RECENT ADVANCES IN PETROCHEMICAL PROCESSES-AN OVERVIEW

DR. R.P. VERMA

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

KEY NOTE LECTURE FOR PRI KACST, Riyadh

JUNE 2011
1

CONTENTS
Petroleum Refining - Petrochemicals The Value Chain Basic/Primary Petrochemicals Petrochemicals - Polymers Polyolefins Catalysts, Process Technologies and Latest Challenges Conclusions
2

PETROLEUM REFINING - THE MOTHER INDUSTRY

TRANSPORT

PETRO CHEMICALS

PETROLEUM REFINING

CHEMICALS & FERTILIZERS

ENERGY

PETROLEUM REFINING/PETROCHEMICALS
CHEMICAL PROCESS TECHNOLOGY HAVING VARIOUS INTEGRATED 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 Information Science)
5

PETROCHEMICALS
BASIC PETRO CHEMICALS [Ethylene, Propylene, Butadiene/s & BTX]

FEEDSTOCKS
[NG, Naphtha, Gas Oil, Kerosene]

PETROCHEMICALS INDUSTRY

PETROCHEMICALS PRODUCTS / INTERMEDIATES [PE,PP,PVC,PS, PBR, MEG, LAB,ACN, AF, PTA, PHA, MA,CPL]

Petrochemicals 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.

Source: Exxon-Mobil

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

Technological Changes - Key Drivers Cyclic Nature of Industry

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 Advancements are highly required.

Technology 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

Adding Value to the Crude

Petrochemical add significant Value

Refinery Streams for Petrochemicals/Chemicals

PROPYLENE CRACKED LPG BUTENE, BUTANE PETROL NAPHTHA FERTILIZERS POWER PLANTS
PETROCHEMICALS/ PETROCHEMICALS

/CHEMICALS

HAN LAN
AROMATICS

REFINERY
ETHYLENE NAPHTHA CRACKER PROPYLENE C4s

CHEMICALS

PETROCHEMICALS/

CHEMICALS

KEROSENE

N-PARAFFINS

PETROCHEMICALS/

CHEMICALS

FUEL

Value Chain from Refinery Streams

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

PSF TEXTILES

HAN

PX

PTA

PFY FILMS, BOTTLES

Products from High Aromatic Naphtha

PET

SK

N-PARAFFINS

LAB

DETERGENTS

Products from Kerosene

LAB : Linear Alkyl Benzene

Value Chain from Refinery Streams

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

PVC, MEG, Styrene

CABLES, FILM, PIPE, FIBRES, POLYSTYRENE, ABS, SBR

LDPE/ LLDPE

POLYMERS- BOTTLES, FILM, PIPE, PLASTICS

ETHYLENE LAN PROPYLENE

HDPE PP
POLYMERS-LUGGAGE, FURNITURE, FILMS, RAFFIA, CONTAINERS, ETC.

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

Products from Low Aromatic Naphtha

PO/PG,ACN ,Acrylic Acid/ Acrylate, Cumene/ Phenol

SPECIALTIES- ACRYLIC FIBRES, PAINTS,

SUPER ADSORBENT POLYMERS, WATER TREATMENT CHEMICALS , BISPHENOL, POLYCARBONATES

17

REFINERY AS THE SOURCE OF PRTROCHEMICAL FEEDSTOCKS

Olefins
Ethylene Propylene Isobutylene FCC - C3/C4,s

Aromatics
Benzene Toluene Xylene REFORMING
18

Olefins & Aromatics feedstock sources

Source: Total Petrochemicals 19

Ethylene & Propylene Yields from Various Feedstocks

0.01 0.40 0.43 0.53 0.58 P/E

20

Advantaged Regions
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
21

2010 Ethylene Production by Feedstock

Production by feedstock - World Production by feedstockMDE
Butane Naptha 2% 13% Propane 14%
Naptha 50% Others 2% Gas Oil 3%

Propane Butane 8% 4% Ethane 33%

Others 1%

Ethane 70%

2010 Production Estimate = 111 Million Metric Tons

Selected Middle East Crackers (Likely Completion by 2011)

Who
Yansab Tasnee Sharq Sipchem Kayan

Where
Saudi Arabia Saudi Arabia Saudi Arabia Saudi Arabia Saudi Arabia

Thousand tpy Ethylene

1300 1000 1300 1300 1350 1400 850 1300

Thousand tpy propylene

400 300 200 ( Both Ethylene & Propylene) 300 750 0 0

Feed
Ethane/propane Ethane/propane Ethane/propane Ethane/propane Ethane/propane Ethane Ethane Ethane

P/E
0.3 0.3 0.2

0.2 Note 0 0

Bourouge II Abu Dhabi Olefins II Kuwait

Ras Laffans Qatar Olefins

Note : Ethylene consumed to make propylene via metathesis; gross ethylene shown
23

