You are on page 1of 87

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
3
PETROLEUM REFINING - THE
MOTHER INDUSTRY

TRANSPORT

PETRO PETROLEUM CHEMICALS


CHEMICALS & FERTILIZERS
REFINING

ENERGY

4
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 PETROCHEMICALS
[NG, Naphtha, INDUSTRY
Gas Oil, Kerosene]

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

6
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 PETROCHEMICALS
CRACKED LPG /CHEMICALS
BUTENE, BUTANE

PETROL

NAPHTHA FERTILIZERS
HAN
POWER PLANTS
LAN
PETROCHEMICALS/
AROMATICS
CHEMICALS
REFINERY

ETHYLENE
NAPHTHA PETROCHEMICALS/
CRACKER PROPYLENE
CHEMICALS
C4s

PETROCHEMICALS/
KEROSENE N-PARAFFINS
CHEMICALS

FUEL
Value Chain from Refinery
Streams
HAN : High aromatic naphtha, PX: Pata-Xylene, PTA:
Purified Terephthalic Acid, PSF: Polyester Staple Fibre, PFY: PSF
Polyester Fibre Yarn, PET: Poly Ethylene Terephthalate
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, CABLES, FILM, PIPE, FIBRES,
HDPE : High Density Poly Ethylene, PP : Poly Propylene, PVC, MEG,
POLYSTYRENE, ABS, SBR
PO: Propylene Oxide, PG : Propylene Glycol, ACN : Styrene
Acrylonitrile, ABS : Acrylonitrile Butadiene Styrene, SBR:
Styrene Butadiene Rubber

LDPE/ POLYMERS- BOTTLES, FILM,


LLDPE
PIPE, PLASTICS
ETHYLENE
HDPE
LAN
POLYMERS-LUGGAGE, FURNITURE,
PROPYLENE PP FILMS, RAFFIA, CONTAINERS, ETC.

Polyethylene (LDPE, LLDPE, HDPE),


Polypropylene and PVC are classified PO/PG,ACN SPECIALTIES- ACRYLIC FIBRES, PAINTS,
as Polymers ,Acrylic SUPER ADSORBENT POLYMERS, WATER
Acid/ TREATMENT CHEMICALS , BISPHENOL,
Acrylate, POLYCARBONATES
Cumene/
Products from Low Aromatic Naphtha Phenol
17
REFINERY AS THE SOURCE OF
PRTROCHEMICAL FEEDSTOCKS

Olefins Aromatics

Ethylene Benzene
Propylene Toluene
Isobutylene Xylene

FCC - C3/C4,s 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 Production by feedstock-
- World MDE

Propane Butane Butane Naptha Others


8% 4% 2% 13% 1%
Ethane Propane
33% 14%

Naptha Ethane
50% 70%
Others
2%
Gas Oil
3%

2010 Production Estimate = 111 Million Metric Tons


Selected Middle East Crackers (Likely
Completion by 2011)
Thousand Thousand
Who Where tpy tpy Feed P/E
Ethylene propylene
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


( Both Ethylene
Sipchem Saudi Arabia 1300 Ethane/propane
& Propylene)
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
Qatar 1300 0 Ethane 0
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

Ethylene &
Feedstock Methanol / Methane Propane C4 – C8 Olefins
Butene
Feed
None Significant Significant None to Little
Pretreatment
Sensitive to
Positive Negative Neutral Positive
Ethylene Price
Major Ethylene & BTX
Ethylene , Water None None
Byproducts Gasoline
Economic Small to
Large Large Small to Large
Size of Plant Moderate
Low to
Investment Moderate to Large Moderate Moderate to Large
Moderate
Commercial No Several Several Sasol

39
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
45
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 VINYL CHLORIDE
DICHLORIDE MONOMER

POLY VINYL CHLORIDE


ALFA- OLEFIN (LAO) HIGHER
ALCOHOLS
PROPYLENE
POLYPROPYLENE

ACRYLIC FIBER

ACRYLIC ESTERS
ACRYLONITRILE ACRYLIC ACID

BY-PRODUCT: METHYL
HYDROGEN CYANIDE METHACRYLATE

POLYURETHANE FOAM
PROPYLENE

PROPYLENE GLYCOL GLYCERINE

PROPYLENE OXIDE OXO-ALCOHOL PLASTICISER

SUPER ADSORBENT
GLACIAL ACRYLIC ACID POLYMER

ACRYLIC ACID

ACRYLATES METHYL ACRYLATE, ETHYL


ACRYLATE, BUTYL ACRYLATE,
2 ETHYL HEXYL ACRYLATE
PROPYLENE contd.

