ELEMENTS OF PETROLEUM PROCESSING D. S. J. Jones Consultant Chemical Engineer, Calgary, Canada DANANG UNIVERSITY INFORMATION RESOURCE CENTRE JOHN WILEY & SONS Chichester’ « New York + Brisbane Toronto - SingaporeCopyright © 1995 by Join Wiley & Sons Lid, ‘Baffins Lane, Chichester, ‘West Sussex PO19 1UD, England National 0128 7977 International (444) 1243 77977 Fics published as a paperback in March 1996 Allright reserved, [No part of this book may be reproduced by any means, oc transmitted, or translated into & machine language without the wate permission ofthe publisher Other Wiley Ediorial Offices John Wiley & Sons, In., 605 Thitd Avenue, New York, NY 10158-0012, USA Jacaranda Wiley Ltd, 33 Park Road, Milton, ‘Queensland 4064, Australie John Wiley & Sons (Cancel) Ltd, 22 Worcester Road, Rexdale, Ontario MOW ILI, Canada John Wiley & Sons (Asia) Pte Lt, 2Clement Lop #0201, Sin Xing Distrpark, Singepore 0512 British Library Cataloguing in Publication Data ‘A catalogue record for this book is evalable fom the British Library ISBN 0471 95254 0; 0.471 96489 1 (pbk) ‘Typeset in 10/12p% Times by Dobbie Typesetting Limited, Tavistock, Devon Printed and bound in Great Britain by Bookeraft (Bath) Lid, Midsomer-Norton, Avon ‘This book is printed on acid-free paper responsibly manufactured from sustainable forest ‘or which at least (wo tres ae planted foreach one used for papor production, :ELEMENTS OF PETROLEUM PROCESSING DANANG UNIVERSITY INFORMATION RESOURCE CENTRECONTENTS List of Figures Preface PART | AN INTRODUCTION TO CRUDE OIL AND ITS .... PROCESSING 1 Crude oil and its products. 3 2 The crude assay . 8 3 Pseudo-components and predicting product properties " 4 Basic processes. . n 5 Refinery configuration development . 36 PART 2 THE DISTILLATION PROCESSES 4 6 The atmospheric crude distillation unit. . 49 7 The crude vacuum distillation unit 107 8 The straight-run light ends units 140 PART 3 THE CONVERSION AND THE TREATING PROCESSES... 179 181 206 9 Catalytic reforming... 10 The hydrotreating processes . 11 Fluid catalytic cracking . 12 Distillate hydrocracking. 13 Residue conversion processes 14 An alkylation process... 319 15 Gas-treating processes ....... rc 355 Appendix 1 General data and correlations .... . 39 Appendix 2 A typical crude assay (Kuwait crude) 1. 396 Appendix 3 Typical product quality specifications . 401 . 405 Index .LIST OF FIGURES Definition of cut and end points. . Definition of mid boiling points Comparison between cale and Lab ASTM . Pseudo comp break down by mid bpt Viscosity blending chart Pour point blending chart, Plash point blending indexes Correlations between MeABP, SG, and mol wt. A lube oil refinery configuration. ‘A petrochemical refinery configuration ........ AA typical flow diagram for MTBE production A refinery block flow ‘An Atmos crude Crude unit fracti Stripping steam. Pseudo components . ‘TBP and EEV curves for whole erude . Whole erude BFV curves ‘Temp correction for sidestream draw-off ‘Absorption and stripping factors ‘Tray spacing vs ‘K’ factor . 7 ‘Types of fired heater configurations. ‘Two phase flow functions. . Pressure drop for two phase flow Crude vacuum distillation unit, Zone of critical decomposition Entrainment vs mol wt of inerts Entrainment ratios vs temperature Suction press vs weight of steam. Motive steam usage correction factor. ‘A typical three stage ejector set... Vacuum unit TBP and EFV curves... Vacuum unit distillate cut points. EFV’s of vacuum unit sidestreams Capacity factor ‘K? vs liquid rate Press drop thro” grid ‘Transfer coefficient for AA straight run light end unit Gilliland correlation . A debutanizer temperature profile ‘Spliter feed pseudo components Catalytic reforming .....:. ‘Typical naphthene contents vs cut points for African crudes . ‘Typical naphthene-contents vs cut points for Middle East crudes Volume of aromatics in reformates . ‘TBP curve of C5+ reformate Hydrofining unit—middle dist Diesel component breakdown . Enthalpy curve for reactor effluent . Fluid catalytic cracking unit FOCU .viii LIST OF FIGURES: Hydrotreated gas oil, yield vs conv 239 Sassan gas oil, yield vs conv . 240 Hydrocracker gas oil, yield vs 240 Straight rum diesel 520-650 °F, yield . mat Hydrotreated diesel 520-650 °R, yield «0.2.2... 241 Hydrocracker gas oil 380-650 °F, yield vs conv. 22 Hydrocracker gas oil 650-750 °F, yield ys conv. 22 Hydrotreated gas oil 380650 °F, yield vs conv , 43 Visbreaker gas oil 380-650 °F, yield vs con 203 ‘Two stage regenerator 245 Heat of combustion vs CO/CO, ratio . 246 Contbaton air requenent vs 00/00, 247 Typical catalyst coolers 49 FCCU product TBP curves 254 FCCU syncrude TBP curve : 254 FCCU syncrude gravity vs mid boilding : 256 FCCU syncrude total sulphur vs mid boiling points . 257 Cat cracker fractionator EFV cruves ..... 259 FCCU C$+ gasoline TBP and pseudo components » 260 Typical syn tower profile ...... 262 Disc and donut shed type surfaces . 268 Disk and donut and shed baffle heat transfer 269 Distillate hydrocracking ca Main fractionator TBP curves 219 Liquid effluent ex hot flash TBP curve. 280 lue cracking and visbreaker units 298 Liguid effluent ex residue HCK hot flash TBP curve. 300 Residue cracker vacuum unit product TBP curves, 300 Coil volume vs temperature ......... 44+ 307 Visbreaking curve of coil temperatare ¥s xa 307 Coil volume vs KT/K800 308 SVF vs conversion . 310 ‘Thermal cracking yields Yawt vs soaking volume factor (stillatz portion) : : 310 ‘Thermal cracking yi (bitumen portion). ... il Visbreaker effluent TBP and EFV curves. 34 Process flow diagram of a typical HF alkylation unit 320 Estimated tower profile of the isostripper ...... 338 ‘Typical alkylate TBP curve and pseudo components . 339 Amine treating wit... 356 ‘A typical DEA or MEA contactor . 358 ASTM—TBP correlation 380 ‘TBP—EFV correlation... : 381 ‘TBP cut point vs ASTM end point. 382, Probability curves for ASTM dist 383 Correlation for Bpt, MW, °API, 384 Vap press curves—high temp 385 ‘ap press curves—low temp. 386 LMTD correction factors 387, 388 Heat of combusion—fuel oils 389 Heat of combusion—fuel gases 390 HIS partial press in MEA 391, 392 Fractionation curves... 393 Kuvait crude TBP curve. 396 Kuwait crude sg vs mid by 397 Kuwait crude sulphur vs mi 398 Kuwait crude pour, cloud, freezing pts 399 Kuwait crude viscosities vs mid bpt . 400PREFACE ‘Much of this book was assembled and compiled by myself into a reference manual for an African oil refining company. The work was in response to a brief by which the client company required a document to serve as a book of reference encompass basic process calculation techniques and rules of thumb relating to the refining processes. The idea was to improve the knowledge and expertise of the refinery’s technical and engineering staff in the process performance evaluation and operation ‘of the refinery. Although the refining company had up-to-date computerized process simulation packages its more junior staff had some difficulty inputting these programs due to their limited refinery process experience. The manual was also meant to improve this situation. ‘The completion and the successful use of the manual over the past few years has prompted the writing of Elements of Petroleum Processing. Some changes and additions have been made to the original work to provide a textbook which is oriented not only to refinery operation but also, in many instances, to basic design practices and techniques. The entire work concerns only the energy-related Refinery and does not include those data, correlations, ete, met with in lube oil and petrochemical oil refineries. This book is divided into three parts, Part 1 includes a brief description of the chemical make-up of crude oil, the various types of crude and their products. It continues with the rules of thumb and techniques used to define product quality and basic correlation. The part also includes a brief description of the more common processes found in an energy-related refinery and makes reference also to the more common non energy refineries. Finally, it provides a simple example of how Part 1 is used to define and establish a refinery process configuration. Part 2 is the first of two parts that introduce the reader to detailed calculation techniques and data concerning the refinery processes. It encompasses those techniques used in the design and operation of the primary crude atmospheric and vacuum distillation plants. It follows with a similar treatment relating to the fractionation of the light fractions of the crude oil. Each chapter of this part includes a description of the process unit in some detail and provides related calculations in stepwise form. A worked ‘example of the calculation topic completes each chapter. Part 3 covers a selection of those units often included in refinery configurations which upgrade low-grade products, This is accomplished by converting them to a different chemical composition. Bach selected process is the subject of the individual chapters contained in this part. The format of these chapters follows closely that of Part 2. However, in some cases in this part there is a more detailed discussion covering the reaction chemistry and design techniques for the processes described.x PREFACE ‘Throughout this work the data and techniques used have been well proven over years of use in design and operation before the days of modem high-speed computer programmes covering the same subject. Much of the contents are taken from personal files and experience over a period of 42 years in or associated with the oil industry. ‘This experience spans the years spent in refinery operations, process development and process engineering with a major international engineering and construction company and, more recently, as a consultant engineer. Stan Jones Calgary, AlbertaPart 1 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING1 CRUDE OIL AND ITS PRODUCTS 1.1 Composition .. 1.2. Types of crude oil . 1,3. Products from crude oil Oil refining and the development of the internal combustion engine haye continued since the latter part of the nineteenth century. Bach have influenced the other in the course of this development, but it is the oil industry and its effect on almost every part of modern living that has been the most spectacular. This part of the book offers an introduction to this industry in the form of outlining the nature of crude oil, its products and the manner in which it is processed to arrive at those products that have become a part of today’s living. The purpose of these introductory chapters is also to describe and define the basic measures and parameters used in the ‘industry. ‘These set the stage for the more detailed examination of those refinery processes provided in subsequent chapters. { 1.1 ‘Composition Crude oil is a mixture of literally hundreds of hydrocarbon compounds ranging: in size from the’smallest; methane, with-only: one carbon-atom, to. large compounds containing 200 or more: A major portion of these compounds are paraffins or isomers of paraffins: These are straight-chain hydrocarbon compounds such as butane, i.e.: — H+. Normal butane. . @enoted simply.as nC;) H— x=—o—=z H | oe | H xr—o—=z xr—o—=4 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING H c—o— ISO butane HOA | (denoted simply as iC,) ‘The remaining hydrocarbon compounds are either cyclic paraffins called naphthenes or aromatics. Below are examples of those compounds: * ato o—2H 2H-CNo, _-C—2H_ | Crslohexane (naphthene) 1 a Br gente oo H—- CN Z0-H i ‘These families of hydrocarbons are called homologues, and because of the large Quantity of these compounds which exist in crude oil, only the simplest of compounds in the homologues can be isolated to some degree of purity. ona commercial scale. Generally, in refining projects, iéolation of- comparatively pure products are restricted to those compounds lighter than-C; s: Most compounds, however, have been isolated and: identified but oily under strict and delicate laboratory conditions. In the industry the products are restricted to groups of these hydrocarbons boiling between selective boiling ranges, Thus products are usually denoted by boiling points rather than by the compounds they contai Not all compounds contained in crude oil ate pure hydrocarbons. The crude does contain certain inorganic impurities such as sulphur, nitrogen and metals, By far the most common of ‘these impurities are the organic. sulphur compounds called mercaptans. These compounds are similar to hydrocarbons but with the addition of ‘one or more sulphur atoms, ¢.g.: H fe ie SH ang mercaplan HOHCRUDE OIL AND [TS PRODUCTS: Bt ‘More complicated sulphur compounds also exist such as thiophenes in the high carbon number range homologues and disulphides in the middie distillate range, Because of the close relationship that exists between these sulphur compounds and neighbouring hydrocarbons in such characteristics as vapour pressures, the compounds cannot be isolated by distillation processes on a commercial scale. ‘Organic chloride compounds are not usually removed from the crude as products but the corrosive effect attributed to these compounds on parts of refinery plants is always a source of concern. A considerable amount of investigation has been, and is stilt being, carried out on prevention of corrosion by HCl generated in the process from these organic chlorides. 5 7 The metals contained in crude are usually nickel, sodium and vanadium, Because these are not very volatile they are found in the heavier products of crude such as fuel oil. They only become a nuisance in certain cases when they can affect further processing of the oil, or if they exist in such large quantities in fuel oil as to limit the saleable value of the product. Their removal can be effected in such cases by an extraction process where they are removed as a part of a bituminous extract called asphaltenes. Before leaving the subject of crude oil composition it is necessary to mention yet another series of organic compounds which, although not always present in the original crude, are often formed during the refining processes, These are unsaturated or double- bond compounds. As mentioned earlier, most compounds contain carbon and hydrogen and are so made up that each carbon atom contains its full quota of four atoms, in the form of either hydrogen or carbon. However, some of these molecules break down under conditions of high temperature and permanently lose one or more of those attached atoms, Such compounds are unstable and readily combine with themselves or other similar compounds to form polymers. They are called unsaturates while the stable hydrocarbons such as paraffins, cycloparaffins and aromatics are called saturated hydrocarbons. An example of such a compound is ethylene, which has the following formula: HoH —C=C—H Note the double-bond linking the two carbon atoms. 