Refining and Petrochemicals

Presenters:

Dhruv Trehan
Mudit Saluja
Prathamesh Singh
Pratitee Basak

Management Trainee-HPL
HISTORY OF
1850
REFINING & 1900

PETROCHEMICALS

1950
1850 - 1900

•1856 -  First Systematic Oil Refinery Ploiești, Poland Daily

Production – 7 tonnes.

•Samuel Kier Known as the “Godfather of American Oil Industry”

became the first person in the U.S to refine Crude,

•1875 - Bradford Oil Field, Warren Pennsylvania

• By 1880, 77% of Global Oil Supply

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1900 - 1950

• 1908 – First major Oil discovery In Middle East (Iran)

• 1925 - Annual Crude Oil production surpassed a Billion

barrels.

• 1930 – New processes such as thermal reforming and

coking came into picture which improved octane no. and
yield of gasoline respectively.

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1950 - 2000

• 1950 - 1960 - Standard Oil develops Catalytic

Reforming replaced Thermal Reforming,
Hydrocracking was introduced to enhance the yield of
jet Fuels.

• 1950 – Benzene is Produced from Petroleum

• 1954 – Synthetic Zeolites are developed which changed

the Catalytic reforming process.

• 1960 -1970 – Environmental Slowdown

• 1979 – OPEC crisis

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Petrochemical Industry in India
•First Petrochemical plant of 20,000 tpa naphtha cracker was set up by Union Carbide (India) Ltd. (UCIL) to
produce ethylene in 1963 at Mumbai.

•Second naphtha cracker of 60,000 tpa was commissioned by National Organic Chemicals Industries
•Limited (NOCIL) in 1968 at Thane.

•Large scale first public sector integrated petrochemical complex was set up by Indian Petrochemical Corp. Ltd.
(IPCL) in 1970 at Vadodara.

•Today, the Indian petrochemical industry is the fastest growing in the world and the fastest growing industrial
sectors in India.

•India could establish close contacts with West Asia, Africa and Europe from the western coast and Southeast
and East Asia from the eastern coast.

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PETROCHEMICAL INDUSTRY IN INDIA - PLAYERS AND THEIR
PRODUCTION CAPACITY
Organisation Locations Capacity

Aromatics: Paraxylene capacity is 4.3 MMTPA and Benzene

Allahabad, Barabanki, Dahej, Jamnagar, Hazira, Hoshiarpur, capacity is 1.4 MMTPA.
Reliance Petrochemicals
Nagothane, Nagpur, Patalganga, Silvassa and Vadodra Polysters: 2.5 million tonnes per annum
Fiber intermediates: Purified Terephthalic Acid (PTA) 5 MMTA

NOCIL Navi Mumbai and Dahej

Haldia Petrochemicals Haldia Ethylene: 7, 00,000 TPA

Total capacity for polymers: 3,50,000 TPA

Paraxylene: 3,60,000 MTPA. Purified Terephthalic Acid from

IOCL Digboi (Upper Assam), Guwahati (Assam), Barauni, Gujarat,
Haldia, Mathura, Panipat, Paradip
Paraxylene: 5,53,000 MTPA of
Naphtha Cracker Plant: Polypropylene: 600,000 tonnes
High Density Polyethylene (HDPE): 300,000 tonnes
Linear Low-Density Polyethylene (LLDPE): 350,000 tonnes
Mono Ethylene Glycol (MEG) plant: 325,000 tonnes

Phthalic Anhydride: 222110 MTPA

Maleic Anhydride: 8000 MTPA
IG Petrochemicals MIDC Taloja (4 plants)
Benzoic Acid: 1300 MTPA
Plasticizers: 8400 MTPA
GAIL Pata (UP)

Propylene Oxide: 27000 metric tonnes

Manali Petrochemicals Limited Chennai Propylene Glycol: 14,000 metric tonnes
Polyether polyol and System polyol: 15,000 metric tonnes

