Petroleum Refining Technology - Dr. Ram Prasad 1st Edition.pdf

Uploaded by:

Ebooks Chemical Engineering https://www.facebook.com/pages/Ebooks-Chemical-Engineering/238197077030

For More Books, softwares & tutorials Related to Chemical Engineering Join Us @facebook: https://www.facebook.com/pages/Ebooks-ChemicalEngineering/238197077030 @facebook: https://www.facebook.com/AllAboutChemcalEngineering @facebook: https://www.facebook.com/groups/10436265147/

ADMIN: I.W

>

PETROLEUM REFINING TECHNOLOGY

Dr.RAM PRASAD B.E.(HO~S.),M.Tech., Ph.D. ASSISTANT PROFESSOR DEPARTMENT OF CHEMICAL ENGINEERING HARCOURT BUTLER TECHNOLOGICALINSTITUTE,

KHANNA PUBLISHERS Operational Office: 4575115, Onkar House, Room No. 3-4, Ground Floor, Darya Ganj, New pelhi-110002 Phone: 23243042 Fax: 23243043 Despatch Office: 11, Community Centre, Ashok Vihar, Phase 2 Delhi-110052. Phone : 27224179 Regd. Office: 2-B, Nath Market, Nai Sarak, Delhi-110006. Ph. 23912380

Published by : Romesh Chander Khanna for KHANNA PUBLISHERS 2-B, Nath Market, Nai Sarak Delhi- 110 006 (India)

-,*

It givesme a great pleasure in presenting the book on "Petroleum RefiningTechnology' .The relvant topics for working Chemical/Petroleurn Engineers in Petroleum-Refineries have.",, been covered. The first chapter gives an account of theories of oil and gas formahon, methods f o p , exploration and drilling for oil and gas. It highlights the development of petroleum refininB industry in India. ,. <

Q All Riehfq,Regerv,ed

,

,

This book orpart thereof cannot be tmnslated or reprodued i n any form (exceptfor review or criticism) without the written permission of the Author and the Publishers.

The knowledgeof chemisty and compositionof crude oil isessentialin the selectionof the refining processes. The characteristics, constituents and classification of crude coils have been. discussed.in chapter 2. Indian crudes such as Bombay l-hgh,Assam are waxy in nature. These require sped; method for transportation. The problems related to the handling of waxy crude oils and their -feasible solutions have heen discussed in chapter 3. Quality control of petroleum-productsisa necessity if the products are to give satisfactory wrformance to the customers. Bureau of ,lndian~Standard; New Delhi sfandaLdizes ~rocedure ind issues specifcationsfor eachpetroleumproducts.~efktion,methodandsignifi-eof the various laboratory tests have been given in chapter 4.

First Edition Fifth Reprint :2008

Price :Rs. 185.00

Computer Typeset and Figures designed by : Steps Computers, D-2/77, Dayd Pur, Delhi 110 094 Ph. 218-1367

Printed at.. Print India. Delhi-95

Chapter 5discusses manufacture,properties and uses of petroleum products. Thischapter covers LPG, naphtha, gasoline, kerosine, ATF, diesel fuel, fuel oil, hydrocarbon solvenk " ' lubricating oils, petroleum waxes, bitumen and petroleum coke. Petroleum refining processes have been discussed in six chapter (611). Crude ou distillation is the first unit in the refinery and carried out in two stages-atmosphericand vacuum, Before discucssing these processes the removal of impurities by electrical desalting process ha, been discussed.The influenceof the process variables on the opera tion of a fractionatingcolumn ?.* and the scope for improvement have been discussed in Chapter 6. Crude oil distilltion produces reside which is to be upgraded. Thennal conversio~~.. processes for this purpose include visbreaking and coking. These processes have been discussea in chapter 7. lh Catalytic conversion processes use catalyst and either change carbon number or carbon/ hydrogen ratio. The most important processes include fluid catalyticcracking, catalytic reforming,hydrocracking,catalyticalkylation, isomerizsltion and polymeriza tion Catalytic isom& tion neither changes carbon number nor carbon/hydrogen ratio. These processes have been dis-,. cussed in chapter 8.

.

Finishing processes are necessary to make the petroleum products suitable for use with respect to performance,corrosivity, suitabilityon storage,odour etc. Various finishing processes such as hydrogen sulphideremoval processes, sulphur recovery processes, sweeteningprocess-,,. es, solvent extraction processes and hydrotreating processes have been discussed in chapter 9.

(iv) L@~&&@p@b*ould possess and maintain proper viscosity, flow as liquid at thehandling and operatingtemperature and have good thermal and oxidation stability. Lubricating oils of various grades are manufactured by mixing of the selected lubricating oils base stock and additives. A modem lube oil complex consists of vacuum distillationunit, solvent deasphalting unit, solvent extraction unit, solvent dewaxing unit and hydrofinishing unit. These processes have been discussed in chapter 10. The details on the manufacture of petroleum waxes have also been presented ir\ this chapter.

Chapter 11discusses the manufatture of bitumen from crude oil.

k

Generationof process engineershave accepted corrosion as a fact of life, an incurablevirus whose progress may be slowedbut never stopped. Corrosioh can reduce the lifeof refinery units. Chpater 12 disucsses typk and forms of corrosion and their control in crude oil distillation, thermal cr?cking, fluid catalyticcracking,amine gas processing,and steamand condensatelines. Air, water and soil are vital of life on this planet. These resources are to be protected and used wisely. Chapter 13 discusses air pollutions, water pollution and sludge treatment and disposal.

2'

1.1 INTRODUCTION 1.2 FORMATION OF OIL AND GAS 1.3 OIL AND GAS EXPLORATION 1.4 DRILLING FOR OIL AND GAS 1.5 PRODUCTION OF CRUDE OIL AND NATURAL GAS 1.6 PETROLEUM REFINING, OPERATION AND OPTIMIZATION 1.6.1 Selection of Processes for Optimization 1.6.2 Optimization in a Running Refinery 1.6.3- Refining Capacity in India

-

Chapter 14, highlights, designs and operation of pebbleurn processing equipments. It is hoped that this book in its present form will be useful for the students of chemical engineering.

1 PETROLEUMEXPLORATION,PRODUCTION AND REF~NING

2 CRUDE OILS CHEMISTRY AND COMPOSITION i

I will be highly grateful, if short comings of this edition inform of contents, errors are highlighted to me. -Ram Prasad K ~ ~ P W

f

I

2.1 INTRODUCTION 2.2 CHARACTERISTICSOF CRUDE OILS 2.3 CONSTlTUENTSOF CRUDE OILS 2.3.1 Hydmarbons 2.3.2 Non-Hydrocarbons 2.4 CLASSIFICATION OF CRUDE OILS 2.4.1 Characterization Factor 2.4.2 Correlation Index 2.4.3 Method of Structural Group Analysis

3 TRANSPORTATION OF WAXY CRUDE OILS 3.1 INTRODUCTION 3.2 PIPELINE TRANSPORTATION 3.3 WAXY CRUDE OILS 3.3.1 Definitions of Rheological Parameters 3.3.2 RheologicalClassification of Fluids 3.4 FLOW PROPERTIES OF WAXY CRUDE OILS 3.5 PUMPABILITY CHARACTERIS~CSOF WAXY CRUDE OILS 3.5.1 Temperature 3.5.2 Yield Stress-Model Pipeline Test 3.5.3 Flow at Restart 3.5.4 Effective Pipelie Viscosity 3.6 METHODS FOR PIPELINE TRANSPORTATION OF WAXY CRUDE OILS 3.6.1 Use of Pow-Point Depressants/Flow Improvers 3.6.2 Mechanism of Flow Improvement 3.6.3 Point of Additive kijection 3.6.4 Pour point Reduction by Additives 3.6.5 Effect of Flow Improvers on Yield Stress and Viscosity 3.6.6 lncorporation of Low Pour Point Crudes in Waxy Crudes 3.6.7 Crude Oil Conditioning -

-

-

1-14 1 2 2 3 5 8 9

10 11

15-28 15 15 16 17 22

25 26 28 28

29-44

(vii)