1.2. Types of Crude Oil Crude oil found in various parts of the world can vary considerably in characteristics. This can readily be seen in the difference in specific gravity that exists between the ‘crudes. For instance, Zelten crude (Libyan) has an API gravity of 39.0 while Bachequero crude has a gravity of 16.0. This difference is due to the fact that although each crude oil contains basically the same hydrocarbon compounds, the proportion. of these hydrocarbon vary considerably from one crude to another. Thus some crudes are relatively rich in paraffins, and this is reflected by the waxy nature of the crude (most Middle East crudes fall into this group). Others contain more cycloparaffins and aromatics (such as Nigerian and some American West Coast crudes).6 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING Although itis theoretically possible to produce any type of refined product from any crude, itis not usually economically feasible to do so, For instance, better yields of reformer stock for aromatics production is obtained from Nigerian crude than from Kuwait, while considerably more residium for fuel oil is obtained from Kuwait than Nigeria, To satisfy the demand of these two products, refineries often blend two such devious crudes, changing the proportion of the blend to satisfy the particular need. If product demands are seasonal, a in the case of many gas oils, imports of specifically selected crudes are scheduled to optimize the production of such cuts for the season. Selectivity of crude type is comparatively easy to effect and is common practice in the refining industry where most oil companies have their own oil wells in various patts of the world, However, occasionally the demand for a particular product or the elimination of a low-value one becomes so persistent that major conversions of a chemical nature have to be adopted. Such processes as thermal and catalytic cracking and, more recently, hydrocracking are used to effect this, These, as processes, are discussed in detail in later chapters of this book. 1.3. Products from Crude Oil In general, the products that are normally obtained from crude oil can be grouped as follows: (1) Volatile products (these are the lightest products) ‘@ Propane LPG (liquefied petroleum gas) @ Butane LPG @ Light naphtha (Css and nC,) (2) Light distillates © Gasolines Heavy naphtha (petrochem naphtha and base for paints) © Kerosene and jet fuels (3) Middle distillates @ Automotive diesel © Heating oils Gas oils (4) Fuels oils ‘Marine diesel @ Bunker fuels (for ships) (3) Lubricating oils Motor Spindle @ Machine oils © Wares Food and paper coating grade Pharmaceutical grade (1) Bitumen @ Asphalt ®CokeCRUDE OIL AND ITS PRODUCTS 7 Products in these groups are produced from distillation processes and treated to meet certain specifications. These specifications are the result of a compromise between desirable performance characteristics in the product and the ability to make such products from the crude and the processing facilities at hand. Wide ranges in physical propetties are often tolerated in these specifications in order to cater for crude oil source, sales arca and the product’s ultimate use.2 | THE CRUDE ASSAY 2.1 Assay data and laboratory tests... 00... cece cee eeeeeeeeeeee 8 The crude assay is a compilation of laboratory and pilot plant data that defines the properties of the specific crude oil. At a minimum the assay should contain a true boiling point curve and a specific gravity curve for the crude oil. However, most crude oil suppliers extend the scope of the assay to include sulphur contents, viscosity, pour points and many other properties. Figures A2.1 to A2.5 in appendix 2 are typical curves taken from a Kuwait crude assay. The character of the crude has changed slightly since these curves were developed, so more recent data must now be used for definitive design work. These curves ate: Figure A2.1 is a plot of the true boiling point of the crude against total distillate recovery (the TBP curve). Figure A2.2 isa plot of specific gravity against mid-boiling points of the crude oil fractions. Figure A2.3 shows the sulphur content of the crude oil fractions against their mid- boiling point. Figure A2.4 isa similar plot of the freezing, pour, and cloud points of the crude fractions against their mid-boiling point. Figure A2.5 isa plot of the viscosity of the crude fractions against their mid-boiling points. These are plotted at 70°F, 100°F, 120°F and 210°F, 2.1. Assay Data and Laboratory Tests To understand fully the significance of these assay curves and data it is necessary to define and explain some of the basic laboratory tests and data used to compile the assay. These are as follows: © TBP curve (true boiling point curve) This s a plot of the boiling points of almost. pure components, contained in the crude oil or fractions of the crude oil. It is accomplished under laboratory conditions using a complex batch-distillation apparatus of a hundred or more equilibrium stages and with a large volume of‘THE CRUDE ASSAY 9 reflux. A typical TBP curve for a whole crude is shown as Figure A2.1. Initially the temperature goes up in well-defined steps representing single components. However, as the temperature rises, the number of close boiling point components increases and the steps become increasingly less distinct until they merge into a smooth curve, This test is rarely used on a routine basis. @ ASTM distillation This is carried out in a simple apparatus designed to boil the test liquid and to condense the vapours as they are generated. Vapour temperatures are noted as the distillation proceeds and are plotted against the distillate recovered. Because only one equilibrium stage is used and no reflux is returned, the separation of components is poor and mixtures are distilled. The initial boiling point is higher than that for the TBP and the final boiling point is lower. ASTM distillations are employed as routine tests to measure quality of refincry products, @ Equilibrium flash vaporization (EFV) When a mixture is heated without allowing the vapour to separate from the remaining liquid the vapour assists in causing the high boiling parts of the mixture to vaporize. In almost all commercial plant operations involving change of liquid vapour phase continuous flash vaporization occurs. The BEV curve of an oil is determined in a laboratory using an apparatus which confines liquid and vapour together until the required degree of vaporization is achieved. The percentage vaporized is plotted against temperature for several runs to give the FV curve. Separation is poorer for this type of distillation than for an ASTM, therefore the initial point will be higher than the ASTM but final boiling point will be lower. Empirical correlations exist to convert from, TBP ASTM and EFV. 2 © API gravity . This is an expression of the density of an oil. Unless otherwise stated, the API gravity.refers to density at 60°F. Its relationship with specific gravity is given by the expression degrees API =(141.5- 131/SP GR). i © Reid vapour pressure (RVP) This isa laboratory test used to determine the vapour pressure of natural gasoline at 100 °F. The true vapour pressure is about 529% higher than the figure obtained by this test. @ Flash points | The. flash point of an oil, is the temperature at which the vapour above the oil will momentarily flash, or explode. This temperature is determined by laboratory testing using an apparatus consisting of a closed cup containing the oil, heating and stirring equipment, and a special adjustable flame, The type of apparatus used for middle distillate oils and fuels. is called the Pensky Marten (PM) apparatus while the apparatus used for kerosene and light distillates is called the Abbel. Full details of test method and description of the equipment is given in the ASTM standards, Part 7 Petroleum Products and Lubricants. This test serves to indicate the temperature below which an oil can be handled safely. There are many empirical methods for determining flash point from the ASTM distillation curve. One such correlation is given, by the expression. Flash point °F =0.77 (ASTM 5% °F-150°F). © Octane Rumber This is a measure of a gasoline’s resistance to knock or detonation ina cylinder of a petroleum engine, The higher this resistance, the higher is the efficiency of the fuel to produce work. There is also a relationship between the anti-knock characteristic of a gasoline (octane number) and the compression ratio10 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING of the engine in which it is to be used. The higher the octane number, the higher the compression ratio that can be used. By definition, the octane number of a gasoline is that percentage of Iso-octane in a blend of Iso-octane and normal heptane which exactly matches the knocking behaviours of the gasoline, Thus a 90-octane gasoline matches the knock characteristic of a blend containing 90% Iso-octane and 10% normal heptane. The knock characteristics are determined in the laboratory using a standard single- cyclinder test engine which is equipped with a super-sensitive knock meter. The reference fuels (Iso, and N C; blend):are run and compared with a second run using the gasoline, Full details of this testis given in the ASTM standards, Part 7 Petroleum Products and Lubricants, ‘Two octane numbers are usually determined. ‘The first is the research octane muimber (ON (res)) and the second is the motor octane number (ON (fum)), The same basic equipment is used for both but the engine speed for the motor method is higher than that for research. The actual octane number obtained in @ commercial engine would be somewhere between these two. The significance of these two octane tests is to evaluate the sensitivity of the gasoline to the severity ‘of operating conditions in the éngine. Invariably the research octane number is higher than the motor octane; the difference between them being quoted as “the sensitivity of the gasoline’. Viscosity The viscosity of an oil is a measute of its resistance to internal flow and is an indication of its lubricating qualities. In the oil industry it is usual to quote viscosities in centistokes (which is the unit for kinematic viscosity), seconds Saybolt Universal, seconds Saybolt Furol or seconds Redwood.’ These units have been correlated and such correlations can’ be found in’ most data books. In the laboratory, test data on viscosity are usually determined at temperatures of 100°F, 30°F or 210 °F, In the case of fuel oils temperatures of 122 °F and 210°F are used. © Cloud and pour points These are tests to indicate the relative Waxiness of an oil. "They do not, however, measure the actual wax content of the oil. The tests merely consist of reducing the temperatute of the oil under controlled conditions. The toinperature at which the oil becomes cloudy or hazy is taken as its'cloud point, while the temperature at which the oil ceases to flow is: taken as its pour point. © Sulphur content This is self-explanatory, and is usually the measure of total sulphur in the oil, ‘There are, of course, many other laboratory tests and data that define the qualities and characteristics of crude oil and its products. The ones listed above’are among the most common, and other tests and’ definitions can be foutid in the appropriate volumes of ASTM Tests and the API manuals.3 PSEUDO-COMPONENTS AND PREDICTING PRODUCT PROPERTIES ul 14 3.1 Terminology ......, 3.2. Predicting product properties . It is not possible to separate the components of crude oil into commercial processes. but groups of these components are produced to meet the requirements ofthe various refinery products. These are called ‘cuts? and each identified as cut ranges. Bach of these ‘cuts? can be further defined by dividing them up into pseudo- (not real) components and relating their properties (such as SG, viscosities, etc.) to comparable real and identified components. Some of the technology used and the method of developing pseudo-components are discussed below. 3.1. Terminology © Cut point A cut point is defined as that temperature on a whole TBP curve that represents the limits of a fraction to be produced. Consider a typical TBP curve shown in Figure 3.1. A fraction with a cut-off point of 100 °F represents a yield of 20% of the whole as that fraction. A boiling range is, more often than not, quoted as the yield between two cut points. Thus a boiling range (TBP) of 100-200 °F represent a fraction with a yield of 30% — 20! 