Fundamentals of Refining

Refining
MB-107
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COLLEGE OF MANAGEMENT AND ECONOMICS STUDIES (CMES)
Course Code: MB-107 Course Name: Refining UNIVERSITY OF PETROLEUM & ENERGY STUDIES
Contents
Unit 1 Unit 2 Unit 3 Unit 4 Unit 5 Unit 6 Unit 7 Unit 8 Unit 9 Unit 10 Unit 11
Growth & Development of Refining Industry in India ................................... 1 Crude Oil and its Characteristics ...................................................................... 7 Specifications of Petroleum Products & Related Tests ................................ 23 Integrated Refinery & Petrochemical Plants ................................................. 53 Future Refining Scenario .................................................................................. 85 Advances in Petroleum Refining ..................................................................... 89 Hydrocarbon Loss Minimization ...................................................................... 93 Energy Conservation ......................................................................................... 95 Gross Refining Margin ...................................................................................... 99 Oil Accounting .................................................................................................. 103 Excise & Custom Petroleum Products ....................................................... 107
Objective
The objective of this course is to give an insight into various facets of petroleum refining for producing finished products of the desired specifications. Various refining processes used in the refineries have been dealt in this module. Characteristics of crude and specifications of various petroleum products have been explained in detail. Dealing with growth and development of petroleum refining industry in India, latest advancements in various technologies for improving profitability of the refineries in the face of increasingly stringent product specifications for meeting environmental stipulations have also been described.
An Overview
Refining of petroleum for producing fuel and related products for automobiles, domestic consumption and meeting the needs of the power sector, petrochemicals, fertilizers etc. and other industries, is very vital for the economic progress of the country. The refining industry in India has made tremendous progress since independence with its march in time with the country's economic growth and overall progress. Starting with the establishment of the first public sector refinery at Guwahati (Assam) in 1962, it has come a long way with the setting up of most modern, state of the art and highly energy efficient refineries of the present day. India has 17 operating refineries processing both indigenous and imported crudes. The crude processing capacity of the country has increased from 6 MMTPA in 1962 to 113 MMTPA as of today. Oil companies in India have met the challenges of the petroleum market product demands with the desired stringent specifications from time to time, by making changes/ improvements in their processes while at the same time sustaining their profitability. The refineries are highly capital-intensive industries with a medium gestation period and produce crucial products for meeting the country's needs including that of defence. For setting up a 6 MMTPA capacity refinery complex with marketing facilities, investments to the tune of Rs 5000 crores are required. These refineries need to be run efficiently so as to make profits, and hence need to be modernised and updated from time to time. The module on refining covers various facets of petroleum refining. Various refining processes used in the refineries have been dealt with in this module. Characteristics of crude oil and specifications of various petroleum products have been explained in detail. Dealing with growth and development of petroleum refining industry in India, latest advancements in various technologies for improving profitability of the refineries in the face of increasingly stringent product specifications for meeting environmental stipulations have also been described.
Unit 1 Growth and Development of Refining Industry in India

Objectives
After studying the unit, the learner will be able to:
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Get an overview of the growth of the Indian Refining Industry after independence. Know about special features of Indian Refining Industry. Get a good idea of various challenges facing the industry in the present time/in future and strategies for meeting the same.
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With the growth of industry and improvement in the living standard of people, demand for petroleum products is increasing rapidly. Consequently, there is a thrust on increasing their supply by enhancing refining capacity. First refinery in India started soon after oil production started in Digboi, Assam. Thereafter addition of refineries and capacity augmentation continued unabated. Now we are having seventeen operating refineries with a total capacity of 113 MMTPA.
The Important Milestones

1866 1889 1893 1899 1901 Oil discovery at Nahorpung, Assam. Oil Production started at Digboi, Assam. First Refinery started at Margharita, Assam. Assam Oil Company was formed. Digboi Refinery was commissioned supplanting the earlier refinery at Margarita. Setting up of three coastal refineries by Multi National Oil Companies (MNCs)
1947- 1957
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Activity 1 A Reader may like to draw a Geneological Chart of the current refineries operative in India. Please classify by company, technology and year of establishment and expanded capacity wherever applicable by the end of 10th 5 year plan i.e. 2006 07. __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u
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2 at Mumbai (Esso & Burmah Shell) 1 at Vizag (Caltex)
The MNCs were already marketing petroleum products in India by then. 1954 Indian Oil exploration with the help of Russian Geologists. Formation of Oil and Natural Gas Commission for exploration and production of crude oil and gas. Discovery of Cambay oil field. Indian Refineries Ltd (IRL) was formed in the public sector to install refineries and pipelines in India. Oil India Ltd (OIL) was formed as a joint venture company between Government of India and Burmah Oil Co. Indian Oil Company formed for marketing of petroleum products. The first refinery in the public sector commissioned at Guwahati (0.75 MMTPA) under IRL. Indian Oil Blending Ltd A JV between Indian Oil Co. and Mobil Petroleum Co. Inc. was formed for manufacture of lube oils and greases. IRL was dissolved and merged with Indian Oil Co. Ltd, to form Indian Oil Corporation Ltd (IOCL). IOBL became part of IOCL. Assets of erstwhile Assam Oil Co. were taken over and vested in IOC as Assam Oil Division (AOD). Panipat Refinery of IOC commissioned.
1956
1958 1958
1959
1962
1963
1964
1974 1981
1998
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UNIT 1
Growth and Development of Refining Industry in India
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Activity 1 B What are various options for increasing the Refining Capacity in the country? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
1999 2000
Reliance Petroleum Refinery at Jamnagar, commissioned. Numaligarh refinery commissioned.
In the five decades since independence, 16 refineries have been added in the public/private/ joint sectors (including three in the private sector by MNCs, which subsequently became PSUs).
Future Outlook* (as per 2025 vision document)

Total Refining Capacity MMTPA 2002 03 Barauni Expansion Haldia Expansion HPCL, Mumbai Expansion CPCL, Nagapatinam RPL Expansion Essar Oil 2003 04 Koyali Expansion Panipat Expansion BPCL Expansion CPCL Expansion BRPL Expansion Paradip Essar Oil Expansion Nagarjuna Oil 2004 05 Kochi Refinery Expansion 2005 06 Essar Oil Expansion RPL Expansion Bhatinda 2006 07 BRPL Expansion Bina
* The anticipated growth in petroleum products may not take place
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176 214
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
No. Refineries MMTPA
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Refining Capacity in India as in the year 2002

Year of Commissioning 1901 1962 1964 1965 1974 1982 1975 1954 1955 1966 1969 1972 1994 1995 1998 1999 2000
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.
Indian Oil Corporation Limited, Digboi Indian Oil Corporation Limited, Guwahati Indian Oil Corporation Limited, Barauni Indian Oil Corporation Limited, Koyali Indian Oil Corporation Limited, Haldia Indian Oil Corporation Limited, Mathura Hindustan Petroleum Corporation Limited, Vizag Hindustan Petroleum Corporation Limited, Mumbai Bharat Petroleum Corporation Limited, Mumbai Cochin Refineries Limited, Cochin Chennai Petroleum Corporation Limited, Chennia Bongaigaon Refineries Limited, Bongaigaon Madras Refineries Limited (CBR), Nagapatinam Mangalore Refineries & Petrochemicals Ltd., Mangalore Indian Oil Corporation Limited Panipat Reliance Petroleum Limited, Jamnagar Numaligarh Refineries Ltd., Numaligarh Total Capacity
0.65 1.00 3.30 (6.0) 13.5 (18) 3.75 (7.5) 7.50 7.50 5.50 8.90 7.50 (10.5) 6.50 (9.5) 2.35 0.50 6.00 (9.0) 6.00 27.00 3.00 112.45
Indian Refining Industry Emerging Scenario

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Shifting product demand Stringent product specifications Stringent environmental regulations Feedstock quality deterioration Globalisation Deregulation of oil and gas sector
Indian Refining Industry Special Features

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Larger requirement of middle distillates (diesel, kerosene) Prevalence of old as well as modern technologies
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UNIT 1
Growth and Development of Refining Industry in India
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Activity 1 C i. Describe special features of Downstream Industry.
A few refineries with size far lower than world standards.
Strategies for Indian Refineries

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Residue upgradation technologies for heavy crudes Technologies for producing lighter fuels Process technologies to improve quality with respect to: performance parameters eco-friendly products
ii. Challenges faced and strategies to meet the same. __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Value addition to refinery streams Increased emphasis on Process Control/ Automation Evolutionary/innovative technological changes expected rather than revolutionary ones Refineries to be integrated ,compact and flexible with respect to crude/ product mix.
Future Technological Challenges

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Meeting higher demand of petroleum products (viz. distillates) Meeting higher standards of product qualities More emphasis on environment Value addition to refineries Technologies to improve margins Zero emission refinery
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Capacity Increase (To Meet Demand of Petroleum Products )

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Low cost revamps/ addition of units Run length improvement of units Infrastructure development for crude receipt/storage/ distribution Installation of matching secondary processing plants.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u u u u
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Value Addition
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Production of value added products from refinery streams Propylene, butene 1, butene 2, N Paraffin, Lab, Benzene, Toluene, Hexane, P Xylene etc. Generation of power from heavy ends
Distillation Range Improvement

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New residue conversion technologies like FCC, Hydrocracker, RDS-RFCC Advanced controls and optimisation Advanced catalysts Continuous simulation of plants/ product mix through computer models Prudent selection of technologies and proper integration of secondary units/ plants.
Review Questions
1. Please identify technological challenges that refineries will face in future.
Unit 2 Crude Oil and Its Characteristics

Objectives
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Activity 2 A How is the crude oil formed? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Understand the chemistry of petroleum, different types of crudes and their characteristics. Develop an insight into the significance of various characteristics of crudes and method of determination of the same. Get an idea of various crudes used in Indian Refineries. Appreciate the difference between Indian crudes and typical middle east crudes.
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Crude Oil Characteristics and its Significance (General Information)

Crude oils are formed by the action of geological processes on the remains of ancient marine life. It is a complex mixture of hydrocarbons and over 16,000 compounds have been identified in one sample. Composition varies widely: By geographical location Mix of individual wells Variance of wells with time
Chemistry of Petroleum
Crude oil contains almost all known hydrocarbons and nonhydrocarbons. As it is drawn from the earth, it also contains impurities like water, mud and salts which get associated during its production and transportation.
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Activity 2 B What are the type of hydrocarbons present in the crude? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Crude oil, the basic raw material of refining industry, is a mixture of eight different hydrocarbon families: i. ii. Paraffins Cyclopentanes
iii. Cyclohexanes iv. v. vi. Cycloheptanes Di-cyclo-paraffins Benzenes
vii. Aromatic cycloparaffins viii. Dinuclear and polynuclear Aromatics are present in smaller amounts in compounds containing metallic constituents such as Vanadium, Nickel, Iron, Copper, Magnesium, Calcium, Zinc, Titanium etc. Besides impurities such as Sulphur, Nitrogen and Oxygen compounds mostly present in high boiling point fractions are also present in crude oil. Based on boiling point, the fractions are separated and given secondary treatment to utilise it as finished products. Based on proportion of types of hydrocarbon, it can be divided into Paraffin, Napthenic and Aromatic categories. The purely hydrocarbon content may be as high as 97% and as low as 50% for heavy crude oils. The non-hydrocarbon portion retains hydrocarbon characteristics as the molecules contain one or two atoms of elements other than carbon and hydrogen. The carbon content is between 83 to 87% and hydrogen content between 11 to 14%. The ratio of carbon to hydrogen increases from the low to high molecular weight fraction due to increase in polynuclear aromatic and multi ring cycloparaffins in these higher boiling fractions. Atmospheric distillation is adopted for separating the compounds present into various fractions upto 366C:i. ii. Overhead gases containing mainly methane, ethane, propane and butane. C590 C light naptha
iii. 90C140C heavy naptha iv. 140C204C Mineral Turpentine Oil (MTO)
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UNIT 2
Crude Oil and its Characteristics
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Activity 2 C i. How do you classify crudes based on proportion of type of hydrocarbon present in them?
v. vi.
140C240C Aviatin Turbine Fuel (ATF) 140C270 Kerosene
vii. 270C340C Gas oil viii. 340C366C Jute Batching Oil (JBO) 366C plus fraction i.e. Reduced Crude Oil (RCO) is subjected to vacuum distillation for obtaining vacuum gas oils, raw Lube Distillate and short residue. Various fractions obtained from atmospheric and vacuum distillation are given further treatment to meet required specifications for use.
ii. What is Crude Assay? How are these Assays utilized? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Crude Assay
Crude Assay is the determination of properties of various fractions of crude oil. This is done to assess the utility of the crude for processing for production of various products and their yields. Crude Assay Data are utilised for the following:
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Crude oil selection Crude oil grading Crude valorization Crude swapping Crude imports Creation of new infrastructure at the existing refineries Grassroot refineries Production planning management Inventory problems Demand/supply gaps
Types of Evaluations
Preliminary Assay
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Crude characteristics Consistency of crude supply.
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Short Evaluation
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Crude characteristics
Absorption of new crude in fuel refinery To study the change in quality of crude over a period of time Detailed characterisation of crude oil including all micro constituents.
TBP assay
Yield data and key u characteristics of straight run cuts in fuel range and long residue
Detailed Evaluation
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Design data for grass root refinery
TBP assay in atmospheric and vacuum range Selection and design of secondary conversion units. Yield and characteristics of sets of distillates in atmospheric and vacuum range with variation in IBP, FBP characterisation of several long and short residues.
Product optimisation
Information Required
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Base and general properties of crude oil Presence of impurities Operating and design data Fractionating or TBP distillation curves Equilibrium of flash vaporization curves API or specific gravity curves of each fraction distilled.
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UNIT 2
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Notes __________________ __________________ __________________ __________________ __________________
Property curves of fractions vs% distilled Mid% curves Yield% curves ISO% curves
Properties and yield of straight run fractions and residues Detailed composition of light distillates Hydrocarbon Type Distribution of Middle and Heavy Distillates
__________________ __________________ __________________ __________________ __________________
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Characteristics of Crude Oil

Basic Properties Density & API Reid Vapour Pressure (RVP) Light End Analysis Pour Point Viscosity Wax Content Asphaltenes Carbon Residue Ash Content Distillation Characteristic (D86 or D285) Base of Crude Oil Impurities Water Content Salt Content BS & W Sulphur Content Nitrogen Content Inorganic and Total Acid Trace Metals
Crude Oil Characteristics and their Significance

Density
Density is used for:
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Weight to volume or vice versa calculations Checking the consistency of crude supply Control of refinery operations Used in various correlations
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Specific GRAVITY= M/V (WATER) u
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Also gives a rough indication of type of crude oil

MASS (M) VOLUME (V) M/V
Density =
141.5
API GRAVITY= SP.GR AT 60/60F
131.5
Examples: Water Kerosene Motor Gasoline = 10 API = 45 API = 58 API
Natural Gasoline = 75 API Crude oils are categorised based on gravity Light grades Medium grades Heavy grades
CRUDE Narimanam Ankleshwar Jotana Bombay High Heera Kalol Rumaila Ratna Rostam Jhalora Basrah Sobashan N. Gujarat Geliki Nahorkatiya Kuwait IF IR. Oman Elmorgan Jorajan Kharsang Lakwa Jhalora Kothana Rudrasagar Sanand N- Kadi Mix Badarpur Santhol
: Above 33 degree API : 23-33 degree API : upto 22 degree API