4 --Q~~&JTY~ONTR OF OPETROLEUM L PRODUCTS

45-64

4.1 INTRODUCTION 4.2 CLASSIFICATION OF LABORATORY TESTS 4.3 DISTILLATION 4.4 VAPOUR PRESSURE 4.5 FLASH POINT AND FIRE POINT 4.6 OCTANE NUMBER 4.7 PERFORMANCENUMBER 4.8 CETANE NUMBER 4.9 ANILINE POINT 4.10 DIESEL INDEX 4.11 CALCULATED CETANE INDEX 4.12 CALORIFIC VALUE 4.13 SMOKE POINT 4.14 CHAR VALUE 4.15 VISCOSITY 4.16 VISCOSITY INDEX 4.17 PENETRATION TESTS 4.18 FREEZING POINT 4.19 CLOUD POINT AND PQUR POINT 4.20 DROP POINT OF GREASE 4.21 MELTING AND SEITING POINTOF WAX 4.22 SOFENING POINT OF BITUMEN 4.23 INDUCTION PERIOD OF GASOLINE 4.24 THERMAL STABILITY OF JET FUELS 4.25 GUM CONTENT 4.26 TOTAL SULPHUR 4.27 ACIDITY AND ALKALINITY 4.28 COPPER-STRIPCORROSION TEST 4.29 SILVER-STRIPCORROSION TEST FOR AVIATION TURBINE FUELS 4.30 ASH 4.31 CARBON RESIDUE 4.31.1 Conradson Method 4.31.2 Ramsbottom Method 4.32 COLOUR 4.33 DENSITY AND SPECIFIC GRAVITY --. 4.34 GAS CHROMATOGRAPHY OF PETROLEUM GASES AND LIQUIDS 4.35 REFRACTIVE INDEX OF HYDROCARBON LIOUIDS --4.36 LEAD IN GASOLINE 4.37 WATER SEPAROMETER INDEX (MODIFIED) (WSIM) 4.38 DUCTILITY -

S PETROLEUM PRODUCTS 5.1 LIQUEFIED PEIROLUEM GASES 5.1.1 Composition of LPG 5.1.2 Properties of LPG 5.1.3 Production of L K 5.1.4 Uses of LPG NAPHTHAS 5.2.1 Methods of Manufacture of Naphthas 5.2.2 Composition of Naphthas

5.2.3 Usesof Naphthas 5.3 MOTOR SPIRIT 5.3.1 Spark-Ignition Engine 5.3.2 Composition of Gasolines 5.3.3 Properties of Gasolines 5.3.4 Types of Additives Used in Gasolines 5.3.5 New Gasoline Blending Components 5.3.6 Alternative Gasoline Fuels 5.4 KEROSINE 5.4.1 Manufacture of Kerosines 5.4.2 Composition of Kerosines 5.4.3 Properties of Kerosines 5.4.4 Uses of Kerosines 5.5 AVIATION TURBINE FUELS 5.5.1 Composition of ATFs 5.5.2 Properties of ATFs 5.5.3 ATF Additives 5.5.4 Storage and Handling Problems

/

Y'

5.6.1 Compression-Ignition FUELS (Diesel) Engine 5.6.2 Composition of Diesel Fuels 5.6.3 Properties.of Diesel Fuels 5.6.4 Additives for Diesel Fuels 5.6.5 Alternative Diesel Fuels T,~NELOILS 5.7.1 Nature and Composition of Fuel Oils 5.7.2 Properties of Fuel Oils 5.7.3 Combustion of Fuel Oils 5.7.4 BumersCharacteristics and Applications 5.7.5 Storage, Handling and Preparationof Fuel Oils 5.8 PETROLBUM HYDROCARBON SOLVENTS 5.8.1 C~ppositionof Hydrocarbon Solvents 5.6.2 Classificationof Hydrocarbon Solvents 5.8.3 Manufacture of Hydrocarbon Solvents 5.8.4 Properties of Hydrocarbon Solvents 5.8.5 Uses of Hydrocarbon Solvents LUBRICATING OILS ,, 5.9.1 Mineral Oil-Based Lubricants vt!'d 5.9.2 Synthetic Lubricants 5.9.3 Basic Functions of Lubricants 5.9.4 Automotive Engine Oils 5.9.5 Indushial Lubricating Oils 5.9.6 Electrical Insulating Oils 5.9.7 Jute Batching Oils 5.9.8 White Oils 5.9.9 Steam Turbine Oils 5.9.10 Metal Working Oils 5.9.11 Miscellaneous Oils 5.10 PETROLEUM WAXES 5.10.1 Types of Petroleum Waxes 5.10.2 Properties of Petroleum Waxes 5.10.3 Manufacture of Petroleum Waxes 5.10.4 Uses of Petroleum Waxes 5.10.5 Quality Requ~rements-Industry-wise/End-use wlsr

@

d3w

-

65-176 LC

A 1 BITUMENS 5.11.1 Asphalts 5.11.2 Petroleum Bitumens 5.113 <y Specificstiow of Bitumens 5.1 1.4 Physical and Chemical Characteristicsof Bitumens 5.11.5 Uses of Bitumens 5.12 PETROLEUM COKE 5.12.1 Types of Petroleum Cokes 5.12.2 Properties of Petroleum Cokes 5.12.3 Storage and Transportation of Petroleum Cokes 5.12.4 Uses of Petroleum Cokes

6 CRUDE OIL DISTILLATION 6.1 INTRODUCTION 6.2 IMPURITIES IN CRUDE OILS 6 3 NEED FOR DESALTING OF CRUDE OILS 6.4 ELECTRICAL DESALTING OF CRUDE OILS 6.4.1 Process Description 6.4.2 P r o m Variables 6.4.3 Typical Operating Conditions 6 5 CRUDE OIL DrsTnLATION 6 6 ATMOSPHERIC DISTILLATION OF CRUDE OIL 6.6.1 Process Description 6.6.2 Prefractionation 6.63 Typical Yield Pattern 6.7 VACUUM DISTILLATION OF REDUCED CRUDE OIL 6.7.1 Process Description 6.8 OPERATION OF FRACTIONATING COLUMNS 6.8.1 Temperature 6.8.2 Column Pressure 6.8.3 Flow Rates 6.8.4 Reflux 6.8.5 Reboiler/Stripping Ste? . 6.8.6 Stability of Column Ope; hon 6.9 IMPROVEMENTS IN FlZACTIONATINGCOLUMNS

'4. THERMAL CONVERSION PROCESSES 7.1 INTRODUCTION 7.2 THERMAL CRACKING REACTIONS 7.3 THERMAL CRACKING 7.3.1 Process Description 7.3.2 Typical Operating Conditions 7.3.3 Typicak Yield Pattern 7.4 VISBREAKING 7.5 CONVENTIONAL VISBREAKING 7.5.1 Process Description 7.5.2 Process Variables 7.5.3 Typical Operating Conditions 7.5.4 Typical Yield Pattern 7.5.5 Decoking of Furnace Tubes

177-191 177 177 178 178 178 180 181 181 182 182 184

I

I

7.5.6 Maximization of Diesel Oil Production 7.6 SOAKER VISBREAKING 7.6.1 Conventional Soaker Visbreaking 7.6.2 High Conversion Soaker Visbreaking 7.7 COKINC 7.8 DELAYED COKING 7.8.1 Process Description 7 8.2 Process Variables 7.8.3 Typical Operating Condi tions 7.8.4 Typical Yield Pattern 7.8.5 Needle Coke Processing 7.9 FLUIDCOKINC 7.9.1 Rocess Description 7.9.2 Typical Operating Conditions 7.9.3 Typical Yield Pattern 7.10 REXICOKING 7.10.1 Process Description 7.10.2 Dual Gasification Flexicoking Process 7.10.3 Comparison of Conventional and Dual Gasification Proresses 7.11 OTHER COKING PROCESSES 7.12 CALCINATION OF GREEN COKE 7.12.1 Process Description 7.12.2 Typical Calcination Data