Pathways for Increased Olefin Production

24

Increasing Ethylene Production with MaxEne Process

25

MaxEne Process Details

26

Global Propylene Supply Development

27

Propylene Demand growth

28

Propylene from Refinery

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

29

Propylene Yield Dependent on Feed Quality, Catalyst & Reactor Severity

30

Balance Competing Reactions For Maximum C3 = Yield

31

Commercial Yields Consistent with Equilibrium Model

32

Propylene is Favored by Low Reactor Partial Pressure and High Temperature

33

Comparative Yields HDT VGO Feed

34

Indmax Process Technology

Typical product yields & process conditions

35

High Propylene FCC (HP FCC) Technology

36

Pilot Plant Results Demonstrate Ability to Recrack Light Olefins

37

Recycling Increases Maximum C3=

38

Comparision of Propylene-on-purpose Technologies

Process MTO / MTP Metathesis C3 Dehydro Olefins cracking

Feedstock

Methanol / Methane

Ethylene & Butene Significant Negative None Small to Moderate Low to Moderate Several

Propane Significant Neutral None Large Moderate Several

C4 C8 Olefins None to Little Positive Ethylene & BTX Gasoline Small to Large Moderate to Large Sasol
39

Feed None Pretreatment Sensitive to Positive Ethylene Price Major Byproducts Economic Size of Plant Investment Commercial Ethylene , Water Large Moderate to Large No

Increasing Propylene and Ethylene Yield with Olefin Cracking Process (OCP)

40

Integration of OCP in Naphtha Cracker

41

Olefin Cracking Process Applications

42

Olicrack Process

43

Olicrack - Feedstock & Products

44

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ETHYLENE
LOW DENSITY POLYETHYLENE (LDPE) LINEAR LOW DENSITY POLYETHYLENE (LLDPE)

HIGH DENSITY POLYETHYLENE (HDPE)

ETHYLENE

ETHYLENE OXIDE

ETHYLENE GLYCOL POLYSTYRENE

ETHYL BENZENE

STYRENE MONOMER

AS, ABS RESINS

SYNTHETIC RUBBER (SBR) ETHYLENE DICHLORIDE VINYL CHLORIDE MONOMER POLY VINYL CHLORIDE ALFA- OLEFIN (LAO) HIGHER ALCOHOLS

PROPYLENE
POLYPROPYLENE ACRYLIC FIBER ACRYLONITRILE ACRYLIC ACID BY-PRODUCT: HYDROGEN CYANIDE POLYURETHANE FOAM ACRYLIC ESTERS

METHYL
METHACRYLATE

PROPYLENE

PROPYLENE GLYCOL PROPYLENE OXIDE OXO-ALCOHOL

GLYCERINE PLASTICISER

GLACIAL ACRYLIC ACID ACRYLIC ACID ACRYLATES

SUPER ADSORBENT POLYMER

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

PROPYLENE
CUMENE

contd.

PHENOL (BY-PRODUCT : ACETONE) BISPHENOL

PROPYLENE

ALLYL CHLORIDE

EPICHLOROHYDRIN

EPOXY RESIN

ACETONE

ISOPRENE

ISOPRENE RUBBER

C4-BASED
SYNTHETIC RUBBER BUTADIENE POLYBUTADIENE RUBBER

METHYL METHACRYLATE MTBE TERTIARY BUTANOL METHYL ETHYL KETONE C4 STREAMS BUTENES BUTENE-1/2 OXO-ALCOHOLS

ISOPRENE POLYISOBUTYLENE, PIB BUTANE MALEIC ANHYDRIDE

SYNTHETIC RUBBER

Butadiene Based
Contd

Polybutadiene
+ Styrene

SBR rubber By-product Butadiene

+ Chlorine

Chloroprene
+ Ammonia

Neoprene rubber

Hexamethylene diamine

Nylon 6/6

50

AROMATIC NAPHTHA
BENZENE CYCLOHEXANE CAPROLACTUM NYLON6,6

MALIECANHYDRIDE TOLUENE DIISOCYANATE

TOLUENE

O-XYLENE

PHTHALIC ANHYDRIDE

AROMATIC NAPHTHA

XYLENE

P-XYLENE

PURIFIED TEREPHTHALATE(PTA) / DIMETHYL TEREPHTHALATE

Global pX Supply / Demand

52

Polymer Demand

Polyolefins have maximum demand and a decent growth rate 53

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 .