Density 0.7920 0.7930 0.8161 0.8278 0.8412 0.8414 0.8448 0.8484 0.8495 0.8496 0.8527 0.8549 0.8553 0.8675 0.8688 0.8698 0.8727 0.8821 0.8910 0.8952 0.8986 0.9000 0.9210 0.9242 0.9340 0.9430 0.9507 API 47.08 46.85 41.80 39.35 36.62 36.55 35.90 35.20 35.00 35.16 34.40 33.99 33.85 31.50 31.30 31.10 30.55 28.84 27.22 26.50 25.87 25.64 22.10 21.45 19.91 18.39 17.29 TYPE I I P I I P I I I I I P I I I I I N N N I I N I I N I TOTAL DISTILLATE UPTO 370C 79.6 78.2 52.0 65.4 60.6 47.0 55.7 51.0 59.7 42.1 52.5 43.0 44.0 54.5 60.9 47.0 48.1 60.7 61.7 53.7 31.8 28.2 60.3 24.4 27.6 60.6 22.9
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________
Sulphur
Crude oils are also categorised based on sulphur.
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Sulfur is a measure of sourness and sweetness of crude Sweet grades<0.5% of Sulphur Sour grades >0.5% of Sulphur
Sulphur is passed on to products as much as regulations or market accepts. It is removed in hydrotreater by reacting with H2 and recovered as elemental sulfur in SRU.
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Reid Vapour Pressure (RVP) and Light End Analysis

RVP indicates relative Percentage of gaseous and lighter hydrocarbons in crude oil.
Component Propane Butane Crude Oil RVP, Kg/cm2 14.1 Kg/cm2 6.6 Kg/cm2 0.01-0.05
Light end analysis carried out by GLC actually gives the percentage of hydrocarbons upto C5 and is the basis of assessing the LPG potential of crude.
TYPICAL HYDROCARBON ANALYSIS Components C1 C2 C3 ISO-C4 N-C4 ISO-CS N-C5 TOTAL % WT on Crude ND TRACES 0.1 0.1 0.3 0.3 0.5 1.3
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Characteristics WAX, % WT Pour Point,C Viscosity Kinematic cst AT 37.8 C, 50C Geological Characteristics Yield Value Dynes/ cm2 AT 32C 24C 18C 16C Plastic Viscosity, C.P. AT 32C 24C 18C 16C 7.9 30.7 43.7 45.0 4.30, 3.32 BH Crude 10.9 +30
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Flow Characteristics of Crude Oils

Basrah Crude 3.5 -24
6.18, 4.84
45.0 85.0 222.0 330.0
2.0 5.0 10.0 12.5
9.6 14.7 16.0 17.3
Pour Point
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Indicates relative amount of wax present in crude oil Is the temperature below which pumping and transportation problems may be encountered Along with viscosity, is used in pumping and design calculations:
Wax Content
Normal paraffins above C16 are solid at somewhat ambient temperatures. These hydrocarbons
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Affect the flow behaviour of crude Affect the product quality of gas oil, VGO and asphalt Lube manufacture is also dependent on wax content of the crude.
Salt Content
It is measure of contamination in crude that will cause overhead corrosion or foul up exchangers by settling and
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UNIT 2
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Activity 2 D i. How do you separate various fractions present in crudes?
sealing. It is removed in desalter by washing and settling mainly chlorides and sulphates of Na, K, Ca, Mg.
Resins Particulates Brine Droplet Asphaltenes Na+ COONa+ COOWaxy Agglomerates
ii. What are various impurities in crudes, their bad effects and how are these impurities removed? iii. Method of determination of salt content, BS&W & Viscosity. __________________ __________________
Alkyl Benzene
Carboxylates
Naphthenates
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FIGURE 2.1 POSTULATED STRUCTURE OF STABLISED EMULSION
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Problems Encountered Due to Salts

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Irregular behaviour in distillation Equipment corrosion in the atmospheric distillation caused by HCL liberated due to hydrolysis of chlorides
Increased Consumption of Amonia

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Salt is a major cause of blocking and fouling of heat exchangers Residual product contamination
100 Total Chloride evolved as HCL % Ashci %
75
50
25
0 0 100 200
300 400
PTB as Salt Content of Crude PTO AS NACL
Salts may vary widely in ratio of metal ions, though common averages are Na: 70-75%, Mg: 15-20%, Ca: 10%.
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Mg is most prolific producer of HCL with Ca and Na in descending order Small quantities of HCL may substantially enhance corrosion of sulphur compounds
Methods for Determination of Salt Content

1. 2. IP 77/72 ASTM D3230 Extraction with water KCNS/Ag No 3 titration Conductivity measurement based on calibration with Na, Ca, Mg chlorides standard solutions in mixed alcohol.
Sediment and Water

Sediment has no relationship with salt but both might increase with connate water Sediment Fine particles of sand clay, volcanic ash, drilling mud, rust, iron sulphide, metals and scale Plugging Abrasion and residual product contamination
Damaging Effects
Water causes irregular behaviour in distillation.
Sediment in crude oil is measured by the following methods: BS & W Sediment by extraction Water content ASTM D 96 ASTM D 4007 DEAN & STARK ASTM D 4006 Sediment in crude is determined for custody transfer purposes Lower the sediments and water, higher the reliability of the unit. It is also a major pointer for corrosive materials in crude.
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UNIT 2
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Activity 2 E Significance of TAN & KUOP. __________________ __________________ __________________ __________________ __________________ __________________
Asphaltenes, Carbon Residue and Ash Content Asphaltenes

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Are polynuclear condensed aromatic hydrocarbons having high molecular weight These are insoluble in heptane and soluble in Benzene/ Toluene Asphaltenes and carbon residue indicate the extent to which heavy hydrocarbons are present in crude oil.
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Ash Content
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Metallic constituents concentrate in the ash of the crude oil
Carbon Residue
Its a carbonacous residue formed after evaporation and pyrolysis of the sample. The residue is coke and determined by Conradson residue method ASTM D 189 Ramsbottom carbon residue ASTM D 624 Micro-carbon residue method ASTM D 4630
Viscosity
It is a measure of resistance to flow and is an important parameter for effective desalting. It is also highly dependant on temperature. High viscosity crudes need high temperatures for effective desalting. There is a limit for temperature in desalters operation.
KUOP
It is a measure of parafinity vis--vis aromaticity of crude. High KUOP is desired for high conversion in FCC, aromatic molecules cannot be cracked in FCC. They will simply take a ride through the plant.
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Activity 2 F What are various crudes processed in Indian Refineries? Where are Indigenous crude found? What is the sulphur content of Indian crudes? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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TAN
TAN is actually Total Acid Number. It is a measure of Naphthenic Acid (NA) contents in crude. This leads to corrosion in various sections of the unit. Over 1,500 known NA species are present in crude. All napthenic acids are not corrosive. Latest research indicates that TAN is not a complete Corrosion Index. TAN with 2.5 may corrode at higher rate than TAN with say 6 ! Detailed metallurgical reviews and monitoring mechanisms must be put in place.
Selection of Crude Oil

Technology trends in petroleum refining are driven by the external forces of product demand, product specifications (including environmental consideration), feed stock quality and availability. Crude oil will gradually become heavier and higher in sulphur content. Refineries, of late, have been sincerely attempting to produce fuels to comply with stricter environmental regulations particularly gasoline and diesel and are in the process of reducing the sulphur levels in distillates and fuel oil. Attention is now also being paid to reduce lead and benzene levels in gasoline. Various gasoline and diesel specifications applicable worldwide are given in the later part of this chapter. Crude processed in India are: 1. Indigenous crude oil sources a. b. c. d. e. Bombay high and satellite fields North Gujarat and Ankaleshwar crude Assam crudes KG Basin-Rava crude Cauvery Basin crude
All the above crudes are low sulphur =<0.5% wt, low metal content, poor potential to yield LOBS and bitumen, and some are waxy in character.
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Activity 2 G What straight run fractions are obtained in Atmospheric Distillation? And in Vacuum Distillation? __________________ __________________ __________________
2.
Imported crudes are sourced mostly from: a. b. c. d. Gulf Region Nigeria Malaysia Australia
The above crudes are specially selected for production of Bitumen/LOBS/ATF, beside fuel products. These crudes are having varying range of sulphur from low of high.
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Comparison of Crudes
Comparison of Indian crudes and typical Middle-east crude mix for yield and key properties of straight run cuts:1. 2. 3. Gases upto 20C Naphtha I.B.P.- 140c KEROSENE 140-250C 4. 5. 6. GAS OIL 250370C Vacuum GAS OIL 370530C, Short Residue 530, C+.
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AROM. 16% Vol NAPH. 52% VOL COTANE NO. 73.7 SMOKE POINT 14mm Arom. 36% VOL. E.P.T.<60C DIESEL INDEX 33 POUR POINT 9C KUOP II-61 KIN. VISC. AT 96.9C 7 0St API 3.8
1-2 15.0
AROW 5.8% VOL. NAPH 40.6% V.O.N.O. SMOKE PT. 23 mm AROM. 1:1 % VOL F.P.T.-54C DIESEL INDEX 57 POUR POINT +3 KUOP 12.10 KIN VISC. AT 100 C 8.120 SI API 13.58 POUR POINT +48 KIN. VISC. AT 100C 150(27 0SI CCR 14.77% Wt.
0.4 4.4 10-1
3.8
AROM: 6.6% VOL OCTANE No. 67.5 SMOKE POINT 27mm AROM. 15% VOL. F.P.T.48C DIESEL INDEX 67 POUR +POINT +6C KUOP 12-70 KIN. VISC. AT 100C 405 0St API 16.5 CCR 9.92% WI. POUR POINT + 68C
24.9
17.6
19.2
22.3
27.1
31.2
23.9
18.8
34.7
27.2
6.3
N.9
ASSAM CRUDE MIX API 29.85 SULPHUR 0.24% Wr. POUR POINT +30C WAX CONTENT 10.8% Wt. KUOP 11.30
NORTH GUJARAT CRUDE MIX API 26.83 SULPHUR 0.17%Wt. POUR POINT+21 WAX CONTENT 6.8% Wt KUOP 12.0
GANDHAR+ANKLESWAR (60. 40 VOLT CRUDE MIX API 46.9 SULPHUR 0.041 % Wt. POUR POINT+27C WAX CONTENT 8.9% Wt.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
API 9.51 CCR 19.2% Wt. POUR POINT +72C BOMBAY HIGH API 39.35 SULPHER 0.17% Wt. POUR POINT+ 30C WAX CONTENT 10.6% Wt. KUOP 11.70
6.2 1.9 2.7
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2.1
ARON 21.3% VOL. NAPH. 25% VOL OCTANE NO. 69-6 SMOKE POINT 17mm AROM. 26.9% VOL. F. PT. -49C DIESEL INDEX 56 POUR POINT +3C KUOP 12.37 KIN VISC. AT 98.9C 5.36 0St
18.6
ARON 4% VOL. OCTANE NO.61.9
30.4
AROM 7.3% VOL OCTANE No. 53.8 SMOKE POINT 26mm AROM. 18.6% VOL. F.P.T.56C DIESEL INDEX 58 POUR +POINT 9C KUOP 11-94 KIN. VISC. AT 100C 5.98 0St API 7.43 CCR 19.85% Wt. POUR POINT + 54C KIN. VISC. AT 100C 903.650St
10.7
20.9
SMOKE POINT 27mm Arom. 16% Vol,. F. PT57C DIESEL INDEX 58 POUR POINT 12C KUOP 12.31 KIN VISC. AT 100C 4.83 0St API 16.35, CCR 10.4 % Wt POUR POINT+ 60C NARIMANAM CRUDE API 47.08 SULPHUR 0.085% Wt. POUR POINT 0 WAX CONTENT 2.8% Wt. KUOP 11.98
24.7
16.1
24.0
21.8
18.1
22.5
28.4
15.7
4.7
30.5
Kuwait+Lt. IRANIAN FOMAN (56: 36: 6 VOL. ) API 31.1 SULPHUR 2.28% Wt. POUR POIN T(30C WAX CONTENT 1.1% Wt. KUOP II.98
Selection of Crude(s) for a Refinery

Based on product demand, type of products, processing schemes of refineries, metallurgy of existing plant and equipment, crudes are selected after evaluating detailed crude Assay Data. Mostly, a mixture of crudes is selected for a refinery to optimise the cost and meeting products quality specifications.
Review Questions
1. Describe different characteristics of crudes dealt with in this unit, their significance and typical values/ units of measurement. Draw a comparison of indigenous crudes with Typical Middle East Crude(s) vis--vis important specifications of Petroleum Products.
2.
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Notes __________________ __________________ __________________ __________________ __________________
3.
From which Indian crudes, can you produce a. b. c. d. e. ATF Bitumen Lubes Micro-crystalline wax Good Quality Calcined Petroleum Coke
__________________ __________________ __________________ __________________ __________________
23
Unit 3 Specifications of Petroleum Products and Related Tests

Objectives
y
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Understand the specifications of various petroleum products, their significance and their determination/tests.
Appreciate crucial specification of HSD & MS from Environmental Pollution Standpoint & Strategies for meeting stringent norms for future Euro III/IV, Bharat III/IV.
Specifications
What are Specifications? Any material which is intended for use in a particular application should have certain characteristics so that it is suitable for use in that application. These characteristics are quantified to make them absolute and also to remove any ambiguity in the interpretation. These quantified characteristics are called specifications.
Some important tests conducted on petroleum products and included in specifications:

Flash Point Pour Point Distillation Copper Corrosion Silver Corrosion Sulphur Viscosity Potential Gum Existent Gum RON MON AKI Cetane Number Cetane Index Smoke Point Aniline Point Carbon Residue Vapour Pressure Color BMCI Bromine Number Benzene Content Density Sediment Water Weathering Test
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Significance of Tests
Flash Point
It is the minimum temperature at which the sample gives sufficient vapour which forms an explosive mixture with air giving a flash when a flame is applied to it under conditions of the test method. Flash point is associated with safety during storage and application in some respects. When a product like kerosene is stored either at home or at a commercial location, it forms vapour above it depending upon the ambient temperature. If the vapour so formed is sufficient to form an explosive mixture with air, there would be explosions when a small naked flame is exposed to it. Each country has it own legislation with respect to flash point depending upon the climatic conditions of the country.
Pour Point
When heavy petroleum oils containing wax are allowed to settle (like in storage tanks), wax separates out from them making the oil immobile. If the oil does not move, it cannot be pumped. The temperature at which the oil becomes immobile (does not move) is termed as pour point when tested under the conditions of the test methods.
Distillation
The volatility of an oil is indicated by its distillation characteristics. Unlike pure compounds, petroleum oils are mixtures of several hydrocarbons and so will have a boiling range instead of boiling point. The oil should have suitable boiling range (volatility) so that it can be used in a particular application. For example, Motor Gasoline which is used in spark ignition internal combustion engines, has the following specifications for distillation: Recovery upto 70o C Recovery upto 100o C Recovery upto 180o C 10 to 45% Min 40 to 70% Min 90% v Min
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Specifications of Petroleum Products & Related Tests
25
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Since the application is in a spark ignition engine, the fuel should easily vaporise to a sufficient degree so that when a spark is applied it can ignite. The specification for recovery at 70 o C is laid to meet this requirement. The maximum limit of 45% is laid to prevent some other undesirable effects such as vapour lock. This quality is called easy start. The specification for recovery at 100oC is set to give power to engine and take load. The specification for recovery at 180oC and final boiling point are set to prevent crank case oil dilution and unburnt hydrocarbon in tail gases (air pollution).
Copper Corrosion
The fuel product comes on contact with metal parts such as transfer pipe from storage tank, storage tank itself, the burner in a kerosene stove, stove body itself, storage and transportation equipment like pumps, storage vessels etc. If the product is corrosive, it will corrode these parts and reduces their life. Copper corrosion test indicates whether the product is corrosive to copper containing alloys or not. This test is applicable to all fuels.
Silver Corrosion
This test is done for Aviation Turbine Fuel (ATF)Jet A1 Type Some aircrafts of civil aviation and defence use a silver lining in the fuel transfer lines. In order to protect this lining, the fuel should not be corrosive to silver. Hence this test is done for ATF. This is a requirement for Indian region only. Western countries and USA do not use this test any more.
Sulphur
Sulphur, besides being corrosive to the fuel systems, is a pollutant to the air and affects life. Global efforts are being made to minimise the sulphur content in motor gasoline, high speed diesel and fuel oils.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Viscosity
Viscosity is the resistance to flow. The unit of absolute or dynamic viscosity is Poise and that of kinematic viscosity is Stoke. Viscosity is an important property for lube oils because it gives the lubricating property to the oil. This is required to prevent wear and tear in the moving parts of a machine on account of metal to metal contact. For fuel oils, it gives flow properties which are needed for pump selection for transporting. Viscosity is measured in several ways. The most common are Kinematic Viscosity measured in centi-stokes and Saybolt Universal Viscosity measured in seconds.
Potential Gum
This test is applicable to motor gasoline which may contain unsaturated hydrocarbons (olefins). Olefins are oxidised by atmospheric oxygen to a gummy material which sticks to the carburetor jet of the vehicle or inlet valve leading to valve sticking which in turn results in the malfunction of the engine. This type of gum is characterised by Potential Gum test. It does not show the exact amount of gum that would form on storage but gives a directional indication. The unit of measurement is mg per liter.
Existent Gum
This test is applicable to motor gasoline. If motor gasoline contains any soluble solid residue, the residue gets deposited in the carburetor and other parts after the gasoline is vaporised. Such deposit may clog the jet and prevent fuel flow due to which the engine stops. That is why this test is done on MS. The specification is 40 mg per litre max. One point should be noted. Some solid material is added to MS deliberately for some purposes. Example: Dye to identify the MS from others. These type of residues are excluded from the specification.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Octane Number
It is defined as the per cent volume of iso octane in a mixture of iso octane and normal heptane that gives the same knocking as that of the fuel when tested under defined conditions. Iso octane is assigned a value of 100 and normal heptane 0 octane number. Normal paraffins have the lowest octane number. Next comes napthenes followed by iso paraffins, olefins and aromatics for the same carbon number. However, this is only a general rule and may differ in the case of iso paraffins. Some of them have lower octane numbers than corresponding napthenes and some other higher octane number depending upon the branching of the iso paraffin. Similarly Octane numbers of olefins may also differ slightly as given below:
l l l l l l l l l l l
n-Hexane Cyclohexane 2,2 Dimethy 1 Butane 2-Methyl Pentane Hexene-2 Benzene N-Heptane Methyl Cyclohexane 2,3 Dimethyl Pentane 2 Methyl Hexene-1 Toluene
24.8 83 91.8 73.4 90 >100 0 75 88 92 107
Octane numbers are not truly additive. When used singly, the hydrocarbons behave in some way and when used in a mixture, they behave in another way. For example, Toluene has a RON 107 when it is a single component system. But when it is mixed with other hydrocarbons, it behaves as if its octane number is > 120. Some schools of thought say that in multi-component systems, like naptha, octane number is additive on weight percent basis. Some others believe that it is additive on mol.
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per cent basis. In effect, there are always some exceptions and some deviations.
Research Octane Number and Motor Octane Number.