Brahmaputra Cracker and Polymer Limited Lepetkata (Odissa) HDPE and LLDPE totalling upto 220000 TPA.
PP: 60000 TPA
Mangalore Refinery and Petrochemicals Limited Katipalla Polypropylene: 4,40,000 MT/annum. 9

HPCL Mittal Energy Limited Punjab Produces range of Homo PP: 467000 KT (kilotonne)

Hindustan Petroleum Corporation Limited Mumbai, Visakhapatnam, Bathinda, Barmer (Rajasthan)

Chennai refinery: 10.5 MMTPA
Chennai Petroleum Corporation Nagapattnam and Chennai
Nagapatnam: 9 MMTPA
 Petroleum

• Petroleum (or crude oil) is a fossil fuel that was formed from the
remains of ancient marine organisms

• Petroleum or crude oil is a naturally occurring mixture of

hydrocarbons, generally in a liquid state

• Although it is often called "black gold" crude oil has a wide ranging
viscosity and can vary in color to various shades of black and yellow
depending on its hydrocarbon composition.

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11
 Types of Petrochemicals

Methane, Ethane, Ethylene, Propylene, Butadiene, Benzene, Toluene, Xylenes

1st
Generation

Styrene, Dimethyl Terephthalate, Ethylene Glycol, Adipic Acid, Acrylonitrile, Vinyl Chloride Monomer
2nd
Generation

Polystyrene, Polyvinyl Chloride, DDT, Azo Dyes, Iso-prenes

3rd
Generation
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Methane

Syn GAS
H2 + CO

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 Methanol Value Addition

2 CH3OH + O2 CH2O + H2O Phenol

Formaldehyde Bakelite
Catalytic Oxidation(Silver) Condensation Poly.

PCl5 , Ethanolic NaCN

Acetic Acid
Carbonylation

Catalytic Dehydration
Methanol Di Methyl Ether
Aluminosilicate Catalyst

NH3
Methylamine
Aluminosilicate Catalyst

Iso butene
MTBE
H2SO4 50o - 900
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15
 H20
Ethanol
Ethanol

H20
Ethylene
Ethylene Ethylene
Ethylene
oxide
oxide Glycol
Glycol
1/202
Thermal Free radical
Ethylene
Ethylene Cracking Vinyl
Vinyl Polymerization Polyvinyl
Polyvinyl
Ethylene Dicholride
Dicholride Chloride
Chloride Chloride
Chloride

Cl2

Polymerization
Polyethylene
Polyethylene

Metal Oxide
(Iron Oxide) Polymerization
Ethylbenzene
Ethylbenzene Styrene
Styrene Polystyrene
Polystyrene
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 Polymerization
Polypropylene

H2O/ H2SO4
Isopropanol

Hydrogen
Peroxide Propylene Alkoxylation
Propylene Polyether Polyols
Oxide

Benzene O2 / H2 O
Cumene Phenol & Acetone

Ammonia
Acrylonitrile

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 SBR Tires, Shoes Soles, Gaskets, Molded & Extruded Mechanical Goods

Methyl
metha
Polymer Modifier, Displays, Surface Coating, Sanitary Ware
acrylate

Polyvinyl
Alcohol
Vinyl based Products, Flooring

Maleic Fumaric Acid, Agricultural Chemicals(Melathion)

Anhydride

Poly Battery Boxes, Gaskets, Hoses, Radial Tyres, Footwear, Sports Goods
Butadiene
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Value addition of Methane

Dollar Pe r t on
1400

1200 1150

1000

800

600
450
400

200
55
0

Methane Methanol MTBE

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 Value addition of Crude Oil

• Taking an example value of Crude oil at $78.39/ton when

fractionated gives naphtha as one of the streams. Dollar per ton
900
• Naphtha is produced at $385/tonne, i.e., nearly 5 times higher 815
800
than crude oil.
697
700
• Naphtha on cracking produces ethylene and the latter is priced
600
at $697/tonne.
500
• Polyethylene is produced from ethylene and it costs $ 385
400
815/tonne.
300

200
Thus in ultimate analysis there is a large amount of 78.39
100
value addition taking place starting from crude oil to
end polymers. 0

Crude Oil Naphtha Ethylene Polyethylene

 Conventional Technology
Steam Cracking
Steam cracking is a petrochemical process in which saturated hydrocarbons are broken
down into smaller, often unsaturated hydrocarbons.
The major problems associated with commercial steam cracking process are:

• It is the most energy-consuming process in the chemical industry.