8 CATALYTIC CONVERSION PROCESSES 8.1

INTRODUCrlnN -

192-221 192

193 194 195 195 1% 196 196 197 138 199 200 200

8.2.1 Development of Fluid Catalytic ~ r a c h g 8.2.2 Technological Aspects of Fluid Catalytic Cracking 8.2.3 Principles of Operhtion 8.2.4 Process Description 8.2.5 Process Variables-Reactor Section 8.2.6 Process Variables-Regeneration Section 8.2.7 Feedstock Characteristics 8.2.8 Typical Operating Conditiow 8.2.9 Typical Yield Pattern 8.3 CATAI.YTIC REFORMING 8.3.1 Reforming Reactions 8.3.2 ReformingCatalysts 8.3.3 Process Description 8.3.4 Process Variables 8.3.5 Typical Operating Conditions 5.3.6 Typical Yields and Product Quality 8.3.7 Pretreatment of Catalytic Refomer Feedstock 8.3.8 Catalytic Reforming For Aromtics Production 8.4 HYDROCRACKNG 8.4.1 Applications of Hydrocracking 8.4.2 Types of I-lydrocracking 8.4.3 Hydrocracking Reactions 8.4.4 Hydrocracking Catalysts 8.4.5 Process Description 8.4.6 Typical Operating Conditions

222-266

(xi)

(4

10.3 VACUUM DISTILLATION 10.3.1 Process Description 10.3.2 Typical Operating Conditions 10.3.3 Typical Yield Pattern and Product Quality 10.4 SOLVENT DEASPHALTING PROCESS 10.4.1 Process Description 10.4.2 Process Variables 10.4.3 Typical Operating Conditions 10.4.4 Typical Yield Pattern and Feed/Product Quality 10.5 SOLVENT EXTRACTION OF LUBE OIL FRACTIONS 10.5.1 Comparison of Furfural, NMP and Phenol 10.5.2 Process Description 10.5.3 Typical Operating Conditions 10.5.4 Typical Yield Pattern and Feed/Product Quality 10.6 SOLVENT DEWAXWG PROCESS 10.6.1 Process Description 10.6.2 Typical Operating Conditions 10.6.5 Typical Yield Pattern and Feed/Product Quality 10.7 HYDROFINISHING PROCESS 10.7.1 Process Descrition 10.7.2 Typical Operating Conditions 10.7.3 Feed and Prod:lct Quality 10.8 MANUFACTURE OF PETROLEUM WAXES 10.9 WAX SWEATING-PRINCIPLESAND APPLICATIONS 10.10SOLVENT DEOILING 10.10.1Fundamentals of Solvent Deoilig 10.10.2Process Description 10.10.3Process Variables 10.10.4Typical Operating Conditions 10.10.5F i s h i n g of Waxes

8.4.7 Typical Yield Pattern 8.5CATALYTIC ALKYLATION 8.5.1 Alkylation Reactions 8.5.2 H,SO, Alkylation Processes 8.5.3 HF Alkylation Processes 8.5.4 Process Variables 8.5.5 Typical Operating Conditions 8.5.6 Comparison of %SO, and HF Alklation Processes 18.6 CATALYTIC ISOMERIZATION 8.6.1 Chemistry and Catalysts of the Process 8.6.2 UOP Butamer Isomerization Process 8.6.3 UOP Penex Process 8.7 CATALYTIC POLYMERIZATION 8.7.1 Chemistry and Catalysts of the Process 8.7.2 UOP Catalytic Polymerization Process 8.7.3 IFP Dimersol Process

9.1 INTRODUCTION 9.2 HYDROGEN SULPHIDE REMOVAL PROCESSES 9.2.1 Absorption by Regenerative Solvents 9.22 Adsorption on Solid Beds 9.3 SULPHUR CONVERSION PROCESSES 9.3.1 Claus Process 9.3.2 Selective Oxidation Processes 9.3.3 Wet Oxidation Based on Aqueous Solutions 9.3.4 Thermal Cracking of Y S 19.4 SWEETENING PROCESSES 9.4.1 Caustic Treatment 9.4.2 Solutizer Process 9.4.3 Doctor Treating Process 9.4.4 Copper Chloride Sweetening 9.4.5 Hypochlorite Sweetening 9.4.6 Air and Inhibitor Treating Process 9.4.7 Merok Processes 9.4.8 Sulphuric Acid Treatment 9.4.9 Clay Treatment 9.5 SOLVENT EXTRACTION PROCESSES 4.5.1 Edeleanu Process 9.5.2 Udex Process 9.53 Sulfolane Process 9.6 HYDROTREATING PROCESSES 9.6.1 Applications of Hydrotreating 9.6.2 Hydrotreating Reactions 9.63 Hydrotreating Process for Distillate Desulphurization 9.6.4 Hydrotreating Process for Smoke Point Improvement

10 LUBE OIL MANUFACTURING PROCESSES 10 1 INTRODUCTION 10.2 EVALUATION OF CRUDE OILS FOR LUBE OIL BASE STOCKS MANUFACTURE

11 MANUFACTURE OF BITUMENS

320-327

11.1 INTRODUCTION 11.2 SELECTION OF CRUDE OIL 11.3 METHODS OF MANUFACTUREOF BITUMENS 11.3.1 Distillation 11.3.2 Solvent Precipitation 11.3.3 Air Blowing 11.4 AIR BLOWING PROCESS 11.4.1 Process Description 11.4.2 Process Variables 11.4.3 Typical Operating Conditions 11.5 TYP!CAL REFINERY PRODUCTION 11.5.1 Cutback Bihunens 11.5.2 Bihunen Emulsions 11.6 HANDLING AND DISTRIBUTION

296-319 296 296

12 CORROSION CONTROL IN REFINING PROCESSES 12.1 TYPES OF CORROSION 12.2 FORMS OF CORROSION

328-338

2

PETROLEUMRERNlMp TECHNp4OQY

1.2 FORMATION OF OIL AND GAS

There are two theories of the genesis of petroleum: the organic theory and non-orgMc theory. The former holds that petroleum is of an organic origin and is the currently favoured proposal. It predicts limited reserves worldwide; moreover Indian reserves are predicted as minimal. The latter maintains that it is of non-organic genesis, supposedly of primordial origin. On the basis of this theory, oil reserves would be much larger than those predicted by the organic theory. India, oil-poor in the organictheory, is predicted to be oil-rich in the non-organic one. The non-organic theory that was much prevalent earlier suggests that oil is formed by the action 'of waikr on metallic caibides or by atmospheric radioactivity or by cosmic radiation. ?he rme occurrence of oil in,meteorite~,igneous dykes and in petrozoic rocks weighs in favour of the non-organic theory. The organic theory which is the most prevalent today, suggests that the petroleum was formed from remains of plants and animals that died millions of years ago and accumulated on ocean floors. Tiny, minute marine animals and plants comprising mainly algae, fungi, diatoms and foraminifera used to float on the surface of the sea and were abundant during the Mesozoic (about 225 million years back) and Cainozoic (about 65 million years back) period. On the other hand, rock surface and land are continuously getting eroded. Broken pieces of material like sand, clay, lime are carried away by rain and subsequentJy depamted on beds of oceans. In millions of years the sediments pile up to a great height (several thousands of metres) and subsequently, pressure and temperature continue tq rise in *ose rocks. Shells and skeletons of dead planktong, sponges and jelly fish sublime.on sea bed and subsequently get buried under the piling sediments. Aerobic bacteria present infie ocean flgor and sediments act as scavengers and attack the organic patter. Some complex chemical bansformation takes place that is facilitated by the enormous overburdeq,:pressure, rising temperature and the absence of oxidizing agent. The process continues through various complicated stages and chemical reactionsforming fats, amino acids, lipids and finally into oil and gas. Oil is produced within the temperature range of 100-200DC. Source rock when subjected to greater overburden pressure and temperature beyond 160°C for a long period does not generate liquid oil but gas. Amongst the different sedimentary rocks like sandstones, shales, clays and limestones, the clays are more suitable for formation of oil and serve as 'source rocks'. With the piling up of sediments, lower sediments get progressively compressed and the fluids in them are squeezed out. Oil formed in the clay rises up or sideways and if the rock above is,like a sandatme with pore spaceo, fissures and fractures, the oil tends to get accumulated in such a reservoir, provided this upward and sideways migration is prevented by the intervention of an impervious layer of rock known as cap rock from moving further. This layer traps the oil. In a normal oil pool gas remains at the top, oil below i t and water further below. These pools remain intad till disturbed by earth. 1.3 OIL AND GAS EXPLORATION