These are determined under different conditions of the test.
Test Condition
RON 600 RPM 13 o -125o F
MON 900 RPM Variable 300 o F 100 o F
Engine speed Spark advance Mixture Temp In Take Air Temp
AKI (Anti Knock Index)

It is defined as the average of RON and MON. AKI = (RON + MON)/2 Anti Knock Index is regarded as more critical for engine performance than RON alone.
Cetane Number
This test is applicable to diesel fuels which use ignition by compression. Cetane number is defined as the per cent volume of n-cetane in a mixture of n-Cetane and alpha methyl naphthalene that would give the same knocking as that of the fuel under test. n-Cetane is assigned a value of 100 and alpha methyl naphthalene a value of 0. Alpha methyl naphthalene has some storage stability problem. It turns red when exposed to air. So, although it is a primary fuel, a secondary fuel for routine use is also stated in the test method. This is hepta Methyl Nonane (HMN). Another consideration for using HMN is its easier availability. This test has reverse characteristics of octane number. Here, normal paraffins have highest cetane number followed by naphthenes, iso paraffins, olefins and aromatics in general
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________
but the order may vary depending upon the chain length of iso paraffins.
Cetane Index
It is an alternative to cetane number. It is nearly equal to cetane number but not an actually determined value required cetane engine. Cetane index is not applicable to fuels containing cetane improves.
Smoke Point
Smoke point is defined as the maximum length of the flame which does not give smoke when tested under prescribed conditions using the prescribed apparatus. Smoke point shows the hydrocarbon nature of the fuel. Paraffins have high smoke points followed by naphthenes and then by aromatics. The test is applicable primarily to kerosene. The main purpose of kerosene is for use in lantern. If the kerosene gives smoke when it burns, it gives less light. As the flame size increases the light given out would also be more. But if the kerosene starts giving smoke, the height of the flame has no meaning. So the higher the flame without smoke, the better. Smoke point is related to hydrogen content of the fuel. The higher the hydrogen content, the higher will be the smoke point. Paraffins contain highest hydrogen content for the same carbon number. So the smoke point of paraffins is highest. The specification of smoke point for kerosene in our country is 18 mm minimum.
__________________ __________________ __________________
Aniline Point
Aniline point is the minimum temperature at which equal volumes of sample and aniline are miscible. Aniline point gives the hydrocarbon nature of the oil. Aromatic hydrocarbons have lower aniline points and paraffinic hydrocarbons have higher aniline points. Naphthenic hydrocarbons have intermediate aniline points.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Aniline point in combination with density /specific gravity/ API gravity gives a quick idea of some important properties like Diesel Index, Aniline-Gravity Product which are important properties for diesel and ATF. Aniline gravity product is an alternative to calorific value.
Carbon Residue
Every oil, when it burns, forms a carbon deposit which is very difficult to burn. This carbon deposits on burner tips chocking the orifices due to which the flow of oil stops and burner tip needs to be cleaned. If this carbon deposit is more, the burner tips have to be cleaned more frequently. Carbon residue test gives an indication of the amount of carbon that would form when the oil is pyrolysed and burned. There are two methods to determine carbon residue: 1. 2. Ramsbottom Carbon Residue (RCR) Conradson Carbon Residue (CCR)
Vapor Pressure
This is an indirect method of estimating most extreme low temperatures under which initial vaporisation can be expected to take place. It can be considered as a semi quantitative measure of the amount of most volatile material present in the product. It can also be used as a means of predicting the maximum pressures which may be experienced at fuel tank temperatures.
Colour
Two types of tests are applicable to petroleum products 1) Saybolt colour and 2) ASTM Color. The former is applicable to white oils like kerosene, naphtha, MTO etc and the other is applicable to diesel, vacuum distillates etc. The colour gives an indication of the degree of refining or contamination with foreign bodies.
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Notes __________________ __________________ __________________
BMCI (Bureau of Mines Correlation Index)

BMCI is an indication of predominant nature of Hydrocarbons in a product. All normal paraffins have BMCI zero or less than zero. A high BMCI indicates predominantly Aromatic nature. A low BMCI indicates predominantly paraffinic nature. Intermediate BMCI indicates mixtures of both and also naphthenic nature. BMCI more than 100 indicates presence of condensed rings. BMCI of some hydrocarbons
Hydrocarbon N Paraffins Iso Paraffins Cyclohexane Benzene BMCI 0 or < 0 < 15 50 99
__________________ __________________ __________________ __________________ __________________ __________________ __________________
BMCI is a calculated value form density and 50% boiling point. It is defined as, BMCI (48640 / K) + (473.7 * G) 456.8 Where, K = 50% Boiling Point in G = Specific Gravity @ 20
o
K / 4o C
There are graphical correlations between BMCI and Viscosity and Density also which are nearly equal to the calculated value.
Bromine Number
Bromine number is defined as the grams of bromine that react with 100 grams of the sample. Bromine number gives the olefinity of the sample.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ CH3CH2CH2CH2CH = CH2+Br2
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Olefins react with bromine giving additional products. Each double bond absorbs two atoms of bromine. Example:
CH3CH2CH2CH2CHBRCH2Br
Benzene Content
This test is applicable to motor gasoline. Benzene is carcinogenic (causes cancer). Its limit in MS is recognised by all countries. The specification for benzene in India is 5%v for general supplies and 1% v max for supplies to NCR.
Density
Petroleum products are liquids. They are sold on a volume basis but the custody transfers are effected on weight basis. Density is required for mass balance calculation and is also useful for several correlations which indicate the hydrocarbon nature and other properties. Some of such correlations are, BMCI, Kuop, VGC.
Weathering Test
This test is applicable to LPG. It indicates the amount of non vaporisable matter in LPG.
Specifications of Petroleum Products

LPG (IS 4796)
Test Density Volatility (95% Ev Temp) C Vapor Pressure @ 38 C Copper Corrosion @ 38 C Sulphur Odor %w -o o o
Unit kg / M3 kg / cm2
Specification Report +2 Max 7 Max 1 Max 0.05 Max Identifiable
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Activity 3 A What are different Petroleum Products? __________________ __________________
Motor Gasoline (IS 2796 - 2000)

Test Color Density @ 15 C Distillation Recover @ 70 C % v Recovery @ 100 C % v Recovery @ 180 C % v Final Boiling Point C Research Octane Number Anti Knock Index Existent Gum (Solvent washed) Potential Gum Sulphur Lead as Pb Reid Vapor Pressure VLI Summer Winter Benzene %v Cu Corrosion @ 50 C for 3 Hrs Water Tolerance Summer Winter Oxygenates % v ASTM D 4815-89 NB: 1) MFA containing Phosphorus compounds should not be used 2) Potential Gum before doping MFA 10 0 15 max
o o o o o o
Unit -kg / M3
Method Visual P:16 P : 18
Requirement Orange 710 770 10 45 40 70 90 min 215 max
__________________ __________________ __________________ __________________ __________________ __________________
P:27 P:26 & P:27 gm/M3 gm/M3 %w gm/1 KPa P:29 p:147 P:34 ASTM D 5059 P:39 --ASTMD 3606 P:15
88 min 84 min 40 max 50 max 0.1 max 0.013 35-60 750 max 950 max 5 max 1max for NCR 1
__________________ __________________
PC Naphtha
Test Appearance Color Density @ 15 C Distillation IBP FBP Total Paraffins Normal Paraffins Iso/Nor Paraffin Ratio n C6 nC7 %w %w kg/M3 C C %w %w ASTM D 5443 ASTMD 5443 Unit Method Visual Visual P:16 P:18 Requirement Clear and Bright Colourless To Report 28 min 160 74 min 36 min 1.05 max To Report To Report
Contd...
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Activity 3 B What are the key specifications of Motor Spirit, LPG, HSD, Petrochemical Naphtha, ATF? How do these affect performance? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Aromatics Olefins Total Sulphur Mercaptan Sulphur Reid Vapor Pressure @ 38C Chlorides Lead Arsenic and Mercury ppm w ppb w ASTMD 4929 P:82 ICP %w %w ppm w ppm w Kpa P:23 P:34 B P:109 P:39
Refining 10 max 1 max 100 250 150 max To Report
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5 max 100 max To Report
Superior Kerosene (IS 1459 - 1974)

Test Acidity (Inorganic) Burning Quality Char value Bloom on chimney Color (Saybolt) Undyed Dyed Copper Corrosion @ 50 o C for 3 Hrs Density @ 15 o C Distillation Recovery @ 200 Final Boiling Point Flash Point Abel Smoke Point Total Sulphur
o
Unit mgKOH/gm
Method P:2
Requirement Nil
mg/kg Oil
P:5
20 max not darker than grey
Units
P:14
+10 Blue
P:15 kg/M3 P:16
Not worse than 1 To Report
%v
o o
P:18
20 min 300 max
C C P:20 P:31 P:34
35 min 18 min 0.25 max
mm %w
Aviation Turbine Fuel (IS 1571 - 1992)

Test Appearance Unit -Method Visual Requirement Bright, Free from solid matter and visually undissolved water. 0.015 max 25 max 5.0 max 0.30 max 0.003
Acidity Total Aromatics Olefins Total sulphur Mercaptan sulphur
mg KOH/gm %v %v %w %w
P:113 P:23 P:23 P:34B P:109
Contd...
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Distillation 10 % v Recovered at 50 % v Recorded at 90 % Recovered at Final Boiling Point Flash Point Density @ 15 C Freezing Point Kinematic Viscosity @ Minus 20 C Aniline Gravity Product Smoke point Naphthalenes Copper Corrosion % 100 degree C for 2 Hrs Silver Corrosion @ 50 degree C for 4 Hours Thermal Stability Pressure Differential Tube Rating Visual mm P:97 Visual 25 max 3 max No Peacock Or abnormal color deposits 7 max 85 min 50 to 450 --IP 227 1 max --P:15 1 max cST --mm %v P:25 P:3 ISO 3014 ISO 3014 8.0 max 4800 25 min 3.0 max degree C degree C degree C degree C degree C kg/M3 degree C P:18 P:18 P:18 P:18 P:20B P:16 P:11 205 max Report Report 300 max 38 min 0.775 to 0.840 Minus 47 max
__________________ __________________
Existent Gum MSEP Electrical Conductivity Lubricity mm
mg/100 ml --ps/M
P:29 P:142 IP 274
ASTMD 5001 Report
High Speed Diesel (IS 1460 2000)

Test
Acidity Inorganic Acidity Total Aah RCR Cetane Number OR Cetane Index Pour Point Copper Corrosion @ 100 degree C for 3 Hrs - - Density @ 15 degree C kg/M3 P;15 P:16 1 max 820-860
Unit
mg KOH/Gm mg KOH / Gm %w %w -------
Method P:2 P:2 P:4 P:8 P:9
Requirement Nil 0.2 max 0.01 0.3 (on 10 % residue) 48 min
ASTMD 4737 46 min P:10 3 Winter
Contd...
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Total Sediments mg/100 ml UOP 413 Distillation Recovery at 350 degree C % v Recovery at 370 degree C % v Flash Point degree C cST %w %w %v deg C P:18 P:18 P:20 P:25 P:30 P:33 P:40 P:110
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85 min 95 min 35 min 2.0 to 5.0 0.05 0.25 0.05 max 6 Winter 18 Summer 1.5 max
Kin Viscosity @ 40 deg C Sediments Total Sulphur Water Content CFPP
__________________
Lubricity HFRR Scardia Micron at 60o C, 400 Proposed
Light Diesel Oil (IS 1460 - 2000)

Test Acidity Inorganic Ash RCR on whole sample Pour Point Unit mg KOH/Gm %w %w deg C Method P:2 P:4 P:8 P:10 Requirement Nil 0.02 max 1.5 max 12 Summer 21 Winter Copper Corrosion @ 100 deg C for 3 Hrs Flash Point (PMCC) Kin Vis @ 40 deg C Sediments Density @ 15 deg C Total Sulphur Water content --deg C cST %w kg / M3 %w %v P:15 P:21 P:25 P:30 P:16 P:33 P:40 2 max 66 min 2.5 to 15.7 0.1 Max Report 1.8 max 0.25 max 1b 66 min 2.5 to 5.0 0.05 max 910 max 0.35 max 0.05 max PSS --0.005 max 0.3 max 0 max 0 max
Petroleum Coke (IS 8402 - 1994)

Test Moisture as Received Moisture after Initial drying Ash on Dry basis Volatile Matter %w %w %w P: 132 P: 126 P: 134 2.0 max 0.45 max 11 max --1.0 Max 8 max Unit %w Method P: 132 Requirement 10 max PSS 8 max
Contd...
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Specifications of Petroleum Products & Related Tests kg/ M3 P: 133 Report 560 min
37
Notes __________________
Density (Dry) Fixed Carbon (On Dry Basis) Total Sulphur Trace metals Silicon as Si Iron as Fe Vanadium as V Nickel as Ni Hardgrove Grindability Index GCV
%w %w
Calculation 85 min P: 33 2.5 max
88 min 7.0 max
__________________ __________________ __________________
ppm w ppm w ppm w ppm w
UOP 389 Report 150 max 1600 max 400 max
150 max
__________________ __________________ __________________ __________________ __________________
ASTMD 4097 50 MIN Kcal/ Kg --8000 min.
__________________
Properties of Petroleum Products and their Significance