• Energy cost accounts for approximately 70% of production costs in typical ethane or
naphtha-based olefin plants.

• Coke deposition on the reactor wall.

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Recent advancement in Steam
Cracker Furnace
• BASF, SABIC and Linde have signed a joint agreement to develop and
demonstrate solutions for electrically heated steam cracker furnaces.

• The partners have already jointly worked on concepts to use renewable

electricity instead of the fossil fuel gas typically used for the heating
process.

• With this innovative approach focusing on one of the petrochemical industries’

core processes, the parties strive to offer a promising solution to significantly
contribute to the reduction of CO2 emissions by as much as 90% within the
chemical industry.

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Fluid Catalytic Cracking (FCC)
Fluid Catalytic Cracking is the conversion process
used in petroleum refineries to convert the high-boiling
point, high-molecular weight hydrocarbon fractions
of petroleum into gasoline, olefinic gases, and other
petroleum products.
The major problems associated with FCC:

• Deposition of various contaminants on cracking

catalyst during FCC process.

• This reduction in catalytic activity and changes in

product distribution of the FCC reactions decreases
the overall yield of the final product.

• There is also a problem of fouling on the reactor.

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 Modern Technology
FCC with Deep catalytic cracking
(DCC)

• The deep catalytic cracking process is a fluidized catalytic cracking

process modified to increase the production of light olefins from
heavy oil feedstock.

• Integrating DCC into a fuel or a petrochemical refinery can

increase profit through new or increased sales of polymer-grade
propylene, ethylene, alkylate, methyl tertiary-butyl ether (MTBE) and
aromatics extracted from the naphtha (BTX).

• DCC is most attractive in areas such as Asia where the value of

propylene is high relative to gasoline. Locational advantages can yield
additional profits.

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Advancements in Catalyst
Technology

ZSM-5 is an aluminosilicate zeolite belonging to the family

of zeolites.
It is widely used in the petroleum industry as a heterogeneous
catalyst for hydrocarbon isomerization reaction.

New types –

• Hollow ZSM 5 Sinopec’s MMC and DMMC Catalyst for

DCC
(i) MMC
(ii) DMMC

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 Nebula® Catalyst
• Jointly developed by ExxonMobil and Albemarle Corporation
Advancements in Catalyst
• up to two times the activity of traditional hydroprocessing catalysts
Technology
• Suitable for Ultra Deep desulfurization and denitrogenation at High
pressure

• Celestia Ultrahigh activity catalyst developed in 2015 is a successor

to Nebula catalyst

BENZOUT
• Technology developed by ExxonMobil in 2011 and licensed by
TechnipFMC.

• BenzOUT process is a commercially proven technology for

benzene reduction in gasoline.

• It avoids octane loss with no hydrogen consumption

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 Propane • The production of propylene from steam crackers is expected to fall
because steam crackers are mostly utilized in the production of
Dehydrogenation ethylene.

Technology (PDH)
• FCC provides only 29% of the propylene supply to the market. Thus,
alternative routes such as PDH can be considered to make up for the
propylene shortage.

• PDH technology is capable of producing a high purity polymer grade of

propylene from a propane rich stream.

• PDH is normally carried at high temperature with a relatively low pressure

and in the presence of either a Platinum (Pt) or a Chromium (Cr)
catalyst to achieve a reasonable conversion of propane into propylene.

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 CATOFIN ABB Lummus

• The CATOFIN process uses fixed-bed catalyst reactors to achieve an appropriate conversion
and selectivity with less energy consumption.

