feedstock advantage

�Middle East has advantage on feedstock :

abundant cheap raw material

� India & China are the two major growth centers :

significant market potential

2010 Ethylene Production

by Feedstock

Production by feedstock - World

Production by feedstock-MDE

Propane

8%

Butane

4%

Naptha

50%

Gas Oil

3%

Others

2%

Ethane

33%

Ethane

70%

Propane

14%

Butane

2%

Naptha

13%

Others

1%

2010 Production Estimate = 111 Million Metric Tons

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Selected Middle East Crackers (Likely Completion by 2011)

Who WhereThousand

tpyEthylene

Thousandtpy

propyleneFeed P/E

Yansab Saudi Arabia 1300 400 Ethane/propane 0.3

Tasnee Saudi Arabia 1000 300 Ethane/propane 0.3

Sharq Saudi Arabia 1300 200 Ethane/propane 0.2

Sipchem Saudi Arabia 1300 ( Both Ethylene & Propylene)

Ethane/propane

Kayan Saudi Arabia 1350 300 Ethane/propane 0.2

Bourouge II Abu Dhabi 1400 750 Ethane Note

Olefins II Kuwait 850 0 Ethane 0

Ras Laffans Olefins

Qatar 1300 0 Ethane 0

Note : Ethylene consumed to make propylene via meta thesis; gross ethylene shown

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Pathways for Increased Olefin Production

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Increasing Ethylene Productionwith MaxEne Process

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MaxEne Process Details

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Global Propylene Supply Development

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Propylene Demand growth

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Propylene from Refinery

� Deep Cat.Cracking(DCC)� Indmax� High Severity FCC (HS FCC)� High propylene FCC (HP-FCC)� Flex Ene� Olicrack /OCP

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Propylene Yield Dependent onFeed Quality, Catalyst & Reactor Severity

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Balance Competing ReactionsFor Maximum C3 = Yield

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Commercial Yields Consistent withEquilibrium Model

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Propylene is Favored by Low ReactorPartial Pressure and High Temperature

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Comparative Yields – HDT VGO Feed

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Indmax Process TechnologyTypical product yields & process conditions

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High Propylene FCC (HP FCC) Technology

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Pilot Plant Results Demonstrate Abilityto Recrack Light Olefins

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Recycling Increases Maximum C3=

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Comparision of Propylene-on-purpose Technologies

Process MTO / MTP Metathesis C3 Dehydro Olefins cracking

Feedstock Methanol / MethaneEthylene &

ButenePropane C4 – C8 Olefins

Feed Pretreatment

None Significant Significant None to Little

Sensitive to Ethylene Price

Positive Negative Neutral Positive

Major Byproducts

Ethylene , Water None NoneEthylene & BTX Gasoline

Economic Size of Plant

LargeSmall to

ModerateLarge Small to Large

Investment Moderate to LargeLow to

ModerateModerate Moderate to Large

Commercial No Several Several Sasol

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Increasing Propylene and Ethylene Yieldwith Olefin Cracking Process (OCP)

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Integration of OCP in Naphtha Cracker

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Olefin Cracking ProcessApplications

43

Olicrack Process

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Olicrack - Feedstock & Products

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ETHYLENE

ETHYLENE OXIDE ETHYLENE GLYCOL

POLYSTYRENE

ETHYL BENZENE STYRENE MONOMER AS, ABS RESINS

ETHYLENE DICHLORIDE

SYNTHETIC RUBBER (SBR)

ALFA- OLEFIN (LAO)HIGHER

ALCOHOLS

POLY VINYL CHLORIDE

LOW DENSITY POLYETHYLENE (LDPE)

LINEAR LOW DENSITY POLYETHYLENE (LLDPE)

HIGH DENSITY POLYETHYLENE (HDPE)

ETHYLENE

VINYL CHLORIDE MONOMER

PROPYLENE

ACRYLIC ACID

BY-PRODUCT:

HYDROGEN CYANIDE

PROPYLENE OXIDE

GLACIAL ACRYLIC ACID

ACRYLATES

ACRYLONITRILE

PROPYLENE GLYCOL

OXO-ALCOHOL

ACRYLIC ACID

PROPYLENE

POLYPROPYLENE

POLYURETHANE FOAM

ACRYLIC ESTERS

METHYL

METHACRYLATE

PLASTICISER

GLYCERINE

SUPER ADSORBENT POLYMER

METHYL ACRYLATE, ETHYL ACRYLATE, BUTYL ACRYLATE, 2 ETHYL HEXYL ACRYLATE

ACRYLIC FIBER

PROPYLENE contd.

