Refining

MB-107

YO

FP

E TR

OLEUM &

EN
ER
GY
ST U DI ES

fo

u
n ~;

UNIV ER SIT

k~ e k ; k ‘ k f D r o’

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. Characteristics of crude and specifications of various petroleum products have been explained in detail. 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. Various refining processes used in the refineries have been dealt in this module. Dealing with growth and development of petroleum refining industry in India.

and hence need to be modernised and updated from time to time. 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. The module on refining covers various facets of petroleum refining. 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. it has come a long way with the setting up of most modern. fertilizers etc. by making changes/ improvements in their processes while at the same time sustaining their profitability. domestic consumption and meeting the needs of the power sector. India has 17 operating refineries processing both indigenous and imported crudes. For setting up a 6 MMTPA capacity refinery complex with marketing facilities. Dealing with growth and development of petroleum refining industry in India. Starting with the establishment of the first public sector refinery at Guwahati (Assam) in 1962. 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. . 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. petrochemicals. investments to the tune of Rs 5000 crores are required. Various refining processes used in the refineries have been dealt with in this module. These refineries need to be run efficiently so as to make profits. state of the art and highly energy efficient refineries of the present day. and other industries.An Overview Refining of petroleum for producing fuel and related products for automobiles. Characteristics of crude oil and specifications of various petroleum products have been explained in detail. is very vital for the economic progress of the country.

.

Consequently. Assam. Thereafter addition of refineries and capacity augmentation continued unabated. Assam. the learner will be able to: y Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Get an overview of the growth of the Indian Refining Industry after independence. First refinery in India started soon after oil production started in Digboi. Assam.1 Unit 1 Growth and Development of Refining Industry in India Objectives After studying the unit. Digboi Refinery was commissioned supplanting the earlier refinery at Margarita. Now we are having seventeen operating refineries with a total capacity of 113 MMTPA.1957 . there is a thrust on increasing their supply by enhancing refining capacity. Get a good idea of various challenges facing the industry in the present time/in future and strategies for meeting the same. Assam Oil Company was formed. Assam. y y With the growth of industry and improvement in the living standard of people. Oil Production started at Digboi. First Refinery started at Margharita. The Important Milestones 1866 1889 1893 1899 1901 Oil discovery at Nahorpung. demand for petroleum products is increasing rapidly. Know about special features of Indian Refining Industry. Setting up of three coastal refineries by Multi National Oil Companies (MNCs) 1947.

e.YO FP E TR OLEUM & EN ER GY 2 Activity 1 A Reader may like to draw a Geneological Chart of the current refineries operative in India. Discovery of Cambay oil field. k ‘ k f D r o’ 2 at Mumbai (Esso & Burmah Shell) 1 at Vizag (Caltex) The MNCs were already marketing petroleum products in India by then. to form Indian Oil Corporation Ltd (IOCL). The first refinery in the public sector commissioned at Guwahati (0. Indian Oil Company formed for marketing of petroleum products. Inc. technology and year of establishment and expanded capacity wherever applicable by the end of 10th 5 year plan i. Ltd. 1956 - 1958 1958 - - 1959 - 1962 - 1963 - 1964 - 1974 1981 - 1998 - . IRL was dissolved and merged with Indian Oil Co. Indian Refineries Ltd (IRL) was formed in the public sector to install refineries and pipelines in India. Indian Oil Blending Ltd – A JV between Indian Oil Co. Formation of Oil and Natural Gas Commission for exploration and production of crude oil and gas. 2006 – 07. UNIV ER SIT ST U DI ES k~ e k . was formed for manufacture of lube oils and greases. were taken over and vested in IOC as Assam Oil Division (AOD). IOBL became part of IOCL. and Mobil Petroleum Co. 1954 Indian Oil exploration with the help of Russian Geologists.75 MMTPA) under IRL. Oil India Ltd (OIL) was formed as a joint venture company between Government of India and Burmah Oil Co. Panipat Refinery of IOC commissioned. Assets of erstwhile Assam Oil Co. Please classify by company. __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~.

UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 1 Growth and Development of Refining Industry in India 3 Activity 1 B What are various options for increasing the Refining Capacity in the country? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 1999 2000 - Reliance Petroleum Refinery at Jamnagar. 16 refineries have been added in the public/private/ joint sectors (including three in the private sector by MNCs. 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 135 __________________ __________________ 170 176 214 221 . Mumbai Expansion CPCL. Future Outlook* (as per 2025 vision document) Total Refining Capacity MMTPA 2002 – 03 Barauni Expansion Haldia Expansion HPCL. commissioned. In the five decades since independence. Numaligarh refinery commissioned. which subsequently became PSU’s).YO FP E TR OLEUM & EN ER GY fo u n ~.

Barauni Indian Oil Corporation Limited.0) 6.50 5. Koyali Indian Oil Corporation Limited.5) 2. 10.5 (18) 3.50 7. Jamnagar Numaligarh Refineries Ltd. Bongaigaon Madras Refineries Limited (CBR). UNIV ER SIT ST U DI ES k~ e k . 12. Refineries MMTPA Refining fo u n ~. Numaligarh Total Capacity 0. 14. Indian Oil Corporation Limited.00 3. 15. 6..50 6. 4.75 (7. 8.. Mumbai Cochin Refineries Limited.YO FP E TR OLEUM & EN ER GY 4 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ No. 17. Mumbai Bharat Petroleum Corporation Limited. kerosene) Prevalence of old as well as modern technologies u .5) 7. Nagapatinam Mangalore Refineries & Petrochemicals Ltd.00 3. Mangalore Indian Oil Corporation Limited Panipat Reliance Petroleum Limited. 5. Vizag Hindustan Petroleum Corporation Limited.00 112.50 8.00 (9.50 (10. 2. 3. Guwahati Indian Oil Corporation Limited. Chennia Bongaigaon Refineries Limited. 13. 16.65 1. 11. Haldia Indian Oil Corporation Limited.30 (6. Cochin Chennai Petroleum Corporation Limited.35 0. 7.45 Indian Refining Industry – Emerging Scenario u u u u u u Shifting product demand Stringent product specifications Stringent environmental regulations Feedstock quality deterioration Globalisation Deregulation of oil and gas sector Indian Refining Industry – Special Features u Larger requirement of middle distillates (diesel.50 (9.5) 6. k ‘ k f D r o’ 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. Mathura Hindustan Petroleum Corporation Limited.0) 13. 9.00 27. Digboi Indian Oil Corporation Limited.90 7.

u .compact and flexible with respect to crude/ product mix. Challenges faced and strategies to meet the same.YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 1 Growth and Development of Refining Industry in India 5 Activity 1 C i. u A few refineries with size far lower than world standards. Describe special features of Downstream Industry. __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u u Value addition to refinery streams Increased emphasis on Process Control/ Automation Evolutionary/innovative technological changes expected rather than revolutionary ones Refineries to be integrated . u Future Technological Challenges u Meeting higher demand of petroleum products (viz. Strategies for Indian Refineries u u u 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. distillates) Meeting higher standards of product qualities More emphasis on environment Value addition to refineries Technologies to improve margins Zero emission refinery u u u u u Capacity Increase (To Meet Demand of Petroleum Products ) u u u Low cost revamps/ addition of units Run length improvement of units Infrastructure development for crude receipt/storage/ distribution Installation of matching secondary processing plants. UNIV ER SIT ST U DI ES k~ e k .

butene – 2. P – Xylene etc. Benzene. 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. . Generation of power from heavy ends Distillation Range Improvement u New residue conversion technologies like FCC. N – Paraffin. Toluene. Lab. u Review Questions 1. Please identify technological challenges that refineries will face in future. Hydrocracker. Hexane. butene – 1. UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY 6 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u u u u Refining fo u n ~. k ‘ k f D r o’ Value Addition u Production of value added products from refinery streams Propylene.

__________________ y y y 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. mud and salts which get associated during its production and transportation. the learner will be able to: y Activity 2 A How is the crude oil formed? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand the chemistry of petroleum. 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. Appreciate the difference between Indian crudes and typical middle east crudes. . Get an idea of various crudes used in Indian Refineries. it also contains impurities like water. different types of crudes and their characteristics. As it is drawn from the earth.7 Unit 2 Crude Oil and Its Characteristics Objectives After studying the unit. It is a complex mixture of hydrocarbons and over 16.000 compounds have been identified in one sample. Develop an insight into the significance of various characteristics of crudes and method of determination of the same.

v. 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. The non-hydrocarbon portion retains hydrocarbon characteristics as the molecules contain one or two atoms of elements other than carbon and hydrogen. The purely hydrocarbon content may be as high as 97% and as low as 50% for heavy crude oils. ii. Dinuclear and polynuclear Aromatics are present in smaller amounts in compounds containing metallic constituents such as Vanadium. it can be divided into Paraffin. is a mixture of eight different hydrocarbon families: i. Atmospheric distillation is adopted for separating the compounds present into various fractions upto 366ºC:i. 90ºC–140ºC heavy naptha iv. ii. k ‘ k f D r o’ Crude oil. Magnesium. propane and butane. Copper. Cycloheptanes Di-cyclo-paraffins Benzenes vii. vi. Zinc. Titanium etc. Iron. Paraffins Cyclopentanes iii. Cyclohexanes iv.YO FP E TR OLEUM & EN ER GY 8 Activity 2 B What are the type of hydrocarbons present in the crude? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. UNIV ER SIT ST U DI ES k~ e k . Calcium. the basic raw material of refining industry. Aromatic cycloparaffins viii. Nitrogen and Oxygen compounds mostly present in high boiling point fractions are also present in crude oil. Overhead gases containing mainly methane. C5–90º C light naptha iii. Nickel. The carbon content is between 83 to 87% and hydrogen content between 11 to 14%. Based on proportion of types of hydrocarbon. Besides impurities such as Sulphur. ethane. 140ºC–204ºC Mineral Turpentine Oil (MTO) . Based on boiling point. the fractions are separated and given secondary treatment to utilise it as finished products. Napthenic and Aromatic categories.

raw Lube Distillate and short residue. 340ºC–366ºC Jute Batching Oil (JBO) 366ºC plus fraction i. Crude Assay Data are utilised for the following: u u u u u u u u u u 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 u Crude characteristics – Consistency of crude supply.e. vi. UNIV ER SIT ST U DI ES k~ e k . This is done to assess the utility of the crude for processing for production of various products and their yields. ii. Reduced Crude Oil (RCO) is subjected to vacuum distillation for obtaining vacuum gas oils. Various fractions obtained from atmospheric and vacuum distillation are given further treatment to meet required specifications for use. . 140ºC–240ºC Aviatin Turbine Fuel (ATF) 140ºC–270º Kerosene vii. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 9 Activity 2 C i.YO FP E TR OLEUM & EN ER GY fo u n ~. 270ºC–340ºC Gas oil viii. How do you classify crudes based on proportion of type of hydrocarbon present in them? v. What is Crude Assay? How are these Assays utilized? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Crude Assay Crude Assay is the determination of properties of various fractions of crude oil.

. FBP characterisation of several long and short residues. k ‘ k f D r o’ Short Evaluation u Crude characteristics u 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 u Yield data and key u characteristics of straight run cuts in fuel range and long residue Detailed Evaluation u Design data for grass root refinery u TBP assay in atmospheric and vacuum range Selection and design of secondary conversion units. UNIV ER SIT ST U DI ES k~ e k . u Product optimisation u u Information Required u u u 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. Yield and characteristics of sets of distillates in atmospheric and vacuum range with variation in IBP.YO FP E TR OLEUM & EN ER GY 10 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~.

k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 11 Notes __________________ __________________ __________________ __________________ __________________ u Property curves of fractions vs% distilled – – – Mid% curves Yield% curves ISO% curves u Properties and yield of straight run fractions and residues Detailed composition of light distillates Hydrocarbon Type Distribution of Middle and Heavy Distillates __________________ __________________ __________________ __________________ __________________ u u 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: u u u u Weight to volume or vice versa calculations Checking the consistency of crude supply Control of refinery operations Used in various correlations . UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY fo u n ~.