• It can be operated at an optimum reactor pressure and temperature to maximize propane

conversion with high propylene yield.

• Catalyst Used- Chromium/Aluminium

• Dehydrogenation of propane and regeneration of catalyst are the most critical parameters in
designing CATOFIN PDH plants.

• Coke deposition results in a decrease in bed temperature and loss of catalyst activity (coke
formation and chromium reduction).

• Reactivation of the catalyst is achieved by blowing hot air on the catalyst bed to burn the
formed coke and recover the bed temperature under oxidizing conditions.
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 UOP OLEFLEX- Honeywell
• UOP OLEFLEX is a continuous catalytic dehydrogenation process technology.

• Catalyst used- Platinum

• It can also be used for dehydrogenation of isobutane, normal butane, or isopentane

feedstock separately or as mixtures.

• OLEFLEX technology includes four series adiabatic reactors which facilitate the
endothermic dehydrogenation reaction.

• A continuous catalyst regeneration (CCR) system is applied to continuously

regenerate spent catalysts and maintain high conversion and selectivity.

• OLEFLEX technology can be integrated with other plant processes to reduce

production expenses of the desired product.

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 Advantages
CATOFIN
CATOFIN OLEFLEX
OLEFLEX

• OLEFLEX is a new route for high-quality

• Low feedstock consumption:
propylene supply for downstream.
• Low operating pressure. • OLEFLEX provides the lowest cash cost of
• Low reactor inlet temperature. production and highest return on investment
• High tolerance for feed impurities when compared to other PDH technologies due
• Low compression energy that reduces to these reasons
compressor investment cost. 1. Low operating costs enabled by low feedstock
• A small amount of coke formation. consumption
• Separate catalyst regeneration facility is 2. Low energy usage
not required. 3. Low capital costs
• Low catalyst cost due to using non- 4. Stable catalysts and ability to change catalysts
precious metal. without interrupting propylene production .

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Steam Active Reforming
(STAR) Process
• The STAR catalyst consists of a platinum promoted basic calcium and zinc
aluminate which is very stable in the presence of steam at high temperatures.

• Regeneration is simple and sustainable by simply using air to burn off coke
deposits and to re-oxidize the precious metal.

• The catalyst completely eliminates the formation of undesired by-products.

• The gas separation and fractionation units efficiently separate light uncondensables
and recover C3 and C4 components.

• Unconverted paraffins are recycled back to the reaction section for further
processing.

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 UOP Advanced MTO Process

• UOP started MTO Development in 1980 using

a proprietary zeolite SAPO 34.

• The small pore size (4 A) of SAPO34 restricts

diffusion of branched hydrocarbons.

• Light Olefins yield 97%.

• In 2009 UOP-INEOS –TOTAL developed

advanced MTO process which integrates MTO
& OCP.

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 Vis - Breaking

• Vis-breaking is one of the many mild cracking

methods. It is one of the most important yet
straightforward and simple process in refineries.

Main Objectives

• Reduce the viscosity of the feed stream.

• Reduce the amount of residual fuel oil produced

by a refinery.

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Aqua Conversion
Process

• This hydrovisbreaking technology uses

catalyst activated transfer of hydrogen
from water added to the feedstock.

• In this process, reactions which form

COKE are suppressed.

• It does not produce any solid by product.

• It does not require Hydrogen source and

can be implanted in Production area.

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Eureka Process

• This process can be used to produce cracked oil

and aromatic residuum from heavy residual
material.

• The process reactions proceeds at a lower cracked

oil partial pressure by injecting steam into the
reactor keeping petroleum pitch in a homogenous
liquid state unlike a delayed coker.

• A higher cracked Oil yield can be obtained.

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Peak Oil Demand !!

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Petrochemical Industry – Consumption Trends and Growth Potential

•India’s Petrochemicals industry is close to $ 50

bn and is expected to grow at a CAGR of 10%
over the next 5 years to reach $ 100 bn by 2025.