55

Classification Of Ziegler-Natta Catalysts

56

Heterogeneous Catalyst

57

Homogeneous Catalysts
Catalyst Metallocenes
Dicyclopentadienyl Titanium dichloride / DEAC Dicyclopentadienyl Zirconium dichloride / MAO Ethylene bis-indenyl ZrCl2 / MAO Ethylene bis-tetrahydroindenyl ZrCl4 / MAO PE PE/APP Iso PP Iso PP SPP E-P (Random)
58

Polymer

Z-N
VCl4 / DEAC (- 450C) VCl4 / DEAC

Development of Polyolefin Catalyst Polypropylene

Generation
1ST

Catalyst System
- TiCl30.33 AlCl3 + DEAC -TiCl3+DEAC

Mileage gm PP/Catalyst
1500

% Ii
90 94

Supported catalysts

2nd

4000

94 97

3rd Generation Mg-Ti Supported Catalysts

Ist TiCl4/ester/MgCl2+ AlR3/ester TiCl4/diester/MgCl2 + AlR3 / dialkoxysilane TiCl4/diether/MgCl2 + AlR3 / dialkoxysilane Morphologically Controlled Catalysts 10000 95 - 99

Growth of catalyst particle

2nd

> 25000

95 - 99

RGT

> 40000

95 - 99

3rd 4th

>40000

96-98

Z-N catalyst developments for Polypropylene

40 - 60 Mileage, Kg PP /g Cat.
ogy ysts l o rph catal lyst) o M led ata rol ical c t n co pher (S

97 - 98 % Isotactic index 88 90,

60

10 - 25,

d pporte u S l / MgC 2 HY-HS ctron e l e , s lyst Ti cata donor

3 - 5,

ed TiCl 3 i f i d o M Donor

1.5,

AlCl 3 3 3 . TiCl 3

Internal donors: Ethers, mono esters, Diesters, Diethers

1953

Late 1960s Mid 1970s Year of Commercialization

1980s

92 94,

95 - 96,

Role of Catalyst
Specific nature of the catalyst has an impact on : # # # Polymer molecular weight and distribution Homo and copolymerization kinetics Degree of sterioregularity Size and shape Porosity Surface area Play an important role in regulating morphology

Other factors:

Expectations from Polyolefin Catalyst

Activity Morphology MWD Copolymer Hydrogen response Stereo-regularity Polymerization Kinetics # Only in case of PP High Regular (Spherical) Controllable High co-monomer Good to very good Controllable Stable Good economics Low catalyst residue Smooth operation Good flowability of powder Tailored polymer processing properties Ability to make broad range of polymers For making wide range of grade slate Polymer with tailed properties Homogeneous material

Catalyst Performance / Parameter Correlation

# For Polypropylene only

63

Evolution of Donors Internal Donors

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.

(Ethylbenzoate)

(Dibutylphthalate)

(Di - ether)

Evolution of Donors External Donor Donors

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.

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
66

Latest Challenges in Polyolefin Catalyst Technologies

Polyethylene
Insitu 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.) 67

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.
68

Process Technologies

PE Technologies High Pressure Processes

Employs free radical catalyst for polymerization Energy intensive process Product with easy processability
Autoclave 70 Tubular

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

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

SCB
71

Low Pressure Process Technologies

72

Classification of Commercial Polyolefin Processes

Polyolefin Process Technologies

Slurry Phase

Gas Phase

Solution Phase (PE Only) CSTR

Heavy Diluent

Light Diluent

FBD

Stirred bed

Loop

CSTR

Vertical Reactor

Horizontal Reactor

PE Technologies First generation

First low pressure process for making linear PE was based on the catalyst developed by Karl Ziegler

Slurry Process

Solution Process

CSTR

Philips Loop reactor

CSTR

ATTRIBUTES: Simple in operation Mild operating conditions High conversions High purity products Medium to High molecular weight products Easy heat removal

ATTRIBUTES: High throughput Less grade C/o penalty Low to medium molecular weight products High purity products Low residence time
74

PE Technologies Second Generation

Gas Phase Process
Simple and safe to operate Highly energy efficient process 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

Higher capital cost as compared to conventional 1st generation slurry process But 20%lower operating cost

Fluidized Bed
Switched to

Low operating cost

Condensation Mode
75

PE Technologies Third Generation

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

76

Polypropylene Processes

Morphologically controlled catalyst Reactor Granule technology (RGT)

Mixed RG Technology Reactor granule technology

1990

Supported catalysts and electron donor Understanding of polymer growth on catalyst particle

1980s
On Product Slate:
In-situ creation of multiphase alloys Catalloy PO-Engineering alloy-Hivalloy by combining Z-N and Radical catalyst

Late1970s

Early 1970s
Supported catalysts

Mid 1970s

Impact on Technology development

On Manufacturing Process:
New high yield processes Elimination of process constrain 78

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

79

Polypropylene Processes Evolution

First Generation
Slurry process

Second Generation
Hexane slurry Liquid bulk with extrusion

Third Generation
Liquid Bulk w/o extrusion Gas phase process

CSTR

CSTR

LOOP

LOOP

Gas Phase, FBD

80

Third Generation Process Gas Phase

Plant size reduced
Propylene recovery
Polymerization

Capital cost high (1015%) but operating cost reduced considerably Very simple to operate Energy intensive Extrusion step required Removal of APP not required

Degassing & deactivation

Extrusion
Polypropylene

Total process steps: 5

(from earlier 8)

81

Latest Development in PP Process

Multizone circulating reactor (MZCR) -Basell
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

82

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
83

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.
84

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.) 85

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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