Oil exploration is a complex process. It begins with prognostication and involves au entire gamut of activities. m e hunt for the hydrocarbons is focused at the favourable or promising areas based on geological considerations. Geological survey aims at selection 'and mapping of such areas which satisfy the criteria of being sedimentary rocks preferably of marine origin with the presence of anticline structures of Mesozoic (50 percent of oil produced belongs to this era), Cainozic (40 percent of oil produced belongs to this era) and Paleozic (10 percent of oil produced belongs to this era) periods.

kfikwkr;~

x ~ t ~ ~ A ~ ~ o h ; ~ AND R b REFINING ~ a r c n o ~

Owing to the presence of fault planes and fissures, a seepage of oil to ihe surface may take place. The analysis of surface samples of soil, water and oil or gGy'in such cake$'; for detection of oil and gas is known as geochemical prospecting. Magnetic surveys are then done. Magnetometer survey is carried out either on the ground or from the air by air-borne magnetometer. It is based on the principle that the magnetic attraction on the surface depends on the magnetic intensities of the rocks and their distance from the surface. It helps to delineate the nature and possible dip angle of the subsurface rocks. Dip is the angle that a geological stratum makes with a horizontal plane (the horizon): the inclination downward or upward of a stratum or bed. The same principle can be applied to the measurement of the gravitational attraction at the surface by a gravimeter. These two methods together help in demarcating areas having thicker pile of sediments with better chances of oil. The seismic method of oil and gas exploration involves generation of a series of shock waves in the subsurface and picking up the reflected waves by sensitive geophones which are laid along a line on the surface. The time taken for the return signifies the velocities through the subsurface rocks and these can be interpreted to assess the nature of rocks and their angle of dip. The field studies are supported by an e q u d y elaborate testing of samples in the laboratory. Sophisticated modern equipment like Electron Microscope, Mass Spectrograph, X-rays Chromatograph, Nuclear Magnetic Resonance (NMR),Spectroscopy, Infia-red, Ultra-violet and Differential Thermal Analysis (DTA) are indispensable aids. On the basis of all these studies, the most suitable places where oil is likely ta be found is selected for drilling. 1 1~ Q L ~ NFOR G OIL AND GAS

The drilling equipment (shown in Fig. 1.1)consists of a tall huge tower called 'derrick' anchored to the ground, engines, Qd pumps, water tanks, draw-works and many other modules. The travelling block is suspended from the crown block (a large pulley at the top of the derrick). The swivel, attached by a large hook to the travelling block, can rotate freely, and the kelly is fitted onto this. Rotary table at the centre of the derrick floor holds the kelly (which has a square or hexagonal cross-section) and can be rotated at a desired speed by the engine. To begin drilling, the kelly is hauled up the derrick, its bottom is fitted with a drill bit and lowered through the rotary table until that bit is resting on the earth. With the starting of the engine, the rotary table rotates the kelly and the drill bit which is pressed hard against the earth by the weight of the drill string above, cuts and penetrates the rock at the bottom. Much of the success of drilling depends on the quality of mud which is a specially prepared slurry of water, various chemicals and adhesives like barytes, bentonites, xanthanite. It is pumped through the drill column to carry out several important functions such as removing cuttings to the surface, cooling the bit (heat generated is due to friction), lubricating the bit, providing buoyancy to the drill string to reduce the hook load, retaining the side wall of the well from caving in, allowing to examine the hole by lowering' a variety of instruments and balancing the formation pressure that prevents the formation fluids from running into the well. With the increase in depth of the open hole, the side walls of the well tend to collapse. To avoid this, a casing pipe is introduced into the hole. The annular portion between the hole and the casing pipe is cemented. M h e r drilling is carried out with smaller diameter bit, and at a certain depth a smaller diameter casing is introduced and cemented in the same manner.

v

z

LC.

3 J

Z m

e,

9* - g = * 1k *gz$. c" z9E m m

m o C

D u,

$ E&e:&g E e ~ s g8

8

= &g.gQ

e

? E a r , 6.9.

eng s't ID . OPg: P3 xgEi z u -,

g:

"9

g s:P 3 skg:g g gJ B 0%

ag

ggf 4 . d p2 8 g B ogmi ak, e , - m

1

g a rEvme,

8. 3m *g ga

B i.3 €i

"

? ;1

g a g $ 8.1.& ape 9 m m 0 E g m

E k " "

;ilc

a m ! $

~ 3 , ~ e =

Fr0

gap

u:gg

! $ a m m q s e lat sr 1r n % C a w B r ,+

E'm

3

r

$ 3 1 -". a $8' 2. goR m3 kg,pg < q U w 0 9 C w m g g $$ @'" 2 B $6.;

0

q

- 0

1 8 - g $ g * C P gg m g s p P :&g 3 5: - i g s e . * , . g g 3 c a c 8 - s l$go"*g "2 %Z " Z ~ E g g1 Eg. m5

? r-$. g g"c$

clmem c

u 8 15."Fa; ZB w,.CLg g 3 q

=

20"s

" W X

ptliwUk,

''

pores. Second limitation is,$hat,the advapcing. water f q n t :bypaqsessjgpif~qt.~rt$n?~~of the reservoir due to difficult :wellplacements and wexpe+g:.,geologi+ c d g u r a t i ~ n s . This lack of a perfect!sweep efficiency is responsible for leavingbehind crude oil'$ -!as not reached by water.flood. ,. Anumber of methodsltechniques are employed to recqver the rem&ing oil. The diffkrent techniques may be ,broadly classified into three categories: ( a )Miscible/immiscible displacement process o

Miscible hydrocarbon displacement (LPG enriched gas & lean gas) Carbon dioxide injection Inert gas injection (Nitrogen, air, etc.)

( b )Thermal recovery processes Steam stimulatibn Steam flooding (including hot water) In-situ combustion (c) Chemical flooding processes

Suifactant$olyrnei injection Polymer injection Alkaline flooding Selection of a suitable EOR method requires a careful analysis of reservoir configuration and the oil properties. Trapping and release of fluids from porous media is a complex phenomena. For a spe.cific system, trapping behaviour is controlled by Ci), the pore geometry of rock matrix, (ii) fluid-rock properties, in particular, wettability and (iii) fluid-fluid i n t e r a ~ o n sincluding viscosity, rock density difference, interfacial tension and, partition coefficient. The general properties of pore system, its shape, size and distribution in the rock plays an important role in trapping of oil. It is established that (1) Trapping of fluids occurs in unique and reproducible patterns which are controlled by capillary forces, (2) Nearly complete networks of interconnected equal size pores exist throughout the pore size distribution, (3).individual pores have good accessibility with adjacent pores, thereby allowing alternate paths of flow around igolated immobile phases, (4) Fluids can be trapped at pore constrictions for all degrees of wetting. Non-wetting pqases are trapped in discontinuous masses whose lengths are largely determined by interfacial tension and potential gradient. For selection of suitable EOR methods laboratory investigation under simulated conditions of reservoir are necessary. Mathematical models (3 phase, 3 dimension) are used to analyze the reservoir geometry. The past performance of the reservoir is matched to predict the performance of reservoir under different operating conditions. Based on these modelling studies, the most suitable EOR methoais selected for maximum~productionof the oil in place. In India, the increase in crude oil production is not significant during the last 4 5 years. No new oil fields with substantial reserve is discovered. The percentage of primary recovery in the total oilgroduction is gradually decreasing. Rate of production from Bombay High is reported to have already shown the declining trend. Some of the old oil fields of Assam and Gujarat under prevailing price structure have already reached their economic limit. On economic terms, both ONGC and OIL may prefer to plug the well, pull

