Introduction

Concept of Hydrocarbon processing Petroleum crude and refining: Present and future trend Major Challenges and future strategies in petroleum refining industry Petroleum and petrochemical integration for value addition Future fuel quality and refinery economics

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Concept of Hydrocarbon processing

Hydrocarbon: Compound made of C and H Major source of hydrocarbon is Petroleum Hydrocarbon Processing Petroleum refining Petrochemicals and value added products Integration of petroleum refinery and petrochemical industry

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ELEMENTAL COMPOSITION OF CRUDE OILS (%WT)

CA B N RO HY R G N DOE SU F R LU ( O ET A M R HN 5 % INH A YM S IP I E V I IS P S ME IC NC U E X A R DS , M D EE S I L AT D NIT O E R GN ( .1 -0 0 .9 % INC L O N N A IF R IA AEI A CUE MR N R D C ) OX G N YE M E AS TL 8 .9 -8 .8 3 6 1 .0 -1 .0 1 4 00 .6 -5 ) % 0 2 -1 0 .0 .7 &S U H OT 0 8 -1 2 .0 .8 0 0 -0 4 .0 .1 -8 0 .0

O R

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Main Constituents of Crude Oil

HYDROCARBONS (C OMPOUNDS COMPOSED OF MATERIAL ) C&H A CCOUNT FOR 75 % OF THE

C ARBON NO.DISTRIBUTIONS IN DIS TILLATES N ATURAL GAS GASOLINE KEROSINE GAS OIL VGO RESIDUE
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PARAFFINS C 1-C 4 PARAFFINS , C 5-C 10 AROMATICS & N APHTHENES DO C11-C 18

DO DO

C18-C 28 C28-C 40 C40 ONWARDS

ASPHALTIC

FORMULA & BOILING POINT RANGE OF DIFFERENT COMPOUNDS

C O PO N S M U D ETH N A E PR PAN O E N-BU A E T N N-PE T NE NA N-HE AN X E N-HE TA E P N N-OCT N A E N-N O N NA E N -DE A C NE N-U N E A E D C N N-D O EC N D A E N-T R E A E ID C N FOR U M LA (C 2H6) (C 3H8) (C 4H 10 ) (C 5H 12 ) (C 6 H14 ) (C 7 H16 ) (C 8H18 ) (C 9H20 ) (C 10 H 22 ) (C 11 H 24 ) (C 12 H 26 ) (C 13 H 28 ) etc. BOILIN G O PO T C IN -88.6 -42.1 -0.5 36.1 68.8 98.4 125.7 150.9 174.0 195.8 216.3 234.0

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Refinery products

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PETROLEUM / CRUDE OIL REFINING

Gases
ASMOSPHERIC DISTILLATION

Crude Oil

250 C) Gas oil / diesel (250 370 C)

Naphtha / Gasoline (Petrol) (C5 140 C) / Jet Fuel (140 Kerosene

DISTILLATION

Atmosph eric Residue (370 C+)

VACUUM

Lube oil fractions (370 540 C)

Heavy Lube Oils/ Bitumen

Vacuum Residue (540 C+)

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Further Processin g

77 Fuel oil

Gasification (CO + H2, Syn Gas)

Seven Basic Operations in Petroleum Processing

Separation
Distillation Solvent refining

Combination
Catalytic polymerization Alkylation

Conversion
Carbon removal Hydrogen addition

Treating, finishing, blending

Gasoline, kerosene and diesel Lubes and waxes Asphalt

Reforming
Catalytic Reforming Steam/ hydrocarbon reforming

Protecting the Environment

Waste water treatment Disposal of solids Sulfur recovery

Rearrangement
Isomerization

Petrochemicals

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Significant Events in Petroleum Processing 1861-2000

Date 1878 1889 1908 1912 1913 1919 1929 1933 1934 1938 1940 1942 1949 Description Thomas Edison invents the light bulb. The use of kerosene lamps starts to decline Gottlieb Daimler, Wilhelm Mayback and (separately) Karl Benz build gasoline powered automobiles Ford Motor Company offers Model Ts for US$950 each William Burton and Robert Humphreys develop thermal cracking Gulf Oil builds the worlds first drive-in filling station in Pittsburgh, Pennsylvania UOP commercializes the Dubbs thermal cracking process Standard Oil of Indiana commercializes the Burton process for delayed coking at Whiting, Indiana UOP introduces the catalytic polymerization of olefins to form gasoline Eugene Houdry, working for Sun Oil, patents Houdry Catalytic Cracking (HCC) A consortium of refiners develops sulfuric acid alkylation, which is first commercialized at the Humble (now Exxon Mobil) refinery in Baytown, Texas Phillips develops HF alkylation Standard Oil of New Jersey (now Exxon Mobil) commercializes the FCC process at Baton Rouge, Louisiana Old Dutch Refining in Muskegon, Michigan starts the worlds first catalytic reforming based on the UOP Platforming processes