PHENOL

(BY-PRODUCT : ACETONE)

ALLYL CHLORIDE

CUMENE

ISOPRENE RUBBER

EPOXY RESIN

BISPHENOL

EPICHLOROHYDRIN

ISOPRENE

PROPYLENE

ACETONE

C4-BASED

BUTADIENE

ISOPRENE

POLYBUTADIENE RUBBER

MTBE

TERTIARY BUTANOL

BUTANE

BUTENES

METHYL METHACRYLATE

MALEIC ANHYDRIDE

SYNTHETIC RUBBER

BUTENE-1/2

METHYL ETHYL KETONE

OXO-ALCOHOLS

SYNTHETIC RUBBER

C4 STREAMS

POLYISOBUTYLENE, PIB

50

Butadiene Based

Polybutadiene

SBR rubber

Neoprene rubber

Nylon 6/6

Chloroprene

Hexamethylene diamine

By-product Butadiene

Contd…

+ Chlorine

+ Ammonia

+ Styrene

XYLENE

O-XYLENE PHTHALIC ANHYDRIDE

P-XYLENE PURIFIED TEREPHTHALATE(PTA) / DIMETHYL TEREPHTHALATE

AROMATIC NAPHTHA

AROMATIC

NAPHTHA

BENZENE CYCLOHEXANE CAPROLACTUM NYLON6,6

MALIECANHYDRIDE

TOLUENETOLUENE DI-ISOCYANATE

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Global pX Supply / Demand

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Polymer DemandPolymer DemandPolymer DemandPolymer Demand

Polyolefins have maximum demand and a decent growth rate

Industry Outlook for Polyolefin Global

• LLDPE is projected as one of the fastest growing polyolefins

• The single site / metallocene LLDPE to continue to grow at higher rates

(12-15%)

• Bimodal HDPE to continue to attract attention since it offers added

advantages over unimodal HDPE

• Long term growth rate of 4.6% is envisaged during the period 2005-2020

for HDPE

• It is expected that development of bimodal catalyst and production of

bimodal resin from single reactor to further boost its growth rate due to

lower production cost for HDPE

• Polypropylene is expected to grow at the rate 4.5% from 2005-2020 .

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56

Classification Of Ziegler-Natta Catalysts

57

Heterogeneous Catalyst

58

Homogeneous Catalysts

Catalyst Polymer

Metallocenes

• Dicyclopentadienyl Titanium dichloride / DEAC PE

• Dicyclopentadienyl Zirconium dichloride / MAO PE/APP

• Ethylene bis-indenyl ZrCl2 / MAO Iso PP

• Ethylene bis-tetrahydroindenyl ZrCl4 / MAO Iso PP

Z-N

• VCl4 / DEAC (- 450C) SPP

• VCl4 / DEAC E-P

(Random)

GenerationCatalyst

System

Mileage

gm PP/Catalyst% Ii

1ST δ- TiCl30.33 AlCl3

+ DEAC

1500 90 – 94

2nd δ-TiCl3+DEAC 4000 94 – 97

3rd Generation Mg-Ti Supported Catalysts

Ist TiCl4/ester/MgCl2+

AlR3/ester

10000 95 - 99

2nd TiCl4/diester/MgCl2

+ AlR3 / dialkoxysilane

> 25000 95 - 99

3rdTiCl4/diether/MgCl2

+ AlR3 / dialkoxysilane

> 40000 95 - 99

4th Morphologically Controlled

Catalysts

>40000 96-98

Supported

catalysts

Growth

of

catalyst particle

RGT

Development of Polyolefin CatalystPolypropylene

60

Z-N catalyst developments for Polypropylene

Mile

age,

Kg

PP

/g C

at.