0% vol. on whole feed. © End points A cut point is an ideal temperature used to predict a yield of a fraction. When that fraction is actually produced commercially, however, its final TBP boiling point will be considerably higher than the quoted cut point. This is due to the inability of the process to separate perfectly the components of one fraction from those in the adjacent one. Its actual final boiling point is called the end point. ‘Thus the relationship of the product TBP curves to the whole crude TBP appears as in Figure 3.1. © Mid- boiling point components In compiling the assay, narrow boiling fractions are distilled from the crude and are analysed to determine their properties.R AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING % volume dstiled Figure 3.1, Definition of cut points and end points Temp. ————-» Figure 3.2, Definition of mid-boiling pointsPSEUDO-COMPONENTS AND PREDICTING PRODUCT PROPERTIES B ‘These are then plotted against the mid-boiling point of these fractions to produce ‘a smooth correlation curve. To apply these curves for a particular calculation it is necessary to divide the TBP curve of the crude or fraction of the crude into mid- boiling point components. To do this consider Figure 3.2, For the first component take an arbitrary temperature point A. Draw a horizontal line through this point from the 0% volume, Extend this line until the area between the line and the curve ‘on both sides of the temperature point A are equal. The length of this horizontal line measures the yield of component A having a mid-boiling point A °F. Repeat for the next component and continue until the whole is divided into these mid- boiling point components. © Mid-volume percentage point components Sometimes the assay has been so constructed as to correlate crude oil properties against components on a mid-volume percentage base instead of mid-boiling point. In using such data as this it becomes necessary to divide the TBP curve into mid-volume point components. This is easier than the mid-boiling point concept and requires only that the curve is divided into a number of volumetric sections. The mid-volume point of each section is the arithmetical mid-point in this case. © Predicting TBP and ASTM curves from assay data The properties of products ‘can be predicted by constructing mid-boiling point components from a TBP curve and assigning the properties to each of these components. These assigned properties may be obtained from the assay data, known components of similar boiling points or established relationships such as gravity, molecular weights and boiling points. However, before these mid-boiling point (pseudo-) components can be developed it is necessary to know the shape of the product TBP curve. The following is a method by which this can be achieved. Good, Connel-et al (1) accumulated data to relate the ASTM end point to a TBP cut. point over the light and middle distillate range of crude. Their correlation curves are given in Figure A{.3 in Appendix |, and are self-explanatory. Thrift (2) derived a probable shape of ASTM data. The probability graph that he developed is given as Figure A1.4 in Appendix 1, The product ASTM curve from a well-designed unit would be a straight line from 0% vol. to 100% vol. on this graph. Using these two graphs it is possible to predict the ASTM distillation curve of a product knowing only its TBP cut range. This is shown in the following example, Eximple Caleulation Calculate the ASTM curve for kerosene, cut between 387 °F and 432 °F cut points on Kuwait crude, SOLUTION Yield of crude =3,9% vol. Cut range =27.3%-31.2% vol. 90% of TBP cut=30.81% vol. = 430°R From Figure A1.3. curve B ASTM EP =432-13 °F=419°F From Figure A1.3. curve G ASTM 90%=430-24 =406°F4 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING 20 40 oop ce 0 o 0 2 10 0 & @ 7m 0 w FOP 4 Vol dstited Figure 3.3. Comparison between calculated ASTM curve and laboratory data ‘These two points are plotted on Figure Al.4 and a straight line drawn through them to define the probable ASTM distillation of the cut. This is plotted Jinearly in Figure 3.3 and can be seen to compare well with laboratory results of the actual product from a crude: distillation unit, The predicted ASTM curve may now be used to arrive at the TBP and BFV curves of the product by the methods described later in this book (see Section 6,3). 3.2. Predicting Product Properties ‘The following describes the prediction of product properties using pseudo-components (mid-boiling point) and assay data. A diesel cut with TBP cut points 432-595 °F on Kuwait crude will be used to illustrate these calculations. The actual TBP of this cut is predicted using the method already described. The curve is then divided into about. six pseudo-mid-boiling point components as described earlier and is shown in. Figure 3.4. ic © Predicting the gravity of the product Using the mid-boiling point versus specific gravity curve from the assay given in Appendix 2 the SG for each Component is obtained. The weight factor for each component is then obtained by multiplying the vol.% of that component by the specific gravity. ‘The’ sum of the weight factors divided by the 100% volume total isthe specific gravity of the as oil cut.PSEUDO-COMPONENTS AND PREDICTING PRODUCT PROPERTIES 10 20 ERIE EE eo so | 560 | F panied co ree | = 07 — so Mia °F 0 soubor cone 0 eat rior 0 Colee a eo cd sods las 0 can | {ss 7 r route Fy o 0 8m oo 8) 0 0 ww ~ Volume % dstited Figure 3.4, Pseudo-component breakdown by mid-boiling points Weight Component Volume % Mid-BPT (°F) SG at 60°F factor 1 13.0 410 (210°C) 0.793 103 2 165 460 (238°C) 0.801 132 3 11.0 490 (254°C) 0.836 116 4 18.0 520 @71 °C) 0.844 15.2 5 185 550 (288 °C) 0.846 18.7 6 13.0 591 (311 °C) 0.850 ALD Total 100.00 - = 83.1 £831 (actual plant data for this cut was 0.829) 816 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING ‘© The prediction of product sulphur content The prediction of sulphur content is similar to the method used for specific gravity. First, the TBP curve for the product is determined and split into pseudo-mid-boiling point components, The weight factor is then determined for each component as before. (Note: sulphur content is always quoted as a percentage weight.) Using the relationship of percentage sulphur to mid-boiling point given in the assay (Appendix 2) the sulphur content of each component is read off. This is multiplied by the weight factor for each component to give a sulphur factor. The sum of the total sulphur factors divided by the total weight factor gives the wt% sulphur content of the fraction. For example, using the same gas oil cut as before, its sulphur content is determined as follows: Weight Sulphur % Sulphur ‘Component factor Mid-BPT (°F) wt factor 1 10.3 410 (210°C) 0.20 2.06 2 13.2 460 (238°C) 0.410 5.4 3 116 490 (254°C) 0.840 14.78 4 15.2 $20 271°C) 1.160 11.63 5 18.7 350 (288 °C) 1.350 21.20 6 Mt 591 GIE°C) 1.500 16.65 Total 83.1 = = 103 Sulphur % weight =(77.7/83.1) x 100:=0,935% wt (actual plant data gave 0.931% wt) © Viscosity prediction from the crude assay Unlike sulphur contents and gravity, viscosities cannot be arithmetically related to components: To determine the viscosity of a blend of two or more components a blending index must be used. A graph of these indices are given in Maxwell's Data Book on Hydrocarbons (3), and part of this graph is reproduced as Figure 3.5. Using the blending index and having split the fraction into components as before, the viscosity of the fraction can be predicted as shown in the following example: Viscosity CS Blending Viscosity Component Volume % Mid-BPT (°F) at 100°F —_—_index factor ) ®) (AxB) t 130 40q@iorc) 1.49 65 825.5 2 165 460238°C) 2.0 538.0 957.0 3 21.0:, 4902540), 24 35.0 1155.0 4 180 S20@N%C) 29 52.5 945.0 5 185, 550(288°C) 3.7 49.0 906.5 6 13.0 SGII°C) 48 46.0 598.0 Total 100.0 = = = 5387.0 ats Overall viscosity index == From Figure 3.5 viscosity =2.65 eSt ' {actual plant result was 2.7 St)PSEUDO-COMPONENTS AND PREDICTING PRODUCT PROPERTIES 7 Blending indox Kinetic viscosity (6S) Kinetic vicoosty (et) on oo os 0 © © 6 © 8 Blending indox Figure 3.5. Viscosity blending chart (Maxwell, Data. Book on Hydrocarbons; used. by permission.) 10% i Frawes on Saves a. ; ASTM st pin onperatures | 10" ( ‘60 40 0 0 0 1 mm BO OO : Pour points (*F) Figure 3.6, Pour point blending chart18 AN INTRODUCTION TO CRUDE Ol. AND ITS PROCESSING 10000, 8 Flashpoint blending index oot a ee) Flash temperature (F) Figure 3.7. Flash point blending indexes can be combined linearly by volume (Reprinted by permission from Hydrocarbon Processing, June 1963, copyright Gulf Publishing Co all. vighs reserved.) © Cloud and pour points In predicting these properties itis not necessary to break- down the product TBP as we have done for API, sulphur, etc. The accuracy of the tests and of blending indices does not warrant ths, These properties are therefore read off directly from the mid-boiling point of the whole product. Considering the gas oll used inthe previous example, its mid-boiling point is about 510 °F. From the crude assay its pour point is ~5 °F and cloud point is +4°R, Determining pour point for a blend of two or more products is rather more difficult. In this case blending indices are used. A graph of these indices is'given as Figure 3.6. This is self-explanatory and its application is explained by the following example: 2000 BPSD of a gas oil having a pour point of -5°F and ASTM distillation 50% point of 500 °F is to be blendéd with 4000 BPSD of a waxy distillate having a pour point of 30°F and a $0% ASTM distillation point of 700 °F. The Pour point of the final ‘blend is predicted below:: H ‘Composition ASTM 50%. Pour Point Components BPSD Fraction 50% Factor Pour PT Index Factor (a) (B) (AxB) © Axo Gas oil 2000 0.33 500165 =5 58 19 Waxy dist, 4000 0.67 700, 469 $3012.78. Total 6000 1.00 4 = 104 From the chart in Figure 3.6 the pour point corresponds to an index of 10.4 and ASTM 50% of 634°F is 22°F. This is the pour point of the blend.PSEUDO-COMPONENTS AND PREDICTING PRODUCT PROPERTIES 19 © Flash points The flash point of a product is related to its ASTM distillation by the expression: Flash point =0.77 (ASTM 5% in °F-150 °F). ‘Thus for the gas oil product in the Example (given below) the flash point is predicted as follows: © Blending products to meet a flash point specification As with pour points and viscosities, the flash point of a blend of two or more components is determined by using a flash blending index. Figure 3.7 gives these indices. Again the indices are blended linearly by volume as in the case of viscosities. Thus consider the following example. 2000 BPSD of kerosene with a flash point of 120 °F is to be blended with 8000 BPSD of fuel oil with a flash point of 250 °F, What will be the flash point of the final blend? ‘Solution See Component Volume Fraction Flash (°F) ‘Flash index Factor (a) @) (AXB) Kero 2000 0.2 120 310 62.0 Fuel 8000 0.8 250 $5 44 Total 10000 1.0 = = 66.4 rom Figure 3.7 the flash point corresponding to 66.4 index= 166 °F ‘This is the final blend flash point © Predicting mole weights of products It is important to know the molecular weights of the hydrocarbon streams to be able to carry out many of the design or other calculations relating to refinery processes or operations. This is particularly so in distillation calculations and where chemical reactions occur. The term ‘moles’ refers to pound moles, A relationship exists between the mean average boiling point (MEABP), API and the molecular weight of petroleum fractions (4) and this is given in Figure 3.8 (see also Figure A1.5 in Appendix). Example calculation Referring again to the example gas oil fraction used eatlier, the ASTM distillation curve corresponding to this fraction is as follows: % vol. oF 0 406, 10 447 30 469 50 487 70 307 90 538 100 57820 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING Slope of the curve is ae 30 538-447, a 1.14 °F/% Tyo OX Tsp) + Tye E 4 Vol. average boiling point _ 447+ 974 + 538 4 =490 Mean average boiling point = 490+(—5 °F). See top curve of Figure 3.8 = 485 °F API is 38.8 as calculated earlier. Mole weight of this fraction is 194 (From Figure 3.8) A rigorous calculation method resulted in a mole weight of 201.PSEUDO-COMPONENTS AND PREDICTING PRODUCT PROPERTIES a ASTID 88 0% 0% lope FP recovered 4 6 Cceracon tobe eed fo wcumabc avorage bing pont CF) be ied ng WOO 20 800 Bi mo ‘Mean average bog pat PF) Figure 3.8. Corelation’ Between MeABP, SG and mol. wt4 BASIC PROCESSES 4.1 The atmospheric crude distillation unit 4.2 The erudle vacuum unit 4.3 The light end unit . 4.4 The catalytic reformer | plant 4.5 The hydrotreating units (desulphurization). 4.6 The fluid catalytic cracking unit (FCCU) 4.7. Hydrocracking 4.8 Thermal; cracking units . 4.9 Other refinery processes . ; 4.10. The non-energy product refineries . 4.11 Oxygenated gasolines ....... “This chapter provides an introduction to some of the most common of the provesses included in a fuel-oriented ‘refinery. These processes are only discussed, here in summary form but later inthe book they are dealt with in some detail. ‘4.1. The Atmospheric Crude Distillation Unit In refining the crude oil itis first broken up into those raw stocks that are the basis of the finished products. This break-up of the crude:is achieved by separating the oil into a series of boiling point fractions which meet the distillation requirements and some of the properties of the finished products. This is accomplished in the crude distillation units, Normally there are two units that accomplish this splitting-up ‘funtction: © An atmospheric unit -@A vacuum unit ‘The entde oil first enters the atmospheric unit where it is desalted (dissolved brine is removed by washing) and heated to @ predetermined temperature. This is accomplished by heat exchange with hot products and finally by a direct-fired heater. The hot and partially vaporized crude is ‘flashed’ in a trayed distillation tower.BASIC PROCESSES 23 Here the vapour rising in the tower is selectively condensed by cooled reflux streams and taken off at various parts of the tower as distillate side-streams. The light oils not condensed in the tower are taken off at the top of the tower to be condensed externally as the overhead product. The unvaporized portion of the feed leaves the bottom of the tower as the atmospheric residue, ‘The unit operates at a small positive pressure around 5-10 psig in the overhead drum, thus its title of ‘atmospheric’ crude unit. Typical product streams leaving the distillation tower are as follows: Overhead distillate Full-range naphtha Gas to 380 °F cut point Ist side-stream_ Kerosene 380-480 °F Ind side-stream Light gas oil 480-610 °F 43rd side-stream Heavy gas oil 610-690 °F Residue Fuel oil +690°F Full details of this unit are given in Chapter 6. 