Escolar Documentos
Profissional Documentos
Cultura Documentos
IN PETROCHEMICAL PROCESSES-AN
OVERVIEW
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
ENERGY
4
PETROLEUM REFINING/PETROCHEMICALS
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.
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
FILMS,
BOTTLES
Products from High Aromatic Naphtha PET
Olefins Aromatics
Ethylene Benzene
Propylene Toluene
Isobutylene Xylene
20
Advantaged Regions
21
2010 Ethylene Production
by Feedstock
Production by feedstock Production by feedstock-
- World MDE
Naptha Ethane
50% 70%
Others
2%
Gas Oil
3%
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
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)
ACRYLIC FIBER
ACRYLIC ESTERS
ACRYLONITRILE ACRYLIC ACID
BY-PRODUCT: METHYL
HYDROGEN CYANIDE METHACRYLATE
POLYURETHANE FOAM
PROPYLENE
SUPER ADSORBENT
GLACIAL ACRYLIC ACID POLYMER
ACRYLIC ACID
PHENOL
CUMENE
BISPHENOL
(BY-PRODUCT : ACETONE)
ACETONE
BUTADIENE
POLYBUTADIENE RUBBER
METHYL METHACRYLATE
MTBE
TERTIARY BUTANOL
OXO-ALCOHOLS
POLYISOBUTYLENE,
PIB
Polybutadiene
+ Styrene
SBR rubber
+ Chlorine
By-product Chloroprene Neoprene rubber
Butadiene
+ Ammonia
Hexamethylene
Nylon 6/6
diamine
50
AROMATIC NAPHTHA
MALIECANHYDRIDE
TOLUENE DI-
TOLUENE
ISOCYANATE
AROMATIC
NAPHTHA XYLENE
52
Polymer Demand
• Long term growth rate of 4.6% is envisaged during the period 2005-2020
for HDPE
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
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
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.
?
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
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
72
Classification of Commercial
Polyolefin Processes
Polyolefin Process Technologies
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
76
Polypropylene
Processes
Morphologically controlled catalyst
Reactor Granule technology (RGT)
Mixed RG
Technology
Reactor granule
1990
technology
80
Third Generation Process
Gas Phase
• Plant size reduced Polymerization
Propylene
recovery
15%) but operating cost
reduced considerably
Degassing &
• Very simple to operate deactivation
81
Latest Development in PP Process
Multizone circulating reactor (MZCR) -Basell
82
Borstar - Hybrid Processes
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.)