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Contd

1950 1960s 1961 1970

Catalytic hydrotreating is patented by Raymond Fleck and Paul Nahin of Union Oil UOP introduces C4 and C5/C6 isomerization processes Standard Oil of California (now Chevron) introduces catalytic hydrocracking The world celebrates Earth Day. The newly created US Environmental Protection Agency passes the Clean Air Act, which requires a 90% reduction in auto emissions by 1975. The European Union issues similar requirements Mobil invents ZSM-5 . During the next three decades, this shape-selective catalyst finds uses in numerous processes, including FCC, catalytic dewaxing, and the conversion of methanol to gasoline. The catalytic converter goes commercial. The phase-out of tetraethyl lead begins The U.S. Congress issues the Clean Air Act Amendment of 1990, which lay the framework for reformulated gasoline and low-sulfur diesel Several processes are developed to remove sulfur from gasoline. These include SCANfining (Exxon), OCTGAIN(Mobil), Prime G (Axens), and S Zorb (Philips) Chevron commercializes Isodewaxing for converting waxy paraffins into high-quality lube base stock The European Commission issues the Auto Oil II report, which includes a timetable for low-sulfur gasoline and ultra-low-sulfur diesel

1972

1975 1990 1990s

1993 2000

Petroleum crude and refining: present scenario

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Global Refining Capacity

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Oil refining

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INDIAN PETROLEUM INDUSTRY

First oil well drilled in Assam Production from Ist Well : : Nov1890 200 gal./day 1901 0.25 MMTPA 37 MMTPA 30 MMTPA :

Digboi refinery commissioned: Refining Capacity 1947/48 Current Installed capacity : Public & Private refineries : Largest Refinery- Reliance Refineries in world
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113 / 178 MMTPA 18 / 20 :

Current crude oil production :

>700
1515

INDIAN PETROLEUM INDUSTRY contd. Oil Exploration & Production companies:

i. Oil India Ltd (OIL) ii. Oil & Natural Gas Corporation (ONGC) iii. Private sector companies

Oil Refining Companies:

i. Indian oil corporation (IOC) (Gujrat, Haldia, Guwahati, Panipat, Barauni, Mathura, Digboi, CPCL and BRPL) ii. Hindustan Pet.Corp.Ltd (HPCL) (Mumbai and Vizag Refineries) iii. Bharat Pet. Corp.Ltd. (BPCL) (Mumbai, Numaligarh, Kochi Refineries) iv. MRPL, Manglore v. ONGC (Tatipaka , mini refinery) vi. Reliance Petroleum ( RPL)

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1616

Sources of energy : Indian scenario

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Indian refineries and capacity

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Rising demand supply gap: oil

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Refining Capacity in India

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Refinery capacity utilization in India

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Global Energy Scenario

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Source: IEA WEO 2009

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Population growth and oil demand

Source: IEA WEO 2007

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Oil utilization

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Oil demand trend

OECD: Organisation for Economic Co-ope

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Fuel specification

The Protocol of 1997 (MARPOL Annex VI)

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Global energy shift

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Refining challenges

Dwindling resources Price volatility, high prices High investments and high gestation period of projects Highly subsidized economy, pricing of automotive fuels APM still in vogue [Administered pricing mechanism : APM] Growing dependence on imported oil Refining challenges new technologies Marketing challenges rising expectation of customers Inadequate rural infrastructure Clean technologies Environmental issues Feedstock - Availability Product mix variation Changing Patterns Environmental Issues Efficiency Improvement Gross Refinery Margin Funding for New Projects

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CHALLENGES FOR THE HYDROCARBON PROCESS INDUSTRY

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International Oil prices INFLUENCING FACTORS.. Supply and demand fundamentals OPEC policies [Organization of the Petroleum Exporting Countries (OPEC) - Original OPEC members include Iran, Iraq, Kuwait, Saudi Arabia .. ] Political/economic developments in the exporting / consuming countries Weather conditions Alternative fuels (natural gas) Environmental considerations Large financial funds/ institutions

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West Texas intermediate (WTI), also known as Texas light sweet, is a type of crude oil used as a benchmark in oil pricing and is the underlying commodity of New York Mercantile Exchange's oil futures contracts. The price of WTI is often referenced in North American news reports on oil prices, alongside the price of North Sea Brent crude. Other important oil markers include the Dubai crude and the OPEC reference basket.