4.2. The Crude Vacuum Unit Further break-up of the crude is often required to meet the refinery’s product slate, This is usually required to produce low-cost feed to cracking units or the basic stocks for lubricating oil production. To achieve this, the residue from the atmospheric unit is distilled under sub-atmospheric conditions in the crude vacuum distillation unit. ‘This unit operates similarly to the atmospheric unit in that the feed is heated by heat exchange with hot products and then in a fired heater before entering the distillation tower. In this case, however, the tower operates under reduced pressure (vacuum) conditions, These units operate at overhead pressures as low as 10mm Hg absolute. ‘Under these conditions the hot residue feed is partially vaporized on entering the tower. ‘The hot vapours rise up the tower to be successively condensed by cooled internal reflux stream moving down the tower as was the case in the atmospheric distillation unit. The condensed distillate streams are taken off as side-stream distillates. There is no overhead distillate stream in this case. ‘The high-vacuum condition met within these units is produced by a series of steam ejectors attached to the unit’s overhead system. Typical product streams from this unit are as follows: ‘Top side-stream Light vacuum gas oil 690-750 °F 2nd side-stream Heavy vacuum gas oil 750-985 °F Residue Bitumen +985 °F ‘This unit is further described and discussed in Chapter 7. 4.3 The Light End Unit ‘The full-range naphtha distillate as the overhead product from the atmospheric crude unit is divided further into the basic components of the refinery’s volatile and light oil products. This is done in the light end plant which contains four separate distillation units:24 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING ©The debutanizer ©The depropanizer ©The de-ethanizer ©The naphtha splitter ‘The full-range naphtha from the atmospheric crude overhead is routed first to the debutanizer unit. The stream is heated by heat exchange with hot products before entering the feed tray of the debutanizer column. This is a distillation column containing between 30 and 40 trays, Separation of butanes and lighter gas from the naphtha occurs in this tower by fractionation. The butanes and lighter are taken off san overhead distillate while the naphtha is removed as the column’s bottom product. ‘The overhead distillate is then heated again by heat exchange with hot streams and fed into a depropanizer column. This also has about 30 to 40 distillation trays and separates a butane stream from the propane and lighter material stream by fractionation. The butanes leave as the column’s bottom product to become the butane LPG product after further ‘sweetening’ treatment (sulphur removal). The column’s overhead distillate is fed to a de-ethanizer column after preheating. Here the propane is separated from the lighter materials and leaves the column as the bottom product. ‘This stream becomes part of the refinery’s propane LPG product after some further sweetening treatment. There will be no overhead distillate product from this unit. ‘The material lighter than propane leaves the overhead drum as a vapour containing mostly ethane, The debutanized naphtha leaving the bottom of the debutanizer is subsequently fractionated in the naphtha splitter to give a light naphtha stream_as the overhead distillate and a heavy naphtha as the column’s bottom product. The light naphtha is essentially C5s and nC6s. This stream is normally sent to the refinery’s gasoline pool as blending stock. The-heavy naphtha stream. contains the cycloparaffin components and the higher paraffin isomers necessary in making. good catalytic reformer feed. This stream is therefore sent to the: a reformer after it has been hydrotreated for desulphurization, 4.4 The Catalytic Reformer Plant ‘The purpose of the catalytic reformer plant is to upgrade low-octane naphtha to the high-octane material required for motor gasoline fuel. It achieves this by reforming some of the hydrocarbons in the feed to hydrocarbons of high octane value, Notable among those reactions is the conversion of cycloparaffin content of the feed to aromatics, This reaction also gives up hydrogen molecules which are subsequently used in the refinery in other processes, The feed from the bottom of the naphtha splitter is hydrotreated in the naphtha hydrotreater for the removal of sulphur and nitrogen. It leaves this unit to be pre- heated to the reforming reaction temperature by heat exchange with products and bya fired heater. The feed is mixed with a recycle hydrogen stream before entering the first of three reactors. The reforming reactions take place in these reactors and the reactor temperatures are sustained and controlled by intermediate fired heaters. ‘The effluent leaves the last reactor to be cooled and partially condensed by heatSSSGESREIRESNSSeeereeeecccccccicenereeeeee BASIC PROCESSES: 25 exchange with cold feed and a condenser. This cooled effluent is routed to a flash drum from which a hydrogen-rich stream is removed as a gas while the reformate is removed as a liquid stream and sent to a stabilizer column, ‘The bottoms from this column is debutanized reformate and is sent to the gasoline pool for blending to meet motor gasoline specifications. Part of the gas leaving the flash drum is recycled to the reactors as the unit’s recycle stream, The remaining gas is normally sent to the naphtha hydrotreater for use in that process, Details of this unit are given in Chapter 9, 4.5 The Hydrotreating Units (Desulphurization) Most streams from the crude distillation units contain sulphur and other impurities such as nitrogen, and metals in some form or other. By far the most common of these impurities is sulphur, and this is also the least tolerable of these impurities, Its presence certainly lowers the quality of the finished products and, in the processing of the crude, invariably affects the performance of the refining processes, Hydro- treating the raw distillate streams removes a significant amount of the sulphur impurity by reacting the sulphur tholecule with hydrogen to form hydrogen sulphide (H,S). This is then removed as a gas, bi ‘Two types of desulphurizing hydrotreaters are presented in this book (see Chapter 10): © Naphtha hydrotreating—Once-through hydrogen © Diesel hydrotreating—Recycle hydrogen In naphtha hydrotreating the naphtha from the naphtha splitter is mixed with the hydrogen-rich gas from the cat reformer unit and preheated to about 700 °F by heat exchange and a fired heater. On leaving the fied heater the streams enters a reactor containing a desulphurizing catalyst (Usually a CoMo on alumina base), The sulphur components of the feed combine with the hydrogen to form H;S, The effluents ftom ‘the reactor are cooled and partially condensed before being flashed in a separator drum. The gas phase from this drum is stil-high in hydrogen content and is routed {0 other downstream hydrogen-user processes: This seam contains most of the H,S ‘produced in the reactors, The remainder leaves the flash drum with the desulphurized naphtha liquid to be removed in the hydrotreater's stabilizer column, Diesel hydrotreating has very much the same process configuration as the naphtha unit. The main difference is that this unit-will almost invariably have a hydrogen- Tich stream recycle. The recycle is provided by the fasted gas stream ftom the flash rum. This is returned to mix with the feed and'a fresh hydrogen make-up streain before entering the preheater system, The.recycle gas.streamn in these units is often treated for the removal of HyS before returning to the reaetots.” » 4.6 The Fluid Catalytic Cracking Unit (FCCU) This cracking process is among the oldest in the oil industry. Although developed in the mid-1920s it first came into prominence during the Second World War as a source of high-octane fuel for aircraft. Inthe early 1950s its prominence as the major26 AN INTRODUCTION TO CRUDE OIL, AND ITS PROCESSING source of octane was somewhat overshadowed by the development of the catalytic reforming process with its production of hydrogen as well as high-octane material. The prominence of the FCCU was re-established in the 1960s by two developments in the process: The use of highly active and selective catalysts (zeolites) ©The establishment of riser cracking techniques ‘These developments enabled the process to produce higher yields of better-quality distillates from lower-quality feedstocks. At the same time, catalyst inventory and consumption costs were significantly reduced. ‘The process consists of a reactor vessel and a regenerator vessel, interconnected by transfer lines to enable the flow of finely divided catalyst powder between them. ‘The oil feed (typically, HVGO from the crude vacuum unit) is introduced to the very hot regenerated catalyst stream leaving the regenerator en route to the reactor, Cracking occurs in the riser inlet to the reactor due to the contact of the oil with the hot catalyst, The catalyst and oil are dispersed in the riser so that contact between them is very high, exposing a large portion of the oil to the hot catalyst. ‘The cracking is completed in the catalyst fluid bed in the reactor vessel. The catalyst fluidity is maintained by steam injection at the bottom of the: vessel. The cracked effluent leaves the top of the reactor vessel as a vapour to enter the recovery section of the plant. Here the distillate products of cracking are separated by fractionation and forwarded to storage or further treating, An oil slurry stream from this recovery plant is returned to the reactor as recycle. The catalyst from the reactor is transferred to the regenerator on a continuous basis, In the regenerator the catalyst is contacted with an air stream which maintains'the catalyst in a fluidized state. The carbon on the catalyst is burned off by contact with the air and converted into CO and CO,, The reactions are highly exothermic, raising the temperature of the catalyst stream to well over 1000 °F and thus providing the heat source for the oil cracking mechanism, Details of this process together with typical yield data are given in Chapter 11. 4.7 Hydrocracking This process is fairly new.to the industry ‘becoming prominent in its tse during the late 1960s. As the name suggests, the process cracks the oil feed in thé p presence of hydrogen. It is a high-preistte process operating normally around 2000 psig. This makes the unit rather costly; and because of this has diminished its importance in the industry. compared with the FCCU and thermal cracking: However, the process is very flexible, It can handle a wide spectrum of feeils including virgin gas oils, vacuum. gas oils, thermal cracker gasioils, FCCU'cycle oils and the like. Its products need very little downstream treating to meet finished specifications. The naphtha stream it produces is particularly high in naphthenes, making it a good reformer stock for atomatic production. ‘The process consists of one or two reactors, a preheat system, recycle gas section, and a recovery section. The oil feed (typically, tHé vacuum gas oils) is preheated byBASIC PROCESSES a heat exchange with reactor effluent streams and by a fired heater. Make-up and recycle hydrogen streams are introduced into the oil stream before entering the reactor(s). (Note: in some configurations the gas streams are also preheated prior to joining the oil.) The first section of the reactor is often packed with a desulphurizing catalyst to protect the more sensitive cracking catalyst further down in the reactor from injurious sulphur, nitrogen and metal poisoning. Cracking occurs in the reactor(s) and the effluent leaves the reactor to be cooled and partially condensed by heat exchange. The stream enters the first of two flash drums, Here the drum pressure is almost that of the reactor. A gas stream rich in hydrogen is flashed off and recycled back to the reactors as recycle gas, The liquid phase from the flash drum is routed to a second separator which is maintained at a much lower pressure (around 150-100 psig), Because of this reduction in pressure a second gas stream is flashed off. This will have a much lower hydrogen content but will contain Cys and C,s. For this reason, the stream is often routed to an absorber column for LPG recovery. The liquid phase leaves from the bottom of the low-pressure absorber to enter the recovery side, where products are separated by fractionation and sent to storage. Further details of this process are given in Chapter 12. 4.8 Thermal Cracking Units ‘Thermal cracking processes are the true workhorses of the oil-efining industry. The processes are relatively cheap when compared with the fluid cracker and the hydro- cracker, but go a long way to achieving the oil-cracking objective of converting low-quality material into miore valuable oil products. The pfocess family of thermal crackers has three members: Thermal crackers © Visbreakers © Cokers ‘The term ‘thermal cracking’ is usually given to those processes that convert heavy oil (usually fuel oil or residues) into lighter produet stock such as LPG, naphtha, and middle distillates by applying only heat to the feed over a prescribed element of time. ‘When applied to a specific process the term refers to the processing of atmospheric residues (long residue) to give the lighter products. ‘Visbreaking’ refers to the processing of vacuum residues. (short residues) to. reduce. the viscosity of the: oil only and thus to meet the requirements of a more valyable fuel oil stock. ‘Coking’ refers to the most severe process in the thermal cracking family. Bither long or short residues can be fed to this process whose objective isto produce the lighter distillate products and oil coke only. The coker process is extinctive—that is, it converts all the feed. In the other two processes there is usually some tinconiverted feed, although the thermal cracker can be designed to be ‘extinctive’ by recycling the unconverted oil. The three therinal cracking processes have.the same basic configuration. This consists of a cracking furnace, a ‘soaking’ vessel or coil, and a product-recovery fractionator(s). The feed is first proheated by heat exchange with hot product streams before entering the cracking furnace or heater. The cracking furnace raises the28 AN INTRODUCTION TO CRUDE OIL, AND ITS PROCESSING temperature of the oil to its predetermined cracking temperature. This is always in excess of 920 °F, and by careful design of the heater coils the oil is retained in the furnace at a prescribed cracking temperature for a predetermined period of time (the residence time). In some cases an additional coil section is added to the heater to allow the oil to ‘soak’ at a fixed temperature for a longer period of time. In other cases the oil Jeaves the furnace to enter a drum which retains the oil at its cracking ‘temperature for a short time. In the coker process the oil leaves the furnace to enter one pf a series of coker drums in which the oil is retained for a longer period of time at its coking temperature for the production of coke, ‘The cracked oil is quenched by a cold heavy oil product stream on leaving the soaking section to a temperature below its cracking temperature. It then enters a fractionator where the distillate products are separated and taken off similar to the crude distillation unit. In the case of the cokers the coke is removed from the drums by high-velocity water jets on a regular batch basis, The coking process summarized here refers to the more simple ‘delayed coking’ process. There are other coking processes which are more complicated, such as the fluid coker and the proprietary Flexi coker. Further details on thermal cracking are provided in Chapter 13, This chapter also includes the treating of residues by hydrocracking and a method of calculating yields and properties of cracked stock. 