.:: .;,

; ~ t o ~ A n o ~ ; ~ ~ bAND ~ uRERNING cno~ &:'A

7

the pipe and abandon t h e lfield. It is beWr ts use EOR meth6da after primary recovery. It is imperative that proper assessment of EOR potential in the country is required for making recovery plans. The successful application of any EOR process depends on its viability. The price of oil is the most important factor for how much will be produced and when. Gas injection may not find wideapplication in India. It is true that natural gas or associated gas, propane, enriched gas and lean gas are available in India. But the pressure required to liquefy the gas is high and it may not suit the shallow Indian reservoirs. So is the case with air and nitrogen gas injection. But in some reservoirs carbon dioxide could be injected. Again it depends on the availability of low cost carbon dioxide in plenty. It is estimated that about 4-6 million cubic feet of CO2 is required to recover a barrel of crude oil, Although thermal methods predominate as most successful EOR processes, they may not be applicable on a large scale in India. Depq of the Indian reservoir and API values of 28 - 45 restrict the injection of steam or hot water for additional recovery because of apparently unattractive cost benefit ratio. Of course in Western sector it may be successful in some reservoirs. In-situ combustion is the most difficult method to predict properly. Moreover, it is economical and successful in heavy oil recovery only. It appears that the chemical flooding viz. polymer flooding or surfactant-polymer flooding may prove successful in India. For alkaline flooding, acid number of the crude must be high which is not so with Indian crudes. Polymer flooding method may become more popular in India not only for its easy handling but also for the economic returns. Surfactant/polymer flooding is required to be assessed properly, particularly the non-compatible nature of surfadant to various monovalent and bivalent metal ions and in Indian reservoimkhese metals are plenty. The production of crude oil in India is given in Table 1.1.From a meagre 0.5 million tonnes of oil produced from one of the oldest oilfields in the world-Digboi in Assam, the indigenous crude production is expected to go up to 44.45 MMTPA (million metric tonnes *r d u r n ) by the turn of the century. Till 1947, India used to produce around 0.5 to 1.0 MMTPA of crude oil from Digboi and Naharkatia fields of Assam. After independence in 1947, two public sector companie~wete formed by Government of India, namely Oil & Natural Gas Commission (ONGC)and Oil India Limited (OIL)to explore and produco oil and liatural gas in India from both onshore and offshore fields. Up to 1960, India was practically depending on imported crude oil. ONGC first struck oil in Cambay in 1958-59 and in Ankaleahwar fields (Gujarat)in 1960, followed by oil finds in other pmta of Gujarat such as Nawagam, Ahmedabad, Mehsana, Gandhar, Kalol, Tapti basin, 'etc. Biggest oil field struck by ONGC was Bombay High r offihore fielda in Arabian sea in 1974. In 1976, ONGC found a large sour gas r e s e ~ o i at South Bassein, south of Bombay High offshore fields. Also, gadoil was found in smaller quantities a t Heera, Panna, Ratna and Neelam offshore fielda in Arabian sea. Crude production in the country has been going through fluctuating fortunes. From a high of 34.09 million tomeu in 1989-90, it dipped to 26.95 million tomes in 1992-93 and stayed a t that level in the following year also. But in the past couple of years there has been a recovery and the crude production was 33.865 million tomes in 1997-98. The offshore reserves account for about 63 percent of total oil produced in the country. This reveals how poor the country is in on shore oil reserves and how much it is dependent on Bombay High. The production of natural gas in the country is currently about 74 million standard cubic metres per day and the total gas availability for sale is about 61 million standard cubic metres per day.

~FTR[31;ELlM,~ERPTORATION~~ODUCTION AND REFINING

Table 1.1 Production of Crude Oil4n &dia

r9

is used as feedstock-fonUdex unitito prPduce benzene an& toluene. Kerosine fkacti~nsfrom certain crudes such as Assam crude do'not meet specification on amoke point due to higb aromatic content. To improve smoke point of these fractions, Edeleanu process is usually employed.

-

*

L

I

1.6 PETROLEUM REFINING, OPERATION AND OPTIMIZATION

Crude oil in its raw form has got very limited use. By adopting various refining processes in the refineries, crude oils are separated into a number of fractions which are suitable for various uses. Crude oils received from oil fields are stored in refinery storage tanks. .From these takes crude oil is fed to the atmospheric distillation unit. All the crude oils are basically mixture of hydrocarbons which can be physically separated in groups of different boiling range by the conventional process of distillation. The fractionation of crude oil yields the following streams in the order of rising boiling ranges : Methane, Ethane and Propane mixture Liquefied Petroleum Gas (LPG) NaphthasfGasoline fractions KerosindAviation Turbine Fuel (ATF) High Speed Diesel Oil (HSD) and Light Diesel Oil (LDO) Reduced crude oil (RCO) Depending upon the crude oils properties and impurities present in them, the above products are further treated to meet the required specification. Reduced Crude Oil is further distilled under vacuum to recover some more lighter fractions. This process produces light vacuum gas oil (LVGO),heavy vacuum gas oil (HVGO) and vacuum residue (VR).In order to meet the viscosity specification of fuel oil, heavy residues such as HVGO, RCO and VR are processed in visbreaking unit to reduce their viscosity. To produce bitumen, the vaccum residue is air-blown in Bitumen Blowing Unit. To maximize the production of middle distillates, heavy residues such as HVGO are processed in fluid catalytic cracking (FCC) unit, hydrocracking unit and coking unit. Straight-run naphtha of low Octane Number is processed in catalytic reforming unit to enhance its Octane Number. Reformate rich in benzenhluene

a

J

1.6.1 Selection of Processes for Optimization Optimization is the process of determining the best poseible way of selecting the proces. scheme and fixing the unit capacities etc. The selection of procesdprocessing scheme is to be optimized considering all the objective functions. The following factors would influence + . decision making in the selection of processes and process scheme for a given refinery : Type of crude Product slate Product specification ~nve*tme;t and operating costs Merits/demerits of alternative processes. Type of crude. The tyRe of c v d e to be processed in a refinery yill have a bearipg on t; process scheme? For example, crudes containing high sulphur require the iqstallation of desulphq+ation processps/sweeteningprocesses for streams. Kerosine from Aghajari c n has a peculiar problem of colour dekrioragon on ptorage which cannot be corrected by treating in an Merox upit apd hence desulphurieatiop w i t would be req%ed. Some crudes are I suitable for m&ing lubricabg oils, a n d , q p ~are e not suitable for making bitumen. In some cases the prodpcts do not require any tieatment like some of the in9genous crudes e+Therefore, each and every stream from the crude distillap?,n unit has to be evaluated tol making a suitable scheme of treatmentdsecondq processing facilities. e o d u c t slate. The capacity of the refiney, the type (lube or non-lube) and size oft., secondary groceseiffgwjb is largely governed by the product slate which jn turn is decided by the dem,pd of petroleum,~roducts,The process scheme is selected so as to match with tproduct slate. b Indiq, generally the yaximization of middle distillates is,the main criteria. In U.S.A., the production ,of light djetillateq particularly, motor spirit is maximized in F r ' unit by keeping high severity operations, If the objective is to maximize HSD in a refinery processing high sulphur crudes, it would be advantageous to provide an FCC unit with 9 desulphurisation unit either for straight-run gap oil or cycle oils so as to,upgrade the heavl-. ends to the maximum poaeible extent as limited by sulphur specifications. For extreme maximization of middle distillates, a hydrociacker can also be considered which upgrades t heavy ends to the middle distillates (ATFkerosineiHSD)better than any other knownprocess. Yield of kerosin$HSD from a hydracracker is of the order of 80 to 85 percent as compared about 50 percent from FCC unit. Product specifications. Geaerally the treatment processes are governed by tF specifications of the products. Depending on the type of crude processed and the quality or streams, a judicious selection of treating processes has to be made from a simple chustic wash Merox sweetening units to a hydro=deeulphurisation unit. The flash point of the midc.distillates are often relaxed, with a view to m-ize these products. Therefore, to take advantage of such relaxed specifications, it would be desirable to provide a naphtha splitt column inthe process scheme, sa that heavy naphtha can be injected into kerosinddiesel cuts. Investment and operating aosts, This is a very important point to be kept in view whilfixing the refrnery capacity, selecting the processes and sizing the unit capacities. However, the selection of process technology at times may entirely be'governed by the products demand rather than by investment cost limitations. Investment costs are function of refinery size ar.-