Gasoline Effect of Chemical Composition on Gasoline Quality
Octane number is the most important property of motor gasoline. Composition of motor gasoline profoundly affects its performance in the engine and equally controls its behaviour under storage and handling.These are described below:
Paraffins (Cn H2n+2)

Thermally and chemically most stable compounds. Have poor octane number Increasing the chain length reduces the octane number Knock resistance increases with branching Adding methyl groups (CH3) to the side chain in the central position increases the knock resistance
Olefins (Cn H2n)

Oxidation and thermal stability is poor in general More knock resistance than their corresponding saturated compounds.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Cycloparaffins (CnH2n)
Poorer knock resistance than corresponding aromatics Lengthening of side chain decreases knock resistance Branching of side chain is beneficial.
Aromatics (CnH2n-6CnH2n-12 etc)

Aromatics have excellent knock resistance qualities.
Properties of Gasoline and Oxygenated Compounds

Property Chem. Formulae Mol. Wt. Oxygen Cont. % mass B.P.C StoichioMeteric A/F Lat. Heat of Vap. Btu/Gal (J/lit) Net Heat comb. MJ/Kg SolubiSolubility in water, g/100g water RON MON 101 82-87 3300 (11.8) 21 2600 (9.3) 28 2100 (7.5) 32 1700 (6.1) 35 900 (3.2) 35 4.8 800 (2.9) 43 Trace 65 6.4 78.3 9.0 82.2 10.3 82.8 11.1 55 11.7 30-20 14.6 32 50 46 35 60 27 74 22 88 18 111 0 Methanol CH30H Ethanol C2H5OH Isopropyl Alcohol C3H70H Tertiary Butyl Alcohol C4H90H MTBE C4H9OCH3 Gasline C8H15 (Av.)
107
108
112
113
116
87-93
Gasoline Properties Needed for Acceptable Performance

Fuel Performance Required Handling and Storage Property Controlled for Automotive Gasoline Volatility Vapour (Water/Sediments/Gum) Copper Corrosion Combustion Engine Cleanliness Octane Number Volatility/Distillation Range Gravity Hydrocarbon Compostion Sulphur Existent Gum Oxidation Stability Pressure Contamination
Combustion and Knock

Before combustion, air and fuel is heated up in combustion chamber, there is an induction period before normal hot
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
flame occurs. During this induction period, oxidation of fuel takes place with the formation of intermediate products such as peroxides, aldehydes and peracids. Formation of peroxides, aldehydes and peracids prevents knock due to their ability to dissociate and promote such type of intermediate reactions.
Knocking Tendency
High Anti-knock Value: Aromatics, Isoparaffins (highly branched) Intermediate Anti-knock Value: Mixed parffins e.g. isoparaffins with little branching, Naphthenes. Low Anti-knock Value: Paraffins
Combustion Chamber Deposits

Deposits are formed by Incomplete Combustion Partial Oxidation Cracking Condensation and Polymerisation of fuel and lubricants May contain nonvolatile reaction products of additives
Deposits can lead to: Pre-ignition Peak pressure and temperature will increase due to apparent increase in compression ratio and poor heat transfer due to heat insulation effect. Loss of power due to reduction in volumetric efficiency Exhaust valve corrosion Spark plug fouling
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Volatility
Volatility of gasoline is its tendency to pass from liquid to vapour phase. Volatility influences: Ease of starting Rate of warm up and acceleration Tendency to vapour lock Carburettor icing Crankase dilation Fuel economy
Ease of Starting
For a cold engine start, enough gasoline in the intake air must be evaporated. Ease of starting depends on:
y y y y
Fuel volatility Engine design Cranking speed Engine oil viscosity
Warm Up and Acceleration

It depends on: 1. 2. Fuel volatility and ambient temperature Provision for thermostatical controlled hot spots. Warm up is mainly a cold weather problem.
Vapour Lock and Percolation

Vapour lock is a function of : 1. 2. 3. Volatility characteristics of fuel Fuel requirement of engine at the moment Ability of fuel pump to handle the vapour
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Notes __________________ __________________ __________________
4. 5.
The temperature and pressure in the fuel system The temperature of ambient air, temperature and barometric pressure. underbonet
Measurement of Volatility
1. ASTM D-86 Distillation Significant temperatures are 2. Initial boiling point Temperature corresponding to 10% Vol. Temperature corresponding to 50% Vol. Temperature corresponding to 90% Vol. FBP Non-volatile residue left in the flask.
__________________ __________________ __________________ __________________ __________________ __________________ __________________
Reid vapour pressure (RVP) Controls the volatility due to lighter ends.
TYPICAL VALUES OF VAPOUR PRESSURES (RVP)
K g /c m
2
PSI 200 80 10
KPa 1 3 8 2 .8 5 4 9 .2 6 8 .6
P ro p a n e B u ta n e M o to r G a s o lin e
1 4 .1 5 .6 0 .7
3.
Vapour lock index (VLI) 10 RVP+ E 70 Gives better indication of vapor locking.
Carburetor Icing
It occurs due to following: Stoppage of the fuel flow due to clogging of the jetice Formation of ice on the walls of carburetor ventenary which causes the engine to stall due to over-rich fuel/ air mixture
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Activity 3 C How is gum formed in motor spirit, what is its impact and how is it overcome? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ l l
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High volatility of fuel Cold and humid climate are favorable for icing.
Remedial Measures
Control of fuel volatility Providing heating of carburetor body or the intake air, particularly during warm up period Providing greater throttle opening during starting By incorporation of anti-icing agents Anti-freeze type Surface active agents
Oxidation Stability
Gum formation takes place in storage due to oxidation/ polymerisation reaction undergone by the unsaturated hydrocarbons and it accelerates at higher temperatures. Gum is a rubber like resinous material and is insoluble in later stage of formation. Sulphur and nitrogen compounds also take part in these reactions Gum formation is influenced by storage conditions, temperature, access of air and light, and catalysts particularly traces of copper.
Impact of Gum Formation

y
May cause intake valve sticking due to deposition of Gum, and may lead to valve burning May cause malfunctioning of carburetor float or impair the functioning of throttle Deposits formed in the intake may restrict engine breathing and reduce the efficiency of hot spots resulting in increased warm up period It can lead to increased sludge and varnish deposits in the engine.
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Notes __________________ __________________ __________________ __________________
Sulphur Compounds and Corrosiveness:

Most of the sulphur compounds are removed in the manufacturing processes. If these H2S and COS are mainly corrosive and RSH is distinctively unpleasant. Sulphur, on oxidation, forms oxides of sulphur which react with water to form sulphuric acid. A direct result of leakage of unburnt fuel can be corrosion of engine parts. Stringent specifications are required to be followed due to environmental considerations. Automotive industry requirement for meeting Euro III/ IV emission standards for Motor Gasoline.
RON 89 91 93 Benzene content Aromatics Olefins Lead Content Sulphur Content Oxygen Content MON 79 to continue for old cars 81 to be widely available 83 to continue for high CR cars 1% Max 40% Max 25% Max 0.005% Max 0.05% Max 2.70 Max
__________________ __________________ __________________ __________________ __________________ __________________
Diesel Fuels
BIS Grades of Diesel Fuels
There are three grades of diesel: High Speed Diesel (HSD) Light Diesel Oil (LDO) Marine Diesel (MD)
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Heavy SR Naphtha Kerosine LT. SR Gas Oil Heavy Gas Oil LT. Cycle Oil Hydro Cracker Go Coker Kerosene
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HSD Blending Components (Typical)

B0ILING RANGE C 148-204 204-260 250-315 315-350 204-343 204-343 204-340 CETANE NUMBER 28-42 45-50 45-50 50-55 15-20 50-60 15-20
FUEL Performance Requirements

Performance Handling & Storage Property - Volatility - Flow - Corrosive constituents - Contaminants Control characteristics - Flash Points - Viscosity - Water & sediments - Copper corrosion - Cloud/Pour pt. - CFPP Combustion - Ignition Delay - Volatility - Heat content - Cetane Number - Distillation Range - Gravity - Cloud & Pour Point Cleanliness Use During - Heavier constituents - Metals - Corrosive constituents Carbon Residue on 10%, Bottom Ash Content, Sulphur Content, Stability Exhaust Emission Standards
Effect of Diesel Fuel Hydrocarbon Type Composition on its Quality Paraffins

Have the best combustion characteristics and highest cetane numbers With molecular weight of n-parrafins, cetane number increases Isoparaffins have lower cetane numbers than the paraffins of same carbon numbers. With branching cetane number is lowered.
Olefins
Olefins have lower cetane numbers than paraffins of corresponding structures and follow similar rules of branching
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Presence of olefins gives rise to poor oxidation stability.
Naphthenes
Naphthenes follow olefins in cetane quality but are a good deal higher than aromatics.
Aromatics
Impart lowest cetane number and most important factor controlling the cetane number of cracked gas oil Aromatics ring condensation and the side chain branching on rings that cause molecular configuration of lowest cetane numbers.
Ignition Quality
This is the most important property that controls combustion process. It is measured as a cetane number which is a measure of ignition delay and is controlled by Fuel composition and characteristics Engine design Fuel and air inlet temperature Degree of atomisation.
As a result of abnormal ignition delay, large quantities of oil are gathered in the combustion chamber. Spontaneous burning and detonation of this surplus fuel in combustion chamber causes rough ignition which is termed as diesel knock or cetane knocking.
Cetane Improver Additives

Base Diesel Cetane No. 44 Additive dozes 1.5% Isoproyle Nitrate n Amyl Nitrate Increase in CN 17 23
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u
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Cyclohexyl Nitrate Octyl Nitrate
22 19
Flow Properties Viscosity

u
Viscosity of diesel fuel has an effect on handling of the fuel by pump and injector system. High viscosities can cause Poor atomisation Large droplets High spray jet penetration
Low viscosity results in a spray which is too soft and thus does not penetrate sufficiently. As a result combustion is impaired and power economy is decreased. Lubricating oil properties of such fuels are usually poor HSD viscosity range is generally 2.0 to 5.0 cst. Heavy distillates, when used as diesel fuel, are generally preheated.
u u u
Cloud Point
u
Congealing wax settles out and blocks fuel system line and filters. The temperature at which precipitation occurs depends on the composition and boiling range of the fuel. Cloud point indicates the temperature at which waxes start precipitating.
Cold Filter Plugging Point (CFPP)

u
Cloud point being a static test does not truly represent actual running conditions. CFPP is defined as highest temperature expressed as a multiple of 1 o C at which the fuel when cooled
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
under prescribed conditions will not flow through a filter or requires more than 60 sec for 20 ml to pass through.
Pour Point
u
Pour point gives a useful guide to the lowest temperature at which the fuel can be cooled with setting.
Cleanliness in Use Carbon Residue

u
Gives some indication of coke forming / deposit forming tendencies in the engine. Deposits are mainly carbonaceous matter, ash, resins etc. Type of deposits is also an important factor. Hard abrasive deposits can do more harm than soft fluffy deposits. The test can also be used to detect contamination by heavy residues. Maintenance life and period of over-haul mainly depends on deposit control.
Ash Content
u
Indicates the presence of small quantities of metallic soap or volatile porphyrines. Unburned metallic constituents have abrasive action and cause wear by adversely affecting the nature of deposits.
Water and Sediments

u
These may come into the fuel through contamination during storage and handling. They can cause clogging of filters. Sediments cause wear and create deposits both in the injection system and engine itself.
u u
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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Sediment and Gum Forming Reactions (Diesel Fuel Stability)

1. Oxidative Gum Reactions Alkenee + Oxygen Reaction time 2. Acid Base Reactions Organic acid + Basic Nitrogen Sediments Reaction Time 3. Esterification reactions Aromatic Hydrocarbons + Hetrocylic Nitrogen + Benzothiols Multi-step Process Reaction Time .. Sediments Weeks to months Hours to weeks .. .. Gum Weeks to months
These are more predominant in diesel fuel instability.
Corrosive Constituents Sulphur Content

u
Strict emission regulations require stringent sulphur specifications Due to high sulphur, combustion products corrode and also contribute to deposit formation. Low speed diesel engines can tolerate more sulphur, because They are large in size and are stationary They are high power output type They run under relatively constant speed and load conditions Their operating temperatures, cooling water and combustion zone temperatures tend to remain at
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
an equilibrium rather than to fluctuate between high and low.
Tests carried out

u u
Estimation of sulphur content Copper strip corrosion test.
Acid value
u u
Total and Inorganic Potentiometeric Acid/Base titration
__________________
Residual Fuels Oils

Changes in quality of fuel oils in Indian refineries are due to:
u u u
Frequent changes in crude quality and blend ratios Intake of more of heavy crudes Introduction of various secondary conversion processes for maximisation of middle distillates.
Components of Residual Fuel Oils

u u u u u u u
Long residue Short residue Heavy cycle oil, clarified oil from FCC Hydrocracker bottoms Visbroken products TAR from thermal conversion process Slop
Uses
u u u u
Steam boilers Industrial applications requiring heat Gas turbines Diesel engines
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Activity 3 D Effect of metals in furnace oil? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Fuel system corrosion Acidic, sulphur compounds, water, sludge Na, V in fuel form low melting point sulphated ash Problems Plugging of fuel lines strainer and burner tips Causes Oxidation of the fuel to produce acid and sludge
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Summary of Fireside Problems Related to Fuel Quality

Solutions Addition of inhibitors and sludge dispersants Application of corrosion inhibitors - magnesium additives - reduce excess air - combination of both
High temperature fouling & corrosion
Effect of Sulphur
u u
Raises dew point of fuel gases Increases formation of sulphur deposits in boiler passages, economiser, airpreheater and chimney Reduces efficiency by reducing permissible temperature Accelerates formation of gum and sediments during storage Corrosion of process and plant equipment Sulphur pick by product.
u u
u u
Effect of Metals
u
Vanadium is a major metallic impurity in residual fuel oil. Causes corrosion in high temperature zone. Sodium is recognised as a potential corrosion problem. In combustion, Na converts to V converts to Na2O + Na2SO4 V2O5 + V2O4 Na2 V2O5, Na2 V2O4 5V2O5 (Low melting ash deposits)
u u
Other ash deposits are SiO2, AI2O3, Fe2O3
NaAIO2 has high melting point (3272 oF). It causes metal spalling or breaking off of pieces of refractory due to its high thermal expansion.
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Notes __________________
Review Questions
1. What is the significance of following tests and to what petroleum product these are related: 2. Flash point Distillation Smoke point Octane number Cetane number Viscosity Silver corrosion BMCI Weathering test Copper corrosion Vapour pressure
__________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
What specifications for Motor Spirit and HSD are related to environmental pollution? What are the limits for these specifications for Euro III / IV standards? What strategies are being adopted to improve these specifications to desired ones from the present values? What would be the impact on cost of production? (Refer Bibliography) What streams of Process Plants in a Refinery are utilised to produce HSD, MS, LPG and PC Naphtha? (Refer Unit 4 & Bibliography).
3.
4.
53
Unit 4 Integrated Refinery and Petrochemical Plants

Objectives
y
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Understand the functioning of various process plants in a refinery and their integration with one another. Give insight into the feeds composition of various process plants for production of finished products. Give an overview of various off-site facilities in a Refinery.
Now a days, to minimise processing cost and optimise product distribution, emphasis is laid on the following: 1. 2. 3. 4. Economies of scale Minimum 9-12 MMTPA refining capacity. Refining and petrochemical plants are integrated. Feedstock flexibility To utilise low cost crudes. Supply chain optimisation from crude to products, provides faster delivery and at lower cost.
A typical integrated refinery and petrochemical plant set up is shown in attached block flow diagram. (Fig. 4.1) Crude is normally received by tankers or pipelines into crude tanks and allowed to settle for separation of water and sludge. Then it is taken to Crude Distillation Unit (CDU) which operates at atmospheric pressure for fractionation into Gas, LPG, Naphtha, ATF, Kerosene, MTO, Diesel, Jute Batching Oil (JBO) and Reduced Crude Oil (RCO). RCO is fractionated in Vacuum Distillation Unit (VDU) to get VGO and raw lube cuts. The raw streams from CDU are treated in Merox, Hydrotreatment, Reforming, Isomerisation and Fluid Catalytic Cracking plants to obtain components of
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Coker Sulfur CRUDE CRUDE TANKS CDU/ VDU FCC Propylene
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Naphtha Kerosen Kerosene