4.9 Other Refinery Processes ‘ ‘The processes summarized above are the more common to be included in a fuel refinery’s configuration, In addition to these there will also be gas-treating processes and often some additional gasoline octane-enhancement processes. These are described in more detail in Chapters 14 and 15, respectively. Gas treating is always required to remove the H,S impurity generated by hydro- treating or cracking from the refinery fuel gas or hydrogen recycle streams, The removal of H,S for these purposes is accomplished by absorbing the sulphide into an amine or similar solution that readily absorbs H,S. Stripping the rich amine Temtoves the HS from the system to be further reacted with air to produce elemental sulphur in a sulphur plant. ‘The octane-enhancement process detailed in this book is the alkylation plant: These types of processes are usually proprietary and are provided to refiners under licence. ‘The process described iri Chapter‘ 14'is the HF alkylation process, which utilizes hydrogen fluoride as thé catalyst to convert unsaturated C,s to high-octane isobutanes. The unit’s recovery side is the aspect dealt with in some detail’ together with a descriptive item on the safe handling of HF. 4,10 The Non-energy Product Refineries ., ‘This book deals with the energy product refineries becaiise this is the basic’and largest of the refinery types, There ‘are, in addition, those petroleism refineries or sections of a refinery that produce lubricating oils and others that produce’ only feedstock for converting 10 petrochemicals. This section briefly describés the'type units that are common to these non-energy refineries.BASIC PROCESSES: 29 Bitumen blending nO eppulds Aner go eppuids wy6r] Lt Light al nl oll poo! | product blending and packaging Figure 4.1. A lube oil refinery configuration THE LUBE OIL REFINERY ‘The schematic flow diagram (Figure 4.1) shows a typical lube oil producing refinery configuration. Only about eight or nine base lube oil stocks are produced from refinery streams. The many hundreds of commercial grades of lubricating oils used in industry and transportation are blends of these base stocks with some small:amounts of30 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING proprictary additives (mostly organic acid derivatives) included to meet their required specifications. There are also two quite important by-products to lube oil: bitumen and waxes. Most refineries include bitumen blending in their configuration but all except the older refineries no longer process the waxes. These are exported to manufacturers specializing in wax and grease production. Lube oil production starts with the vacuum distillation of atmospheric residue. This feedstock is usually cut into three distillate streams, each having a boiling range which gives streams with viscosities mecting the finished blending product specifications. The lighter stream is taken off as the top side-stream and is further distilled again under vacuum to three light lube oil blending cuts. These are called spindle oils and when finished will form the basis of light lubes used for domestic purposes such as sewing machine, bicycle and other home lubricant requirements, Some of the heavier spindle oils are also used as blerid stocks for light motor oils. These spindle oils require very little treatment for: finishing, usually only mild hydrotreating suffices to meet colour requirement. ‘The second distillate side-stream is de-waxed and sent to the motor oil pool. It may also be blended with the heavier bottom side-stream as heavy engine oil stock, The bottom side-stream is one of the base blending stocks for heavy engine oils and the turbine oil stocks. To meet colour and other specifications these heavier oils must be treated for the removal of undesirable componets (such as heavy aromatics) by solvent extraction. This is accomplished prior to the stream being dewaxed and routed to storage. The heavy vacuum residue from the vacuum tower is routed to a propane de-asphal unit. Here the very thick bituminous asphaltenes are removed by extraction with liquid propane. The raffinate from this extraction process is the heaviest lube oil blending stream commonly called Bright stock. This stream is also routed to the solvent extraction unit and the de-waxing process before storage. Solvent extraction is accomplished in a trayed column by contacting the oil feed and solvent counter currently in the tower. The lighter raffinate stream leaves the top of the tower to be siripped free of the solvent in an associated stripper column before entering the de-waxing unit. The extracted components leave the bottom of the tower also’to be stripped free of the solvent in an associated stripper column, ‘The extract in this case may be routed to the propane de-asphailting unit or simply sent to the refinery fuel supply. The solvent in modern refineries is cither fufural, phenol or a proprietary solvent based on either of these chemicals, In earlier plants oleum or liquid SO, was used for this purpose. ‘The oil streams routed to the de-waxing plant are contacted and mixed with a crystallizing agent such as methyl ethyl ketone (MEK) before entering a series of chiller tubes. Here the oil/MEK mix is reduced in temperature to a degree that the wax contained in the oil crystallizes out. The stream with the wax now in suspension enters a series of drum filters where the wax and oil are separated. Both streams are stripped free of the MEK in separate columns. The MEK is recycled while the de-waxed oil is sent to storage and blending. The wax may be retained as a solid in a suitably furnished warehouse or remelted and stored in special tanks with an inert gas cover. ‘The asphalt from the propane de-asphalting unit is stripped free of propane and any other light ends using inert gas as the stripping agent, It leaves the unit to proceed either directly to the bitumen pool or. to be further treated by air blowing, TheBASIC PROCESSES 3L air-blowing process increases the hardness of the bitumen where this is required to meet certain specifications. It is accomplished either as a batch process or on a continuous basis, The hot stripped asphalt from the de-asphalting unit enters the air blower reactor under level control (if the process is continuous). Air is introduced via a small compressor to the bottom of the reactor vessel and allowed to bubble up through the hot oil phase. The air removes some of the heavy entrained oils in the asphalt and reacts mildly to partially oxidize the asphaltenes. The hot oil vapours and the unused air leave the top of the reactor to be burned in a suitably designed incinerator. The blown asphalt leaves the reactor as a side-stream to bitumen storage or blending. ‘The production of lube oils usually takes place in a section of an energy refinery. ‘The various grades of the oils are also proctuced in a blocked operation using storage facilitics between the units. This is feasible as the amounts of lube oils required to be produced are relatively small and normally do not justify separate treating facilities for each grade. REFINING FOR PETROCHEMICALS Feedstocks for the production of petrochemicals originate from refineries with processes similar to those described in this book for producing fuels. Indeed, there are only a few refineries worldwide that cater only for petrochemical requirements. Most petrochemical feedstocks are produced by changing operating parameters of the normal fuel refinery processes. In catering for the petrocheinical needs much of the refinery product streams are tailored as follows: © Aromatic streams—high in benzene, toluene, xylenes © Olefin streams—high in ethylene, propylene and C,s Producing the aromatic feedstock ‘The production of aromatics feedstocks originates with the catalytic reforming of refinery stream of a heavy naphtha range (say, 120-420 °F) and rich in naphthenes. ‘A typical stream that meets this criterion would be a naphtha stream from a hydro- cracker. Thus, in meeting petrochemical needs, a hydrocracker forming part of a fuel refinery configuration would be operated to maximize naphtha production. This would mean running the unit ona low space velocity with.a higher oil recycle rate (that is, most recovered product heavier than the naphtha would be recycled back to the reactors). : ‘Another source of high naphthene feed to the cat reformer would be hydrotreated FCCU naphtha, Of course, the hydrotreating of unsaturates has a high demand on the refineries hydrogen system, but this is balanced to some extent by the additional hydrogen produced in reforming the naphthenes. Should the refinery configuration include a thermal cracker and/or a steam cracker the hydrotreating of the naphtha cut from these“units would also yield high naphthene cat reformer feedstock. Catalytic reforming of the high naphthene content naphtha produces aromatics but there is also present some unreacted paraffins and some naphthenes. The32 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING ‘Thermal naphtha Coke Figure 4.2. A petrochemical refinery configuration downstream petrochemical units that separate and purify the aromatic reformate are expensive in both capital and operating costs. The specification for the BTX (benzene, toluene, xylene) feed therefore is very stringent and excludes non-aromatic components as much as possible, Another process.tmay therefore be included in the refinery configuration to ‘clean up’ this aromatic feed stream before leaving the refinery. This is an aromatic extraction plant, i.e. a licensed process using solvent to’separate the paraffins and aromatics by counter-current extraction. The rich aromatic stream is then forwarded to the BIX plant where benzene, toluene, ethyl benzene and o- xylene are separated by fractionation while the para-xylene is usually separated by crystallization. The meta ‘xylene’ may also be recovered by super-disillation but more often than not it is converted into o-xylene in an isomerization unit. Producing the olefin feedstock ‘The source of olefins in a refinery configuration is from the FCCU, a thetmal cracker, or a steam cracker. The olefins produced as a gas are ethylene, propylene, and the C,s such as butylenes, butadiene, etc. Liquid olefinic products from these units are normally hydrotreated to make reformer feedstock and thus the BTX feed. All products, of course, are treated for sulphur control and clean-up-before: leaving the refinery as petrochemical feedstock. The specifications for these products are stringent and usually the ‘clean-up’ plants are dedicated to the treatment of these products. Olefins are used mostly in the production of polymers such as the vinyl polymers (vinyl chloride, vinyl acetate and the like), the polyethylene products, and the polypropylene products, The heavier C,s are a major constituent in the production of synthetic rubbers.BASIC PROCESSES 33, Figure 4.2 shows a configuration for an actual petrochemical feedstock-producing refinery. This configuration differs a little from the general description given above insofar as there is no FCCU, Instead, all the olefins are produced in a steam cracker and coker. Hydrotreaters are not shown but they do exist. Note that the steam cracked naphtha in this case is sent directly to the aromatics and the HDA units. The latter unit accomplishes the hydrogenation of this stream and the extracted naphtha is then recycled to the reformer. 