rw

P E 7 R r % g E U M f E X W a ~ ~ ~ E I M : T lAND O N REFINING

i t & a s n p ~ ~ ~ ~ y t ~ f ~ h ltihe e tm'1~1wmp1~xityi~ze6ults :fox~ as!the capa@f increases. ~ n v 8 8 k r n ~ n ~ p e m ~ r w e s s i n g , c a p progressively acity go,down.h some cas$s,,apartidar planh~siree~~~eomeieW~miud~md k s o m e othea w e e it maypot be.ecoaomie;JI. For example; some oil companies do not consider it economical to provide FCC Unit of less than 0.6 MMTPA capacity. Similarly, the latest trends are to provide single crude distillation unit of 8 to 10 MMTPA capacity. , i .-$Qxp~f$he,plants*tveconsuming high amount of fue1,ahd utilities. This aspect has to be kept i P ~ X i e w ~ ~ w ~ ~ s e 3 eacprocess-For ting. example, inxase ofhyQrgcracker, thetotal energy c ~ n s ~ p t ' i bo spr ~ b ~ $ u.6 t times than that of Fluid catalytic cracker. Fufiher, a substantial quantity,q&p~pSlthai~ copsumed to meet the hydrogen, requirelpent of h y & g c ~ ~ & n gThe . total energy consumption in a fuel refinery would.be of the order of 10 to 11percent. One has to be cautious in the selection of new process technology keeping in viey the situation, location and availability of local expertise. Some of the technol~giesfor upgradation of the heavy residues may not be straight way made applicable @ Indian conditions. Develop ments like continuous catalyst regeneration may not be verJ;atractive to refineries which upqaSI&qaphthaf?r #e production of motor spirit ?f bqder*te o c h k q u m ~ t . ' ~ e s u l P h ~ s a tio~iof Gel oil which i s $ow being practiced elsewhere with7 the okijedive df rMucing$ollution in concd+qa$ed @au$+al flrei-i? rimy-not &e appli,cable+@s?in_e other situations, y h e p p:ol$t$m - h @ s a$$ow. HydroqackinP ddugb a "e$j yitd pmck$s fo; h&hiking'niiddle distillates h p a soEh@dcatkdmi!llurgy and ikgu+ea szecid operatibnd &d rnewnqnce c a i e : ~ o c e s , o , w a@ted,forJFct hydiocrack@g"ofreeidu'es abuld call yo; s f i & q t high i'?vestm~tsand Gg'hop,perqkirig costs becaube df the hjrdrdgen rkquirementh,,pa&~ularlykor high [email protected]&des'.'R.eddced d v d e oil; fiod indigent& crucY$d because oftheir low ?ulpRur and metal conbl;t$ &ohla dre better suitedto thiktype of te&ology. Me$ta/demqets alterqdivq pyoces&ir: There may be more than qne prvess to do the '&me m e OF operatidin. Fbr exhljk, th'e'r~are various'types of swebtenihgl$hce~sfor naphtha@and ultihat&ly chohh has to be & b e on the meritk &&demerits of aeihdiyidual processes, opkrating cpqp t+d quality of t&e pfoduct etc. Fo* extractipn of aromatics:fiom kerosine, apart from conventional Edelead~prdcess one coqd possibly choose shlfolane process or &d,hydr"dgenation in orddr to irp~rovethec'amoke'poiht. For the extraction of arqmatics f r ~ m t h lube e oil distillates either furfural or phenol extraction could be adopted. i

..

,I-

OF

1.6.2 ~ ~ t & i ? h t iin ~ an R ~ n n i n Refinery g dPtimization ofthe operition bf a runxi&;! refineiy is sutij&d to the influence of various factors. There are, some factors which are beyond refinery's control. These include : I (a) c h h e mixture (b) Type of processing units (c) Demaqd pattern (d) Movement constraints (el Product specifications E a r n a l streams (g) Industrial relations. Those factors which are within refinery's control are given below. (a) To investigate the possibilities of improving over processing capacities not only for crude oil but also for secondary processing units. (b) To adopt various effective measures of controllingthe erosion/corrosionin processing units to improve their service factors.

(c) To.plan(shut downs of vari6us unitsratoptimum time tu avoid the&@?&ed htiiitieb

consqmptions. ,,I,, (d) Various streams obtained f ~ diffvrent m pftcesslirg units a i 6 5 ~ z :.b,,:;.7!t$; ~ y ~j !;,;~ : ;.,:,.t;.3: ... c ,~:.., ~ ~ ~. ~.. ~ ,: ,?..! i!.

,

:

. .-

. . .., ,.. .

,

,

.,.I>'!> ,

,, ~ , ~ ~ , ~ , , mu i i h k s s of ~saturated a and l unsaturated l ~ hydrocar.!bdtSgl$ be:cyand ~r~~&-f,p~-~h'sis~ af.o*?r rn0fe of fie foll&ghydrocarbons: ' * Propylene (C3H6) h o p b e......... (C3Hsj . . . . ., . . . . . . . . . 0' . n-butane &!jH$) '. . . . . ..,. 1~0-6uta" . Butylene (C4Hs) ~races'tosmnli auantiti&sof one or more of the follow&g hydrocarbons may. also be presen.. I Ethylene (CzH4) Ethane (CzH6) -Penbane (c5H12) Pentene (CsHlo) )ii . \) ,i)~ P separated G from heavier hydrocarbons by r straight distillation process contains only the saturated hydrocarbons wliereas ZPGaobtained from conversion processes such as tht macatalytic cracking, ,:< ., ;' reforming , c :.and hydmcracking contains unsaturated hydrocmtio~ . . as

- ..

,,

gq10j

...L.,

~

.

:

~

@li+.

: Bulleau of Tndian811Standarde-4BIS)have categoised

LPG as under: Commercid b u t m e k a-hydmcarbon-product - . composed re dominantly of butane ibutyleneb or their mixtures. (I%)' Comme~ciakbutaneapropane mixture - a hydrocarbon ~ r o d u c tcomposr ' predominantly of a mixture of butanes andlor butylenes with propane andJ~1 propylene. ' (C) Commercial propane- a hydqocarbon product composed predorninandflfprophpropylene or their mixture. The requirements of LPG are e v e n in Table 5.1. LPG produced at Indian refinen conforms to grade B. I

,

.(A)

>

.