9 .5 43.0 59.8 28.8161 0.8727 0. UNIV ER SIT ST U DI ES k~ e k .0 65.22 26.7 53.8675 0.8952 0.8553 0.8278 0.85 31.0 44.84 27.8496 0. k ‘ k f D r o’ Also gives a rough indication of type of crude oil MASS (M) VOLUME (V) M/V Density = 141.39 17.2 52.8448 0.0 54.99 33.35 36. Gujarat Geliki Nahorkatiya Kuwait IF IR.7920 0.5 API GRAVITY= SP.7 42.8549 0.8527 0.3 24.6 78.8412 0.64 22.16 34.55 35.20 35.7930 0.62 36.4 60. Oman Elmorgan Jorajan Kharsang Lakwa Jhalora Kothana Rudrasagar Sanand N.00 35.6 22.9242 0.8688 0.8910 0.90 35.55 28.8986 0.1 52.29 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 370ºC 79.08 46.30 31.50 25.10 21.80 39.7 61.5 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.9340 0.YO FP E TR OLEUM & EN ER GY 12 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Specific GRAVITY= M’/V (WATER) u Refining fo u n ~.6 47.Kadi Mix Badarpur Santhol : Above 33 degree API : 23-33 degree API : upto 22 degree API Density 0.0 48.2 60.8414 0.45 19.5 60.8821 0.7 51.9000 0.9210 0.4 27.9 47.8495 0.87 25.9430 0.10 30.9507 API 47.1 60.6 60.85 41.7 31.8698 0.50 31.40 33.8484 0.GR AT 60/60°F –131.0 55.91 18.

01-0. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 13 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Sulphur Crude oils are also categorised based on sulphur.3 0. __________________ __________________ __________________ Reid Vapour Pressure (RVP) and Light End Analysis RVP indicates relative Percentage of gaseous and lighter hydrocarbons in crude oil.3 0.3 .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. UNIV ER SIT ST U DI ES k~ e k .1 0.5% of Sulphur Sour grades >0.1 Kg/cm2 6. u Sulfur is a measure of “sourness” and “sweetness” of crude Sweet grades<0. It is removed in hydrotreater by reacting with H2 and recovered as elemental sulfur in SRU.1 0.5% of Sulphur Sulphur is passed on to products as much as regulations or market accepts. TYPICAL HYDROCARBON ANALYSIS Components C1 C2 C3 ISO-C4 N-C4 ISO-CS N-C5 TOTAL % WT on Crude ND TRACES 0. Kg/cm2 14.YO FP E TR OLEUM & EN ER GY fo u n ~. Component Propane Butane Crude Oil RVP.6 Kg/cm2 0.5 1.

7 45. % WT Pour Point. Salt Content It is measure of contamination in crude that will cause overhead corrosion or foul up exchangers by settling and .32 BH Crude 10.0 2.0 12.84 45.7 16. VGO and asphalt Lube manufacture is also dependent on wax content of the crude.0 5. 50°C Geological Characteristics Yield Value Dynes/ cm2 AT 32°C 24°C 18°C 16°C Plastic Viscosity.0 85.YO FP E TR OLEUM & EN ER GY 14 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Characteristics WAX.5 9.7 43.0 222. AT 32°C 24°C 18°C 16°C 7.0 10.0 4.9 +30 Refining fo u n ~.9 30.P. C. 3. k ‘ k f D r o’ Flow Characteristics of Crude Oils Basrah Crude 3.°C Viscosity Kinematic cst AT 37.5 -24 6.6 14.18.8 °C. UNIV ER SIT ST U DI ES k~ e k . These hydrocarbons u u u Affect the flow behaviour of crude Affect the product quality of gas oil.30. 4.0 330.0 17. is used in pumping and design calculations: u Wax Content Normal paraffins above C16 are solid at somewhat ambient temperatures.3 Pour Point u u Indicates relative amount of wax present in crude oil Is the temperature below which pumping and transportation problems may be encountered Along with viscosity.

YO FP E TR OLEUM & EN ER GY fo u n ~. Ca. Resins Particulates Brine Droplet Asphaltenes Na+ COONa+ COOWaxy Agglomerates ii. What are various impurities in crudes. UNIV ER SIT ST U DI ES k~ e k . Mg. . Method of determination of salt content. K. __________________ __________________ Alkyl Benzene Carboxylates Naphthenates __________________ __________________ FIGURE 2.1 POSTULATED STRUCTURE OF STABLISED EMULSION __________________ __________________ __________________ __________________ __________________ __________________ Problems Encountered Due to Salts u u Irregular behaviour in distillation Equipment corrosion in the atmospheric distillation caused by HCL liberated due to hydrolysis of chlorides Increased Consumption of Amonia u Salt is a major cause of blocking and fouling of heat exchangers Residual product contamination 100 Total Chloride evolved as HCL % Ashci % u • • • • 75 50 25 • 0 0 100 200 • 300 400 PTB as Salt Content of Crude PTO AS NACL u Salts may vary widely in ratio of metal ions. though common averages are – Na: 70-75%. their bad effects and how are these impurities removed? iii. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 15 Activity 2 D i. It is removed in desalter by washing and settling mainly chlorides and sulphates of Na. How do you separate various fractions present in crudes? sealing. Ca: 10%. Mg: 15-20%. BS&W & Viscosity.

YO

FP

E TR

OLEUM &

EN

ER

GY

16
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u

Refining

fo

u
n ~;

UNIV ER SIT

ST U DI ES

k~ e k ; k ‘ k f D r o’

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.

YO

FP

E TR

OLEUM &

EN

ER

GY

fo

u
n ~;

UNIV ER SIT

ST U DI ES

k~ e k ; k ‘ kf D r o’

UNIT 2

Crude Oil and its Characteristics

17
Activity 2 E Significance of TAN & KUOP. __________________ __________________ __________________ __________________ __________________ __________________

Asphaltenes, Carbon Residue and Ash Content Asphaltenes
u

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.

u

u

__________________ __________________ __________________ __________________

Ash Content
u

Metallic constituents concentrate in the ash of the crude oil

Carbon Residue
It’s 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-à-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.

YO

FP

E TR

OLEUM &

EN

ER

GY

18
Activity 2 F What are various crudes processed in Indian Refineries? Where are Indigenous crude found? What is the sulphur content of Indian crudes? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________

Refining

fo

u
n ~;

UNIV ER SIT

ST U DI ES

k~ e k ; k ‘ k f D r o’

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.

VISC.6% VOL OCTANE No.–48ºC DIESEL INDEX 67 POUR +POINT +6ºC KUOP 12-70 KIN. 15% VOL. 52% VOL COTANE NO. AT 100ºC 405 0St API 16.85 SULPHUR 0. 5. 16% Vol NAPH. 2. 0. E. 23 mm AROM. Imported crudes are sourced mostly from: a.T.0 GANDHAR+ANKLESWAR (60. c.9 3 17. beside fuel products. d.6% V.140ºc KEROSENE 140-250ºC 4. POUR POINT+27ºC WAX CONTENT 8.2 6 6. Gases upto 20ºC Naphtha I. 36% VOL.4 4.30 NORTH GUJARAT CRUDE MIX ºAPI 26.P.-54ºC DIESEL INDEX 57 POUR POINT +3 KUOP 12. 3. b. These crudes are having varying range of sulphur from low of high.2 23.N.17%Wt. 40 VOLT CRUDE MIX ºAPI 46. 1:1 % VOL F.8% Wt KUOP 12. UNIV ER SIT ST U DI ES k~ e k . KUOP 11.8% VOL.3 4 27. VISC.4 10-1 3.9 ASSAM CRUDE MIX ºAPI 29.T. VISC.83 SULPHUR 0.3 N.8 AROM: 6.9 SULPHUR 0.<–60ºC DIESEL INDEX 33 POUR POINT –9ºC KUOP II-61 KIN. AT 96.2 22..041 % Wt.10 KIN VISC. 73. AT 100º C 8.6 19.B. C+.58 POUR POINT +48 KIN.9% Wt.92% WI.8 5 34. AT 100ºC 150(27 0SI CCR 14.24% Wr.5 SMOKE POINT 27mm AROM. POUR POINT + 68ºC 24.9 18.P. .1 31.7 SMOKE POINT 14mm Arom.7 27. Gulf Region Nigeria Malaysia Australia The above crudes are specially selected for production of Bitumen/LOBS/ATF. F.120 SI ºAPI 13.8% Wt.P. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 19 Activity 2 G What straight run fractions are obtained in Atmospheric Distillation? And in Vacuum Distillation? __________________ __________________ __________________ 2.5 CCR 9. __________________ 1 2 AROM.O. POUR POINT +30ºC WAX CONTENT 10. POUR POINT+21 WAX CONTENT 6. NAPH 40.T. 6. __________________ __________________ __________________ __________________ __________________ __________________ Comparison of Crudes Comparison of Indian crudes and typical Middle-east crude mix for yield and key properties of straight run cuts:1. GAS OIL 250–370ºC Vacuum GAS OIL 370–530ºC.8 1-2 15.O. 67.9ºC 7 0St ºAPI 3.77% Wt.P. SMOKE PT.YO FP E TR OLEUM & EN ER GY fo u n ~.0 AROW 5. Short Residue 530º.

16% Vol.43 CCR 19.61. Draw a comparison of indigenous crudes with Typical Middle East Crude(s) vis-à-vis important specifications of Petroleum Products. Mostly. AT 100ºC 903. 18. CCR 10.35 SULPHER 0.7 16. crudes are selected after evaluating detailed crude Assay Data.4 15. their significance and typical values/ units of measurement. -49ºC DIESEL INDEX 56 POUR POINT +3ºC KUOP 12.5 28.1% Wt.8% Wt. Review Questions 1.7 20. 26. 69-6 SMOKE POINT 17mm AROM.70 6.17% Wt.. POUR POINT +72ºC BOMBAY HIGH ºAPI 39.5 Kuwait+Lt.37 KIN VISC.98 0St API 7. PT.51 CCR 19.1 ARON 21. metallurgy of existing plant and equipment.85% Wt.7 4. PT–57ºC DIESEL INDEX 58 POUR POINT –12ºC KUOP 12. POUR POINT + 54ºC KIN.1 SULPHUR 2.3% VOL. KUOP II.650St 10. type of products. POUR POINT 0 WAX CONTENT 2.085% Wt.35.6% VOL. POUR POIN T(–30ºC WAX CONTENT 1.98 24. a mixture of crudes is selected for a refinery to optimise the cost and meeting products quality specifications.7 Refining fo u n ~. F. UNIV ER SIT ST U DI ES k~ e k . F.4 % Wt POUR POINT+ 60ºC NARIMANAM CRUDE ºAPI 47. IRANIAN FOMAN (56: 36: 6 VOL. AT 100ºC 5.2 1.1 24. 53. KUOP 11.4 AROM 7.8 18.3% VOL OCTANE No. 2.28% Wt.1 22. NAPH. processing schemes of refineries. POUR POINT+ 30ºC WAX CONTENT 10.9ºC 5.2% Wt. F.9 30.08 SULPHUR 0.36 0St 18. Describe different characteristics of crudes dealt with in this unit.6 ARON 4% VOL. OCTANE NO.P. AT 98. 25% VOL OCTANE NO.8 SMOKE POINT 26mm AROM. AT 100ºC 4.31 KIN VISC.9 2. VISC. ) ºAPI 31.9 SMOKE POINT 27mm Arom. .7 30.0 21.T.YO FP E TR OLEUM & EN ER GY 20 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ ºAPI 9.–56ºC DIESEL INDEX 58 POUR +POINT –9ºC KUOP 11-94 KIN. k ‘ k f D r o’ 2.83 0St API 16.6% Wt. VISC.9% VOL.98 Selection of Crude(s) for a Refinery Based on product demand. KUOP 11.

From which Indian crudes. b. ATF Bitumen Lubes Micro-crystalline wax Good Quality Calcined Petroleum Coke __________________ __________________ __________________ __________________ __________________ . can you produce a.YO FP E TR OLEUM & EN ER GY fo u n ~. e. UNIV ER SIT ST U DI ES k~ e k . c. d. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 21 Notes __________________ __________________ __________________ __________________ __________________ 3.

.

the learner will be able to: y Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand the specifications of various petroleum products. 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. Bharat III/IV.23 Unit 3 Specifications of Petroleum Products and Related Tests Objectives After studying the unit. their significance and their determination/tests. 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 . These quantified characteristics are called “specifications”. These characteristics are quantified to make them absolute and also to remove any ambiguity in the interpretation. y Appreciate crucial specification of HSD & MS from Environmental Pollution Standpoint & Strategies for meeting stringent norms for future Euro III/IV.