Gasolene Petro
Diesel LPG Aro PP MPP Paraxylene Polypropelene Power
FIGURE 4.1 INTEGRATED REFINERY AND PETROCHEMICAL BLOCK DIAGRAM
finished saleable products. VGO is treated in FCCU to get LPG, Propylene, Petrochemical feedstocks and components for motor spirit and diesel. Raw lube cuts are treated for removal of aromatics and wax and are hydrotreated to get lube oil base stock. The short residue obtained from VDU fractionator bottom is partly treated in coker unit to get lighter value added products alongwith raw petroleum coke. Vacuum residue can also be treated to extract out Deasphalted Oil (DAO) and the residue left is asphalt. DAO is treated in aromatic extraction unit, dewaxing unit and hydrofinishing unit to obtain bright stock which is used for Lube oils and grease manufacture. Asphalt and vacuum residue can also be utilised for production of bitumen or as fuel for furnaces and boilers. From FCCU, olefins, propylene, various aromatics and naphthas are obtained which are used as raw materials for polypropylene and aromatic petrochemical plant. The Raw Petroleum Coke (RPC) is used for generation of power and calcined petroleum coke. Sulphur present in crude and various streams is converted to H 2S during processing. In Sulphur plant, it is converted to elemental sulphur which is sold as by-product. This also helps in environmental protection. Hydrogen plant is installed to produce hydrogen for meeting the requirement of various Hydrotreatment processes.
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Integrated Refinery and Petrochemical Plants
55
Notes __________________ __________________ __________________ __________________
Crude Distillation
Brief process descriptions have been provided (please refer block flow diagram of CDU, VDU and SGU). This part has three main sections. 1. 2. 3. Desalting Distillation-Atmospheric & Vacuum Saturated Gas Concentration Unit (SGU)
Other streams from other limits S G C Lean Gas LPG to Marox Naptha to Hydrotreater
__________________ __________________ __________________ __________________ __________________ __________________
Crude in
Desalter Flash Drum Water in Brine Out Preheat 2 Preheat 3
Preheat 1
F u r n a c e
Atm osp heri c Col.
LK/ATF HK Diesel JBO LVGO V a c. C o l.
Fumace
HVGO TO FCC
Lube distillates
Vacuum Residue to Belayed Coker/ Bitumen.
FIGURE 4.2 BLOCK FLOW DIAGRAM OF CDU/VDU/SGU
FIGURE 4.3 CRUDE AND VACCUM DISTILLATION UNIT IN A REFINERY
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Desalting
The crude oil is contaminated with various impurities mainly salts of Ca, Mg, Na, CI, SO4, etc. These salts, however, in small proportions in crude, can cause severe corrosion in crude units, particularly in the overhead section. Several refineries worldwide have faced emergency shutdowns or have had to release hydrocarbons due to corrosion and material failures. Hence, it is important to remove the salts from crude prior to distillation. The desalters are designed for 99% salt removal and reach less than 1 ptb (part per thousand barrels) in desalted crude. Crude oil received from tank farm is heated from 30 to 140150C in cold preheat trains. This is done by recovering heat from outgoing products streams from the unit. This prepares crude for efficient desalting. Then it is passed through a desalter after being mixed with de-emulsifier and water thru a mixer valve. In the desalter, crude passes through high electric field. The salt dissolved in water settles at the bottom as brine and desalted crude with less than one parts per thousand barrel comes out from the top of the vessel. Separation of water containing salt is enhanced by deemulsifier. Desalters remove salts, sludge and mud from crude to avoid corrosion and fouling in exchangers columns and downstream equipment.
Distillation Atmospheric & Vacuum

The desalted crude is then heated from 140 to 190 C at 25 Kg/a2 pressure by heating with a heavier hot stream. Then it is taken to the flash drum. From the top we get lighter components which directly go to the crude column. The flashed crude is passed through hot preheat exchangers and further heated from 190C to 250260C. The purpose of hot preheat train is to recover heat from pump arounds to reduce furnace duty. Furnace provides required heat for fractionation in atmospheric column and crude is heated upto 385C. The heated crude is fractionated in atmospheric distillation column of CDU. The fractions below 165C are withdrawn as column overheads and sent to SGU. Here mainly gases, LPG and FRN are separated. Heavies boiling at more than
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386 C are reheated under vacuum condition (to avoid cracking) and fractionated in vacuum column of VDU. Besides the straight run products such as LPG, Naphtha, LK, HK and Diesel, the other distillation products are intermediates viz. (1) Gas Oil (HAGO+LVGO+HVGO) which become feedstock for FCC after treatment in VGOHT and (2) VR which becomes feedstock for delayed coker. The LPG is sent to LPG Merox unit for treatment before sending to RTF. The FRN is directly sent to the HNUU in the aromatics complex. The Light Kero (LK) fraction is routed as SKO to RTF directly or via Kero Merox unit as ATF. The Heavy Kero (HK) fraction is blended with diesel fraction. The diesel fractions can be routed to DHT or RTF as required.
Saturated Gas Concentration (SGU)

The overhead liquid and gases from CDU, reformer and hydrotreaters of petro-chemical complex are passed through this plant to separate into following fractions: 1. Gases (C 1+C 2 ) for burning into furnaces or as petrochemical feedstock after H2S is removed in Amine Treating Unit. LPG (C 3+C 4) for domestic and industrial use after removal of Mercaptanes in Merox Unit. Naptha (C 5 to 165C) for sending to fertilizer or petrochemicals plants as feedstock.
2. 3.
The typical streams obtained from crude oil by Atmospheric and Vacuum distillation are given in the following table:
% of crude input 0.01 to 0.03% 1.0 to 1.5% 11 to 14% 10 to 11% 6 to 7% 16 to 17% 2.5 to 3.0% 2.5 to 3.5% 21 to 22% 23 to 26% Cut range deg C < C2s C3C4s C5s to 16s 165 227 227 270 270 370 370 392 <392
Fuel Gas LPG FRN LK / ATF HK Diesel HAGO RCO (Atm. Residue) LVGO HVGO VR
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Product specifications and significance of the same is given in Unit 3 Operating issues which need attention are: 1. 2. 3. 4. 5. 6. 7. 8. Crude mix and product yield pattern Corrosion impact on various equipment should be known. Health of equipment and run length of unit is vital. Operating parameters such as pressure, temperature, flows. Quality control of crude and products. Health, safety and environment (HSE) aspects. Energy conservation knowledge and skills of operating crews.
Diesel Hydro-Treatment
The purpose of diesel hydrotreating unit is to:
u u u
Remove sulphur and nitrogen Convert olefins/aromatics to saturated compounds. Remove contaminants like organomettalic compounds. oxygenates and
The catalysts used in this plant are oxides of Ni and Mo/Co & Mo impregnated on alumina base.
Salient Features
u
98% desulphurisation and 70% denitrification (VGO hydrotreater). Produce low sulphur, colour stable diesel. Reduce aromatics and nitrogen in diesel. Improve Diesel cetane no.
u u u
The feed to the unit consists of a mixture of SR diesel and heavy kerosene from the Crude Unit, light coker
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Notes __________________
gas oil, HCO from the Delayed Coking Unit and LCO from FCCU
Diesel Hydrotreater
Make up H2 Ovhd. condensor Recycle gas Diesel Diesel VGO LN VGO Product separator Stripper Hydrotreater To waste water system LN
__________________ __________________
Offgas to SGCU
__________________ __________________ __________________ __________________ __________________ __________________ __________________
FIGURE 4.4 HYDROTREATER BLOCK-FLOW DIAGRAM
Brief Description of the diesel hydro-treater follows. The feed is pumped through cold and hot feed-reactor effluent exchangers and then with recycled gas streams through the combined feed heater. The combined feed heater heats the feed up to the reactor inlet temperature. The reactor consists of one vessel with two beds of catalysts, consisting of one inert and three different types of catalysts. Recycled gas is added as a quench between the beds to quench the top bed heat of reaction. The reactor effluent is cooled through a series of heat exchangers where it, in turn, heats up the fresh feed, the stripper feed, the recycled gas and then provides heat for generation of HP, MP and LP steam. A wash water stream is then injected into the reactor effluent before final cooling in the air-product condenser. From the product condenser, the reactor effluent enters the separator. The separator is a horizontal vessel with a water boot that separates the recycled gas from the stripper feed and the wash water from the stripper feed. The recycle gas goes through a recycled gas water cooler and knockout drum to remove heavier hydrocarbon components before entering the
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recycled gas scrubber. This scrubber is used to remove H2S from the recycled gas by bringing it in contact with a liquid stream of lean amine. The top of the vessel contains a water wash section to pick up any entrained amine. The recycled gas exits from the top of the recycle gas scrubber, and is then mixed with makeup gas hydrogen before entering the recycle gas compressor. The stripper feed is heated in a series of exchangers where it in turn cools the stripper bottoms, reactor effluent, before entering the stripper column. The stripper is used to remove H2S from the diesel product, and also to separate unstabilised naphtha from the diesel product. Both the net off gas and the unstabilised naphtha liquid that are produced are routed to the Saturated Gas Concentration Unit. The stripper bottom is cooled through a series of exchangers, then further cooled by air and water before entering the diesel product coalescer and the salt drier which removes water prior to routing to the diesel product blending system.
VGO Hydro-treatment
This is similar to diesel hydro-treater and is used for preparing feed for FCC.
FIGURE 4.5 HYDRO-TREATER/ HYDRO-CRACKER IN A REFINERY
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Notes __________________
Hydrogen Production and Management

Hydrogen Production Plant
Hydrogen is produced commercially using following technologies: (i) Partial oxidisation
__________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
(ii) Coal gasification (iii) Electrolysis of water (iv) Steam hydrocarbon reforming (v) Platforming as a by-product. Refer hydrogen plant block flow diagram
Recycle H2 Refinery fuel gas Natural gas LPG Main pumping section Naphtha (future) Refinery general fuel gas Waste gas Feed gas compr. HP BFW Steam Generator HP steam export Product H2
__________________
Feed purification
Steam reformer
Shift & gas cooling
Gas purification
FIGURE 4.6 HYDROGEN PLANT BLOCK FLOW DIAGRAM
Hydrogen Feed
Feed for hydrogen production plant (i) Refinery fuel gas, (ii) saturated LPG, (iii) Natural gas, (iv) Light Naphtha.
Process Description
Feed (Refinery Fuel Gas, or Natural Gas or LPG or Hydrotreated Light Naphtha) is first mixed with recycle hydrogen and passed through pre-treatment section. The function of pre-treatment section is to remove sulphur in feed by hydrogenation, in the form of H2S, and removal of chloride by sodium aluminate, the catalyst used is CoMo or NaMo. H2S is absorbed in Zno bed.
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If sulphur is <200 ppm, then single stage pre-treatment is adopted. For sulphur >200 ppm, double stage pre-treatment is used. The De-sulphurised feed is pre-heated with steam and passed through Nickle Catalyst packed in Vertical narrow tubes mounted in the reformer furnance. This process is endothermic and heat is supplied by fuel firing. Following reactions take place:
Steam Reforming
CH4 + H2O l 3H2 + CO CO + H2O l H2 + CO2
Water Gas Shift

CO + H2O l H2 + CO2 Steam is added in excess to promote above reactions. Hydrogen gas produced is purified by pressure swing adsorption (PSA) method.
PSA Cycle
One PSA cycle is built up of 2 basic phases: Adsorption and Regeneration
Regeneration of PSA Bed

The regeneration phase is a chain of sub-phases consisting of:
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High to low pressure transition: Expansion Provide purge and dump Purging at low pressure Low to high pressure transition back to adsorption pressure: Repressurization.
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Hydrogen Management
Hydrogen gas in the refinery comes from (i) Hydrogen production plant as described above
(ii) Catalytic reformers in the refinery in the integrated petro-chemical plant
__________________ __________________ __________________ __________________ __________________
The hydrogen from both the sources is supplied to various consumers like hydro-treatment plants etc. through high pressure compressors and the excess gas is led to refinery fuel gas system. Need of hydrogen is increasing day after day for treating the products like motor spirit, HSD, fuel oils and feeds for FCC and other plants for bringing down sulphur.
Merox (Mercaptan Oxidation) Treatment

Process Description
Merox is the abbreviation of Mercaptan Oxidation. In this process mercaptan is separated from hydrocarbon by washing with caustic solution. The separated merceptan is oxidised into disulfide form which can be disposed of in slop stream. Organic sulphur from LPG, ATF/Kerosene and Gasoline are removed by this process. Hydrogen Sulfide (H2S) from LPG is removed by extraction with regenerated lean Amine in Amine Treating Unit (A TU). Treated LPG is passed through reactor and mixed with caustic solution containing merox catalyst. Then it passes through extractor to remove mercaptan. Then, it is washed with water to remove caustic. Treated sweet LPG free of H2S and Mercaptan is sent to storage. In case of ATF/Kerosene and Gasoline treatment, first it is mixed with caustic, air and catalyst and then passed to reactor to convert mercaptanes to Disulfides, which is separated from caustic and product in caustic sulphur. Caustic in recycled. Sweetened product is stored in intermediate tanks before blending into finished product.
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Following reactions take place Mercaptan gets converted into disulfides 4RSH + O2 2RSSR + 2H2O
Caustic Regeneration RSH + (oil phase) NaOH Aqueous phase NaSR+ H2O (Sodium Mercaptide soluble in Aqueous phase) Catalyst 4NaSR+02+2H2O (Aqueous Phase) 45C 2RSSR+4NaOH (oil Phase)
The purpose of caustic in Merox process is:

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To transfer the mercaptane, or the thiol portion of the mercaptane, to the aqueous phase. To supply the alkaline environment needed for the reaction to proceed in the desired direction.
FIGURE 4.7
MEROX TREATMENT PROCESS BLOCK FLOW DIAGRAM
This process is used for treating LPG, Gasoline and ATF.
Sulphur Recovery Plant

The objective of sulphur recovery plant is to convert H2S to elemental sulphur.
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Sulphur recovery is required because of:

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Increasing demand for environmental friendly fuels. Increased used of high sulphur and heavier crudes in future. Tightening of emission standards by government/ Regulatory bodies.
__________________ __________________ __________________ __________________ __________________ __________________
Salient features of sulphur plant are:

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Minimum sulphur recovery level of 98.7% Ammonia destruction capability Turndown capability 25%
__________________ __________________
Process Description
Refer sulphur plant block flow diagram (Figure 4..8) Acid gasses from Amin Recovery Unit (ARU) and sour gasses from sour water stripper are heated in pre-treater and burnt in presence of regulated quantity of air from CLAUS Air Blower in CLAUS Reaction Funance. The product from claus reaction funance is passed thru 1st and 2nd pass condensers. . Acid gases
from ARU Thermal reactor Claus reactor CBA reactor
Air
Condenser 1
Condenser 2
Condenser 3
To tail gas incinerato
Sour gases from WWSU
Liquid sulfur degassing pit Air
To sulphur granulation unit
FIGURE 4.8 SULPHUR PLANT BLOCK FLOW DIAGRAM
The sulphur condensed is routed to Liquid Sulphur Degassing Pit. The unreacted vapour is passed thru claus reactor. The vapour from the claus reactor outlet is passed
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thru 1st and 2nd pass condensers. The condensed sulphur is taken to Liquid Sulphur Degassing Pit. The uncondensed vapour is passed through Cold Bed Adsorption (CBA) Reactors 1st and 2nd passes. The outlet vapour is passed thru 1st and 2nd pass of CBA condenser. The condensed sulphur is routed to liquid sulphur degassing pit and the remaining gases are taken to tail gas incinerator for burning and releasing thru high stack. Sulphur after Degassing is taken to granulation unit from where it goes for despatch to market. The off-gases from sulphur degassing pit is recycled to CBA section for recovery of sulphur.
What is Claus Reaction?