PHENOL
CUMENE
BISPHENOL
(BY-PRODUCT : ACETONE)

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 SYNTHETIC RUBBER

POLYISOBUTYLENE,
PIB

BUTANE MALEIC ANHYDRIDE


Butadiene Based
Contd…

Polybutadiene

+ Styrene
SBR rubber

+ Chlorine
By-product Chloroprene Neoprene rubber
Butadiene
+ Ammonia
Hexamethylene
Nylon 6/6
diamine

50
AROMATIC NAPHTHA

BENZENE CYCLOHEXANE CAPROLACTUM NYLON6,6

MALIECANHYDRIDE

TOLUENE DI-
TOLUENE
ISOCYANATE

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 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)
58
Development of Polyolefin Catalyst
Polypropylene
Catalyst Mileage
Generation % Ii
System gm PP/Catalyst Supported
1ST δ- TiCl30.33 AlCl3 1500 90 – 94 catalysts
+ DEAC

2nd δ-TiCl3+DEAC 4000 94 – 97


Growth
of
3rd Generation Mg-Ti Supported Catalysts catalyst particle
Ist TiCl4/ester/MgCl2+ 10000 95 - 99
AlR3/ester

2nd TiCl4/diester/MgCl2 > 25000 95 - 99 RGT


+ AlR3 / dialkoxysilane

TiCl4/diether/MgCl2 > 40000 95 - 99


3rd + AlR3 / dialkoxysilane

4th Morphologically Controlled >40000 96-98


Catalysts
Z-N catalyst developments for
Polypropylene

97 - 98
40 - 60

o l ogy ysts
o rph catal lyst)
M led ata
n trol ical c
co pher
Mileage, Kg PP /g Cat.

% Isotactic index
(S
10 - 25,

d
pporte

95 - 96,
l Su
/ MgC 2
HY-HS s, electron
lyst
Ti cata
donor
3 - 5,

92 – 94,
Mo difi ed TiCl 3
Donor

88 – 90,
Internal donors: Ethers, mono esters,
1.5,

Diesters, Diethers
.33 AlCl 3
TiCl 3

1953 Late 1960s Mid 1970s 1980s


Year of Commercialization 60
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
Good economics
Activity High
Low catalyst residue
Smooth operation
Morphology Regular (Spherical)
Good flowability of powder
Tailored polymer processing
MWD Controllable
properties
Ability to make broad range of
Copolymer High co-monomer
polymers
For making wide range of
Hydrogen response Good to very good
grade slate
Stereo-regularity
# Controllable Polymer with tailed properties
Polymerization
Stable Homogeneous material
Kinetics
# Only in case of PP
Catalyst Performance /
Parameter Correlation

63
# For Polypropylene only
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
• 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.)
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 Tubular


process

• Product with easy


processability

Autoclave
70
Product Capability/Grade Slate

Autoclave Tubular
• Homo-polymer LDPE • Homo-polymer LDPE
Density: 0.910-0.935g/cm3 Density: 0.915-0.935g/cm3

• VA content up to 40 wt % • VA content up to 30 wt %

• Specialty copolymers: EMA, EAA • Very high clarity films for specialty
and EBA applications

• Extrusion coating grades • Polymer with more of SCB & less


• High clarity grade for film LCB
applications
• Polymer with more LCB & less
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 Light FBD Stirred bed


Diluent Diluent

Loop CSTR Vertical Horizontal


Reactor 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 CSTR


reactor

ATTRIBUTES: ATTRIBUTES:
• Simple in operation • High throughput
• Mild operating conditions • Less grade C/o penalty
• High conversions • Low to medium molecular
• High purity products weight products
• Medium to High molecular weight • High purity products
products
• Low residence time
• Easy heat removal
74
PE Technologies Higher capital cost as
Second Generation compared to conventional
1st generation slurry process
But 20%lower operating cost

Gas Phase Process


Fluidized Bed
• Simple and safe to operate
• Highly energy efficient process Switched to

• 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
Condensation
Mode
75
PE Technologies
Third Generation

• Able to produce high to very Cascade


Technology
high molecular weights
• Easy operation to alter the
product characteristics
• Easy heat removal
• New product slate with
improved performance
• Investments costs are about Borstar
10-15% higher than gas Hybrid Slurry
phase process

76
Polypropylene
Processes
Morphologically controlled catalyst
Reactor Granule technology (RGT)
Mixed RG
Technology

Reactor granule
1990
technology

Supported catalysts 1980s


and
electron donor
On Product Slate:
Understanding of
In-situ creation of multiphase alloys Catalloy
polymer growth on Late1970s
catalyst particle PO-Engineering alloy-Hivalloy by combining
Z-N and Radical catalyst

Early Mid 1970s


Impact on Technology
1970s
development
Supported
catalysts 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 Second Generation Third Generation
Hexane slurry Liquid Bulk
Slurry process w/o extrusion
Liquid bulk with
extrusion Gas phase process

CSTR CSTR LOOP LOOP


Gas Phase,
FBD

80
Third Generation Process
Gas Phase
• Plant size reduced Polymerization

• Capital cost high (10-

Propylene
recovery
15%) but operating cost
reduced considerably
Degassing &
• Very simple to operate deactivation

• Energy intensive – Extrusion


Extrusion step required
Polypropylene

• Removal of APP not Total process steps: 5


required (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.
86
87