4.11 Oxygenated Gasolines ‘The concentration of vehicles on the roads in most of the cities in the modern world has increased dramatically over the last two decades. The emission of pollutants from these vehicles is adding significantly to the already-critical problem of atmospheric pollution. The problem is now so acute that governments of most First World countries are seeking legislation to curb and minimize this pollution and most countries will sce the implementation of Clean Air Acts in the 1990s. Petroleum-refining companies have been working diligently for many years to satisfy the requirements of Clean Air legislation. This began in the 1970s with the elimination of tetra-cthyl lead from most gasoline requirements, Processes such as. isomerization and polymerization of refinery streams were developed together with a surge in the use of the alkylation process. However, the further decrease in pollutants now requires ‘a move away from the traditional gasoline octane enhancers such as the aromatics and the RVP adjusters such as the C,s. Catalytic reforming produces gasoline streams to meet octane requirements. mainly by converting cycloparaffins to light aromatics. Fluid catalytic. cracking also produces gasoline blending stocks by cracking paraffins to light olefins and the products from these two processes still make up the bulk of a refinery’s gasoline pool. Unfortunately, the aromatics are ‘dirty compounds’ in that they produce a sooty exhaust emission— unacceptable in meeting the Clean Air requirements. The light olefins are also unacceptable because of their ‘evaporative emission’ properties. Considerable work is begin done with alcohols to take the place’of aromatics as octane enhancers and the C,s used for meeting other gasoline specifications such as RVP.' The work thas had some success and some companies in North Ametica use ethanol in the gasoline blend. ‘The greatest success in reducing aromatics in gasoline to date, however, has been in the production and blending of oxygenated compounds into the gasoline pool. ‘A press release by a number of companies in’ 1989 is quoted as follows: © Adding oxygenates reduces the amount of exhaust emissions, (hydrocarbons and carbon monoxide) and the benefits have been quantified, Reducing aromatics and/or boiling range of gasoline can either reduce or increase exhaust emissions, depending upon vehicle type. ‘Oxygenates are ether compounds derived from their respective alcohols. There are three candidates of these ethers to meet the gasoline requirements: “” Methyl tertiary butyl ether (MTBE) @Ethy! tertiary butyl ether (ETBE) © Tertiary amyl methyl ether (TAME)34 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING Guard reactor tstreactor nd reactor Debutaniser sto ‘Aly unt ) J, ed Melia! Figure 4.3. Atypical flow diagram for the production of MTBE Of these three candidates MTBE looks most likely to be the one that will be most satisfactory in meeting all the gasoline, pool objectives. This compound has the blending quality of 109 octane, a RVP blending of 8-10 psi and a boiling point of 131 °F, There are a number of commercial units already in operation producing MTBE, 7 ETBE production is currently still in the pilot plant stage. Its.octane-blending properties seem to be slightly better than MTBE and so does jts RVP. blending qualities. The ethanol feed stream; of course, is not so readily available as methanol. It is believed in North America that the first ETBE plant will be built in the Mid. West, where ethanol is more readily available, . ” ‘TAME has an average dctane number of 104 and a RVP blending of 3-5 psi: Except for the lower octane value, TAME has sitnilar blending properties to BTBE. The ether in this case is formed by the reaction of 2-methy!-2-butene and 2-methyl-l-butene olefine feed and methanol, Commercial plants already operate in the UK and parts of Burope producing TAME. The compound is used in Europe as a gasoline product and not as a gasoline blend stock. The front end of a cracked gasoline stream is used in this manufacture to provide the olefin. Considerable work in the research of ethers as fuel components is still in its early stages, bu it seems that the oxygenated gasolines offer a solution to curbing emissionBASIC PROCESSES 35 pollutants. The physical characteristics of heavy hydrocarbons in gasoline suggests that the problem compounds are at the higher end of the gasoline boiling range. Further work currently being done with the higher ethers, alcohols, and esters may contain the solution of replacing the present troublesome heavy hydrocarbons to meet the Clean Air philosophy. THE PRODUCTION OF THE ETHERS (MTBE) ‘There are several licensed processes for the production of methyl tertiary butyl ether by the etherification of a C,/C; olefin stream and methanol. These processes have very similar configurations and are flexible enough to be converted quite simply to the production of the other ethers. Figure 4.3 is a typical flow diagram for this process. ‘The olefin feed from a FCCU or a steam cracker is combined with a methanol stream to enter a guard reactor which removes any impurities. A small hydrogen stream is added to the hydrocarbon from the guard reactor prior to entering the first ether reactor. This reactor contains a special resin catalyst and the reactor feed flows ‘upward through this catalyst bed at modetate temperatiite and pressure and in the ‘iquid phase. The reaction is exothermic arid temperature control is maintained by externally cooling a recycle stream from the first of two reactor vessels. “The catalyst in this case performs three reactions simultaneously: etherification of branched olefins, selective hydrogenation of the unwanted diolefins, and hydro- isomerization of olefins by a double-bond switch. The reactor effluent leaves the top of the second reactor vessel to, be heated in a feed heat exchanger with the debutanizer bottoms product. The overheads from the debutanizer is a Cy and methanol stream. ‘These streams are separated in a-separation vessel, the. methanol stream is recycled to the first reactor while the Cys are returned to the FCCU light ends unit. The bottom product is Cs* enriched with MTBE (or. TAME, depending on the olefin feed used),5 REFINERY CONFIGURATION DEVELOPMENT 3.1. Solution. fs 37 5.2. Crude unit yields (including the naphtha splitter) 38 5.3 Yield summary and crude throughput . .. 40 5.4 Conclusion .... 45 Much wotk has to be completed ‘before a refining company cai commit'the large expenditure required to’ upgrade’ an existing refinery or to build a new facility. Certainly, ‘duting the early phases ‘of the stidy work maniy’ different’ processing coitfigurations will be developed arid evaluated. This will be necessary to det which processing route will be the best to meet the refinery’s commercial objectives. ‘All these corifiguration studies‘ will be initiated ‘by predicting’ the yields “and quality of the products obtainable from the selected crudes the refinery intends to process. Calculations similar to those given in this chapter will be used to develop these preliminary data. The evaluation studies will continue to include capital and operating costs of the various units considered in these early configurations and then examine their economic impact to arrive at a selected processing route. In this chapter a very simple refinery configuration is developed from knowledge of the correlations and processes given in this book. The product specifications for this exercise is given at the end of the book as Appendix 3. Consider the following scenario, A small oil company desires to build a refinery to produce the following marketable products by processing 3 million metric tons/year of Kuwait crude oil: C3 LPG C4 LPG 93 ON (RES) premium gasoline 84 ON (RES) regular gasoline Kerosene (for cutter stock) Automotive grade diesel (to be maximized) No. 6 fuel oilREFINERY CONFIGURATION DEVELOPMENT a7 ‘The sensitivity of the premium gasoline is to be seven octane numbers. It is required to define the product scheme and to specify the size of the individual units in terms of their stream capacity. 5.1 Solution ‘The following isa solution and a configuration that will be considered as a candidate for further economic analysis and possible selection as the processing scheme. Due to the different service factors (ratio of onstream time to total time) that exist for the various processes that will make up the configuration, the calculations will be made in barrels per calendar day (BPCD). This is the number of barrels processed per day over 365 days. ‘This refinery will be oriented principally to produce auto diesel, LPGs, and gasoline. ‘The following units will be considered to achieve this objective: © An atmospheric crude distillation unit A naphtha hydrotreater A naphtha splitter @A catalytic reformer @LPG recovery—debutanizer, depropanizer and a de-ethanizer A diesel hydrofiner Parameters for these units are as follows: (1) The crude unit This will be a single-stage unit (ie, no vacuum distillation). ‘A full-range naphtha cut will be taken off as an overhead distillate, a small kero stream as the first side-stream, and a light and heavy gas oil taken off as second and third side-streams respectively. Taking a full-range: naphtha as overhead distillate enables the column to be operated at close to atmospheric pressure at @ realistic overhead condensing temperature and still retain most of the LPG. The diesel is taken off as a light and heavy gas oil to minimize the size of the diesel hydrofiner, The light gas oil will be cut to meet a sulphur content acceptable to blending into diesel without further treating. Only the heavy gas oil stream will therefore require hydrofining, and the hydrofiner can remove 85% of the sulphur in the heavy gas oil. The kero stream will be blended into the atmospheric residue as far as possible. The constraint in this case will be the flash point specification of No. 6 fuel oil. (2) The naphtha hydrotreater The full-range naphtha from the crude unit will be hydrotreated before being sent to the Tight ends recovery units. This removes the necessity of treating the ight streams individually for sulphur removal downstream. ‘This may have to be changed as a result of the economic analysis later. (3) The naphtha splitter This unit’s function is to prepare reformer feed from the hydrotreated naphtha. In this scheme the LPG recovery is going to be affected after the splitter. There will be some methane and some hydrogen in the fed to the spliter although the material has been stabilized. These will be removed with the overhead distillate from the splitter. To operate the column at reasonable conditions of temperature and pressure, however, requires the presence of the light gasoline components to hold these very light materials in the distillate. Should the hydrogen38 AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING and methane be vented at this point from the overhead dram they would carry some LPG with them and these would probably be lost as products, Thus the reason for debutanizing etc, after naphtha splitting in this case is to maximize LPG recovery. (4) The catalytic reformer The sensitivity specification for the premium gasoline necessitates reforming to a lower octane number and meeting the gasoline octane by blending in TEL (tetra-ethyl lead). The following are the cat reformer data as supplied by the licensor: Feed: 194 IBP to 347 °F FBP ASTM distillation Severity: 86 ON (RES) clear Reformate +1.5 Mls/IG TEL: 93 ON (RES) 86 ON (MOTOR) Reformate yield: 83.24% on feed H, to Cy 5.2% on feed Propa 5.0% on feed Butanes: 6.6% on feed ASTM dist. 10% vol.: 162 °F 195 °F illate from the splitter will be debutanized in the light ends recovery unit debutanizer. The overhead distillate from this column will contain all the butanes and the propane for LPG recovery. The distillate stream. from the cat reformer unit will also be added to this LPG-tich stream, These will then be fed to the depropanizer column for butanes recovery. The distillate from the depropanizer will then be routed to the de-ethanizer for propane LPG recovery. (6) The diesel hydrofiner The heavy gas oil side-stream from the crude’ unit will be hydrofined for the removal of 85% of its sulphur content, ‘This now completes the basic parameters that will be used for this exercise. Some of the details pertaining to this process scheme must now be filled in, and this centres on a better definition of the crude unit’s operation. 5.2 Crude Unit Yields (including the naphtha splitter) NAPHTHA The reformer feed requires the ASTM end point of the heavy naplitha to be 347°P. From curve A in Figure A1.3 of Appendix 1 the cut point limit is 357°R, From the crude assay this gives a total full-range naphtha yield of 24.8% vol. on crude. On a naphtha splitter we could expect to obtain fractionation meeting 25 °F gap between the ASTM 95% vol, of the light naphtha and ASTM 54% vol. of the heavy naphtha, By drawing the heavy naphtha ASTM curve as a straight line between 0% and 100% on the probability graph at 194 °F and 347 °R, respectively, the 5% ASTM point of the heavy naphtha and 95% ASTM of light naphtha are fixed. Draw the light naphtha ASTM line on probability paper parallel to the heavy naphtha lineREFINERY CONFIGURATION DEVELOPMENT 39 through the 95% point at 174 °F, From the ASTM end-point of the light naphtha calculate its cut point by using Figure A1.3. This is found to be 170 °F and is equivalent to 9.0% on crude. ‘There is 2:8% of Cys and lighter in Kuwait crude. Knowing this, the yields of gas, light naphtha and heavy naphtha are predicted as follows: Gas: 2.8% vol. Light naphtha: 9.0~2.8% vol Heavy naphtha: 24.8 ~9.0% vol. Constructing the TBPs of the light and heavy naphtha from the ASTM cutve and using the method described in Chapter 6 the specific gravities of the cuts and other properties can be calculated. KERO YIELD The front end of the kero ASTM is fixed by what can reasonably be expected by crude unit fractionation, We could expect to attain a fractionation ASTM gap of 20°F between 5% kero and 95% naphtha in a crude unit, Thus, as we know the 95% ASTM of the naphtha, the 5% ASTM point of the kero can be fixed at 20°F above the naphtha 95%: point which is at-335 °F. i Now the back end of the kero (and therefore the yield) determines what the front end‘of the light gas oil will-be.