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Global strategic challenges

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CO2 emission

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Forecast on India

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Oil price trend

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CO2 reduction target

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Energy / CO2 by area in typical refinery

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Excess naphtha

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Polyester consumption

PET: Polyethylene terephthalate

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Upgrading vacuum residue

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Alternative to Coker

Residue Hydrocracking UOP's Uniflex process is a unique high-conversion slurry hydrocracking process that obtains very high yields of desirable transportation fuels when processing vacuum residues 4/27/12

Energy and hydrogen optimization

R&D needs on Gasification Systems

Oxygen Membrane Gas Stream Cleanup
High Efficiency Turbine
Power
Fuel Cell

Air Gasification Separation

Coal, biomass, pet. coke

Gasifier

Process Heat/Steam Electricity

Gas Cleaning
Fuels

H2

Liquids Conversion

Fuels/Chemicals

Feedstocks Flexibility

Products/ CO2 Byproducts H2/CO2 Utilization Separation

Co-Production

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Renewable

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Product demand and refining capacity

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Strategy for profit making

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Refinery petrochemical integration

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Value addition through integration

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Integration

PBR: Polybutylene rubber; MEG: Mono ethyl glycol; CAN: Acrylonitrile; 4/27/12

Petrochemical processes within refinery

LCO: Light cycle oil LCGO: Ltight Coker Gas Oil HCGO: Heavy coker ags oil

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Production of lower alkenes from oil

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Production of lower alkenes from natural gas

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Petrochemicals and downstream

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Refinery petrochemical integrated complex at RIL Jamnagar

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Sulfur Specifications

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Clean Fuels: Limits on Sulfur

Country US34-36 Gasoline Diesel, on-road Diesel, of road Canada 37 Gasoline Diesel Germany 38 Gasoline Diesel Sweden 39 Diesel Other EU38 Gasoline Diesel Australia 40 Gasoline Diesel Korea (South) 41 Gasoline 4/27/12 Diesel 2004 Level >300 500 2000-3500 Fuel Sulfur Content, wppm Target Level Target Date 2004-2008 July 1, 2006 July 1, 2010 2007 2010 2005 2006 2003 2003 1995 2005 2008 2005 2008 2005 2008 2006 2006

30 15 500 15 30 15 10 10 10 50 10 50 10 150 30 30 50

150 500 10 10 10 150 350 500 500 100 300

EU Specifications for Automotive Diesel

Specification Cetane number Cetane index Density @ 15oC

Units

Year 2000 Limits 51 (min) No spec 0.845 (max) no spec 680 (max) no spec no spec 360 (max) no spec 11 (max) no spec 350 (max)*

Possible Future Limits 55 (min) 52 (min) 0.84 608 (max) 644(max) 662(max) 320(max) 340(max) 350(max) 2(max) 15(max) 10(max)

Distillation
90% boiling point 95% boiling point Final boiling point 90% boiling point 95% boiling point Final boiling point Polyaromatic hydrocarbons (PAH) Total aromatics Sulfur

g/cm3 oF oF oF oC oC oC wt% wt% wppm

* As discussed elsewhere, diesel sulfur will be limited to 50 wppm in 2005

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Changing Motor Fuel Specifications and Environmental Issues

GASOLINE REFORMULATION

Low aromatics and benzene C5/C6 isomerisation Alkylation Benzene management processes Oxygenates FCC for Olefins production Deep desulfurisation Hydro dearomatisation

DIESEL SPECIFICATION

REDUCTION OF SOX AND NOX USE OF NON-CORROSIVE ENVIRONMENTALLY SAFE CATALYSTS

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Refinery of the Future

Crude Oil Refining Separation Gasification Reforming Natural Gas Syn Gas Production Chemicals Hydrogen O2, N2, CO2, H2SO4, Sulfur Transportation Fuels

Resid

Fischer Tropsch

Naphtha Diesel Jet Fuel Wax

CO, SNG Fertilizer Methanol Ethanol Acetic Acid Electricity

Power

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