, i

h 1d'fldi~~Mtkl~ie~h8'c~fig1(~~~) uiifir the Yeed~&sfi&\ffb$W"hi'&xddp &-fed SU-+& j f l r- ; v v C Q ~ ~ ~ ~ to U the O Ureactor B \ ~ tower, fmm which, a t thetsamet&e,kk8alyhtia k&5&jw1@h&nf combus$on .< ed&es, it is e&emely to a regenerator where coke deposited on the catalys6is burnt & ~ ~ h ' & n t k a d f f l ~ $ o h ~ t h e h g and hardening, steel;utting e t c h f u e for i n . I reactor is fractionated in main fractionating column into so called light endq;mf~dkb&t~late good, but it has yet ta l e c o m e p o p u1 l ~ . and heavy fraction#. Uncondensed overhead gases and catalytically c r a o k & i q g ~ e l ~are e , ik routed for LPG recovery. The uncondensed gases are compressed, moledaq~pha&$&uqces5,2 NAPHTHAS sively to two absorbers which employ cracked gasoline and light cycle oil respectively as name give? td light hydrocarbons bgilin&$he:ge.gasoline range. I t is , Naphtha is a absorbents to increase hgbt ~ ? ~ r ~ ~ ~ v e w ~ , ~ ~ fmm h g aabsmber s o l i p is45tfi8p&,d, e off its refipwg of crude:~il.y e bo~lingfiiagesof various types of -, kfedto a debpta?iger ~ ~ l ~ ~ , ~ ~ b , & ~ i a c k e datlight distillate obtaine4,frop lighter ends in a stripperjl'he stripped g~sol$ne naphthas produced include: C5 85OC. Cs 118C, C5 140°d, CS; ~ ~ O O C C5 , 1 7 5 0 and ~ LPG is taken as overhead producp. L P q q 4:yerhead product from debptahipfr ,$oJu+n is . t treated further to conform to required specikations. C5 200°C. In these iiitial boilink point (IBP) is c o n s t s n t . ~ ~ t ~ ~ b o ranges i l i n ~ can be -. Coker gases are compressed in two stage compressor and routed to the bloi~&$$&k~~orber 60 - 85Oc, 85 - llo0C, p + l l p - 140",~.w a s are u s u a l l ~classified a s light.hterme&ate ~ $ @ d f ? ~ ~ ;is $used, ? ~as~absorbing ~ medium. Gases from ap$tha a sorber to are and heavy naphthas. I t t h h a p h t h a fraction ~ lbe1ovk1000($, s it ii,"c1bsified as l g h t naphtha. ~k'& interniediate naphtha ~ k b @ % $ & ~ ~ g < ? ibetween es ;&aer a sqrbe, ,,,y coker'kerpsi$, ~L%"kerosifibkord kerdsine a!sor~& % d ~ ~ ~ R the 'v H~~~ naphgaboils above 150°C. For Imw$$a$tidnating,k71mnnb,!the ,ckkii;~*li8?%ighte'rrehds (C1 and-cijkre s,thr&qdffG o d * 4 ' 3 Ti)OPC. ' rich nabhka in a $ l p $ y r ?ndtc$&et'riom' ?,' / stri$eP$re ?? - . . . . . . . : V h f & ~ ( ~ a r n i&;nuf&ture:and sh pi$&inaphtha ~:r: . . . -. . --. .. .. :.: . . . . r . . . . . :. , .. ,.. , ..,,.. . ~. . . r paint& va&ishes,jacquPs ... ' i, :. . . .. .. . .> . ' ... . . .. .. . .. .. . . - ( 6~ h i n n efor . ,. . . > .' (=) s t o d d a d ~ulvefit?&ecib &l&&&foi\:dijc& m$ng'*idk::. ' . . .. .. . -. . , .- . .,.: @ r ~ ~ ~ o x i d o ~ a . d ; ~ h y d r d ~ al cra W v i nnb~n i b m n oiidca h,nchq$.::T.he !l$t$.;ib ::;*5gjhflpltJ$&;mm.\, .,,.,?, ,., , i L '-$ ,11h b u ~ p t~o&&b~:-lifit l s h i n ef r a a . ~ ~ I no yi91 t r * 1.. I , -- l,x)fsv,,, *ne:t L 1,. !zLv :I!;~CI~,~;;xx d -. , 1

.



; b

\

!

depe*degt

I

~ e O B ~ ~ ~ ~ f i ~ f a 'md:$&me:methm&l~einextr ~ ~ Y ~ ~ & ~ d%i?=$e~l ~ ~ ~ ~ ~ n ~ l ~ f i g ~ # i j f h ~ d t & & f ~kEe ~h f f~ i~ iong ei h . a ~ i d ~ a t i , b 1 r n o n d r i d & u a r a m i m 8 ~ ~ ~ ~ 1t1givesil l@d r@gd of&~yd~oc,atb'bn~ of dif%mtid& I~d@&~Qh~gi~~~&& s(aa&b'#~ b G ( & ~tif ffox&eh&ert SLID?&'BS i a l ~ ~ f ~dfi:k~f6DL~8881* i~l~' &Q~&a&$w&@&~&&&ei& P --_.._ ~ ~frbnt;th&htct6~ ----~ t s tail gab & e h p & & e n & @qujh&b@Wed ~ ~ ~ o a u e p ~ h p' t~~ e~s see fssuch u ~a3e iaamerkatibn~ ~ ~ ~~la.tiAnl p ~ ~ $ t ~ m ~ ~ ~ ~ I [ ~ . l I ~ ~ ~ ~ B, x u~ i ; k. . i ~ s s e r i e s i~ii~~&ri'~~~~~b~~~h~r~&hno~and~thand11h2t~ f u e ~ ~ f d r s ~ ~ k ~ iengines. ~ n i t i o nethanol and ethanol differ m y k r a & ~ ~ m g h ~ b ~ b ~ ~ b a d t i ~ t i c s i t h a J ; , wimporkant e to t h e i f i d i s t r i b ~ t i ~ ~uselas r n d a &el-fon w=k+i&on &$-&Pf.,Ql2 &~$a~J5tflr;4';:

ti

..I

)(

1

-

,,

!

""

L

I & g # & u$ . undask .n p&d$Qfd&@h~.i$qwKip!d~~%!in n..1fI~f~~~~@3frh6a~% e1

Y'

+&d~&it@&~~Wk~~i@$5#~ l{ilihlYiiij &5&8 ,-l{tc

r

:p I * I , . I ' r t j + S q : , q ; ~ j * r C c ,v~ :,

., :.

;

'/'

'

'

'.'

4 w a q u! daSAko aq$ 1sa(qeu8osp .uo!qsnqnroa ~4$iiaIqeua# ~ ~ k I i n n ~ ~ n ~ . ~ a m 4tifphj%fi$&i1+pi&$ eYiikYSnqd@@ftj* 'r +

,+

*

,lc

.h6g&Foar;x F~$'+bJd

2-q ' au!so~ay~o raLe1 ~ o p qXs ~ A m LIa3 sad4 Jaw .Ia&'ii@ i58~iffffn#nPltf&dtlatto55 ~ 5 ~ & d h ~ P d &4'dkdd ~ t $ b'~6t.d %q$sa'$$t~~dh u n q a&tq%a!~~~, aqi+$&S asd6~%iq&@ri~kri1~~q ~ u a u t + % 3 &3!5 quapg)ns Bqaq a q s o ~ a q30 41J9810~ qua~aqtf! a q uo b1a~s r a u o d ~ ~ $ 1 ~,n'.~uC"!~e~~fi rrprri;p!c i.a z a i s : .r i;o..-..*:-ti.~i .-;*;.i . g i ~ z l ~ ~ $ ~ & w ~ & A Jag!. 6 r d f i & k ~ 1 ) $ ~ % ~ ~ ~ ' ~ ~ & ~ f s%~U~bk$a@;a~kt$~!tadmq 5pa~qjd q!B@sea~aq PUB fiif@ffi@%@36%& 'Q'd8$ks'wf~q&~q .!&i@~fb#'h o , ~ p z ~ f i & ' + \ ~ ~ + q ~ e JO s&U6~~fi~@f~C&5'4k1r%b!$~'~ode~a aqq a s e a o q q h s s a a a u s! qf'nrwmq agsamop u! p * d a ~ ~ $ g 0 ~ ~ 4 ~ t l 4 a t d % ! ~ ;anappe t ~ u ~ o& ~ p.L1arols s u o o l sqsrodena a q s o ~ ~a n~ q ' s a l ~ ~ ~ a ~ s p ~ ~ ~ ~ q ~ ~ ~ w ~ ~ ~ ~ ~ ~ d 1 ~ !w pd~8oa W 5 j~! a~wam lq ~ ~ 4 d m a L p a ~ m m ~ b g e x ~ ~ # ~ w U a t r ~ q doqs paaodxa w~pqq uaqm quapa autos oq a z o d s a aupofay s + h a o l ~ r n m a 1 0 ~ 1i ~w d! ' a m u r . a r q a v q u r q u w o p q o!ar qaa.um ew q z pa q q u a a oaq~x7pQaqw p m a n o d w o ~ 0aqq3u!aq 4 s s q 31 -aqswp!nbg aqq q quanq aq qortusa au!so~ax? p g 0 9 b rR~ aBa~~-%v!l!oqt~w~~~!o ~~ q p g o u~!qae,gaqe~~qs!l(anrssaupos@, *ti . 2 . , - - > r < ,'ti ,,.: 02 U

O

~

~ L1snonquoa J ~

B

~~l~~'hpiw~wft~ql~.sw~*~

I

1

*, :.'i~lf!q,

-

.

A

+ I

3fils~j~~e

uther extra t' Qce qes for the sep atipn of aromatics a d o n - o atics use solvents with much highBr'?fk'B$$biiie$ ~H&"~%B~~$'~I~~W&~BQ&S#~~'~~G"&Q~~~ very in that rafthates with very low, as well as extracts with very high arpmatics contentr can be -- ..--. made, Of the processes ayaJpRIe? the Shell%.ulfi&e extra,,;

. , ,^.