1953 Late 1960s Mid 1970s 1980sYear of Commercialization

TiCl 3.33AlCl 3

Donor Modified TiCl3

HY-HS/ MgCl 2Supported

Ti catalysts, electron

donor

Morphology

controlled catalysts

(Spherical catalyst)

% Isotactic index

1.5,

3

-5,

10

-25

,

40 -

60

88 –

90,

9

2 –

94,

9

5 -

96,

97 -

98

Internal donors: Ethers, mono esters, Diesters, Diethers

Role of Catalyst

Specific nature of the catalyst has an impact on :

# Polymer molecular weight and distribution

# Homo and copolymerization kinetics

# Degree of sterioregularity

Other factors:

� Size and shape

� Porosity

� Surface area

Play an important role in regulating morphology

Expectations from Polyolefin Catalyst

Activity HighGood economics

Low catalyst residue

Morphology Regular (Spherical)Smooth operation

Good flowability of powder

MWD ControllableTailored polymer processing

properties

Copolymer High co-monomerAbility to make broad range of

polymers

Hydrogen response Good to very good For making wide range of

grade slate

Stereo-regularity#

Controllable Polymer with tailed properties

Polymerization

KineticsStable Homogeneous material

# Only in case of PP

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Catalyst Performance / Parameter Correlation

#

# For Polypropylene only

� Internal donor is an important component which has contributed in improving

the catalyst efficiency, hydrogen response and reduced the dependency on use

of external donor.

� Development of Diethers as internal donors is the an example where external

donor is not required along with catalyst during polymerization.

Evolution of Donors

Internal Donors

(Ethylbenzoate) (Dibutylphthalate) (Di - ether)

� Like internal donor, external donors also influence the catalyst efficiency,

%XS and hydrogen response.

� Without external donors 3rd generation supported catalysts will have very

high catalyst efficiency but relatively high XS.

� However, addition of external donors decreases the %XS but at the cost of

activity.

Evolution of DonorsExternal Donor Donors

?

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Interaction Of Catalyst, Cocatalyst And External Donor

• Many complex reactions occur when catalyst, cocatalyst and external donor come in contact with each other

• Ti+4 get reduced to Ti+3

• Cocatalyst and external donor form complex which is also known as stereorgulating agent (SRA)

• Excess cocatalyst also reacts with the catalyst and in the process the internal donor is leached out

• This makes the active site non-isotactic

• Such active sites once again get converted in to isotactic sites with the help of SRA

67

Latest Challenges in Polyolefin Catalyst Technologies

�Polyethylene

• In–situ Creation of Branching (w/o Comonomer)

• Creation of Multi Site Catalyst for Bi/Tri/Multi –Modal Product.

• Activity Enhancement of Single Site Catalyst (SSC)/ Metallocene on Silica Support to Increase Mileage.

• Cost Effective SSC Catalyst (using Fe/Co/Ni) with Stable Kinetics.

(Contd.)

68

Latest Challenges in Polyolefin Catalyst Technologies (Contd.)

�Polypropylene

• Almost Reached at Maturity Stage.

• Creation of Branching to have High Melt Strength Product.

• Replacement of Non-Environment Friendly Component/s (eg., Dibutylphthalate) in Z-N Catalysts.

• Very Low Mol.Wt. Polypropylene (MFI > 800 g/10 min) Production.

Process Technologies

70

PE TechnologiesHigh Pressure Processes

• Employs free radical catalyst for polymerization

• Energy intensive process

• Product with easy processability

Tubular

Autoclave

71

Product Capability/Grade Slate

Autoclave

• Homo-polymer LDPE

Density: 0.910-0.935g/cm3

• VA content up to 40 wt %

• Specialty copolymers: EMA, EAA and EBA

• Extrusion coating grades

• High clarity grade for film applications

• Polymer with more LCB & less SCB

Tubular

• Homo-polymer LDPE

Density: 0.915-0.935g/cm3

• VA content up to 30 wt %

• Very high clarity films for specialty applications

• Polymer with more of SCB & less LCB

72

Low Pressure Process

Technologies

Polyolefin Process Technologies

Slurry Phase Gas Phase Solution Phase (PE Only)

CSTR

Heavy Diluent

Light Diluent

Loop CSTR

FBD Stirred bed

Vertical Reactor

HorizontalReactor

Classification of Commercial Polyolefin Processes

74

PE TechnologiesFirst generation

Slurry Process

ATTRIBUTES:

• Simple in operation

• Mild operating conditions

• High conversions

• High purity products

• Medium to High molecular weight products

• Easy heat removal

Solution Process

ATTRIBUTES:

• High throughput

• Less grade C/o penalty

• Low to medium molecular

weight products

• High purity products

• Low residence time

First low pressure process for makinglinear PE was based on the catalyst developed by Ka rl Ziegler