Pour Point When heavy petroleum oils containing wax are allowed to settle (like in storage tanks). Each country has it own legislation with respect to flash point depending upon the climatic conditions of the country. 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 . Flash point is associated with safety during storage and application in some respects. If the oil does not move. If the vapour so formed is sufficient to form an explosive mixture with air. 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. k ‘ k f D r o’ 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. petroleum oils are mixtures of several hydrocarbons and so will have a boiling range instead of boiling point.YO FP E TR OLEUM & EN ER GY 24 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Unlike pure compounds. wax separates out from them making the oil immobile. The oil should have suitable boiling range (volatility) so that it can be used in a particular application. Motor Gasoline which is used in spark ignition internal combustion engines. When a product like kerosene is stored either at home or at a commercial location. For example. it forms vapour above it depending upon the ambient temperature. it cannot be pumped. UNIV ER SIT ST U DI ES k~ e k . there would be explosions when a small naked flame is exposed to it.

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). . If the product is corrosive. Western countries and USA do not use this test any more. This quality is called “easy start”. UNIV ER SIT ST U DI ES k~ e k . the fuel should not be corrosive to silver. Global efforts are being made to minimise the sulphur content in motor gasoline. it will corrode these parts and reduces their life. Copper Corrosion The fuel product comes on contact with metal parts such as transfer pipe from storage tank. The specification for recovery at 100oC is set to give power to engine and take load. storage vessels etc. The specification for recovery at 70 o C is laid to meet this requirement. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 25 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Since the application is in a spark ignition engine. In order to protect this lining. Sulphur Sulphur. storage and transportation equipment like pumps. the burner in a kerosene stove. besides being corrosive to the fuel systems. This test is applicable to all fuels. high speed diesel and fuel oils. the fuel should easily vaporise to a sufficient degree so that when a spark is applied it can ignite. 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. stove body itself. is a pollutant to the air and affects life. The maximum limit of 45% is laid to prevent some other undesirable effects such as vapour lock. This is a requirement for Indian region only. storage tank itself. Copper corrosion test indicates whether the product is corrosive to copper containing alloys or not.YO FP E TR OLEUM & EN ER GY fo u n ~. Hence this test is done for ATF.

The most common are Kinematic Viscosity measured in centi-stokes and Saybolt Universal Viscosity measured in seconds. Such deposit may clog the jet and prevent fuel flow due to which the engine stops. Viscosity is measured in several ways. If motor gasoline contains any soluble solid residue. it gives flow properties which are needed for pump selection for transporting. This is required to prevent wear and tear in the moving parts of a machine on account of metal to metal contact. Viscosity is an important property for lube oils because it gives the lubricating property to the oil. Example: Dye to identify the MS from others. This type of gum is characterised by Potential Gum test. 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. That is why this test is done on MS. The unit of absolute or dynamic viscosity is Poise and that of kinematic viscosity is Stoke. UNIV ER SIT ST U DI ES k~ e k . Some solid material is added to MS deliberately for some purposes. k ‘ k f D r o’ Viscosity Viscosity is the resistance to flow. Potential Gum This test is applicable to motor gasoline which may contain unsaturated hydrocarbons (olefins). One point should be noted.YO FP E TR OLEUM & EN ER GY 26 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. For fuel oils. These type of residues are excluded from the specification. The unit of measurement is mg per liter. the residue gets deposited in the carburetor and other parts after the gasoline is vaporised. It does not show the exact amount of gum that would form on storage but gives a directional indication. Existent Gum This test is applicable to motor gasoline. . The specification is 40 mg per litre max.

they behave in another way.4 90 >100 0 75 88 92 107 Octane numbers are not truly additive. this is only a general rule and may differ in the case of iso paraffins. But when it is mixed with other hydrocarbons. Toluene has a RON 107 when it is a single component system. like naptha. the hydrocarbons behave in some way and when used in a mixture. When used singly. Some others believe that it is additive on mol.3 Dimethyl Pentane 2 Methyl Hexene-1 Toluene 24. it behaves as if its octane number is > 120. For example. olefins and aromatics for the same carbon number. octane number is additive on weight percent basis. However. Some of them have lower octane numbers than corresponding napthenes and some other higher octane number depending upon the branching of the iso paraffin. UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 27 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. Next comes napthenes followed by iso paraffins. . 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 2.8 83 91.8 73. Iso octane is assigned a value of 100 and normal heptane 0 octane number.YO FP E TR OLEUM & EN ER GY fo u n ~.2 Dimethy 1 Butane 2-Methyl Pentane Hexene-2 Benzene N-Heptane Methyl Cyclohexane 2. Normal paraffins have the lowest octane number. Some schools of thought say that in multi-component systems.

a secondary fuel for routine use is also stated in the test method. It turns red when exposed to air. So. iso paraffins. 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. In effect. k ‘ k f D r o’ per cent basis. UNIV ER SIT ST U DI ES k~ e k . 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. Here. Cetane Number This test is applicable to diesel fuels which use ignition by compression. Alpha methyl naphthalene has some storage stability problem. normal paraffins have highest cetane number followed by naphthenes. These are determined under different conditions of the test. olefins and aromatics in general . Another consideration for using HMN is its easier availability. although it is a primary fuel. This is hepta Methyl Nonane (HMN). Research Octane Number and Motor Octane Number. n-Cetane is assigned a value of 100 and alpha methyl naphthalene a value of 0. there are always some exceptions and some deviations. AKI = (RON + MON)/2 Anti Knock Index is regarded as more critical for engine performance than RON alone.YO FP E TR OLEUM & EN ER GY 28 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. This test has reverse characteristics of octane number.

The higher the hydrogen content. 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. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 29 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ but the order may vary depending upon the chain length of iso paraffins. Naphthenic hydrocarbons have intermediate aniline points. The test is applicable primarily to kerosene. UNIV ER SIT ST U DI ES k~ e k . Smoke point shows the hydrocarbon nature of the fuel. But if the kerosene starts giving smoke. Cetane Index It is an alternative to cetane number. So the higher the flame without smoke. The specification of smoke point for kerosene in our country is 18 mm minimum. the height of the flame has no meaning. . Paraffins contain highest hydrogen content for the same carbon number. it gives less light. the better. As the flame size increases the light given out would also be more.YO FP E TR OLEUM & EN ER GY fo u n ~. Paraffins have high smoke points followed by naphthenes and then by aromatics. Aniline point gives the hydrocarbon nature of the oil. __________________ __________________ __________________ Aniline Point Aniline point is the minimum temperature at which equal volumes of sample and aniline are miscible. Aromatic hydrocarbons have lower aniline points and paraffinic hydrocarbons have higher aniline points. The main purpose of kerosene is for use in lantern. If the kerosene gives smoke when it burns. It is nearly equal to cetane number but not an actually determined value required cetane engine. So the smoke point of paraffins is highest. Cetane index is not applicable to fuels containing cetane improves. the higher will be the smoke point. Smoke point is related to hydrogen content of the fuel.

YO

FP

E TR

OLEUM &

EN

ER

GY

30
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________

Refining

fo

u
n ~;

UNIV ER SIT

ST U DI ES

k~ e k ; k ‘ k f D r o’

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.

YO

FP

E TR

OLEUM &

EN

ER

GY

fo

u
n ~;

UNIV ER SIT

ST U DI ES

k~ e k ; k ‘ kf D r o’

UNIT 3

Specifications of Petroleum Products & Related Tests

31
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

0

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.

YO

FP

E TR

OLEUM &

EN

ER

GY

32
Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ CH3CH2CH2CH2CH = CH2+Br2

Refining

fo

u
n ~;

UNIV ER SIT

ST U DI ES

k~ e k ; k ‘ k f D r o’

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

05 max To Report To Report Contd..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. .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..YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 33 Activity 3 A What are different Petroleum Products? __________________ __________________ Motor Gasoline (IS 2796 . UNIV ER SIT ST U DI ES k~ e k .1 max 0.

k ‘ k f D r o’ 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 C %v o o P:18 20 min 300 max C C P:20 P:31 P:34 35 min 18 min 0. LPG.015 max 25 max 5.YO FP E TR OLEUM & EN ER GY 34 Activity 3 B What are the key specifications of Motor Spirit. .. UNIV ER SIT ST U DI ES k~ e k .25 max mm %w Aviation Turbine Fuel (IS 1571 ..30 max 0. HSD.1992) Test Appearance Unit -Method Visual Requirement Bright.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. 0. Free from solid matter and visually undissolved water. ATF? How do these affect performance? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Aromatics Olefins Total Sulphur Mercaptan Sulphur Reid Vapor Pressure @ 38ºC 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 fo u n ~.0 max 0. Petrochemical Naphtha.

0 max 4800 25 min 3.775 to 0.0 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...Density @ 15 degree C kg/M3 P.YO FP E TR OLEUM & EN ER GY fo u n ~.01 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 . UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 35 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 8.2 max 0.15 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..3 (on 10 % residue) 48 min ASTMD 4737 46 min P:10 3 Winter Contd.

.0 to 5.YO FP E TR OLEUM & EN ER GY 36 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 Refining fo u n ~.0 Max 8 max Unit %w Method P: 132 Requirement 10 max PSS 8 max Contd.02 max 1.45 max 11 max --1. 400 Proposed Light Diesel Oil (IS 1460 . .0 0.35 max 0.0 0.2000) 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 0.5 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 2.7 0..0 max 0.5 max Kin Viscosity @ 40 deg C Sediments Total Sulphur Water Content CFPP __________________ Lubricity HFRR Scardia Micron at 60o C.1994) Test Moisture as Received Moisture after Initial drying Ash on Dry basis Volatile Matter %w %w %w P: 132 P: 126 P: 134 2.05 max PSS --0.005 max 0.25 max 1b 66 min 2. UNIV ER SIT ST U DI ES k~ e k .25 0.3 max 0 max 0 max Petroleum Coke (IS 8402 .5 to 5.05 max 910 max 0.8 max 0.05 max 6 Winter 18 Summer 1.05 0.1 Max Report 1.5 to 15. k ‘ k f D r o’ 85 min 95 min 35 min 2.

Composition of motor gasoline profoundly affects its performance in the engine and equally controls its behaviour under storage and handling.YO FP E TR OLEUM & EN ER GY fo u n ~. UNIV ER SIT ST U DI ES k~ e k . __________________ 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.5 max 88 min 7. k ‘ kf D r o’ UNIT 3 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.These are described below: Paraffins (Cn H2n+2) – – – – – Thermally and chemically most stable compounds.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…………. . 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.

Properties of Gasoline and Oxygenated Compounds Property Chem.0 82. Oxygen Cont.) 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. Heat of Vap.3 9.ºC StoichioMeteric A/F Lat. Btu/Gal (J/lit) Net Heat comb. Wt.3) 28 ∞ 2100 (7.1 55 11.8) 21 ∞ 2600 (9.P. Aromatics (CnH2n-6CnH2n-12 etc) – Aromatics have excellent knock resistance qualities. UNIV ER SIT ST U DI ES k~ e k .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.9) 43 Trace 65 6.8 800 (2.3 82. there is an induction period before normal hot .1) 35 ∞ 900 (3.2 10.YO FP E TR OLEUM & EN ER GY 38 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. air and fuel is heated up in combustion chamber. k ‘ k f D r o’ Cycloparaffins (CnH2n) – – – Poorer knock resistance than corresponding aromatics Lengthening of side chain decreases knock resistance Branching of side chain is beneficial.8 11.5) 32 ∞ 1700 (6.4 78.2) 35 4.7 30-20 14. g/100g water RON MON 101 82-87 3300 (11. Formulae Mol. % mass B. MJ/Kg SolubiSolubility in water.

UNIV ER SIT ST U DI ES k~ e k .g. Knocking Tendency High Anti-knock Value: Aromatics. isoparaffins with little branching. During this induction period. – – – Loss of power due to reduction in volumetric efficiency Exhaust valve corrosion Spark plug fouling . Naphthenes. oxidation of fuel takes place with the formation of intermediate products such as peroxides. 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. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 39 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ flame occurs. Formation of peroxides. Isoparaffins (highly branched) Intermediate Anti-knock Value: Mixed parffins e.YO FP E TR OLEUM & EN ER GY fo u n ~. aldehydes and peracids prevents knock due to their ability to dissociate and promote such type of intermediate reactions. aldehydes and peracids.

2. UNIV ER SIT ST U DI ES k~ e k . 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. 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. Volatility characteristics of fuel Fuel requirement of engine at the moment Ability of fuel pump to handle the vapour . 2.YO FP E TR OLEUM & EN ER GY 40 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Vapour Lock and Percolation Vapour lock is a function of : 1. enough gasoline in the intake air must be evaporated. Warm up is mainly a cold weather problem. Fuel volatility and ambient temperature Provision for thermostatical controlled hot spots. k ‘ k f D r o’ Volatility Volatility of gasoline is its tendency to pass from liquid to vapour phase. 3.