. , , , O , >

..

~ . ,

.

.'

: ,

, -

!DIESELFUELS . .. . . . .. . . . .: :::~l,~,:'a.+::,;.,, . ;:~i. ?, . . . . . . .,,: . - . . ,?,. , k i g h speed die~el toil (HSJWand,ligh~diesel;oil(ZW)~tiretpro~ur~:~~~~.Ogr .cowtw.~ H ~ D is:Wldely usedindiesel:engine f ~ r a . u t o ~ o t j r r ; e ; . ~ . ~ ~ o ~ e S . , , a ~ ~ p ~ ~ ~ e s ; ~ o ~ ~ ~ ~ ~ ~ j ~ ~ ~ ~ ~ ~ ~ ~ p t j v e s . Statjlonary.anti marine! diese1:engisas:as:. hsfa!J.ed;iqn?;hips,or .ugg$.f~r:;dec@yi$yge,neratiqn ompared ...b :theIr~et,qfrwor~d,. ! ~ d i a ' s , ~ e q ~ d [ . ~ ~ ; d i*, ~A",.. ~rowhly ~ ~ f ~ ~sijr ls,is. gasqline. .~irlces&rakhkru~~#e:sel fj-$ctlpfiifo5;p,@~&:5~.%!dq,?il;~.ifiWSd, 'varying amduots..@fselected: cracke,dddij;sti!l.akp: from iconvqcsipn;. p$c@pee . ' s ~ c ~ , , g ~ , f l q i d d rata!@k crackipgV.h~dr~cr,8cking, cykiqg areiwd,t.o:[email protected] ay.qjlabl.e:'formeeting the growing demand of diesel fuels. . . .:.: i T k ,P ~ W ! ~X + i ~ , f ? ~ t %?$ern! $ ~ ~ p f~f;..~?vp~;e.9,sio?~i,~tip,n~e&$~~~f f aqy;qpl.ustion, volatility .and.~ieanli,~~~fi.~$:b?~hi~ r ~ ; @ n ~ ~ ! ~ d . , t ~ : i r ~ ~ ~qq~,e:def i d ~ i ~ ~$'$y2,yl ~~ th~(Bt p ~ t r Pd F ~ ~ c~, U&@ Y a~c.li?@d:i~;~91)~~.~t{8,,$?~&~p9E~l$e.pd;,p.19 relates those properties which directly affect the abilitjr'dhi.~fudto $;properly. ieiil f&ls must be suitable for handling by the injection equipment. The handlingialid storage characteristic is a function of volatility, fluidity, contami?a,ti,qn ddfin: yfinement and product s h i ~ 9?r!qovement. ~t The characteristic,of cl&"filihebsdu~n~liki~sk633f&.t~d~&&i~tikition. . . . ti[ace:contamlnation,dfid kh&&gre$ :of +~$i:$n~~~tab;ili~j;of t h I;di-ti~ar;I'~:fi~l:. . !::.: . . : ! ~ i e ~ ~ l ~ u ; ~ ' f o ~(I&& begded gbo;d igniti;niiuali+, o ensufe '.... $ d&y staitirig aha ~ u l ~ l i conteit ur m u s t bk c;iti&liy c6~&bll&'~6.iiii;ii&h&.eiivit~~~~fit~l Poll,ution,Combsion,wear and .

automot+

I



,f:2,

$,

..

'

:

Fig. 5.2. Typical oscilloscopetraces forcompression ignition

. .

PETROLEUMRfflNlNa TECHNOLOQY ....

and

'

i!

.': !! .!i;

r.: ;.: ,? r,:fhtr'$ ....... 3,

.

. . .,- . < .

Q!I~ u?*% q + y a A m d q ""4~ b A W q O 4 01q!98Od 8! )! ' ~ E Z3Sw .qld c 4 z e n ezw8s!wep m a m p $am1 .h.op p~!dQ,*swamaawo p m addm aAF1?PPB P ~ Z ~ P ~ ~ b Q 1 p W q amq * a w uo gqpuadaa -qsqp Xppm aa u u o l d ~ sin . h i O b * i ~,~OF)P% ~ Lq eIaj lasap 30 u o g s ~ o u ~ apus p UQg!80dTpp3ap 7r?bW~3%q!p a V hI I W , P P . v I %y L!, l a & o i i anq) ,pm q a q 3d uoguppo @q& >.,. t i . - -L-!t

-3.i

I < I

i

l~

3

I

5

!,I*

\

r-.,,

.

Slw~

r-

r'>:'

' t

!

~ psaqr.baa lmu pue uo!eorro3 moq r n a @ w . ~ ~ ym~ o 1 7 . " a ? a r d - a y ) ~ e n L r p a a , y ? ~ ww>pm mv@fi)@@;B.i".g 9~ ~ P W XIFPwaJ P pya.pmodmm am a a a o l d q am)aa ~ ~ f i ~ ; u o ~ ~ ~s . qsa3u)rm o x i m a w aarqlldw8m & ~ 1 ~ 1 0 j a ~ P u f WJIWt$Ysbp l p d ~ "4f!J!q8???P;~94? ' : ~ ~ o Iaq k 'mdo!s.)ma ~ ~m q~x a 6aahibd' a s ~ lu d o - ~2q.mp y 939" @now s3qpdyI pa7qd 0) .pmp.ru ~QAY!PPB ~ w ! g ~ ~ p r P ~ ~ ~ 0 . J @ 9 W g S 9 ~ n h ~ WQrSslPra e-90&?~~s Plm a p q q q 3 9 a 8apadard pq~1a.xw ~ ~ t l l l o)O~ aqmPa! & , . ~ n d : og ~ oz ~ Lp ~s g Qe c ; l p $ u ~ Tp! pyi uO~@! Uo!s8a!dmm ~ W ~ a pl! m wyi ama ayq q q a r 1qqg, 8 p Iasag 4p q q s u a g ~ w ~ n b p apyold s ~ w a d v -map n raluou U Opw ~ ~ m 5 ~ ~ .9~'s 3~ . F P~ P& ~@ ~- -~ ~ rwuanP J -__, ~ A o i8'+ni la'ig 9ald&iii'gnmaA szaqm~q3uo!prlqmoa a q go s a j s p s a q daaq pmBq!lL6dap, am$%qua~e&W J ~ ! % W & ~ qaIdmm ~ u a n ~ k ~ ~ ~ ' ? % V~ O~- ~? ! ~ , ~Ilav~m ~ hW @ &ag[ :ilwla ? ~ uo; wq s 0 p ~ ~ a . psa3sj~m m q w e m q a o p q w p s~e;~iX~qvCa'fj+?p~.~n,e;a@ d~qy7gBrnmPw W W m d mS93-Pa'EI. .I1siJtr, 3W.T9f"9 u '~018sazdm03 d k 6 ~ s . i t 4 ~ + & ~ aapun Kl!pwa~ q !@ .LI!SE? uom az!moqs pus dn Tazq q w ~ d I?v,apl q ayyr. sap!P!FWv!€!us @yYI?@&J 1sap!m8Llod su. qans saA~:pps,,a?~;~m lwsadalp ' d o ~ a al a s ~ s,Ian3 s Pvefioi

.

T

I..&I,.

A

L~I cauo!auar S.I~Ya w a?wy~ m ? a q . ~ d ~ q:e~t-6:ap7 jaq w , ~ a:'+?F+@l@~t~ t ;s7pudap PUB ~ ~ $ ~ ~ P , W Q . Q W J ~ W 1 r ?a ~, 2 R ? ~ ~ ? : vt- ci:itGul : s I ~ a n r , a 3 ~ . x ? . ~ J r e . uol)~$m~~~~. pB~&! ~q 1~ ~ B ,*.: I Bh;iIruj~ Y v 6 s a ~s !~~ q~a ms~ q u o ! s a r a ; p w ~ S p ~ d ~ ~iguJw al!bq!w e ~ y o p o ~ X ~ , efxl~ s+ p r - t : t q m J a p aaqTmJ7paqqcLp&za~~