When two molecules of Hydrogen Sulphide (H2S) react with one molecule of Sulphur Dioxide (SO 2) to give elemental sulphur in the presence of Alumina Catalyst, the reaction is called Claus Reaction 2H2S + SO2 3/nSn + 2H2O
n=No. of atoms in Sulphur molecule.

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1/3rd of total H2S in feed gas is burned to SO2, this SO2 reacts with remaining H2S to give elemental Sulphur in Claus Reactor H2S+3/20 2SO2+H2O 2H2S + SO23/n Sn+2H2O Overall Reaction 3H2S + 3/2 O23/nSn + 3H2O
Process Variables
Air to Acid Gas Ratio
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H2S/SO2 Ratio = 2:1 344C 650+ 50C
Claus Reactor Outlet Temp Incinerator Temperature
Amine Treating Unit (ATU)

The purpose of this process unit is to remove H2S from fuel gases to meet environmental requirements.
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Process Description
Refer figure 4.9 simplified block flow diagram The fuel gas containing H2S is introduced in Middle section of Amine Absorber Column where Lean Methyl Diethanol is introduced near top section. By counter current flow H2S is absorbed in Amine and sweet fuel gas (FG) free of H2S comes out from column top. The rich Amine from bottom of the absorber column is taken to Flash Drum where any fuel gas carried over is separated out. The rich Amine is then pumped through heater where it is heated by the hot lean amine stream coming from bottom of Amine stripper. In the stripper, Amine Acid Gas from top of the column is routed to sulphur recovery plant along with sour gases from other process units. The lean Amine from bottom of the stripper exchanges heat with Rich Amine and then pumped to storage tank through cooler for recycling to Amine Absorber.
Absorption Section Sweet FG
__________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Lean Amine FG Abs Stpr
Regeneration Section
Lean Amine Header Rich Amine Header Amine Storage Section
FIGURE 4.9
SIMPLIFIED BLOCK DIAGRAM ATU
Process Chemistry
The circulating amine is 35% MDEA solution, Hydrogen sulfide H2S OR HSH is a weak acid and ionizes in water to form hydrogen ions and sulfide ions. HSH H+ + SH
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Ethanol amines or weak bases ionize in water to form amine as hydroxyl ions (CH 2OHCH 2)2NCH 3+H 20 CH2OHCH2)2NHCH3+OH
When H2S dissolves into the solution containing the amine ions, it will react to form a weakly bonded salt of the acid and the base. (CH2OHCH 2)2 NCH 3+SH (CH2OHCH2)2NSCH3
The sulfide ion is absorbed by the amine solution. Overall (CH 2OHCH 2) 2NCH 3+H 2S (CH2OHCH2)2NSCH3
Delayed Coking
Coker Unit
The purpose of coking unit is to produce valuable distillates and Petroleum coke (by-product) by upgrading heavy residual stocks from vacuum distillation and other process units generating heavy stock. This unit is also known as delayed coker. Slops from various other process units which do not find proper home can also be processed in coker to get valuable products. The feed to this unit is subjected to severe thermal cracking thereby producing refinery fuel gas, coker gasoline, coker kerosene, coker gas oil, coker furnace oil, residual furnace oil and coke.
Process Description
Refer block flow diagram of coker Feed is preheated by exchanging heat with hot streams. Thereafter, it is heated to 250C in convection section of the furnace before it enters the bottom section of fractionator column. The hot cracked hydrocarbon vapours from coke chambers top via a separator enters the zone of abovementioned fractionator column. The heavy hydrocarbon fractions in these vapours condense in lower section of the column and are withdrawn from bottom along with primary feed by secondary feed pump.
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Heavy cycle gas oil HP flare Light cycle gas oil To HNUU To LNUU Unsat LPG Merox unit
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LLP Flare
Vacuum Residue tank Coker
Unsat gas conc. unit
To LPG spheres
FG distribution system
To flare Coker consumption To light slop oil tank
FO tank
Rich amine Lean amine Amine treating Coke handling system
To heavy slop oil tank
__________________
To ETP
FIGURE 4.10
COKER BLOCK FLOW DIAGRAM
The secondary feed is heated in the remaining part of the convection section and full radiation section of the furnace to around 500C and enters the coke chambers where final cracking takes place. The vapours from top of the coke chambers is quenched with cold vacuum distillates before it enters the separator. The liquid product accumulated at separator bottom is pumped out as Residual Fuel Oil (RFO). The vapour is routed to bottom of fractionator as mentioned earlier. From the fractionator, products withdrawn are Light Kerosene (LK), Heavy Kerosene (HK), gas oil and coking fuel oil (CFO). Fractionator vapour top is condensed in over head condenser to produce gas and coker gasoline and coker naphtha (light coker naphtha and heavy coker naphtha). The petroleum coke is accumulated in coke-chamber, is cooled by steam and water and thereafter removed by hydraulic de-coking method which cuts the hard coke with high pressure water jets. The coke is removed by grab crane. After crushing and sizing, it is transported to store yard or sent to coke calcination plant. Facilities are also provided in the plant to produce LPG and release fuel gases to fuel gas system.
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Advantages of Delayed Coker

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Minimum investment for given value addition Zero fuel oil generation Coke can be used as fuel for power plant. No catalyst cost. Capability to process refinery slops and sludge.
Mechanism of Coking
Cracking is a phenomenon by which large oil molecules are thermally decomposed into smaller lower-boiling molecules: at the same time some of these molecules, which are reactive, combine with one another to give even larger molecules than those in the original stock. The more stable molecules leave the system as cracked Naphta, Kero, Diesel (LCGO), Gas oil (HCGO) etc. and the reactive once polymerise, forming cracked fuel oil and coke.
Fluidised Catalytic Cracking (FCC)

Fluid Catalytic Cracking has developed into a major upgrading process in the oil refining industry for conversion of heavy fuel oil into more valuable products ranging from light olefins to LPG, naphtha and middle distillates. The attractiveness of FCC process is to its flexibility to process wide range of feedstocks from a variety of crudes and its favourable economics of operation. The objective is to maximise Olefins, LPG, C7 C9 aromatics, high throughput and minimise LCO and bottoms. Hot regenerated catalyst is mixed at the bottom of reactor with raw feed and steam. After pre-acceleration, it is brought in to contact with the staged feeds supplied as finely atomised droplets. Feed instantaneously vaporises and travels up the riser with the catalyst where conversion reaction takes place. At the top of reactor, the vapour is disengaged from catalyst. The vapour is sent to main fractionating column. In this column, mainly LPG, Gasoline, middle distillates and decanted oil are obtained. The spent catalyst is steam stripped to remove hydrocarbon vapour and then sent to two stage regenerators for burning coke before it is recycled to reactor alongwith makeup catalyst to reactor.
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Air is injected in catalyst regenerator for burning coke. Water generated in the system leaves with flue gas from Power Recovery Train. Flue gases are sent to CO boiler and thereafter to a clean up system to remove particulates, SOx and NOx. ZSM additive is added to catalyst to increase LPG yield. Residues are also used as feedstock in RFCC.
FCC
__________________ __________________ __________________ __________________
FIGURE 4.11
FCC UNIT BLOCK FLOW DIAGRAM
Petrochemical Process Plants

Aromatics Plant
The aromatics complex is a fully integrated facility for the production of paraxylene and orthoxylene, comprising of platformer primarily to produce feed for main plants. Aromatics complex processes special cut naptha to produce paraxylene and orthoxylene as the major products and some other by-products which include Benzene, Light Reformate, LPG, H2, Fuel Gas and heavies. The Paraxylene plant consists of the following units. (Refer figure 4.12 Aromatics Complex Block Diagram Flow).
Heavy Naphtha Unionfining Unit (HNUU)

The function of this hydrotreating unit is to treat the feed naphtha and remove impurities like heavy metals, sulfur,
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nitrogen and olefins, which are poison for Platformer catalyst.
Platformer Unit
The platformer unit processes hydrotreated naphtha from the Heavy Naptha Unifining unit, stripper column bottoms, for the production of aromatics for downstream unit processing and separation. Major reactions taking place in platforming unit are as follows: 1. 2. 3. 4. Dehydrogenation of naphthenes Hydrocracking of paraffins Isomerisation Dehydrocyclisation of paraffins
The spent catalyst is regenerated continuously in situ, which takes place in Cyclemax CCR.
Xylene Fractionation Unit

Xylene fractionation unit includes a xylene column and associated equipments to fractionate Isomar Deheptaniser bottoms and Tatoray Toluene column bottoms into an overhead product that is suitable as feedstock to the Parex process unit. The column is designed to both recover Orthoxylene into the bottom product or to minimise the loss of Orthoxylene into the bottom products Xylene rich overhead vapor are used as heating medium in Raffinate & Extract . Column Reboilers & also to generate MP Steam.
Orthoxylene Fractionation Unit

This unit includes an orthoxylene column and associated equipments for the production of a high purity orthoxylene product and a heavy aromatic column and associated equipments for the production of a C9-C1O aromatic overhead stream to be used as feed to the Tatoray unit, a sidecut stream with a 215C endpoint for use as a gasoline blending component and a heavy aromatic bottom stream to be used as fuel oil.
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Parex Process Unit

The process is selective adsorption of Paraxylene (PX) on molecular sieve and subsequent desorption of PX by a suitable desorbent. The molecular sieve is basically Y type zeolite (alumina silica) which preferentially adsorbs PX. Toulene column bottoms and C8 isomerates from Isomar section are fed to the xylene fractionation column. The overhead product of the xylene columns are feed to the parex unit. Feed and desorbent goes to the Parex adsorbent chambers via rotary valve. PX gets adsorbed on the molecular sieve and subsequently desorbed. Two streams come out of the chambers known as raffinate stream and extract stream. Raffinate stream is fed to the raffinate column. Its side cut product which is mixed xylenes lean in paraxylene, is fed to isomer unit while the bottom product desorbent is recycled back to Parex adsorbent chambers. The extract stream consist of PX, Toluene and Desorbent. PX and Toluene are separated as overhead products in extract column (feed to finishing column) while the bottom product Desorbent is recycled to Parex absorbent chambers. PX and Toluene are separated in a finishing column. Paraxylene is withdrawn from bottom and overhead product Toluene is recycled back to Tatoray unit. Isomer is a catalytic isomerisation process to efficiently convert a mixture of C8 aromatics to a near equilibrium mix that favours PX and OX production from metaxylene and ethyl benzene. The Tatoray unit includes reformer splitter column, two parallel reactor trans, stripper, benzene are toluene column. Objective of the units is to maximise xylene production by transalkylation of C7 and C9 aromatics.
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Polypropylene
It is designed to produce homo, random and impact copolymer. The main raw materials are propylene and hydrogen. (Refer Figure 4.13 Propylene Block Flow Diagram) The plant consists of: 1. Purification Section: For propylene to remove impurities like Sulphur, CO, CO 2 , O 2 ' purification section for hydrogen and nitrogen gas before supplying them to reaction area. Impurities like CO, CO2 from H2 and O2 from N2 are removed.
FIGURE 4.12 AROMATCS COMPLEX BLOCK FLOW DIAGRAM
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FIGURE 4.13
POLYPROPYLENE BLOCK FLOW DIAGRAM
2.
Reaction Section: Here polymerisation reaction of purified propylene takes place in fluidised bed reactor in the presence of slurry catalyst (TiC14, supported on MgCl2 in slurry form in mineral oil); co-catalyst Triethyl Aluminium, purified hydrogen and selectivity control agent Peraethoxy Ethyl Benzoate or N-Proypl Trimethoxy Silane in the reactor. Pelleting Section: Polypropylene (PP) resin is transferred from reactor to product receiver using dense phase conveying system. The conveying gas which is a mix of hydrocarbon and nitrogen is separated from the resin in disengaging section of product receiver. The unreacted monomers are purged with light recycles and sent for recovery to vent recovery system. PP requires the incorporation of a variety of additives to aid its processing and achieve the end use properties. The polymer is fed into the melt pump to develop necessary pressure for extrusion through the die plate. The Polymer strands are palletised in underwater pelletiser and the pellets are carried by pellet water system to agglomerate remover where chunks and clusters are removed. The pellets are then dried, classified and conveyed to the blending silos from where they are bagged.
3.
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4.
Vent Recovery Section: This system is designed to recover monomer, polymer and nitrogen. All waste flammable gases are vented to the HP or LP flare header, which are passed through knockout pot and burnt at flare stack burning tip.
Typical Refinery and Petrochemicals complex Product Pattern

Propylene LPG Gasoline Naphtha Reformate (Petrochemicals feed) HSD/SK/ATF Coke Sulphur Fuel and Loss 2.0% 7.0% 8.0% 8.5% 9.5% 48.0% 8.0% 1.5% 7.5%
Typical Refinery Product Pattern

Input Crude Oil Products LPG Net Naphtha MS Others Light Distillates ATF SKO HSD LDO Others Middle Distillates LSHS for sale Others Heavy Ends Total Prods Gross F&L Total 2.1 5.0 11.2 -18.3 2.6 9.0 35.1 16.0 1.1 63.7 3.3 7.9 11.6 93.6 6.8 100.0 % of Crude 100.0
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Typical Yield Pattern of FCC

Feed: Low S VGO CGO DWO VR Output Gas H2S LPG Gasoline TCO CLO Coke Loss Total 3.9 0.5 12.7 12.5 53.4 8.6 7.9 0.5 100.0 100% 53.7 20.3 9.0 17.0
__________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Typical Yield Pattern of Delayed Coking Unit

Input = RCO Output: LPG Cok. Gasoline Cok. Kero-I (LK) Cok. Kero-II (HK) Cok. Gas Oil (CGO) CFO RFO RPC GAS Loss Total 2.5 4.5 22.5 -24.5 14.5 6.5 16.3 6.3 2.4 100.0 100%
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Input: VGO H2 Total Output H2S GAS LPG LT. Naphtha Hy. Naphtha SKO/ATF HSD Bottoms Loss Total 1.2 1.3 3.0 11.5 4.0 27.0 43.8 10.0 0.2 102.0 100.0 2.0 102.0
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Typical Yield Pattern of Hydro-treater
Offsite Facilities and its Management

In a Refinery, 80% to 90% area is covered by offsite facilities. Traditionally, more attention used to be given to process units. However, with Refinery margin shrinking, stringent safety, Health and Environmental stipulations, and increased customer expectations, now more and more emphasis is given for improved profitability through:
l l l l
Improved operations Advanced process control system Good inventory management Optimisation of storage facilities & other offsites.
Major offsite functions in a Refinery are:
1. Crude oil receipt

Normally crude oil is received in land locked refineries through crude pipelines from the production source. Before bringing the crude from oil fields, gas, water and sludge are removed by settling and processing through desalters. In
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coastal refineries, crude oil is received through tankers. Depending on the capacity of the refinery, crude tankage available, draft available at receiving oil jetty, size of crude oil tanker varies from small to very large. Quantity of crude received in the refinery is monitored by measuring dip of receiving tank and flow metre readings installed on crude pipeline. India imports almost 70% of its crude oil requirement. Due to strategic reasons, crude oil storage is being increased from 15 days to 45 days of the refinery capacity.
2. Crude preparation for feeding to distillation units

Though in the oil field, major quantity of sludge, water and associated salts are removed before bringing crude to refineries, yet some quantities of sludge and water still are received in the refinery tanks. This is removed by allowing the crude to settle in the tanks and draining from bottom to the effluent treatment system. The final removal of water associated with salts and sludge takes place in desalter in the crude distillation unit. Unless crude preparation is done properly, the unit performance will be affected adversely due to fouling of pipes, exchangers, furnace tube corrosion, corrosion of various equipments and upsets in plant operation. This will also lead to increased fuel consumption and loss in the units.
3. Receiving rundown streams from various units

