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TRANSCRIPT
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
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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
27
Global Propylene Supply Development
28
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
35
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
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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
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Heterogeneous Catalyst
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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
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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
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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
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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
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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)
82
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
83
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.
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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.
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