7 3.1 5 . TYPICAL VALUES OF VAPOUR PRESSURES (RVP) K g /c m 2 PSI 200 80 10 KPa 1 3 8 2 .8 5 4 9 .6 P ro p a n e B u ta n e M o to r G a s o lin e 1 4 . The temperature and pressure in the fuel system The temperature of ambient air.6 0 . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 41 Notes __________________ __________________ __________________ 4. UNIV ER SIT ST U DI ES k~ e k . Vapour lock index (VLI) 10 RVP+ E 70 Gives better indication of vapor locking. Initial boiling point Temperature corresponding to 10% Vol. Temperature corresponding to 50% Vol.YO FP E TR OLEUM & EN ER GY fo u n ~. 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 . __________________ __________________ __________________ __________________ __________________ __________________ __________________ Reid vapour pressure (RVP) Controls the volatility due to lighter ends. FBP Non-volatile residue left in the flask.2 6 8 . Temperature corresponding to 90% Vol. temperature and barometric pressure. 5. ASTM D-86 Distillation Significant temperatures are – – – – – – 2. underbonet Measurement of Volatility 1.

YO FP E TR OLEUM & EN ER GY 42 Activity 3 C How is gum formed in motor spirit. and catalysts particularly traces of copper. 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. 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. Remedial Measures – – Control of fuel volatility Providing heating of carburetor body or the intake air. y y y . k ‘ k f D r o’ – – High volatility of fuel Cold and humid climate are favorable for icing. Impact of Gum Formation y May cause intake valve sticking due to deposition of Gum. what is its impact and how is it overcome? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ l l Refining fo u n ~. UNIV ER SIT ST U DI ES k~ e k . access of air and light. 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. temperature.

Sulphur. If these H2S and COS are mainly corrosive and RSH is distinctively unpleasant. Automotive industry requirement for meeting Euro III/ IV emission standards for Motor Gasoline.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) .005% Max 0. A direct result of leakage of unburnt fuel can be corrosion of engine parts. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 43 Notes __________________ __________________ __________________ __________________ Sulphur Compounds and Corrosiveness: Most of the sulphur compounds are removed in the manufacturing processes.YO FP E TR OLEUM & EN ER GY fo u n ~.05% Max 2. Stringent specifications are required to be followed due to environmental considerations. 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. UNIV ER SIT ST U DI ES k~ e k . forms oxides of sulphur which react with water to form sulphuric acid. on oxidation.

k ‘ k f D r o’ HSD Blending Components (Typical) B0ILING RANGE ºC 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 .Ignition Delay .Flash Points .Cloud & Pour Point Cleanliness Use During .Corrosive constituents . SR Gas Oil Heavy Gas Oil LT.YO FP E TR OLEUM & EN ER GY 44 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Heavy SR Naphtha Kerosine LT.Copper corrosion .Corrosive constituents Carbon Residue on 10%. UNIV ER SIT ST U DI ES k~ e k . cetane number increases Isoparaffins have lower cetane numbers than the paraffins of same carbon numbers. . Bottom Ash Content.Metals .Contaminants Control characteristics .Volatility .Water & sediments .Flow . Cycle Oil Hydro Cracker Go Coker Kerosene Refining fo u n ~.Volatility .Heavier constituents .Cetane Number .Viscosity . Sulphur Content.Cloud/Pour pt. 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.Distillation Range .CFPP Combustion . With branching cetane number is lowered.Heat content .Gravity . Olefins – Olefins have lower cetane numbers than paraffins of corresponding structures and follow similar rules of branching .

UNIV ER SIT ST U DI ES k~ e k . As a result of abnormal ignition delay.5% Isoproyle Nitrate n – Amyl Nitrate Increase in CN 17 23 . – 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. 44 Additive dozes 1. 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. large quantities of oil are gathered in the combustion chamber. Naphthenes – Naphthenes follow olefins in cetane quality but are a good deal higher than aromatics.YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 45 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ – Presence of olefins gives rise to poor oxidation stability. 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.

are generally preheated. u u Cold Filter Plugging Point (CFPP) u Cloud point being a static test does not truly represent actual running conditions.0 cst. Cloud point indicates the temperature at which waxes start precipitating. when used as diesel fuel. 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. High viscosities can cause – – – Poor atomisation Large droplets High spray jet penetration u Low viscosity results in a spray which is too soft and thus does not penetrate sufficiently. CFPP is defined as highest temperature expressed as a multiple of 1 o C at which the fuel when cooled u .YO FP E TR OLEUM & EN ER GY 46 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u Refining fo u n ~. Lubricating oil properties of such fuels are usually poor HSD viscosity range is generally 2. As a result combustion is impaired and power economy is decreased.0 to 5. Heavy distillates. UNIV ER SIT ST U DI ES k~ e k . k ‘ k f D r o’ 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.

ash. Sediments cause wear and create deposits both in the injection system and engine itself. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 47 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ under prescribed conditions will not flow through a filter or requires more than 60 sec for 20 ml to pass through. UNIV ER SIT ST U DI ES k~ e k . They can cause clogging of filters.YO FP E TR OLEUM & EN ER GY fo u n ~. Type of deposits is also an important factor. The test can also be used to detect contamination by heavy residues. Unburned metallic constituents have abrasive action and cause wear by adversely affecting the nature of deposits. Maintenance life and period of over-haul mainly depends on deposit control. Pour Point u Pour point gives a useful guide to the lowest temperature at which the fuel can be cooled with setting. resins etc. u Water and Sediments u These may come into the fuel through contamination during storage and handling. Hard abrasive deposits can do more harm than soft fluffy deposits. Deposits are mainly carbonaceous matter. Cleanliness in Use Carbon Residue u Gives some indication of coke forming / deposit forming tendencies in the engine. u u u u Ash Content u Indicates the presence of small quantities of metallic soap or volatile porphyrines. u u .

Oxidative Gum Reactions Alkenee + Oxygen Reaction time 2. combustion products corrode and also contribute to deposit formation. k ‘ k f D r o’ Sediment and Gum Forming Reactions (Diesel Fuel Stability) 1. Corrosive Constituents Sulphur Content u Strict emission regulations require stringent sulphur specifications Due to high sulphur..YO FP E TR OLEUM & EN ER GY 48 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. UNIV ER SIT ST U DI ES k~ e k . ….. 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. Low speed diesel engines can tolerate more sulphur. cooling water and combustion zone temperatures tend to remain at u u – .. Gum Weeks to months These are more predominant in diesel fuel instability. Sediments Weeks to months …… Hours to weeks …. Esterification reactions Aromatic Hydrocarbons + Hetrocylic Nitrogen + Benzothiols Multi-step Process Reaction Time …… …. Acid – Base Reactions Organic acid + Basic Nitrogen …… Sediments Reaction Time 3.

UNIV ER SIT ST U DI ES k~ e k . Components of Residual Fuel Oils u u u u u u u Long residue Short residue Heavy cycle oil. Tests carried out u u Estimation of sulphur content Copper strip corrosion test.YO FP E TR OLEUM & EN ER GY fo u n ~. 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. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 49 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ an equilibrium rather than to fluctuate between high and low. 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 .

In combustion. Sodium is recognised as a potential corrosion problem. sulphur compounds. u u u u Effect of Metals u Vanadium is a major metallic impurity in residual fuel oil. sludge Na.reduce excess air .YO FP E TR OLEUM & EN ER GY 50 Activity 3 D Effect of metals in furnace oil? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Fuel system corrosion Acidic. economiser. 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 Refining fo u n ~. Na converts to V converts to Na2O + Na2SO4 V2O5 + V2O4 ® Na2 V2O5.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. Na2 V2O4 5V2O5 (Low melting ash deposits) u u u Other ash deposits are SiO2. UNIV ER SIT ST U DI ES k~ e k . water.magnesium additives . It causes metal spalling or breaking off of pieces of refractory due to its high thermal expansion. Causes corrosion in high temperature zone. AI2O3. Fe2O3 NaAIO2 has high melting point (3272 oF). k ‘ k f D r o’ Summary of Fireside Problems Related to Fuel Quality Solutions Addition of inhibitors and sludge dispersants Application of corrosion inhibitors . air–preheater 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. .

3. LPG and PC Naphtha? (Refer Unit 4 & Bibliography). MS.YO FP E TR OLEUM & EN ER GY fo u n ~. . 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. What is the significance of following tests and to what petroleum product these are related: 2. 4. UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 51 Notes __________________ Review Questions 1.

.

Reforming. Diesel. Isomerisation and Fluid Catalytic Cracking plants to obtain components of . 4. Give insight into the feeds composition of various process plants for production of finished products. (Fig. provides faster delivery and at lower cost. to minimise processing cost and optimise product distribution. Give an overview of various off-site facilities in a Refinery. Supply chain optimisation from crude to products. ATF. The raw streams from CDU are treated in Merox.53 Unit 4 Integrated Refinery and Petrochemical Plants Objectives After studying the unit. 3. Economies of scale – Minimum 9-12 MMTPA refining capacity. Naphtha. MTO. 4. the learner will be able to: y Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand the functioning of various process plants in a refinery and their integration with one another. A typical integrated refinery and petrochemical plant set up is shown in attached block flow diagram. emphasis is laid on the following: 1. RCO is fractionated in Vacuum Distillation Unit (VDU) to get VGO and raw lube cuts. y y Now a days.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. Refining and petrochemical plants are integrated. 2. Feedstock flexibility – To utilise low cost crudes. Kerosene. LPG. Jute Batching Oil (JBO) and Reduced Crude Oil (RCO). Hydrotreatment.

Raw lube cuts are treated for removal of aromatics and wax and are hydrotreated to get lube oil base stock. Petrochemical feedstocks and components for motor spirit and diesel. olefins. Vacuum residue can also be treated to extract out Deasphalted Oil (DAO) and the residue left is asphalt. it is converted to elemental sulphur which is sold as by-product. DAO is treated in aromatic extraction unit. Hydrogen plant is installed to produce hydrogen for meeting the requirement of various Hydrotreatment processes. propylene. Sulphur present in crude and various streams is converted to H 2S during processing. dewaxing unit and hydrofinishing unit to obtain bright stock which is used for Lube oils and grease manufacture. Propylene. UNIV ER SIT ST U DI ES k~ e k . From FCCU. VGO is treated in FCCU to get LPG. . Asphalt and vacuum residue can also be utilised for production of bitumen or as fuel for furnaces and boilers. k ‘ k f D r o’ 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. In Sulphur plant.YO FP E TR OLEUM & EN ER GY 54 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Coker Sulfur CRUDE CRUDE TANKS CDU/ VDU FCC Propylene Refining fo u n ~. The short residue obtained from VDU fractionator bottom is partly treated in coker unit to get lighter value added products alongwith raw petroleum coke. This also helps in environmental protection. 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.

3 CRUDE AND VACCUM DISTILLATION UNIT IN A REFINERY . FIGURE 4. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 55 Notes __________________ __________________ __________________ __________________ Crude Distillation Brief process descriptions have been provided (please refer block flow diagram of CDU. 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. Fumace HVGO TO FCC Lube distillates Vacuum Residue to Belayed Coker/ Bitumen. LK/ATF HK Diesel JBO LVGO V a c. This part has three main sections. VDU and SGU). 3. 1.2 BLOCK FLOW DIAGRAM OF CDU/VDU/SGU FIGURE 4. UNIV ER SIT ST U DI ES k~ e k . C o l.YO FP E TR OLEUM & EN ER GY fo u n ~. 2.

however. 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. Na. These salts. sludge and mud from crude to avoid corrosion and fouling in exchangers columns and downstream equipment. The heated crude is fractionated in atmospheric distillation column of CDU. Hence. Then it is passed through a desalter after being mixed with de-emulsifier and water thru a mixer valve. Desalters remove salts. Here mainly gases. crude passes through high electric field. Furnace provides required heat for fractionation in atmospheric column and crude is heated upto 385°C. This is done by recovering heat from outgoing products streams from the unit. The desalters are designed for 99% salt removal and reach less than 1 ptb (part per thousand barrels) in desalted crude. etc. can cause severe corrosion in crude units. it is important to remove the salts from crude prior to distillation. Mg. SO4. This prepares crude for efficient desalting. Crude oil received from tank farm is heated from 30 to 140150ºC in cold preheat trains. The fractions below 165°C are withdrawn as column overheads and sent to SGU. CI. Heavies boiling at more than . particularly in the overhead section. The purpose of hot preheat train is to recover heat from pump arounds to reduce furnace duty. UNIV ER SIT ST U DI ES k~ e k . In the desalter. Distillation – Atmospheric & Vacuum The desalted crude is then heated from 140º to 190º C at 25 Kg/a2 pressure by heating with a heavier hot stream. k ‘ k f D r o’ Desalting The crude oil is contaminated with various impurities– mainly salts of Ca. Separation of water containing salt is enhanced by deemulsifier. LPG and FRN are separated. in small proportions in crude. Then it is taken to the flash drum. The flashed crude is passed through hot preheat exchangers and further heated from 190°C to 250–260°C. Several refineries worldwide have faced emergency shutdowns or have had to release hydrocarbons due to corrosion and material failures.YO FP E TR OLEUM & EN ER GY 56 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. From the top we get lighter components which directly go to the crude column.