From crude distillation unit and other secondary units, we get various products streams, most of which are to be treated in secondary processing units and blended in required proportion to produce finished products which are then dispatched to the market. Except LPG and Naptha, all other products are blends of various streams from different units. Depending on the capacity of refinery, number of products marketed, types of crude oil processed, complexity of the refinery, the tankages provided for receipt of rundown streams varies. Facilities for water draining and reprocessing of offspec. streams are provided. Flexibility is also provided for alternative routing of streams incase there is change in demand in product pattern. Light and heavy
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slop tanks are also provided to receive offspec. Streams during start up, shutdown, emergencies and upsets in the plants. The same are reprocessed in the units in a regulated manner during normal run. By on-line blending and utilising advanced process control, the tankage for receiving rundown streams can be minimised. Pump stations are provided for transfer of products.
4. Blending the rundown streams

Various straight run streams and secondary processing units streams are mixed in suitable proportion for the production of finished marketable petroleum products. The mixture is circulated in the tank to make it of uniform quality. After settling in tank for draining any water and testing the sample in the laboratory to ensure that it meets quality specifications, it is dispatched to market. Storage facility at various locations particularly for MS, SKO and HSD is being augmented. It is proposed to provide 35 days storage capacity based on 75% utilisation factor.
5. Co-ordination with laboratory

After blending of various streams and circulation in tank, samples of products are sent to the laboratory for testing. Once the product meets the quality specification as per BIS or customers requirement, then the certificate of quality is issued by the laboratory. Thereafter, product is despatched to market.
6. Despatch of finished products:

The certified products are stored in finished product tanks before dispatch. Petroleum products are evacuated from the refinery by following modes: 1. 2. 3. 4. Pipelines Rail Road Coastal
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1.
Pipelines: Out of the above dispatch modes of petroleum products, maximum dispatch takes place through pipelines (60 - 70%). Pipeline systems have following in-built advantages over other means of transportation available for petroleum products: 1. It is the second cheapest mode of transport next to large capacity tankers. With advanced control system and proper operation, it is possible that the products reach their destination in a "refinery-good" condition. This is so even in respect of sensitive quality control products such as ATF, Naptha etc. Minimum transit loss Planned product movement Flexibility in operation independent of other transportation systems. During floods and natural calamities, it is not affected.
2.
3. 4. 5.
2.
Rail: Tank wagons are the second bulk carrier specially constructed for this purpose and can take products to far off places. The wagons for transporting heavy products such as FO, LSHS etc, are provided with steam coils for heating the product before unloading at the destination. Road: The third mode of transportation is tank lorries or tank trucks, which are used to supply product to nearby locations by road. Steam coils are provided to heat the product before unloading in case of tank trucks for Bitumen, LSHS, FO, etc. Coastal: Tankers of various capacities are used for dispatch of product from coastal refineries. For short distance and small quantity of coastal product movement, barges are used. The large capacity tankers are the cheapest mode of transport. The products movement of the refinery gets adversely affected due to failure/breakdown of transport system.
3.
4.
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Flexibility to a small extent exists to switch over from one mode to other mode. However, refinery builds up stock in its tanks during such emergencies, to an extent beyond which through-put of process units is cut thus affecting the production.
7. Flare management
To take care of emergency release of gaseous hydrocarbon, flare headers are provided for collecting off gases from process units and offsite areas. After seperating the entrained liquid, the gas is burnt at high point to avoid hazard and pollution. Three categories of flare systems are provided: a. b. c. High pressure flare Low pressure flare H2S flare
8. Refinery water supply

The following important water supply systems exist in the refinery. 1. Fresh water supply system: This provides utility water supply, make up to the circulating water system, make-up to fire water supply system and make up to drinking water treatment system. Fire water supply system: Throughout the process units and offsites areas, the fire water supply pipeline network is laid in the form of ring. Firewater tanks are provided in offsites area to have an immediate supply source for fighting any major fire. In critical areas, long distance throw nozzles are provided. Recirculating hot and cold water system: For cooling of hot products, this system is provided. It is having chemical treatment system to avoid scaling and corrosion in related pipelines and equipment. Cooling Towers are also provided in the system where water is cooled by evaporation before recirculation. Blow-down
2.
3.
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UNIT 4
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
in the form of leakage and manual draining is provided to avoid build up of salt concentration. Make up water is taken from fresh water system. In some of the coastal refineries, once through cooling water system is used and sea water is utilised for the cooling of products. 4. Captive power plant: To provide uninterrupted power and steam supply for running the pumps, compressors and other equipment, captive power plant is provided in the refinery. For meeting any emergency, alternative source of power supply from outside is also lined up. Superheated and saturated steam at various pressures are also supplied for process units and offsites area from this system. Steam is used for heating, stripping in columns, atomisation of fuel oil before burning in furnace, fire-fighting, driving steam turbines and power generation. Fresh water is used in DM plant before utilising in boilers for steam generation. To ensure supply of steam and power to critical plants/equipment in emergencies, load shedding scheme exists. Fuel oil and fuel gas system: For providing fuel supply to process units furnaces, and boilers in captive power plant, this system is provided. In fuel gas, mostly methane, ethane and purged gases from hydrogen units are used. The supply system is maintained at constant pressure. For fuel oil, varying range of fuels from LDO to Asphalts are used. Storage tanks, blending facilities and pumping system are provided for supply of fuel oil to furnaces and boilers. Hydrogen, Nitrogen and air supply systems: Hydrogen is generated in Hydrogen plant or catalytic reformer unit. It is utilised in hydro-treatment units. It is a very hazardous gas to handle as the flame can not be seen. Nitrogen is used for catalyst regeneration, blanketing tanks from atmospheric oxygen in the case of lubes and other products which form explosive mixture when coming in contact with air, and maintaining inert atmosphere in the process unit equipment. Nitrogen is
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6.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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produced in generators installed in the refinery or is purchased from outside. Air is used for utility purposes, catalyst regeneration, decoking of furnace tubes and instrumentation etc. It is taken from atmosphere and compressed before using.
Review Questions for Offsites

1. 2. What are the important offsite facilities in a refinery? How do these facilities affect the proper functioning of the refinery? Explain each facility wise, specially their impact whenever there is a failure.
Review Questions for all Process Plants

1. Explain briefly in your own works. i. ii. The function of each process plant (11 plants) Feed composition
iii. Yield pattern. iv. 2. Critical parameters for optimal operation
Which components of various process streams in different process plants (% wise) are utilized for the prouction of LPG, MS, HSD, ATF, Furnace Oil, PC Naphtha and Fertilizer Naphtha.
85
Unit 5 Future Refining Scenario
Activity 5 A Describe the scenario of availability of sweet & sour crudes in the next two decades. __________________ __________________ __________________ __________________ __________________
Objectives
y
__________________ __________________ __________________ __________________ __________________
Understand Future Refining Scenario in terms of availability of crudes, stringent specifications of various petroleum products, dwindling refinery margins etc. Strategies for overcoming various challenges.
Keeping in view environmental considerations, cost optimisation, energy conservation and product quality requirement, it is envisaged that future refineries will have to face many challenges they will be highly complex, integrated, diversified and fully automated. Worldwide availability of sweet and light crude is decreasing, therefore, future refineries will have to be ready to process heavy and sour crudes. This will call for superior metallurgy in the plants and pre and post treatment of oil products leading to higher capital and operating costs. To improve profitability and meet statutory requirements, following actions need to be taken:
u u u u u u u
Distillates yield improvement Production of high value products Energy optimisation Hydrocarbon loss minimisation Effective environmental management Product quality upgradation Product inventory reduction
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Activity 5 B What do you understand from Integration of Refinery with petrochemicals/ fertilizers, power plants? How does it improve the Bottom Lines? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u
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Besides conventional process units, future refineries will also have:

u
Quality related units: Facilities for benzene management DHDS (Diesel Hydro-desulphurisation) Fuel oil HDS (Hydro-desulphurisation) Hydrotreatment.
Environment management related units: Tail gas treatment High efficiency SRUs (Sulphur Recovery Units) Bottom of the barrel upgradation related unit Computerised integrated refinery Energy efficient processes Diversified and integrated refinery with power plant, petrochemicals and fertilizers
Synergy in power with fertilizer co-production Efficient utilisation of low value refinery residue for production of power. Power plant supplies power and steam required in refinery. Co-production of value added fertilizer. No additional raw material handling and common fire fighting facilities. Overall economics considerably enhanced Already under way in the USA, the Netherlands and Italy.
Refinery of 21st century Operate with fewer & highly educated people Few operators grouped in a central blast proof control room like the cockpit of modern aeroplanes.
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Future Refining Scenario
87
Notes __________________ __________________ __________________
Possible employment of robots Computerised system supervising operations automatically On-line analysers and blending Computerised performance monitoring Automated dispatch and offsites operations Flexible work hours
__________________ __________________ __________________ __________________ __________________ __________________ __________________
In the new refineries, following technology gaps and to be covered:

u u
Reduction of S (sulphur) from MS, HSD and FO. Reduction of FO production and increase in distillate production to 85%+. Plant/ equipment should require less space.
Review Questions
1. What modifications would be needed in refinery process plants for Changing over from sweet crude to sour crude Technological improvements/additions for meeting future more stringent specifications of HSD and MS. So as to conform to Emission norms. To increase/improve profitability.
2.
What do you understand from flexibility of Refinery operations in the competitive environment?
89
Unit 6 Advances in Petroleum Refining

Objectives
y
Note __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Understand in a generic fashion advances in refining process technologies For making eco-friendly products For value addition to improve the bottomline For best practices in refining operations For energy optimization
Various issues faced by the refining industry have led to many major developments in this area. The challenges are: 1. Crude oil is becoming heavier and higher in sulphur and metal content. Reduced growth in fuel oil demand. Rapid growth in light/middle distillates. Stringent environmental regulation for cleaner products/processes and demand for quality products. Declining refining margins Improved engine design/automobiles need better quality fuel and lubricating oils.
2. 3. 4.
5. 6.
Advances in refining technology can be broadly divided into the following categories. 1. Improved and integrated refining
u
Production of better quality products
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Activity 6 A What are known/proven improvements as on date, in Refining Process Technologies? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u
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Residuation in residues/heavier ends Management of power and utilities.
2.
Value addition
u u u u
Petrochemicals production Better quality and increased lube oil production Power generation from heavier petroleum products Speciality chemicals production.
Improvements are taking place in many areas. Some of them are listed below:
u u
Distillation Fluid Catalytic Cracking (FCC), Resid Fluid Catalytic cracking (RFCC). Delayed coking Needle coke manufacturing, VisbreakerSoaker Technology. Hydro processing Hydro treatment of various streams including residues. Hydro cracking
Super Oil Cracking (SOC) of heavy distillates to get 90% conversion to distillates. Mobil distillate Dewaxing (MDDW) to upgrade heavy fuel oil to high quality distillate and gas yield of 93- 95%. Isomerisation Catalytic Reforming Alkylation Etherification Power generation by petroleum residue and coke by using Gasification Combined Cycle (GCC) technology.
u u u u u
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Advances in Petroleum Refining
91
Notes __________________ __________________ __________________
In this process alongwith power, steam and H2 can be produced which are required in the refinery.
u u
More and more use of information technology. Modelling simulation are being used for: Information Gathering, Decision Making and Business Profitability. Accurate process models for different processes (e.g., FCC, Hydrocracking, Cat Reforming, etc) are being developed and increasingly used for optimization, trouble shooting, design and optimal control and technology development. Typical application of information technology in a refinery
Refinery planning Primary logistic management
__________________ __________________ __________________ __________________ __________________ __________________ __________________
Guide logistic planning
Refinery scheduling
Primary logistic management
Secondary logistic management
Significance of process modelling

Trouble shooting Reactor design Pilot plant scale up
Catalyst health monitoring
Modelling and simulation
Catalyst selection & optimisation
Operator training Feedstock selection
Process optimisation
u u
Refinery integration and value addition strategies Small and medium refineries
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Activity 6 B What are various routes for value addition in Petroleum Refining? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u
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Integration with speciality chemicals for value addition Anode grade coke, needle coke production Microcrystalline wax production Alpha-olefins production
Larger refineries Petrochemical integration and speciality products Integration of refining and power generation IGCC Technology Lubes and fuel integration
Other major strategies of integration Integration with IT Process simulation and optimisation Advanced control and hierarchical control systems
Review Questions
1. Explain the following processes and relate the same to the relevant products: 2. Isomerization Alkylation Etherification DHDS Catalytic reforming Catalytic cracking Thermal cracking (Refer Bibliography)
Explain the known/proven processes of Hydrogen Generation from heavy residues/petroleum coke/ coal bed methane? How is IT utilised for improved/on-line performance monitoring of refineries?
3.
93
Unit 7 Hydrocarbon Loss Minimisation

Objectives
y
Activity 7 A i. What should be ideal losses in any Process Control? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Understand the significance of losses in a refinery and their impact on profitability Understand sources/areas of losses and measures adopted by the refineries for their reduction.
During the processing of crude petroleum products, handling and dispatches from refinery, hydrocarbon losses take place on various accounts. Efforts are to be made to bring the loss to a level of less than 0.3% of crude processed. Auditing of the systems and operations will lead to continuous improvement. Following areas need to be monitored/looked into: A. Apparent losses i. ii. B. Measuring devices in storage tanks and custody transfers for proper accounting Automating road/rail dispatch facilities.
Real losses i. ii. Vapour recovery from flare and product loading facilities Handling of light hydrocarbon slop in process unit and offsite area in closed blow down system
iii. Conversion of fixed roof tanks to floating roof tanks for low flash products including diesel and use of proper type of roof seals.
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Activity 7 B i. What are international standards for Refinery Losses? What methods have been adopted in Indian refineries to bring down the losses to International standard?
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iv. v.
Automatic tank gauging Use of proper mixers in crude tanks for minimising sludge formation and modern method of removal and recovery of only sludge/oil to reduce loss Minimising slop generation to reduce evaporation loss in slop handling system
vi.
ii. What is BS&W? How is it related with losses in Refining operations? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
vii. Close monitoring of BSW in crude processed to avoid plant upsets and increased losses. viii. Routing of all sour gases to sulphur recovery unit ix. Routing of off gases from vacuum column to furnaces.
Review Questions
1. What will be the order of magnitude of savings in a six million tones per year capacity refinery, if the losses are reduced by 0.2%, cost of crude being $ 25/barrel?
95
Unit 8 Energy Conservation
Activity 8 A i. What strategies have been adopted to optimize energy consumption. For old refineries For grass-root refineries
__________________ __________________ __________________
Objectives
y
__________________ __________________ __________________
Appreciate the role of/ urgency for energy conservation and optimisation of energy consumption in refining industry. Get a generic idea of various strategies adopted for energy optimisation.
__________________ __________________ __________________ __________________
Conservation of oil and gas has assumed greater importance in view of the emphasis on demand side management of energy. Average fuel loss in the refineries in India during 200001 was 7-35% which is higher compared to global levels (of similar configuration). Energy optimisation for a refinery begins early in the development and design stage with the establishment of a set of energy saving guidelines applicable to the project. Some of the areas given below need to be looked into: 1. Integration of heat exchange system of the units to utilize the heat from hot stream of another unit crude distillation unit and vacuum distillation units are heat integrated. Optimisation of heat exchangers train use of pinch technology. Direct hot feed from one unit to another unit without passing through intermediate tanks. Energy efficient processes/equipment such as furnaces, pumps, exchangers etc. Provision of air preheter in furnace. Proper insulation of hot products and steam lines.
2. 3.
4.
5.
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Activity 8 B How do DDCS and advanced process controls help conserve energy? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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6.
Optimisation of i. ii. Reflux ratio in distillation process Solvent feed ratio in extraction process
7. 8.
Use of soaker technology for visbreaking. Use of microprocessor based control system alongwith DDCS (Digital Distributed Control System) and advanced process control. Heat recovery from process streams for heating colder process streams/ boiler feed water.
9.
10. Power generation in new refinery will be through combined cycle operation integrated with gasification. 11. Steam system High pressure steam will be cascaded down to lower level by back pressure turbines either generating power or coupled with various key process compressors and pumps. Pressure reduction of steam through a control valve will be minimised. 12. Minimise leakage through glands/seals of pumps, compressors and turbines. 13. Low level heat recovery. 14. Soot blowers for convection section of furnaces to improve heat recovery in furnaces. 15. Steam generation from hot streams. 16. Benchmarking, gap analysis and setting targets. 17. Energy audit for continuous improvement of energy performance.
Review Questions
1. How does energy consumption at Indian refineries compare with best run refineries over-seas? Express this in energy consumption indices like EII (Energy Intensity Index) NRG Factor in MBTU's per NRGF for fuel + loss
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UNIT 8
Energy Conservation
97
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
2.
Explain the role of house-keeping measures for bringing down energy consumption resulting in energy conservation. Enumerate some important measures of this nature which the refineries/ chemical industries take.
99
Unit 9 Gross Refining Margin
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________
Objectives
y
__________________ __________________ __________________
Provide an appreciation for various elements affecting GRM which in essence is the profitability of a refinery. Acquaint with the netback estimation method used for selection of crude for any refinery.
Gross Refining Margin (GRM) is the differential between the product realisation and the cost of crude processed to obtain these products. GRM of a particular refinery will depend upon various internal and external factors. Some of these factors are discussed below:
Internal Factors
u
The crude mix (low sulphur and high sulphur) processed by the refinery The secondary processing facilities available with the refinery which affect the product yield of the refinery The fuel used and losses incurred in the production processes.
External Factors
u u
The international prices of various crudes and products The demand and supply balance of various products refined by the refinery The duty structure prevailing in the country relating to crude and products.
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Activity 9 A What are various factors which affect GRM? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u
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Operating Cost of the Refinery