•India’s per capita plastic consumption is lowest in

the world which provides huge headroom for
growth.

•Key sectors driving petrochemical consumption

are expected to grow at ~10% CAGR during 2018
to 2030.

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Source – Deloitte Report, IMF Report
Importance of the Integrated
Project
 Refinery-petrochemical integration works on maximizing the return
on the entire hydrocarbon value chain.

 Conservation of operating costs

 Boosted the shrinking margins of refinery products

 Reduced Transportation cost

 Increased flexibility to respond to market changes for fuels and

chemicals

 Operational Efficiency

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 Future Aspects

• A new technology being employed in the industry is Crude Oil-to-

Chemical Technology.

• It allows the direct conversion of crude oil to high-value chemical

products instead of traditional transportation fuels.

• It enables the production of chemicals exceeding 70-80% of the barrel

producing chemical feedstock as opposed to around 10% in a non-
integrated refinery complex.

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Difference Between Integrated Refinery – Petrochemical
Complex & Crude Oil to chemical Plants

• A conventional refinery is set up to produce fuels and a

petrochemical plant is to produce petrochemicals.
Comparison of Chemical yield of different
units
• The key to refinery profitability is crude flexibility, while 50
the key to petrochemical complex is feed flexibility.
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30
• However, even when integrated, refinery is still aiming at 20
producing fuels while the petrochemical complex focuses 10
on chemical production. 0
Naptha yield

Refinery Integrated petrochemical complex

• Whereas in a crude oil to chemical plant the sole objective Crude to Chemical Plant
is of producing more chemicals.

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Challenges : Crude to
Chemicals

For a sustainable C2C Plant we would

require to:

• Reduce heavy residue to lower molecules

• Raise H:C ratio around 2 for all

chemicals

• Reduce sulfur and metal impurities

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Upcoming Projects
• ExxonMobil, Saudi Aramco and Hengli Petrochemicals
have already invested in COTC technologies.

• 2019 - Hengli started-up a huge 20 MMbbl/Y crude oil

refinery with the aim of maximizing chemicals production,
up to 40% of output.

• 2020 - Zhejiang Petroleum & Chemicals also started up a

similar refinery in China.

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43
• Aramco/SABIC announced that its Joint Venture will process a light crude with 20
million tons per year capacity to produce 9 million tons per year of chemicals ( 45%
conversion).

• Aramco, CB&I and Chevron Lummus Global partner up to commercialize Thermal

Crude to Chemicals (TC2C™).

• King Abdullah University of Science and Technology (KAUST), in partnership

with Aramco, demonstrated a technology which converts crude oil to light olefins
in a single-reactor system.

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• ExxonMobil has a high conversion, maximum
chemicals configuration in the form of its Flexicoking
unit.

• This unit converts vacuum residue to coker naphtha

and gas oils. Light gases from the Flexicoker and coker
liquid are combined in the FCC gas plant.

• To maximize chemicals production, light paraffins are

processed in a dehydrogenation plant for propylene and
butylene production.

• An aromatics plant produces benzene, toluene, and

mixed xylenes or para-xylene to meet local market
needs.

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 Industry 4.0

• Petrochemical companies are increasingly turning to Artificial

Intelligence (AI).

• AI is used to provide more value to petrochemical companies, by

providing lower operating costs and greater efficiencies.

• Dow Chemical Company has partnered with 1QBit, a Canadian-based

firm, to introduce AI in its petrochemical manufacturing.

• BASF partnered with Hewlett Packard in 2017 to develop the world’s

largest supercomputer for AI in petrochemical industry.

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• Sensors from an average size petrochemical complex can produce
2TB of data per day, analyzing and making sense of this data can be
done using Big Data.

• IoT allows O&G companies to be available at all hours to manage

issues ranging from spills to emergency shutdowns, and remote field
operations.

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List of Major Investments

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Conclusion
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References

Deloitte and IMF Reports

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THANK YOU

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