Gases (C 1+C 2 ) for burning into furnaces or as petrochemical feedstock after H2S is removed in Amine Treating Unit. The Heavy Kero (HK) fraction is blended with diesel fraction. (1) Gas Oil (HAGO+LVGO+HVGO) which become feedstock for FCC after treatment in VGOHT and (2) VR which becomes feedstock for delayed coker.5 to 3.5% 21 to 22% 23 to 26% Cut range deg C < C2s C3–C4s C5s to 16s 165 – 227 227 – 270 270 – 370 370 – 392 <392 Fuel Gas LPG FRN LK / ATF HK Diesel HAGO RCO (Atm. HK and Diesel. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 57 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 386º C are reheated under vacuum condition (to avoid cracking) and fractionated in vacuum column of VDU. The LPG is sent to LPG Merox unit for treatment before sending to RTF. UNIV ER SIT ST U DI ES k~ e k . Naptha (C 5 to 165ºC) for sending to fertilizer or petrochemicals plants as feedstock.0 to 1.YO FP E TR OLEUM & EN ER GY fo u n ~. reformer and hydrotreaters of petro-chemical complex are passed through this plant to separate into following fractions: 1. The Light Kero (LK) fraction is routed as SKO to RTF directly or via Kero Merox unit as ATF. Saturated Gas Concentration (SGU) The overhead liquid and gases from CDU. The FRN is directly sent to the HNUU in the aromatics complex. LPG (C 3+C 4) for domestic and industrial use after removal of Mercaptanes in Merox Unit. The typical streams obtained from crude oil by Atmospheric and Vacuum distillation are given in the following table: % of crude input 0. Residue) LVGO HVGO VR . The diesel fractions can be routed to DHT or RTF as required. 3. LK.0% 2.5 to 3.5% 11 to 14% 10 to 11% 6 to 7% 16 to 17% 2.01 to 0. the other distillation products are intermediates viz. Besides the straight run products such as LPG.03% 1. Naphtha. 2.

8.YO FP E TR OLEUM & EN ER GY 58 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Diesel Hydro-Treatment The purpose of diesel hydrotreating unit is to: u u u Remove sulphur and nitrogen Convert olefins/aromatics to saturated compounds. 2. Operating parameters such as pressure. 5. safety and environment (HSE) aspects. flows. Energy conservation knowledge and skills of operating crews. 4. 6. temperature. Salient Features u 98% desulphurisation and 70% denitrification (VGO hydrotreater). u u u The feed to the unit consists of a mixture of SR diesel and heavy kerosene from the Crude Unit. Health. k ‘ k f D r o’ Product specifications and significance of the same is given in Unit 3 Operating issues which need attention are: 1. Reduce aromatics and nitrogen in diesel. Quality control of crude and products. light coker . Improve Diesel cetane no. UNIV ER SIT ST U DI ES k~ e k . Produce low sulphur. oxygenates and The catalysts used in this plant are oxides of Ni and Mo/Co & Mo impregnated on alumina base. Remove contaminants like organomettalic compounds. 7. Health of equipment and run length of unit is vital. Crude mix and product yield pattern Corrosion impact on various equipment should be known. 3. colour stable diesel.

From the product condenser. UNIV ER SIT ST U DI ES k~ e k . The reactor consists of one vessel with two beds of catalysts.YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 59 Notes __________________ gas oil. condensor Recycle gas Diesel Diesel VGO LN VGO Product separator Stripper Hydrotreater To waste water system LN __________________ __________________ Offgas to SGCU __________________ __________________ __________________ __________________ __________________ __________________ __________________ FIGURE 4. the recycled gas and then provides heat for generation of HP. HCO from the Delayed Coking Unit and LCO from FCCU Diesel Hydrotreater Make up H2 Ovhd. The feed is pumped through cold and hot feed-reactor effluent exchangers and then with recycled gas streams through the combined feed heater. MP and LP steam. 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. Recycled gas is added as a quench between the beds to quench the top bed heat of reaction.4 HYDROTREATER BLOCK-FLOW DIAGRAM Brief Description of the diesel hydro-treater follows. heats up the fresh feed. consisting of one inert and three different types of catalysts. A wash water stream is then injected into the reactor effluent before final cooling in the air-product condenser. the stripper feed. The recycle gas goes through a recycled gas water cooler and knockout drum to remove heavier hydrocarbon components before entering the . The reactor effluent is cooled through a series of heat exchangers where it. in turn. the reactor effluent enters the separator. The combined feed heater heats the feed up to the reactor inlet temperature.

The stripper feed is heated in a series of exchangers where it in turn cools the stripper bottoms. VGO Hydro-treatment This is similar to diesel hydro-treater and is used for preparing feed for FCC. and also to separate unstabilised naphtha from the diesel product. k ‘ k f D r o’ recycled gas scrubber. 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. The stripper bottom is cooled through a series of exchangers. Both the net off gas and the unstabilised naphtha liquid that are produced are routed to the Saturated Gas Concentration Unit. The top of the vessel contains a water wash section to pick up any entrained amine. This scrubber is used to remove H2S from the recycled gas by bringing it in contact with a liquid stream of lean amine. The stripper is used to remove H2S from the diesel product. FIGURE 4. and is then mixed with makeup gas hydrogen before entering the recycle gas compressor.5 HYDRO-TREATER/ HYDRO-CRACKER IN A REFINERY . UNIV ER SIT ST U DI ES k~ e k . before entering the stripper column. reactor effluent. The recycled gas exits from the top of the recycle gas scrubber.YO FP E TR OLEUM & EN ER GY 60 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~.

and removal of chloride by sodium aluminate. UNIV ER SIT ST U DI ES k~ e k . or Natural Gas or LPG or Hydrotreated Light Naphtha) is first mixed with recycle hydrogen and passed through pre-treatment section.6 HYDROGEN PLANT BLOCK FLOW DIAGRAM Hydrogen Feed Feed for hydrogen production plant — (i) Refinery fuel gas. 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. in the form of H2S. (ii) saturated LPG. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 61 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. (iii) Natural gas. Process Description Feed (Refinery Fuel Gas. . (iv) Light Naphtha. the catalyst used is CoMo or NaMo.YO FP E TR OLEUM & EN ER GY fo u n ~. HP BFW Steam Generator HP steam export Product H2 __________________ Feed purification Steam reformer Shift & gas cooling Gas purification FIGURE 4. The function of pre-treatment section is to remove sulphur in feed by hydrogenation. H2S is absorbed in Zno bed.

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: l l l l High to low pressure transition: Expansion Provide purge and dump Purging at low pressure Low to high pressure transition back to adsorption pressure: Repressurization.YO FP E TR OLEUM & EN ER GY 62 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. k ‘ k f D r o’ If sulphur is <200 ppm. For sulphur >200 ppm. . 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. double stage pre-treatment is used. then single stage pre-treatment is adopted. Hydrogen gas produced is purified by pressure swing adsorption (PSA) method. The De-sulphurised feed is pre-heated with steam and passed through Nickle Catalyst packed in Vertical narrow tubes mounted in the reformer furnance. UNIV ER SIT ST U DI ES k~ e k .

.YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 63 Notes __________________ __________________ __________________ __________________ __________________ 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. The separated merceptan is oxidised into disulfide form which can be disposed of in slop stream. Sweetened product is stored in intermediate tanks before blending into finished product. which is separated from caustic and product in caustic sulphur. through high pressure compressors and the excess gas is led to refinery fuel gas system. In case of ATF/Kerosene and Gasoline treatment. Hydrogen Sulfide (H2S) from LPG is removed by extraction with regenerated lean Amine in Amine Treating Unit (A TU). Treated sweet LPG free of H2S and Mercaptan is sent to storage. HSD. Then. Caustic in recycled. Merox (Mercaptan Oxidation) Treatment Process Description Merox is the abbreviation of Mercaptan Oxidation. Need of hydrogen is increasing day after day for treating the products like motor spirit. it is washed with water to remove caustic. Then it passes through extractor to remove mercaptan. ATF/Kerosene and Gasoline are removed by this process. Treated LPG is passed through reactor and mixed with caustic solution containing merox catalyst. In this process mercaptan is separated from hydrocarbon by washing with caustic solution. first it is mixed with caustic. Organic sulphur from LPG. air and catalyst and then passed to reactor to convert mercaptanes to Disulfides. UNIV ER SIT ST U DI ES k~ e k . fuel oils and feeds for FCC and other plants for bringing down sulphur.

Gasoline and ATF.7 MEROX TREATMENT PROCESS BLOCK FLOW DIAGRAM This process is used for treating LPG. to the aqueous phase.YO FP E TR OLEUM & EN ER GY 64 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. or the thiol portion of the mercaptane. . UNIV ER SIT ST U DI ES k~ e k . k ‘ k f D r o’ 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) 45ºC 2RSSR+4NaOH (oil Phase) The purpose of caustic in Merox process is: u To transfer the mercaptane. Sulphur Recovery Plant The objective of sulphur recovery plant is to convert H2S to elemental sulphur. u FIGURE 4. To supply the alkaline environment needed for the reaction to proceed in the desired direction.

The unreacted vapour is passed thru claus reactor. 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. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 65 Notes __________________ __________________ Sulphur recovery is required because of: l l Increasing demand for environmental friendly fuels. . __________________ __________________ __________________ __________________ __________________ __________________ l Salient features of sulphur plant are: l l l Minimum sulphur recovery level of 98. Tightening of emission standards by government/ Regulatory bodies.YO FP E TR OLEUM & EN ER GY fo u n ~.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. Increased used of high sulphur and heavier crudes in future.8 SULPHUR PLANT BLOCK FLOW DIAGRAM The sulphur condensed is routed to Liquid Sulphur Degassing Pit. The product from claus reaction funance is passed thru 1st and 2nd pass condensers.7% Ammonia destruction capability Turndown capability 25% __________________ __________________ Process Description Refer sulphur plant block flow diagram (Figure 4.. The vapour from the claus reactor outlet is passed . UNIV ER SIT ST U DI ES k~ e k .

The outlet vapour is passed thru 1st and 2nd pass of CBA condenser. k ‘ k f D r o’ thru 1st and 2nd pass condensers. this SO2 reacts with remaining H2S to give elemental Sulphur in Claus Reactor H2S+3/20 2àSO2+H2O 2H2S + SO2à3/n Sn+2H2O Overall Reaction 3H2S + 3/2 O2à3/nSn + 3H2O Process Variables Air to Acid Gas Ratio u H2S/SO2 Ratio = 2:1 344ºC 650+ –50ºC 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. 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. The off-gases from sulphur degassing pit is recycled to CBA section for recovery of sulphur. The condensed sulphur is taken to Liquid Sulphur Degassing Pit.YO FP E TR OLEUM & EN ER GY 66 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. UNIV ER SIT ST U DI ES k~ e k . of atoms in Sulphur molecule. The uncondensed vapour is passed through Cold Bed Adsorption (CBA) Reactors 1st and 2nd passes. 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. u 1/3rd of total H2S in feed gas is burned to SO2. Sulphur after Degassing is taken to granulation unit from where it goes for despatch to market. the reaction is called Claus Reaction” 2H2S + SO2 3/nSn + 2H2O n=No. .