The operating cost of the refinery includes various elements, some of which are as under:
u
Power and fuel: Fuel is used either directly in the refining process or to generate power and utilities to be used in the refining process. Fuel may be purchased from outside suppliers (like natural gas), power from electricity board or internal refined products (like LSHS, FO or HSD) may be used as fuel. Chemicals and catalysts: During the refining process of petroleum products, various chemicals and catalysts are used. The purpose of chemicals is mainly to improve the quality of products so as to meet the desired specifications. Catalysts are used in various reformers and other secondary processing facilities. Establishment cost: This is related to the manpower deployed and includes the salary and wages paid to staff, overtime, bonus etc. Repair and maintenance cost: It is incurred in various mechanical, electrical and civil jobs carried out for the maintenance of plant and machinery. General administrative cost: This cost includes expenses such as traveling. Printing, insurance and other related overhead expenditure. Depreciation: Operating cost includes depreciation on plant and machinery, furniture, equipment and other fixed assets used in the refining process towards general wear and tear.
Net Margin
The net margin is the difference between gross margin and operating cost. This is virtually the net profit to the refinery. Net Margin = Gross margin Operating cost.
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UNIT 9
Gross Refining Margin
101
Activity 9 B Explain how netback estimation method is used for crude selection for a refinery? __________________ __________________ Rs/Crores __________________ __________________ __________________
For higher profitability, gross margin should be increased and operating cost reduced by increased efficiency in refining operations. Attachment 1 shows a sample calculation for gross and net margin for a refinery.
ATTACHMENT 1: GROSS MARGIN
Realisation of transfer of products Cost of crude (inclusive of freight, wharfage, customs duty) Gross margin Thput-MMT GROSS margin Rs/MT Margin Rs/BBL Margin US $/BBL Less: Operating cost Rs/MT Net margin Rs/MT
4050 3720 330 3.98 829 112 US $ 2.30 500 329
__________________ __________________ __________________ __________________ __________________
Net back estimation

In the net back system, the estimated realisation is calculated on the basis of expected yield from the particular refinery for a specific crude. For the purpose of procurement of crude for a particular refinery, net back estimation is used to evaluate the suitable crude for the refinery. The crude which is having higher net back to the refinery is normally procured for it. Attachment 2 gives a sample netback calculation to select the best crude out any of seven crudes, considered. All these 7 crudes are sweet (low sulphur) crudes. F.Dos gives the highest netback of Rs 1054/MT vs TAPIS with lowest netback of Rs 41/MT.
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
CRUDE PRICE LPG NAP MS SKO HSD OF L.SHS RPC SULPHUR SL. WAX F&L TOTAL DIST% CRUDE VALUE,RS/MT PROD VALUE, RS/MT LESS IPN COST, RS/MT NET BACK, RS/MT 421 1054 740
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ATTACHMENT 2: SAMPLE WORKING OF NETBACK CALCULATIONS

PROD PRICE RS/MT 14599 12260 14832 13617 14361 10100 10100 5535 256 13851 0 BRENT BL 11987 7 8 12 11 48 0 1 2 1 0 10 100 86.0 11987 12408 0 1 1 0 12 100 86.0 11361 12415 F.DOS 11361 5 0 12 11 58 BON. LT. 11714 5 5 12 11 54 0 0 1 1 0 11 100 87.0 11714 12454 LABUAN 11994 4 2 12 11 58 0 0 2 1 0 10 100 87.0 11994 12570 0 6 100 82.0 11987 12593 6 6 ESCRAVOS 11987 2 5 13 11 51 TAPIS 12859 5 10 12 11 53 0 0 1 0 0 8 100 91.0 12859 12900 MIRI 11994 4 3 12 11 59 0 0 1 1 0 9 100 89.0 11994 12780
100 476 606 41
100 686
Review Questions
1. What are the most crucial factors and which are indeed controllable, affecting GRM? What are various options for reducing Refining Costs in competitive world?
2.
103
Unit 10 Oil Accounting
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________
Objectives
y
__________________ __________________ __________________
Provide a general idea of accounting methods for crude and petroleum products and its significance.
While the physical handling of crude oil, intermediates and finished petroleum products is done by operations personnel, the Oil Accounting Section of the finance department of a refinery/warehouse is responsible for correct depiction of the quantitative and financial records pertaining to the crude oil and petroleum products. Quantitative accountal and correct payment of duties on finished petroleum products is the focal area of the oil accounting section. The following are its key functions. 1. Accounting of Crude Oil Receipts and Duty Implications Thereon Crude oil received under bond from port locations and rewarehoused in a refinery needs to be accounted on FIFO basis and appropriate customs duty is required to be paid and accounted for the quantity taken in the process of refining. This is known as ex-bonding of crude. 2. Accounting of Manufactured Petroleum products and Those Received for Blending, etc. The duty liability on petroleum products arises when the process of manufacture is completed, although the discharge of duty obligation is allowed to be deferred to the time of removal from the refinery/onward removal to warehouse. Hence, tank accountal of receipts and removals is to be
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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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maintained by taking dip measurements and quality testing reports. 3. Despatch of Finished Petroleum Products Assessment to central excise duties is invoice-based. Whether the goods removed are duty-paid or under bond, the excise duty liability is determined at the time of removal from the refinery warehouse. With the invoice being the document in support of cenvat credit claim that may accrue to a customer, the invoice/application for duty-free removal is the cornerstone for correct excise assessment of removals. 4. Compliance of Excise Procedure and Maintenance of Records The excise department tests compliance of law and procedure primarily through the records maintained by the oil accounts section of the assessee. For duty-paid goods, the liability likely to arise during a working day is to be deposited in advance through treasury challan at the bank and the deposit credit is to be utilised in accordance with the invoices issued for the clearances. This is done through the PLA (Personal Ledger Account). The DSA (Daily Stock Account) is to be maintained for opening balances, production, dispatch and closing balances of all certified finished products of the refinery warehouse. Intimations/declarations are to be submitted to the range office for any act or action that may be regarded as having an impact on revenue. 5. Material Balancing, Production Statistics and Periodical returns and Statements As the crude oil is processed through a combination of distillation and blending, intermediary products arise during the course of manufacture of certified finished petroleum products. The control over inputs and outputs during this refining process is achieved through the daily material balancing done through the quantitative measurement of tank and line-fill quantities of the crude, intermediaries and finished products. The production statistics are correlated to the standard product pattern and the actual distillate yield for any particular period of time.
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UNIT 10
Oil Accounting
105
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________
Statutory returns as per excise procedure are filed periodically by the oil accounts section with the range office. Records, returns, documents, etc prepared by the oil accounting section are open to inspection by the range office. Letters, show cause notices, if any, are normally issued through the oil accounts section.
Review Questions
1. Method and system of accounting crude and petroleum products in a refinery? How is the excise/customs procedure followed by oil accounting section?
__________________ __________________ __________________
2.
107
Unit 11 Excise and Custom Petroleum Products

Objectives
y
Activity 11 A What is the present level of custom and excise duties on crude and various petroleum products? What is the rationale for fixing the same? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
Give an overview of excise and customs procedures/formalities as applicable. Provide an appreciation for the manner in which custom and excise duties affect profitability.
The removal of petroleum products manufactured in refineries is either to direct customers or through marketing network (warehouses/ depots/terminals, etc) for sale therefrom. Products belonging to oil marketing companies are also dealt through intercompany transactions. These products are either removed on payment of excise duty, or under bond without payment of excise duty. In the latter case, the duty obligation on the manufactured goods is discharged from the warehouse when it is finally cleared for sale. In certain cases, the goods are removed under bond to special industrial undertakings like SEBs, FCI, etc who are licensed to deal with manufactured excisable goods without payment of duty. The products are removed through pipelines, tank wagon (railways), tank lorries (oil tankers), or barges (through waterways). The primary raw material for finished petroleum products is crude oil, indigenous and imported. Indigenous crude oil attracts Nil rate of excise duty, whereas imported crude oil attracts 10% customs duty. Indigenous crude oil is sourced from Gujarat and Assam oilfields and from offshore oilfields of India. Imported crude of different varieties as per
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Activity 11 B When is it desirable to export/ import any product based on custom/excise duties prevailing? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
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processing requirement are brought through different ports of the country. While crude oil only attracts the basic customs duty, other items of import attract additional duty of customs (equivalent to the excise duty attracted for such items under the central excise tariff) and special additional duty of customs on selective basis as notified. The additional duty of customs levied under the Customs Tariff Act and the excise duty levied under the Central Excise Tariff Act are allowed to be set-off as duty credit by the refineries (manufacturer) under the Cenvat Credit Scheme of central excise. During discharge of excise duty obligations arising on the removal of finished petroleum products from the refineries on duty-paid basis, the refineries use the accumulated cenvat credit in lieu of cash payment. Other than basic excise duty, there is a levy, on selective basis by notification, of special excise duty, additional duty of excise (Re. 1 per litre on Motor Spirit commonly known as petrol and on high speed diesel oil commonly known as diesel), and recently introduced special additional duty of excise on MS. Petroleum products are handled under the SelfAssessment Scheme of Self Removal Procedure (SRP) of central excise. The excise assessee is required to take necessary actions to be within the legal and procedural requirement of excise and customs law, without physical supervision of the department. At the refinery/warehouse, the department is represented by the jurisdictional officerin-charge (superintendent) of the Excise Range Office who has been given power of unified customs and central excise control over imported crude oil and excisable finished products of the refinery.
Review Questions
1. In the event of excess refining capacity (with glut in the market), what level(s) of production should be maintained to meet domestic demand and export the product? What is the significance of bonded warehouse? How are crude and products removed and accountal done?
2.
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UNIT 11
Excise and Custom Petroleum Products
109
Notes __________________
Bibliography
1. Advanced Petroleum Refining, Dr. G.N. Sarkar, Khanna Publishers, Delhi Reading Material of Programme on Petroleum Refining and Petrochemical Technology, Indian Institute of Petroleum, Dehradun. Reading materials of programme on Refining & Petrochemicals of various Petroleum Companies. Petroleum Refining Engineering, W.L. Nelson, Mc.Graw Hill. Handbook of Petroleum Refining Process, Robert A. Meyers A layman's Introduction to Oil Refining - D.G. Crook "Managing Modern Offsite Operation" by Patrick B. Truesdale and J. Dauglas AMOS Course contents on Refinery Loss Control by Dr. Eric Robinson and Dr. John Miles at Singapore, 20-21st May, 1996.
__________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________
2.
3.
4.
5.
6. 7.
8.
References
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. Advanced Petroleum Refining, Dr. G.N. Sarkar, Khanna Publishers, Delhi Petroleum Refining Engineering, W.L. Nelson, McGraw Hill Modern Petroleum Refining Processes, Dr. B.K. Bhaskar Rao, IIT, Kharagpur Advances in Petroleum Chemistry and Refining - Kennetha A. Kobe, John J. Moketta The Chemistry and Technology of Petroleum (Mercel Dekkar), Speight J.G. Petroleum Monthly Publication, Malaysia Hydrocarbon Processing New Challenges, Technologies Options for Refineries - IOC, R&D Report No. 96018, March, 1996 KBC Petrofine Users Manual A Layman's Introduction to Oil Refining - D.G. Crook Refinery Loss Controls - Course Manual Presented by Dr. Eric Robinson and Dr. John Miles on 20-21 May 1996 at Singapore.

Fundamentals of Refining

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Refining

COLLEGE OF MANAGEMENT AND ECONOMICS STUDIES (CMES)

Unit 1 Growth and Development of Refining Industry in India

The Important Milestones

2 at Mumbai (Esso & Burmah Shell) 1 at Vizag (Caltex)

Growth and Development of Refining Industry in India

Reliance Petroleum Refinery at Jamnagar, commissioned. Numaligarh refinery commissioned.

Future Outlook* (as per 2025 vision document)

Refining Capacity in India as in the year 2002

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.

Indian Refining Industry Emerging Scenario

Indian Refining Industry Special Features

Growth and Development of Refining Industry in India

A few refineries with size far lower than world standards.

Strategies for Indian Refineries

Future Technological Challenges

Capacity Increase (To Meet Demand of Petroleum Products )

Distillation Range Improvement

Unit 2 Crude Oil and Its Characteristics

Crude Oil Characteristics and its Significance (General Information)

iii. Cyclohexanes iv. v. vi. Cycloheptanes Di-cyclo-paraffins Benzenes

Crude Oil and its Characteristics

140C240C Aviatin Turbine Fuel (ATF) 140C270 Kerosene

Crude characteristics Consistency of crude supply.

Design data for grass root refinery

Crude Oil and its Characteristics

__________________ __________________ __________________ __________________ __________________

Characteristics of Crude Oil

Crude Oil Characteristics and their Significance

Also gives a rough indication of type of crude oil

Examples: Water Kerosene Motor Gasoline = 10 API = 45 API = 58 API

: Above 33 degree API : 23-33 degree API : upto 22 degree API

Crude Oil and its Characteristics

__________________ __________________ __________________

Reid Vapour Pressure (RVP) and Light End Analysis

Flow Characteristics of Crude Oils

45.0 85.0 222.0 330.0

2.0 5.0 10.0 12.5

9.6 14.7 16.0 17.3

Crude Oil and its Characteristics

FIGURE 2.1 POSTULATED STRUCTURE OF STABLISED EMULSION

__________________ __________________ __________________ __________________ __________________ __________________

Problems Encountered Due to Salts

Increased Consumption of Amonia

PTB as Salt Content of Crude PTO AS NACL

Methods for Determination of Salt Content

Sediment and Water

Water causes irregular behaviour in distillation.

Crude Oil and its Characteristics

Asphaltenes, Carbon Residue and Ash Content Asphaltenes

__________________ __________________ __________________ __________________

Metallic constituents concentrate in the ash of the crude oil

Selection of Crude Oil

Crude Oil and its Characteristics

__________________ __________________ __________________ __________________ __________________ __________________

0.4 4.4 10-1

ARON 4% VOL. OCTANE NO.61.9

Selection of Crude(s) for a Refinery

Crude Oil and its Characteristics

__________________ __________________ __________________ __________________ __________________

Unit 3 Specifications of Petroleum Products and Related Tests

Some important tests conducted on petroleum products and included in specifications:

Specifications of Petroleum Products & Related Tests

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