-The flash point of the light gas oil depends on the 5% ASTM point, so:let us fix the 5% point of the gas oil to meet a flash point of, say, 175 °P. (This allows some latitude in the design and operation of the unit to ‘bé able to meet spécification diesel at 125 °F flash point minimum.) From the cortelation of ASTM and flash point given by the equation flash point=0,77 (5% ASTM:150°F), the gas oil 5% point is calculated as'380 °F. ‘We can reasonably expect to attain a 10°F gap between 95% ASTM of the kero and 5% ASTM of the light gas oil. Using this, the kero 95% ASTM is fixed at 310°. The kero ASTM is drawn on the probability curve as the-straight Tine between 5% and 95% at 335 °F and 370 °F, respectively. From the ASTM efid point of the kero the cut point is predicted using Figure AJ.3. The TBP curveis that calculated from the ASTM curve. The cut point for the kero is found to be 387 °F and is equivalent to 27.8% vol. on crude. The yield is therefore 27.8-24.8% vol. =3.0% vol. From the ASTM and TBP curves the kero lids the following properties: SG at 60°F 0,780 Sulphur (Total) 0.13% wt Viscosity at 100°F — 1.1 ¢St Viscosity at 122°F 0.95 cSt Flash point 142°F LIGHT DIESEL YIELD ‘The front-end cut-point of this fraction has already been fixed.and so has the 5% ASTM and flash point. Now the critical specifications to be met when the light and40 AN INTRODUCTION TO CRUDE OIL AND.ITS PROCESSING heavy gas oils are blended together will be pour point and sulphur. As a first guess, let the mid-boiling point of the total diesel cut be such as to give 10°F pour point. From inspection of the crude assay this limits the cut to about 700°F TBP cut point. Let us take the light gas ‘oil component to about 0.8% wt sulphur, giving a light gas oil cut, say, approximately between 27.8% vol. and 45.8% vol., a yield of 18.0% vol. (387 °F ~ 595 °F cut points). ‘The 90% concept is used in this case as we are not going to be specific or design for specific fractionation between light and heavy gas oil. The end point could, in practice, bea lot higher than that derived on-a straight-line probability rélationship. The TBP curve is calculated from the probable ASTM curve and the following properties are defined: SG at 60°F 0.820 Sulphur 0.8 wt Pour point 30°F Viscosity at 100°F 2.0 cSt Viscosity at 122 °F ‘1.8 cSt HEAVY DIESEL The 5% ASTM point of the heavy diesel will be set at 10°Fbelow the 954%, point . of the light diesel (at'570 °F). A:10 °F overlap is reasonable'in this section of the crude tower. Taking a final cut point-of 700 °F on crude the yield of heavy gas oil becomes 54% —45.8% vol.=8:2% vol. This may have to be adjusted later. ‘Again using the 90% ASTM/TBP cut point relationship the ASTM 90% point is fixed at 646 °F. The ASTM curve is defined as a straight:line on the probability graph between the 5% point at $70 °F and 90% at 646 °F. The TBP curve is calculated from the probable ASTM curve and the following properties predicted from-it; SGat 60°F, 0,874 Pour point 40°F Sulphur 23% wt zanae Viscosity-at 100°F, 8.0 cSt. fl Viscosity at 122 °R; 5,3 St Flash point... 200°F 5.3. Yield Summary and Crude Throughput ‘The total crude throughput to the refinery is calculated as follows: .. Capacity required=3 million tons/year : In BPCD (bartels per calendar day) this is 3.000000%2205 _ 1 1 million Ib per day 365 Ib/gal of Kuwait crude=7.22 ‘Then BPCD=(18,1)(105 _ ry ay 732689 BPCD,REFINERY CONFIGURATION DEVELOPMENT 41 ‘The stream yields are now summarized from the yield calculations as follows: % vol, on crude BPCD Gas 28 1611 Light naphtha 62 3701 Heavy naphtha 15.8 9431 Kero 3.0 1791 Light gas oil 18.0 10744 Heavy gas oil 8.2 4894 Residue 46.0 21437 Total 100.0 59689 From these base yields the blending recipes and unit capacities can now be determined. PRODUCT BLENDING Regular gasoline ‘The yield of reformate is given by the licensor as 83.2% on feed. Consider that the regular gasoline will be made up of all the light naphtha make and with sufficient reformate to meet 80 octane number clear and will then be blended with about 3,0 ml/IG of TEL to make the specification octane. The light naphtha octane number is 75 RES Clear. Let x be the volume of reformate in the blend. Then: x(86) + (1—x)75=80 x= 0,454 vol. Total light naphtha= 3701 BPCD= 54.6% vol. of the gasoline stream : 3701 Total regular gasoline= 545 =6778 BPCD Reformate to regular gasoline = 3077 BPCD Premium gasoline ‘Total reformate make=0.832(0431)= 7847 BPCD Reformate to regular gasoline Reformate to premium gesoline ‘This reformate when blerided with 1.5ml/IG TEL will meet 93 ON (RES) ‘The predicted ASTM distillation is Specification Predicted 10% min, vol, received at 167°F 167°F 50% min, vol. received at 284 °F 250 °F 90% min. vol. received at 392°F , 30°Fa AN INTRODUCTION TO CRUDE OIL AND ITS PROCESSING The vapour pressure can always be adjusted by allowing more Cys in the reformer stabilizer bottom product. Diesel blending ‘The blending of the straight-run light gas oil and desulphurized heavy gas oil meets Specification as shown, Pour point ‘The blended pour point will be as follows: 5% ASTM Composition Pour Pour ASTM 50% Pour point (°F) (CR) 4% vol. index factor factor Light diesel —30 470 68.7 27 1.85 323, Heavy diesel +40 20 31.3 6 8.14 194 Blend 100.0 9.99 317 Blended pour point is 10 °F. Therefore this sets the limit of the diesel product yield. Sulphur Total blended diesel sulphur is as follows: — sc Weight = Sulphur Sulphur favol. at 60°F factor == wh) factor Lighter diese] 69.7 0.820 36.30 08 0.45 Heavy diesel 31.3 0.874 24 0.35 0.095 Total 100.0 83.7 0,545 ‘SG at 60°F of blend =! Sulphur=0.65% wt which meets spec. ASTM distillation ‘The 90% of heavy diesel is 650 °F, This, as it is, meets spec. The 90% of the blend will be considerably lower than this, therefore the spec. is met, Viscosity Final viscosity of the’ blend will be as follows: At 100°FREFINERY CONFIGURATION DEVELOPMENT 43 Viscosity Viscosity % vol. at 100°F Index Factors Light diesel 8.7 2.0 cSt 58 40 Heavy diese! 313 8.0 cSt at 12.8 Blend 100.0 528 a eet Blend viscosity at 100 °F =2.8 cSt which meets spec. At 12°F wn Viscosity % vol. at 22°F Factors Light diesel 87 1.8 cSt o | a Heavy diese! 313 5,3:cSt 45 14 Blend 100.0 : 44 Blend viscosity =2.4 cSt which meets spec. Fuel oil product Residue from crude unit is 46% From assay data (not shown in Appendix 2) SG at 60 972 Viscosity at 100 °F = 1800 oSt Viscosity at 210°F = 58 cSt Blending with total kerosene yield gives the following properties: Flash point 7 PEPE EEE eee ee Flash point % vol, cH Index Factor Reside is 98.9 350 0.65 0.61 Kero 61 voy 510 311 Blend 100.0 . 31.72 Blend NNO Flash point= 188 °F which meets spec. Viscosity at 100 °F a Vol. at Viscosity vol. 100°F Index Factor Residue : 93.9 1800 16 15 Kero 64 ir 70 4 Blend 100.0 19 Blend EO Viscosity = 700 cSt at 100°F which meets spec.44 AN INTRODUCTION TO CRUDE OIL, AND ITS PROCESSING Viscosity 4% vol. at 122°F Index Factor Residue , 93.9 700. 19 11.8 Kero 61 0.95 "4 45 Blend 100.0 22.3 Viscosity at 12°F =260 cSt which meets spec. LPG Products Assume that the LPG streams will meet specification if 70% of the C; and 80% vol. of Cy are recovered as LPG. Actual volume Recovered as product From straight crude C,s1134,1 BPCD 907 BPCD Gs 477.2 BPCD 334 BPCD Gas 59.7 BPCD 430 BPCD From reformer Cs 622 BPCD 498 BPCD Cs 472 BPCD 330 BPCD , Gas 490 BPCD 156 BPCD The refinery scheme can now be shown-diagramatically as a schematic flow sheet igure 5.1). Figure 5.1. Crude oil and its products--a refinery block flow diagram.REFINERY CONFIGURATION DEVELOPMENT 45 Plant capacities ‘The individual units will have the following service factors and their capacities are calculated by dividing BPCD by the service factor: Service factor Capacities (BPSD) Crude unit 09 66000 ‘Naphtha hydrotreater 0,80 18500 Naphtha splitter 0.80 18500 Platformer 0.80 11.000 Debutanizer 0.80 6320 ‘Depropanizer 0,80 3830 De-ethanizer 0.80 2176 Diesel hydrofiner 0.70 7000 5.4. Conclusion ‘The basie refinery configuration and unit sizes are then established by the methods shown, The example, of course, reflects a simple exercise in utilizing the crude assay and process characteristics. Very often this type of study work encompasses the need for including conversion units to meet shortfalls in a refinery marketing programme, Such studies require complex optimization of an investment and technical nature. Some of these can be so complex that true solutions may only be provided by the use of linear programming and high-speed computers. Nevertheless, even the most complex studies commence with the definitions and methods described here,Part 2 THE DISTILLATION PROCESSES6 THE ATMOSPHERIC CRUDE DISTILLATION UNIT 6.1 Process description (typical crude distillation unit) 49 6.2 Fractionation ... ; st 63 Developing the true boiling point curve (TBP) and the equi flash vaporization curve (BFV) from lab ASTM distillation 54 6.4 Procedure for establishing flash zone conditions ; 6 6.5 Estimating tower diaw-off temperatures. . 6 6.6 Calculating tower-top conditions . 69 6.7 Fractionation and internal reflux at the tower-top section - n 68 Calculating the top (naphtha) pumparound duty to meet an reflux requirement . B 69 Caleulating the required external reflux to 15 6.10 Establishing the internal reflux between side-streams.. 6 6.11 Calculation to establish pumparound and overflash that will meet internal reflux requirements . 1 Overall tower heat balance 1” Side-stream stripper performance .. . 2 Prediction of tray and tower performance 85 A procedure for evaluating exchanger thermal performance . m1 Evaluating the heater’s thermal performance. ..... 95 Calculating the pressure drop in the crude heater transfer line . 9 Evaluation of reflux drum oil/water separation ... 105 6.1 Process Description (Typical Crude Distillation Unit) The first process encountered in any conventional refinery is the atmospheric ‘crude distillation unit. In this unit the crude oil is distilled to produce distillate streams which will be the basic streams for the refinery product. slate.. These streams will either be subject to further treating down stream or become feedstock for conversion units that may be in the refinery configuration.50 ‘THE DISTILLATION PROCESSES THE PROCESS Crude oil is pumped from storage to be heated by exchanges against hot overhead, product and pumparound streams in the crude unit (see Figure 6.1), At a temperature of about 200-250°F the crude enters the desalter. Free salt water contained in the crude is washed out and separated by means of an electrostatic precipitation contained in the desalter drum. The water phase from the drum is sent to a sour water stripper to be cleaned before disposal to the oily water sewer, The oif phase enters a second surge drum where some of the light ends are flashed off and routed directly to the distillation tower (they do not pass through to the heater). The crude distillation booster pump takes suction from this drum and delivers the desalted crude under flow control to the fired heater via the remaining heat exchange train. The crude oil is heated in the heater to a temperature that will vaporize the distillate products in the crude tower. Some additional heat is added to the crude to vaporize about 5% more than is required for the distillate streams, This is called overflash and is used to ensure good reflux streams in the tower, ‘The unvaporized portion of the crude leaves the bottom of the tower via a steam stripper section. This is the atmospheric residue and is cither further distilled, or becomes feed to a thermal cracker, or is routed to fuel oil product storage, ‘The distillate vapours move up the tower counter current to the cooler liquid reflux streams coming down, Heat and mass transfer take place on the trays contained in the tower. Distillate products are removed from the various sections of the tower, LPG and naphtha ter d | I] {Steam am Crude L_Gas oll feed a a Reduced crude (residue) Heat exchange — Desalting Heat exchange Heater Distilation ‘Stripping Figure 6.1. An atmospheric crude distillation unit (CDU)‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 51 steam stripped and sent to storage. The full naphtha vapour is allowed to leave the top of the tower to be condensed and collected in the overhead drum. A portion of this stream is returned as reflux while the remainder is delivered to the light end processes for stabilizing and further distillation. The side-stream distillates shown in Figure 6.1 are: @ Heavy gas oil (has the highest boiling point) © Light gas oil (will become diesel) © Kerosene (will become jet fuel) ‘A pumparound section is included at the light gas oil draw-off. This is simply an internal condenser which takes heat out of that section of the tower. This in turn ensures a continued reflux stream flow below that section. ‘The overhead system described here is perhaps the most common system encountered in this process. There are other configurations that are used by many refineries, Indeed, the one used as an example of overhead calculation methods in this book uses an external pumparound stream from the top tray to provide the internal reflux required. All these methods are well proven in refinery operation and have their advantages and disadvantages. 