9 SIMPLIFIED BLOCK DIAGRAM – ATU Process Chemistry The circulating amine is 35% MDEA solution. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 67 Notes __________________ __________________ Process Description Refer figure 4. UNIV ER SIT ST U DI ES k~ e k .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. Amine Acid Gas from top of the column is routed to sulphur recovery plant along with sour gases from other process units. HSH H+ + SH– . By counter current flow H2S is absorbed in Amine and sweet fuel gas (FG) free of H2S comes out from column top. Absorption Section Sweet FG __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Lean Amine FG Abs Stpr Regeneration Section Lean Amine Header Rich Amine Header Amine Storage Section FIGURE 4. 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.YO FP E TR OLEUM & EN ER GY fo u n ~. The rich Amine from bottom of the absorber column is taken to Flash Drum where any fuel gas carried over is separated out. In the stripper. The rich Amine is then pumped through heater where it is heated by the hot lean amine stream coming from bottom of Amine stripper. Hydrogen sulfide H2S OR HSH is a weak acid and ionizes in water to form hydrogen ions and sulfide ions.

coker furnace oil. coker gasoline. coker kerosene. k ‘ k f D r o’ 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. residual furnace oil and coke. Thereafter. it is heated to 250ºC in convection section of the furnace before it enters the bottom section of 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. UNIV ER SIT ST U DI ES k~ e k . coker gas oil. This unit is also known as delayed coker. (CH2OHCH 2)2 NCH 3+SH (CH2OHCH2)2NSCH3 The sulfide ion is absorbed by the amine solution. it will react to form a weakly bonded salt of the acid and the base. .YO FP E TR OLEUM & EN ER GY 68 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Slops from various other process units which do not find proper home can also be processed in coker to get valuable products. The hot cracked hydrocarbon vapours from coke chambers top via a separator enters the zone of abovementioned fractionator column. Process Description Refer block flow diagram of coker Feed is preheated by exchanging heat with hot streams. The feed to this unit is subjected to severe thermal cracking thereby producing refinery fuel gas. 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.

is cooled by steam and water and thereafter removed by hydraulic de-coking method which cuts the hard coke with high pressure water jets. 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). k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants Heavy cycle gas oil HP flare Light cycle gas oil To HNUU To LNUU Unsat LPG Merox unit 69 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ LLP Flare Vacuum Residue tank Coker Unsat gas conc. products withdrawn are Light Kerosene (LK). 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. Heavy Kerosene (HK). The vapours from top of the coke chambers is quenched with cold vacuum distillates before it enters the separator. The petroleum coke is accumulated in coke-chamber. .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 500ºC and enters the coke chambers where final cracking takes place. The liquid product accumulated at separator bottom is pumped out as Residual Fuel Oil (RFO). The coke is removed by grab crane. The vapour is routed to bottom of fractionator as mentioned earlier. gas oil and coking fuel oil (CFO). UNIV ER SIT ST U DI ES k~ e k . 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.YO FP E TR OLEUM & EN ER GY fo u n ~. From the fractionator.

At the top of reactor. Gasoline. which are reactive. it is brought in to contact with the staged feeds supplied as finely atomised droplets. 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. high throughput and minimise LCO and bottoms. Feed instantaneously vaporises and travels up the riser with the catalyst where conversion reaction takes place. Hot regenerated catalyst is mixed at the bottom of reactor with raw feed and steam. UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY 70 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u u u Refining fo u n ~. Diesel (LCGO). 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. 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. mainly LPG. and the reactive once polymerise. LPG. After pre-acceleration. naphtha and middle distillates. forming cracked fuel oil and coke. The objective is to maximise Olefins. the vapour is disengaged from catalyst. k ‘ k f D r o’ Advantages of Delayed Coker u Minimum investment for given value addition Zero fuel oil generation Coke can be used as fuel for power plant. . 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. Capability to process refinery slops and sludge. Gas oil (HCGO) etc. Kero. 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. C7 – C9 aromatics. middle distillates and decanted oil are obtained. No catalyst cost. In this column. The vapour is sent to main fractionating column.

SOx and NOx. Aromatics complex processes special cut naptha to produce paraxylene and orthoxylene as the major products and some other by-products which include Benzene. ZSM additive is added to catalyst to increase LPG yield. The Paraxylene plant consists of the following units.12 Aromatics Complex Block Diagram Flow). Residues are also used as feedstock in RFCC. Water generated in the system leaves with flue gas from Power Recovery Train. FCC __________________ __________________ __________________ __________________ FIGURE 4. H2. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 71 Notes __________________ __________________ __________________ __________________ __________________ __________________ Air is injected in catalyst regenerator for burning coke.YO FP E TR OLEUM & EN ER GY fo u n ~. sulfur. Fuel Gas and heavies. comprising of platformer primarily to produce feed for main plants. Flue gases are sent to CO boiler and thereafter to a clean up system to remove particulates. UNIV ER SIT ST U DI ES k~ e k . . LPG. Heavy Naphtha Unionfining Unit (HNUU) The function of this hydrotreating unit is to treat the feed naphtha and remove impurities like heavy metals. (Refer figure 4. Light Reformate.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.

which takes place in Cyclemax CCR. k ‘ k f D r o’ nitrogen and olefins. Platformer Unit The platformer unit processes hydrotreated naphtha from the Heavy Naptha Unifining unit. for the production of aromatics for downstream unit processing and separation. 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. a sidecut stream with a 215°C endpoint for use as a gasoline blending component and a heavy aromatic bottom stream to be used as fuel oil. Dehydrogenation of naphthenes Hydrocracking of paraffins Isomerisation Dehydrocyclisation of paraffins The spent catalyst is regenerated continuously in situ. UNIV ER SIT ST U DI ES k~ e k . Major reactions taking place in platforming unit are as follows: 1. 2. 4. 3. . stripper column bottoms.YO FP E TR OLEUM & EN ER GY 72 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. which are poison for Platformer catalyst. 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”.

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 gets adsorbed on the molecular sieve and subsequently desorbed. Objective of the units is to maximise xylene production by transalkylation of C7 and C9 aromatics. Paraxylene is withdrawn from bottom and overhead product Toluene is recycled back to Tatoray unit. The extract stream consist of PX. stripper. Its side cut product which is mixed xylenes lean in paraxylene. two parallel reactor trans. Raffinate stream is fed to the raffinate column. The molecular sieve is basically Y type zeolite (alumina silica) which preferentially adsorbs PX. UNIV ER SIT ST U DI ES k~ e k . benzene are toluene column. Feed and desorbent goes to the Parex adsorbent chambers via rotary valve. Toluene and Desorbent. Toulene column bottoms and C8 isomerates from Isomar section are fed to the xylene fractionation column. Two streams come out of the chambers known as raffinate stream and extract stream. PX and Toluene are separated in a finishing column. 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.YO FP E TR OLEUM & EN ER GY fo u n ~. The Tatoray unit includes reformer splitter column. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 73 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Parex Process Unit The process is selective adsorption of Paraxylene (PX) on molecular sieve and subsequent desorption of PX by a suitable desorbent. is fed to isomer unit while the bottom product desorbent is recycled back to Parex adsorbent chambers. . The overhead product of the xylene columns are feed to the parex unit.

12 AROMATCS COMPLEX BLOCK FLOW DIAGRAM . FIGURE 4. Purification Section: For propylene “to remove impurities like Sulphur. The main raw materials are propylene and hydrogen. UNIV ER SIT ST U DI ES k~ e k . O 2 ' purification section for hydrogen and nitrogen gas before supplying them to reaction area. (Refer Figure 4. CO 2 .13 Propylene Block Flow Diagram) The plant consists of: 1. k ‘ k f D r o’ Polypropylene It is designed to produce homo. CO2 from H2 and O2 from N2 are removed. CO. random and impact copolymer. Impurities like CO.YO FP E TR OLEUM & EN ER GY 74 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~.

co-catalyst Triethyl Aluminium. classified and conveyed to the blending silos from where they are bagged. 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.13 POLYPROPYLENE BLOCK FLOW DIAGRAM 2. The polymer is fed into the melt pump to develop necessary pressure for extrusion through the die plate. . PP requires the incorporation of a variety of additives to aid its processing and achieve the end use properties. Reaction Section: Here polymerisation reaction of purified propylene takes place in fluidised bed reactor in the presence of slurry catalyst (TiC14. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 75 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ FIGURE 4. The pellets are then dried. The unreacted monomers are purged with light recycles and sent for recovery to vent recovery system. 3. 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.YO FP E TR OLEUM & EN ER GY fo u n ~. UNIV ER SIT ST U DI ES k~ e k . supported on MgCl2 in slurry form in mineral oil). The conveying gas which is a mix of hydrocarbon and nitrogen is separated from the resin in disengaging section of product receiver.

2 -18.1 5.1 16.5% 7.0 .YO FP E TR OLEUM & EN ER GY 76 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~.3 2.0% 8. Vent Recovery Section: This system is designed to recover monomer.6 9. polymer and nitrogen. UNIV ER SIT ST U DI ES k~ e k .0% 1. which are passed through knockout pot and burnt at flare stack burning tip.0 35.5% 48.0% 7. k ‘ k f D r o’ 4.0% 8. All waste flammable gases are vented to the HP or LP flare header. Typical Refinery and Petrochemicals complex – Product Pattern Propylene LPG Gasoline Naphtha Reformate (Petrochemicals feed) HSD/SK/ATF Coke Sulphur Fuel and Loss 2.0% 8.1 63.6 6.0 % of Crude 100.5% 9.0 1.0 11.5% 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 2.8 100.6 93.3 7.9 11.7 3.

k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 77 Notes __________________ Typical Yield Pattern of FCC Feed: Low ‘S’ VGO CGO DWO VR Output Gas H2S LPG Gasoline TCO CLO Coke Loss Total 3.0 17.5 22. UNIV ER SIT ST U DI ES k~ e k .5 -24.5 53.4 8.5 12. Gasoline Cok.5 6. Gas Oil (CGO) CFO RFO RPC GAS Loss Total 2.9 0.9 0. Kero-I (LK) Cok.0 100% 53.0 100% .3 6.5 16.YO FP E TR OLEUM & EN ER GY fo u n ~.4 100.5 100.5 14.3 9.6 7.3 2. Kero-II (HK) Cok.5 4.7 20.7 12.0 __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Typical Yield Pattern of Delayed Coking Unit Input = RCO Output: LPG Cok.

0 27.0 0. k ‘ k f D r o’ Typical Yield Pattern of Hydro-treater Offsite Facilities and its Management In a Refinery. Naphtha Hy. UNIV ER SIT ST U DI ES k~ e k . Health and Environmental stipulations. and increased customer expectations. Traditionally. However. In .2 102. more attention used to be given to process units. Crude oil receipt Normally crude oil is received in land locked refineries through crude pipelines from the production source.YO FP E TR OLEUM & EN ER GY 78 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Input: VGO H2 Total Output H2S GAS LPG LT.0 Refining fo u n ~.8 10. with Refinery margin shrinking.5 4. water and sludge are removed by settling and processing through desalters.0 2. gas. Before bringing the crude from oil fields.0 102. Major offsite functions in a Refinery are: 1.0 11.0 43. 80% to 90% area is covered by offsite facilities.0 100. 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. stringent safety.2 1. Naphtha SKO/ATF HSD Bottoms Loss Total 1.3 3.

exchangers. Crude preparation for feeding to distillation units Though in the oil field. 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. The final removal of water associated with salts and sludge takes place in desalter in the crude distillation unit. India imports almost 70% of its crude oil requirement. Light and heavy . we get various products streams.YO FP E TR OLEUM & EN ER GY fo u n ~. Depending on the capacity of the refinery. Depending on the capacity of refinery. the unit performance will be affected adversely due to fouling of pipes. furnace tube corrosion. 3. Receiving rundown streams from various units From crude distillation unit and other secondary units. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 79 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ coastal refineries. major quantity of sludge. 2. types of crude oil processed. size of crude oil tanker varies from small to very large. Flexibility is also provided for alternative routing of streams incase there is change in demand in product pattern. corrosion of various equipments and upsets in plant operation. the tankages provided for receipt of rundown streams varies. This is removed by allowing the crude to settle in the tanks and draining from bottom to the effluent treatment system. crude tankage available. Unless crude preparation is done properly. Except LPG and Naptha. water and associated salts are removed before bringing crude to refineries. streams are provided. UNIV ER SIT ST U DI ES k~ e k . number of products marketed. complexity of the refinery. yet some quantities of sludge and water still are received in the refinery tanks. draft available at receiving oil jetty. all other products are blends of various streams from different units. crude oil storage is being increased from 15 days to 45 days of the refinery capacity. crude oil is received through tankers. Quantity of crude received in the refinery is monitored by measuring dip of receiving tank and flow metre readings installed on crude pipeline. Facilities for water draining and reprocessing of offspec. Due to strategic reasons. This will also lead to increased fuel consumption and loss in the units.