Philips Loop reactor

CSTR CSTR

75

Gas Phase Process

• Simple and safe to operate

• Highly energy efficient process

• Low operating cost

• Easy to alter molecular weight and MWD

• Condensation mode give high per pass conversion

• Gas phase plants with streamlined

design to manufacture granular PE

has about 20-25% lower capital cost

Fluidized Bed

Condensation Mode

PE TechnologiesSecond Generation

Switched to

Higher capital cost as compared to conventional

1st generation slurry processBut 20%lower operating cost

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• Able to produce high to very

high molecular weights

• Easy operation to alter the

product characteristics

• Easy heat removal

• New product slate with

improved performance

• Investments costs are about

10-15% higher than gas

phase process

Cascade Technology

Borstar Hybrid Slurry

PE Technologies Third Generation

Polypropylene Processes

78

Morphologically controlled catalystReactor Granule technology (RGT)

On Product Slate:

In-situ creation of multiphase alloys Catalloy

PO-Engineering alloy-Hivalloy by combining Z-N and Radical catalyst

Supported catalysts

Understanding of polymer growth on catalyst particle

Supported catalysts and

electron donor

Reactor granule technology

Mixed RG Technology

Impact on Technology development

On Manufacturing Process:

• New high yield processes• Elimination of process constrain

1990

1980s

Late1970s

Mid 1970sEarly 1970s

79

Impact of catalyst development on polyolefin manufacturing processes

• A silent revolution in the field of process

development changed PP technology.

• The new catalysts were providing

polypropylene with very high activity and

stereo-selectivity.

• Eliminated atactic polypropylene (APP)

removal and catalyst de-ashing step.

Lowering of capital cost and saving in energy, Decreased the variable cost

80

Polypropylene Processes Evolution

Slurry process

Hexane slurry

Liquid bulk with extrusion

Liquid Bulk w/o extrusion

Gas phase process

First Generation Second Generation Third Generation

CSTR CSTR LOOP LOOP Gas Phase, FBD

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• Plant size reduced

• Capital cost high (10-15%) but operating cost reduced considerably

• Very simple to operate

• Energy intensive –Extrusion step required

• Removal of APP not required

Polymerization

Degassing & deactivation

Polypropylene

Pro

pyle

nere

cove

ry

Extrusion

Third Generation ProcessGas Phase

Total process steps: 5

(from earlier 8)

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Multizone circulating reactor (MZCR) -Basell

Latest Development in PP Process

� HIGHLY HOMOGENOUS MULTI MONOMER RESINS UNIMODAL OR BIMODAL FROM SINGLE REACTOR

� POLYMERS WITH EXTREMELY HIGH PURITY

� MORPHOLOGY CONTROL OF PARTICLE SIZE, SHAPE AND DISTRIBUTION

� REQUIRES ANOTHER GAS PHASE REACTOR TO PRODUCE IMPACT COPOLYMER

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Borstar - Hybrid Processes

� Very similar to Spheripol process

� Employs super critical propane as medium of polymerization

� Narrow to broad molecular weight capability

� Broader properties window� Product with better creep,

high melt strength and better processability

84

Latest Challenges in Polyolefin Reactor Technologies

�Single Reactor System for Higher Capacity Production (800k TPA & Above).

�Maximum Heat Integration.

�Separation of H2 from Polypropylene.

�Proper Mathematical Modeling of Special Reactor Systems, eg., Multi Zone Circulating Reactor.

85

Conclusions�Petrochemicals Industry Involves Chemical Process Technologies Having Various Integrated Disciplines (Good Scope for R&D and Academics).

�Middle East Provides Cost Advantaged Feedstocks & Asia (India & China) Growing Markets.

� Recent Developments eg.,MaxEne Process Gives >30% Increase in Ethylene Yield With No Loss of Propylene.

�FCC/RFCC Plays Major Role in Integrating Refinery with Petrochemicals. (Contd.)

86

Conclusions (Contd.)

�Considerable Catalysts & Process Developments Have Taken Place in Maximising Propylene from FCC/RFCC eg., Indmax.

�Alternative/On-Purpose Propylene Process Technologies eg.,OCP , Olicrack Give More Propylene.

�Considerable Evolution & Revolution Have Taken Place in Both Polyolefins Catalysts & Reactor Technologies.

�Latest Challenges in Above Areas Discussed.

87