5. Once the product meets the quality specification as per BIS or customers requirement. Pump stations are provided for transfer of products. 6. SKO and HSD is being augmented. 4. the tankage for receiving rundown streams can be minimised. 2. The mixture is circulated in the tank to make it of uniform quality. samples of products are sent to the laboratory for testing. Thereafter. then the certificate of quality is issued by the laboratory. it is dispatched to market. Storage facility at various locations particularly for MS. UNIV ER SIT ST U DI ES k~ e k . Pipelines Rail Road Coastal . k ‘ k f D r o’ slop tanks are also provided to receive offspec. 4. emergencies and upsets in the plants. Petroleum products are evacuated from the refinery by following modes: 1. By on-line blending and utilising advanced process control. After settling in tank for draining any water and testing the sample in the laboratory to ensure that it meets quality specifications. Co-ordination with laboratory After blending of various streams and circulation in tank. product is despatched to market. The same are reprocessed in the units in a regulated manner during normal run. Streams during start up. 3. Despatch of finished products: The certified products are stored in finished product tanks before dispatch. shutdown. It is proposed to provide 35 days storage capacity based on 75% utilisation factor.YO FP E TR OLEUM & EN ER GY 80 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. 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.

This is so even in respect of sensitive quality control products such as ATF. Steam coils are provided to heat the product before unloading in case of tank trucks for Bitumen. 3. During floods and natural calamities. UNIV ER SIT ST U DI ES k~ e k . Coastal: Tankers of various capacities are used for dispatch of product from coastal refineries. Naptha etc. are provided with steam coils for heating the product before unloading at the destination. etc. 3. 4. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 81 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 1. which are used to supply product to nearby locations by road. The wagons for transporting heavy products such as FO. Pipeline systems have following in-built advantages over other means of transportation available for petroleum products: 1. The large capacity tankers are the cheapest mode of transport. . 2. With advanced control system and proper operation. Minimum transit loss Planned product movement Flexibility in operation independent of other transportation systems. Pipelines: Out of the above dispatch modes of petroleum products. it is possible that the products reach their destination in a "refinery-good" condition. It is the second cheapest mode of transport next to large capacity tankers. LSHS etc. barges are used. FO.YO FP E TR OLEUM & EN ER GY fo u n ~. 4. it is not affected.70%). Rail: Tank wagons are the second bulk carrier specially constructed for this purpose and can take products to far off places. For short distance and small quantity of coastal product movement. LSHS. 2. The products movement of the refinery gets adversely affected due to failure/breakdown of transport system. 5. maximum dispatch takes place through pipelines (60 . Road: The third mode of transportation is tank lorries or tank trucks.

Blow-down 2. Firewater tanks are provided in offsites area to have an immediate supply source for fighting any major fire. Fresh water supply system: This provides utility water supply. UNIV ER SIT ST U DI ES k~ e k . 1. long distance throw nozzles are provided. the fire water supply pipeline network is laid in the form of ring. . It is having chemical treatment system to avoid scaling and corrosion in related pipelines and equipment. Flare management To take care of emergency release of gaseous hydrocarbon. Refinery water supply The following important water supply systems exist in the refinery. Cooling Towers are also provided in the system where water is cooled by evaporation before recirculation.YO FP E TR OLEUM & EN ER GY 82 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. However. refinery builds up stock in its tanks during such emergencies. make up to the circulating water system. High pressure flare Low pressure flare H2S flare 8. Fire water supply system: Throughout the process units and offsites areas. flare headers are provided for collecting off gases from process units and offsite areas. k ‘ k f D r o’ Flexibility to a small extent exists to switch over from one mode to other mode. After seperating the entrained liquid. to an extent beyond which through-put of process units is cut thus affecting the production. this system is provided. In critical areas. the gas is burnt at high point to avoid hazard and pollution. make-up to fire water supply system and make up to drinking water treatment system. 7. c. 3. Three categories of flare systems are provided: a. b. Recirculating hot and cold water system: For cooling of hot products.

atomisation of fuel oil before burning in furnace. driving steam turbines and power generation. Fuel oil and fuel gas system: For providing fuel supply to process units furnaces. and boilers in captive power plant. 4. For fuel oil. varying range of fuels from LDO to Asphalts are used. blending facilities and pumping system are provided for supply of fuel oil to furnaces and boilers. alternative source of power supply from outside is also lined up. blanketing tanks from atmospheric oxygen in the case of lubes and other products which form explosive mixture when coming in contact with air. ethane and purged gases from hydrogen units are used. load shedding scheme exists. stripping in columns. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 83 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ in the form of leakage and manual draining is provided to avoid build up of salt concentration. Steam is used for heating. mostly methane. Nitrogen and air supply systems: Hydrogen is generated in Hydrogen plant or catalytic reformer unit. 6. this system is provided. Nitrogen is used for catalyst regeneration. Hydrogen. . Storage tanks. To ensure supply of steam and power to critical plants/equipment in emergencies. compressors and other equipment. fire-fighting.YO FP E TR OLEUM & EN ER GY fo u n ~. Make up water is taken from fresh water system. and maintaining inert atmosphere in the process unit equipment. UNIV ER SIT ST U DI ES k~ e k . Nitrogen is 5. Captive power plant: To provide uninterrupted power and steam supply for running the pumps. captive power plant is provided in the refinery. Fresh water is used in DM plant before utilising in boilers for steam generation. The supply system is maintained at constant pressure. It is utilised in hydro-treatment units. once through cooling water system is used and sea water is utilised for the cooling of products. It is a very hazardous gas to handle as the flame can not be seen. In fuel gas. For meeting any emergency. In some of the coastal refineries. Superheated and saturated steam at various pressures are also supplied for process units and offsites area from this system.

Explain briefly in your own works. MS. Critical parameters for optimal operation Which components of various process streams in different process plants (% wise) are utilized for the prouction of LPG.YO FP E TR OLEUM & EN ER GY 84 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. UNIV ER SIT ST U DI ES k~ e k . What are the important offsite facilities in a refinery? How do these facilities affect the proper functioning of the refinery? Explain each facility wise. Furnace Oil. specially their impact whenever there is a failure. Yield pattern. 2. . i. Air is used for utility purposes. HSD. It is taken from atmosphere and compressed before using. ii. k ‘ k f D r o’ produced in generators installed in the refinery or is purchased from outside. ATF. Review Questions for all Process Plants 1. Review Questions for Offsites 1. The function of each process plant (11 plants) Feed composition iii. iv. PC Naphtha and Fertilizer Naphtha. 2. catalyst regeneration. decoking of furnace tubes and instrumentation etc.

Worldwide availability of sweet and light crude is decreasing. cost optimisation. This will call for superior metallurgy in the plants and pre and post treatment of oil products leading to higher capital and operating costs. diversified and fully automated. stringent specifications of various petroleum products. energy conservation and product quality requirement. integrated. To improve profitability and meet statutory requirements. future refineries will have to be ready to process heavy and sour crudes. it is envisaged that future refineries will have to face many challenges – they will be highly complex. 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 .85 Unit 5 Future Refining Scenario Activity 5 A Describe the scenario of availability of sweet & sour crudes in the next two decades. Strategies for overcoming various challenges. __________________ __________________ __________________ __________________ __________________ Objectives After studying the unit. therefore. dwindling refinery margins etc. y Keeping in view environmental considerations. the learner will be able to: y __________________ __________________ __________________ __________________ __________________ Understand Future Refining Scenario in terms of availability of crudes.

k ‘ k f D r o’ Besides conventional process units. Overall economics considerably enhanced Already under way in the USA. – – – – u 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.YO FP E TR OLEUM & EN ER GY 86 Activity 5 B What do you understand from Integration of Refinery with petrochemicals/ fertilizers. 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 u Synergy in power with fertilizer co-production – Efficient utilisation of low value refinery residue for production of power. future refineries will also have: u Quality related units: – – – – Facilities for benzene management DHDS (Diesel Hydro-desulphurisation) Fuel oil HDS (Hydro-desulphurisation) Hydrotreatment. power plants? How does it improve the Bottom Lines? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u Refining fo u n ~. . Power plant supplies power and steam required in refinery. the Netherlands and Italy. Co-production of value added fertilizer. No additional raw material handling and common fire fighting facilities. UNIV ER SIT ST U DI ES k~ e k .

2. 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. UNIV ER SIT ST U DI ES k~ e k . What do you understand from flexibility of Refinery operations in the competitive environment? . Plant/ equipment should require less space. HSD and FO. k ‘ kf D r o’ UNIT 5 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.YO FP E TR OLEUM & EN ER GY fo u n ~. To increase/improve profitability. u Review Questions 1. Reduction of FO production and increase in distillate production to 85%+.

.

Crude oil is becoming heavier and higher in sulphur and metal content. 5. 6. Improved and integrated refining u Production of better quality products . Advances in refining technology can be broadly divided into the following categories. Reduced growth in fuel oil demand. Declining refining margins Improved engine design/automobiles need better quality fuel and lubricating oils. the learner will be able to: 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. Stringent environmental regulation for cleaner products/processes and demand for quality products. 3. Rapid growth in light/middle distillates. 2. 4. 1.89 Unit 6 Advances in Petroleum Refining Objectives After studying the unit.

Visbreaker–Soaker Technology.95%. u u u u u u .YO FP E TR OLEUM & EN ER GY 90 Activity 6 A What are known/proven improvements as on date. Value addition u u u u Petrochemicals production Better quality and increased lube oil production Power generation from heavier petroleum products Speciality chemicals production. Delayed coking – Needle coke manufacturing. UNIV ER SIT ST U DI ES k~ e k . in Refining Process Technologies? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~. Resid Fluid Catalytic cracking (RFCC). Isomerisation Catalytic Reforming Alkylation Etherification Power generation by petroleum residue and coke by using Gasification Combined Cycle (GCC) technology. Hydro cracking u u – u Super Oil Cracking (SOC) of heavy distillates to get 90% conversion to distillates. k ‘ k f D r o’ Residuation in residues/heavier ends Management of power and utilities. Improvements are taking place in many areas. Hydro processing – Hydro treatment of various streams including residues. 2. Mobil distillate Dewaxing (MDDW) to upgrade heavy fuel oil to high quality distillate and gas yield of 93. Some of them are listed below: u u Distillation Fluid Catalytic Cracking (FCC).

FCC.. UNIV ER SIT ST U DI ES k~ e k . etc) are being developed and increasingly used for optimization. Accurate process models for different processes (e. Hydrocracking. Decision Making and Business Profitability. Cat Reforming. trouble shooting. design and optimal control and technology development. u u More and more use of information technology.g. k ‘ kf D r o’ UNIT 6 Advances in Petroleum Refining 91 Notes __________________ __________________ __________________ In this process alongwith power. Modelling simulation are being used for: – Information Gathering.YO FP E TR OLEUM & EN ER GY fo u n ~. Typical application of information technology in a refinery Refinery planning Primary logistic management __________________ __________________ __________________ __________________ __________________ __________________ __________________ – – Guide logistic planning Refinery scheduling Primary logistic management Secondary logistic management u 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 . steam and H2 can be produced which are required in the refinery.

. k ‘ k f D r o’ – – – – Integration with speciality chemicals for value addition Anode grade coke. 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.YO FP E TR OLEUM & EN ER GY 92 Activity 6 B What are various routes for value addition in Petroleum Refining? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~. Explain the following processes and relate the same to the relevant products: 2. 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. UNIV ER SIT ST U DI ES k~ e k .

y During the processing of crude petroleum products. Real losses i.3% of crude processed.93 Unit 7 Hydrocarbon Loss Minimisation Objectives After studying the unit. Apparent losses i. hydrocarbon losses take place on various accounts. 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. Measuring devices in storage tanks and custody transfers for proper accounting Automating road/rail dispatch facilities. Following areas need to be monitored/looked into: A. the learner will be able to: y Activity 7 A i. Auditing of the systems and operations will lead to continuous improvement. . ii. Efforts are to be made to bring the loss to a level of less than 0. handling and dispatches from refinery. Conversion of fixed roof tanks to floating roof tanks for low flash products including diesel and use of proper type of roof seals. ii. B. 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.

Review Questions 1. v.YO FP E TR OLEUM & EN ER GY 94 Activity 7 B i. What is BS&W? How is it related with losses in Refining operations? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ vii. ii. viii. What will be the order of magnitude of savings in a six million tones per year capacity refinery. UNIV ER SIT ST U DI ES k~ e k . Close monitoring of BSW in crude processed to avoid plant upsets and increased losses. Routing of off gases from vacuum column to furnaces. 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. if the losses are reduced by 0. cost of crude being $ 25/barrel? .2%. Routing of all sour gases to sulphur recovery unit ix. k ‘ k f D r o’ iv. What are international standards for Refinery Losses? What methods have been adopted in Indian refineries to bring down the losses to International standard? Refining fo u n ~.

. exchangers etc. 4. Optimisation of heat exchangers train – use of pinch technology. 3. Get a generic idea of various strategies adopted for energy optimisation. Energy efficient processes/equipment such as furnaces. 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. 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. Direct hot feed from one unit to another unit without passing through intermediate tanks. __________________ __________________ __________________ __________________ y Conservation of oil and gas has assumed greater importance in view of the emphasis on demand side management of energy. For old refineries For grass-root refineries __________________ __________________ __________________ Objectives After studying the unit. Proper insulation of hot products and steam lines. the learner will be able to: y __________________ __________________ __________________ Appreciate the role of/ urgency for energy conservation and optimisation of energy consumption in refining industry. Provision of air preheter in furnace. pumps. What strategies have been adopted to optimize energy consumption. 5. Average fuel loss in the refineries in India during 2000–01 was 7-35% which is higher compared to global levels (of similar configuration). Some of the areas given below need to be looked into: 1. 2.95 Unit 8 Energy Conservation Activity 8 A i.

Use of microprocessor based control system alongwith DDCS (Digital Distributed Control System) and advanced process control. UNIV ER SIT ST U DI ES k~ e k . Steam generation from hot streams. 10. Minimise leakage through glands/seals of pumps. 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 . ii. 11.YO FP E TR OLEUM & EN ER GY 96 Activity 8 B How do DDCS and advanced process controls help conserve energy? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. 14. 12. Benchmarking. 9. 17. gap analysis and setting targets. Reflux ratio in distillation process Solvent feed ratio in extraction process 7. Energy audit for continuous improvement of energy performance. k ‘ k f D r o’ 6. Optimisation of i. 15. Soot blowers for convection section of furnaces to improve heat recovery in furnaces. 16. Low level heat recovery. Use of soaker technology for visbreaking. Heat recovery from process streams for heating colder process streams/ boiler feed water. compressors and turbines. Power generation in new refinery will be through combined cycle operation integrated with gasification. 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. 8. Pressure reduction of steam through a control valve will be minimised. 13. Review Questions 1.

Enumerate some important measures of this nature which the refineries/ chemical industries take. . k ‘ kf D r o’ UNIT 8 Energy Conservation 97 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 2. Explain the role of house-keeping measures for bringing down energy consumption resulting in energy conservation. UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY fo u n ~.

.

u u 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. Acquaint with the netback estimation method used for selection of crude for any refinery. u .99 Unit 9 Gross Refining Margin Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Objectives After studying the unit. 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. y 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. the learner will be able to: y __________________ __________________ __________________ Provide an appreciation for various elements affecting GRM which in essence is the profitability of a refinery.

The purpose of chemicals is mainly to improve the quality of products so as to meet the desired specifications. UNIV ER SIT ST U DI ES k~ e k . u u u u Net Margin The net margin is the difference between gross margin and operating cost. overtime. electrical and civil jobs carried out for the maintenance of plant and machinery. various chemicals and catalysts are used. equipment and other fixed assets used in the refining process towards general wear and tear. FO or HSD) may be used as fuel. insurance and other related overhead expenditure. . Depreciation: Operating cost includes depreciation on plant and machinery. This is virtually the net profit to the refinery. k ‘ k f D r o’ Operating Cost of the Refinery The operating cost of the refinery includes various elements. Fuel may be purchased from outside suppliers (like natural gas). Chemicals and catalysts: During the refining process of petroleum products. bonus etc. power from electricity board or internal refined products (like LSHS. Catalysts are used in various reformers and other secondary processing facilities. Repair and maintenance cost: It is incurred in various mechanical. Printing. Establishment cost: This is related to the manpower deployed and includes the salary and wages paid to staff. 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.YO FP E TR OLEUM & EN ER GY 100 Activity 9 A What are various factors which affect GRM? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u Refining fo u n ~. General administrative cost: This cost includes expenses such as traveling. furniture. Net Margin = Gross margin – Operating cost.

YO FP E TR OLEUM & EN ER GY fo u n ~. considered.98 829 112 US $ 2. gross margin should be increased and operating cost reduced by increased efficiency in refining operations. customs duty) Gross margin Th’put-MMT GROSS margin Rs/MT Margin – Rs/BBL Margin – US $/BBL Less: Operating cost Rs/MT Net margin Rs/MT 4050 3720 330 3. The crude which is having higher net back to the refinery is normally procured for it. Attachment 1 shows a sample calculation for gross and net margin for a refinery.30 500 329 __________________ __________________ __________________ __________________ __________________ Net back estimation In the net back system. . wharfage.Dos gives the highest netback of Rs 1054/MT vs TAPIS with lowest netback of Rs 41/MT. k ‘ kf D r o’ 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. ATTACHMENT 1: GROSS MARGIN Realisation of transfer of products Cost of crude (inclusive of freight. F. 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. All these 7 crudes are sweet (low sulphur) crudes. net back estimation is used to evaluate the suitable crude for the refinery. Attachment 2 gives a sample netback calculation to select the best crude out any of seven crudes. UNIV ER SIT ST U DI ES k~ e k .

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. RS/MT NET BACK. k ‘ k f D r o’ 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. WAX F&L TOTAL DIST% CRUDE VALUE. RS/MT 421 1054 740 Refining fo u n ~.0 11361 12415 F.DOS 11361 5 0 12 11 58 BON.SHS RPC SULPHUR SL. What are the most crucial factors and which are indeed controllable. affecting GRM? What are various options for reducing Refining Costs in competitive world? 2.0 11994 12780 100 476 606 41 100 686 Review Questions 1. LT.0 11987 12408 0 1 1 0 12 100 86. . 11714 5 5 12 11 54 0 0 1 1 0 11 100 87. UNIV ER SIT ST U DI ES k~ e k .0 12859 12900 MIRI 11994 4 3 12 11 59 0 0 1 1 0 9 100 89.RS/MT PROD VALUE.YO FP E TR OLEUM & EN ER GY 102 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ CRUDE PRICE LPG NAP MS SKO HSD OF L.0 11714 12454 LABUAN 11994 4 2 12 11 58 0 0 2 1 0 10 100 87. RS/MT LESS IPN COST.

although the discharge of duty obligation is allowed to be deferred to the time of removal from the refinery/onward removal to warehouse. This is known as ex-bonding of crude. 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. Hence. the learner will be able to: y __________________ __________________ __________________ Provide a general idea of accounting methods for crude and petroleum products and its significance. etc. The duty liability on petroleum products arises when the process of manufacture is completed. 2. Quantitative accountal and correct payment of duties on finished petroleum products is the focal area of the oil accounting section.103 Unit 10 Oil Accounting Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Objectives After studying the unit. tank accountal of receipts and removals is to be . intermediates and finished petroleum products is done by operations personnel. Accounting of Manufactured Petroleum products and Those Received for Blending. 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. While the physical handling of crude oil. 1. The following are its key functions.

intermediaries and finished products. 3. Whether the goods removed are duty-paid or under bond. 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. the excise duty liability is determined at the time of removal from the refinery warehouse. This is done through the PLA (Personal Ledger Account). Despatch of Finished Petroleum Products Assessment to central excise duties is invoice-based. UNIV ER SIT ST U DI ES k~ e k . 5. 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. . Material Balancing. the invoice/application for duty-free removal is the cornerstone for correct excise assessment of removals. production. k ‘ k f D r o’ maintained by taking dip measurements and quality testing reports. With the invoice being the document in support of cenvat credit claim that may accrue to a customer. The DSA (Daily Stock Account) is to be maintained for opening balances. For duty-paid goods. 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. 4.YO FP E TR OLEUM & EN ER GY 104 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. dispatch and closing balances of all certified finished products of the refinery warehouse. The production statistics are correlated to the standard product pattern and the actual distillate yield for any particular period of time. 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. 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.

Records.YO FP E TR OLEUM & EN ER GY fo u n ~. Review Questions 1. documents. show cause notices. if any. are normally issued through the oil accounts section. UNIV ER SIT ST U DI ES k~ e k . Method and system of accounting crude and petroleum products in a refinery? How is the excise/customs procedure followed by oil accounting section? __________________ __________________ __________________ 2. returns. etc prepared by the oil accounting section are open to inspection by the range office. Letters. k ‘ kf D r o’ UNIT 10 Oil Accounting 105 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Statutory returns as per excise procedure are filed periodically by the oil accounts section with the range office. .

.

Provide an appreciation for the manner in which custom and excise duties affect profitability. the learner will be able to: 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. Indigenous crude oil is sourced from Gujarat and Assam oilfields and from offshore oilfields of India. Imported crude of different varieties as per . Products belonging to oil marketing companies are also dealt through intercompany transactions. the goods are removed under bond to special industrial undertakings like SEBs. or barges (through waterways). These products are either removed on payment of excise duty. The products are removed through pipelines. tank wagon (railways). In certain cases. In the latter case. whereas imported crude oil attracts 10% customs duty. or under bond without payment of excise duty.107 Unit 11 Excise and Custom – Petroleum Products Objectives After studying the unit. FCI. tank lorries (oil tankers). the duty obligation on the manufactured goods is discharged from the warehouse when it is finally cleared for sale. y The removal of petroleum products manufactured in refineries is either to direct customers or through marketing network (warehouses/ depots/terminals. etc who are licensed to deal with manufactured excisable goods without payment of duty. indigenous and imported. etc) for sale therefrom. The primary raw material for finished petroleum products is crude oil. Indigenous crude oil attracts Nil rate of excise duty.

additional duty of excise (Re. UNIV ER SIT ST U DI ES k~ e k . 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. In the event of excess refining capacity (with glut in the market). 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. While crude oil only attracts the basic customs duty. there is a levy. . without physical supervision of the department. 1 per litre on Motor Spirit commonly known as petrol and on high speed diesel oil commonly known as diesel).YO FP E TR OLEUM & EN ER GY 108 Activity 11 B When is it desirable to export/ import any product based on custom/excise duties prevailing? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. and recently introduced special additional duty of excise on MS. The excise assessee is required to take necessary actions to be within the legal and procedural requirement of excise and customs law. Review Questions 1. the refineries use the accumulated cenvat credit in lieu of cash payment. Petroleum products are handled under the SelfAssessment Scheme of Self Removal Procedure (SRP) of central excise. During discharge of excise duty obligations arising on the removal of finished petroleum products from the refineries on duty-paid basis. At the refinery/warehouse. 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. on selective basis by notification. k ‘ k f D r o’ processing requirement are brought through different ports of the country. 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. of special excise duty. Other than basic excise duty.

Kennetha A. Moketta The Chemistry and Technology of Petroleum (Mercel Dekkar). Crook "Managing Modern Offsite Operation" by Patrick B. G. G. Malaysia Hydrocarbon Processing New Challenges. Reading materials of programme on Refining & Petrochemicals of various Petroleum Companies. 5. Dr. 9. Eric Robinson and Dr. Nelson.K. Dehradun. IIT. Dauglas AMOS Course contents on Refinery Loss Control by Dr. Sarkar. Truesdale and J. Sarkar. 20-21st May. Khanna Publishers. Crook Refinery Loss Controls . 7. 8. __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 2. Petroleum Monthly Publication. March. 5. W. McGraw Hill Modern Petroleum Refining Processes. 3.N.N.D. John J. 4. W. 1996.D.G. Kobe. k ‘ kf D r o’ UNIT 11 Excise and Custom – Petroleum Products 109 Notes __________________ Bibliography 1. 11. Kharagpur Advances in Petroleum Chemistry and Refining . 7. Dr. B. John Miles on 20-21 May 1996 at Singapore. 2. 8. Speight J. Indian Institute of Petroleum. Meyers A layman's Introduction to Oil Refining . References 1.L. Dr. Advanced Petroleum Refining. 4. Mc.Graw Hill. 1996 KBC Petrofine Users Manual A Layman's Introduction to Oil Refining .G. 10. Robert A. John Miles at Singapore. 96018. Bhaskar Rao.L. Nelson. 6. UNIV ER SIT ST U DI ES k~ e k . R&D Report No. Petroleum Refining Engineering. Handbook of Petroleum Refining Process. . Khanna Publishers. Eric Robinson and Dr. 3.Course Manual Presented by Dr.IOC. Delhi Reading Material of Programme on Petroleum Refining and Petrochemical Technology.YO FP E TR OLEUM & EN ER GY fo u n ~.G. 6. Technologies Options for Refineries . Advanced Petroleum Refining. Delhi Petroleum Refining Engineering.

Sign up to vote on this title
UsefulNot useful