6.2 Fractionation ‘The degree of fractionation in a crude distillation unit is measured by the temperature difference between the 95% vol. ASTM of the lighter product and the 5% vol. ASTM. temperature of the adjacent heavier one. When the 95% point of the lighter product is less than the 5% point of the heavier the difference is called an ASTM gap. When the 95% point is higher than the adjacent product’s 5% point the difference is called an ASTM overlap. ‘A relationship exists between the number of trays, the internal reflux ratio and the gap of overlap between the products (5). This relationship is given in Figure 6.2. ‘This is in the form of a family of four curves, two curves at no steam present and two at maximum stripping steam. Two of the curves refer to the separation between side-streams only while the other two are for the separation of the overhead product and the first side-stream. Obviously, the best fractionation performance is when there is an ASTM gap between the products. As fractionation deteriorates and gaps become overlaps more and more of the components of the adjacent products are not separated. It must be stressed that good fractionation can be expected between naphtha and kero and also between kero and LGO (i.e, ASTM gaps). Lower in the column, however, and in vacuum columns such separation is not possible. In this level of distillation high overlaps will be experienced. The following example illustrates the use of this method to establish the internal reflux required for a kero and gas oil side-stream separation. STRIPPING STEAM Stripping steam is used in the crude distillation unit to remove the entrained light ends froth the draw-off products. When the side-stream product is drawn off theur si¥id dos Zutexus smodea ionpord suOTTeS [e102/MojJI9A0 JOY suOTTES = One xNSy weauis-opts Jeddn ogy Smuaus smodea ionpoad [e101 Woasi20q siujod woReTNSMP PeatiTOA0.waoMiNg SitIOd WORUTNSIP %OS U! BousI05IIP Je (q) ur aed syo-mexp wreans-apts dor pre (e) sureans-ops r2a0] 941 Ye J0 uMeIP pInby| pue s1eId J30-meIP %%0S UE souBIFFIP J, oN wssAdex ayy (q) UT. “ureans-opis doi pu aq1 wasordax Samo 977 UO sroqumu ay} (e) UI “pasn AyjessUas wreeys Suddins “wew ——— “ueais ou ——"“sionposd umeans-ops on aon opi (@) pu nonpoud teenie epi dot o1 Peatzond (@) soy foamne monetOheN Nee Ee ola SILJOD LOREINSID %G6 - %S HOReUO_IELS ‘swujod uoSeIN=1P 7686 - % VORBUCROES * oot te oe a ae Oe ee ee ee Oe oe T T iE Poe T T T T T T 8 ‘sionpoid weenseprs o1 Wwesasepis (a) = wBenseprs dor or peor (e) ae ot Bo 8 i f ze ae i o Fo 5 : : o ae or ov oe oo oe oe cor co‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 33 Percentage (vol.) removed by stripping ° od OR te eo Bh Pound steam per gal product Figure 6.3. Stripping steam main column it will contain entrained light components from the vapours passing through thé draw-off tray. This draw-off product is routed to a side-stream stripper ‘anid steam is introduced to the bottom of the tower to flow counter-curréntly to the liquid. The sttipper usually contains four trays which promote the c6ntact between oil and the steam. The entrained light ends ire rémoved by thie steaim’and they and ‘the steam te-nter'the main column, "The residue’ from the bottom of the main distillation tower is also steam stripped before leaving the tower: The quantity of steam and the percentage stripout is given in Figure 6.3. » Example Y Total vapour flow through Kero draw-off tray i8 naphtha plus kero products, Based on Kuwait crude the 50% TBP. point for this stream is 290 °F. ‘The $0% point of the LGO stream ‘in this case is about 550 °F. : ‘Therefore ATS0% = 260°F “In this tower there are eleven trays between kero and LGO, and we would expect 40°F gap between the products, Maximum stripping steam will be used.34 ‘THE DISTILLATION PROCESSES From the Packie (5) curves the refluxx tray product is 4.4 Therefore reflux ratio is “a =0.4 Knowing the total gallons of hot product vapour passing through the kero draw-off tray (this will be overhead naphtha plus kero products), the hot volume of internal reflux can:be calculated: Assume'total products = 18 000 gal/h ‘The required overflow from kero tray will be x 18000 7200 hot gal/h : =04 6.3 Developing the True Boiling Point Curve (TBP) and the Equilibrium Flash Vaporization Curve (FY) from Lab ASTM Distillation 7 ‘Two items of data must be available to produce a meaningful TBP curve and therefore an BFV curve: | @ The ASTM distillation:curve for each. product. @ The flow rate for each product and the crude feed flow rate, The flow rates will be used to determine the yield of each product on crude, CONVERTING THE PRODUCT ASTM DISTILLATION, TO TBP Most eryde distillation units takea full Lrange, naphtha cut as the overhead product. This cut contains all the ight ends ethane through pentanes and, of course, the heavier .-Raphtha range. All the light ends are gases in, solution, therefore it is not possible + {0 prepare. a. meaningful ASTM distillation, on this material, directly. Usually, the laboratory data give the ASTM distillation on a stabilized naphtha, and a separate analysis, is used to. determine the composition, of the light ends, There are two well-proven methods to develop the TBP curve from ASTM data. The first is that by Wayne Edmister given in his book Applied thermodynamics (6) and the second by Maxwell in Databook on Hydrocarbons (3). The correlations from both these sources are given in Appendix as Figures Al.1 and-A1.2. The'Edmister method, is used in this, book for, developing the TBP curve, ‘The ASTM distillation is tabulated as the temperatures for IBP, 10% , 30%, 50%, 70%, 90%, FBP. The IBP is the initial boiting point of a sarnple (equival over) and the FBP is the final’ boiling point (equivalent to 100% over). The temperatures between the IBP and the FBP are read off at the respective volume percentages distilled. Using Figure Al.1 the $0% vol, TBP is read.off from the 50% point of the ASTM distillation, “‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 55 Figure Al.1 is again used to determine the TBP temperature differences between the IBP and 10%; 10% and 30%; 30% and 50%; 50% and 70%; 70% and 90%; and 90% and FBP. From the established value of the TBP 50% point and the temperature differences determined from Figure A1.1 the TBP temperatures for IBP, 10%, 30%, 70%, 90%, FBP can now be tabulated. IDENTIFYING AND USING PSEUDO-COMPONENTS TO MAKE AN OVERALL TEMPERATURE VERSUS RELATIONSHIP (TBP) CURVE Each product TBP curve is split into pseudo-components and the ranges of these components established on a temperature basis. Any number of these components may be used. However, when a component is identified in terms of its temperature it must be used in all product distillation curves where this specific range exists. ‘The volume percentage of each pseudo-component is listed for each product. Multiplying these percentages by the yield of the respective product on crude provides the percentage on crude of each pseudo-component. The accumulated volume of each can now be related to a cut point temperature and thus @ cumulative TBP curve, ‘The very heavy end of the TBP curve is not calculated but is usually determined by extrapolation, It plays no major role in any future calculations for the processes described in this book. DEVELOPING THE EQUILIBRIUM FLASH VAPORIZATION CURVE ‘The Maxwell curves given in Figure A1.2 are used to develop the BFV curve from the ‘TBP. The EFV curve gives the temperature at which a required volume of distillate will be vaporized. The distillate vapour is always in equilibrium with its liquid residue and the developed FV curve is always at atmospheric pressure. Other pressure and temperature- related conditions are determined using vapour pressure curves or by constructing a phase diagram. ‘The TBP reference line (DRL) is first drawn as a straight line through the 10% point and the 70% point on the TBP curve. The slope of this line is determined as temperature difference per volume per cent. This slope is then used to determine the 50% volume temperature of a flash reference line (FRL). The curve in Al.2 which relates ATs) (DRL~FRL) to the DRL slope is used for this. Finally, the curve in Figure Al.2 relating the ratio of temperature differences between the FRL and the flash curve (EFV) and the ratio for the TBP to DRL is applied to each percentage volume of the FRL to arrive at the atmospheric EFV curve. ‘A sample calculation for the compilation of both TBP and EFV curves follows. Note that TBP curves are used to define product yields while EFV curves are used to define temperature/pressure conditions for distillation. Example calculation Building a crude TBP curve from ASTM lab data ‘This example is based on Kuwait crude: ‘Top product is full-ange naphtha and its yield is gas to 25% vol.56 ‘THE DISTILLATION PROCESSES Second product is kerosene and its yield on crude is 10% vol. (plant data). Thitd product is light gas oil with a yield of 12% vol. on crude. Fourth product is heavy gas oil which is 7.0% vol. on crude, (@) Converting lab ASTM data to TBP The overhead naphtha cut It will not be possible to test this whole cut using ASTM distillation. The front end is very light hydrocarbons ranging from C,s ethane to Cy. The front end will be analysed separately using the POD (Podblinka) apparatus. The result of this was: C, 0,11 % vol. on crude C3 0.84% vol. on crude iC, 0.40% vol. on crude nC, 1.53 % vol. on crude iCs ie! | 302% vol, on cre Cs 3.6% vol. on crude C; 4.5% vol. on crude Total 14.0 % vol. on crude A 14.0 ‘This represents ons” of the naphtha cut = 56% vol. ‘The ASTM distillation on the heavy end of the full-range naphtha is.as follows: 50% vol. over —300°F 70% vol. over 310 °F 90% vol. over 330° FBP 358 °F We will now convert this to TBP using a method by Edmister. See Figure Al.t in Appendix 1, This is as follows: Vol. ASTM ‘TBP °F A°F ATF °F 50% 300 305 10% 310 10 14 319 90% 330 20 2 346‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT ‘The kero cut, Converting this cut from ASTM to TBP is as follows: Vol. % — -ASTM (lab test) ‘TBP °F arr ATP oF 1BP, 345 287 10 316 31 37 344 30 400 4 44 388 50 419 19 32 420 10 436 n 1 447 90 460 4 3 480 FBP 495 35 38 518 ‘The light gas oil cut ASTM (lab test) ‘TBP r Are... ATF F 1BP 495 487 40 520 2s 48 505 30 532 12 5 530 50 543 i 29, 550. 0 559 16 6 516 90 572 13 19 595 FBP 595 B 2 62 ‘The heavy gas oil cut ASTM (Lab test) ‘TBP oF ATF ATR °F 1BP. 595 568 10 615 20 40 608 30 026 nr 5 633 50 633, 1 “ 647 0 640 1 2 659 90 658 18 25 684 FBP 615, a 20 104 7 ‘This completes the:conversion-of the atmospheric distillates to TBP and these are plotted in Figure 6.4. : ‘We now require to define the TBPs on the vacuum distillates. These are developed similarly to the atmospheric one except that the ASTM tests are done at 10mmHg. ‘These, however, are converted and quoted at atmospheric pressure.58 ‘THE DISTILLATION PROCESSES %%volumo Figure 6.4. Pseudo-components Light vacuum gas oil cut (LVGO) ASTM (lab test) TBP °F ATF ATR F IBP 18 605 10 68 25 49 654 30 668 25 a7 701 50. 682 4 23 76 0 700 18 un 780 90 720 20 2 753, FBP 760 40 43 823 Heavy vacuum gas oil (HVGO) EEE EEE eee ASTM (lab test) ‘TBP SF ATR APR oop TBP 640 637 10 102 a 95 732 30 0 61, 38 6 193 50 760 20 2 825 70 805 6. 59 884 90 836 St 59 943 FBP 925 9 16 1019‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 59 This completes the conversion of the vacuum distillate ASTMs to TBP. The yield of LYGO was 11% vol. on crude and HYGO was 20%. (0) Making the component balance Yields vol. % on ernde Cat points Total yields Components of _Naphihe Kero LGO HGO LVGO_HVGO Vol. frac. Cumul. G = aul out ll q = ase 08085 ic, = 040 040135 ac, = 153 1328 m ZT jim 3 5.90 G = 3.0 30 930 G = 450 430 14.00 Prego! to 2800 ST 517 19.17 Pseudo 2 50 283s : 303 22.20 Pseudo 3 36528615 436 26.36 Psaudo 4 405 Ode 200 24 28.00 Pseudo 5 440 25 250 3130 Pseudo 6 $50 28 06 aa 3490 Pseudo 7 sis 07 18 250 sd Paendo 8 550 36 300 41,00 Pseudo 9 ss 24 014 035 30 08 Pseudo 10600 24 038 044 3947.28 Poeudo 1625 12 126 033 279 S007 Piewdo 2680 175 oat 29 5226 Pesido 13615 259 04 040 3355.09, Poeudo 16725, oot 308 120. 5.9.88 Prewdo IS 180 2.20 143.6048 Preudo 16800 308380. 688 71.36 Pseudo 17880 om 520 S68 71.00 Pseudo 18 900 300 300-500 Pseudo 19980 340340 83.40 Pseudo 201020, 1 6085.00 Resi. +1020 15400 100.00 ‘Totals 0100 20 70 ao ‘This curve is shown as Figure 6, (©) Developing the equilibrium flash vaporization curve ‘The Maxwell curves given in Figure Al.2 in Appendix { will be used. ‘The distillation reference line (DRL) is drawn through the 10% and 70% vol. of the TBP, Slope of this line: 50% vol. 600 °F 40% vol. 500°F 100 _ 199 Slope=-Fq= 10°R/%60 ‘THE DISTILLATION PROCESSES From the top curve in Figure A1.2 slope of the flash reference line (FRL)~ 6.8 °F/% From the middle curve in Figure A1.2: AT sy (ORL—FRL)=39.5 ‘The 50% point of FRL then equals temperature at 50% DRL—39.5 °F. = 600—39.5 = 560.5 Say 561 °F ‘The FRL can now be drawn and is given in Figure 6.5. Using the bottom curve of Figure A1.2 the EFV curve can be developed thus: | 4 (AT TBP/DRL) _AT (flash/FRL)* EFV °F AT (TBP/DRL) AT flash/FRL °F 0 100 0.2 20 200 10 0 04 0 290 20 0 0.38 0 355 30 +25 0.37 9 434 40 +40 037 15 510 50 425 0337 9 569 0 +20 037 1 81 0 0 037 0 700 80 0 037 0 70 90 100 031 7 87 100 o 037 = & * From Figure Al.2 Temp. CF) ‘hvoume Figure 6.5. TBP and EFV curves for whole crude |‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 61 6.4 Procedure for Establishing Flash Zone Conditions Flash zone conditions, particularly flash zone temperature, is difficult to measure accurately, This is due to the profiles set up in the flash zone by’ turbulence of the feed entering and vapour disengaging. Knowledge of flash zone conditions is, however, essential when evaluating the unit performance and troubleshooting the unit, This section therefore deals with a calculation procedure to establish these conditions. THE FLASH ZONE “ The flash zone is the area in the crude distillation tower where the distillate vapours are allowed to separate from the unvaporized liquid. The transfer line from the heater centers the flash zone, The vapours rise up through the tower to be condensed by cold reflux streams coming down, Steam enters the flash zone from the Uatiom product stripper section located below the flash zone. Steps to calculate flash zone conditions © Step 1 Establish the total flash zone pressure. This is done by setting the tower- top reflux drum pressure, then by adding condenser pressure drop, tower and condenser line pressure drop to the reflux pressure. A total pressure in the flash zone is obtained. © Step 2 Set the quantity of stripping steam to be used for bottoms stripping. This ‘was discussed in Section 6.2. Normally a quantity of about 1.2 1b steam per gallon of product is used. © Step 3. From the material balance calculate the moles per hour of vapour leaving the flash zone. Now this will be the total moles of products plus a quantity called overflash. The overflash is never drawn off as ‘a product but is the mechanism whereby additional heat is transferred to the tower to provide Teflux. © Step 4 Set the amount of overflash. Normally this will be 3-5% volume on crude above the total product cut point. Thus if it is intended to vaporize 54% of the total crude as distillate products we would actually operate at a temperature sufficient to vaporize 57-59% of the crude. The amount of overflash depends on operating economics and the degree of fractionation required. © Step 5 Construct the equilibrium flash vaporization curve. This is described and discussed in Section 6.3, Set the cut point to include overflash, remembering that this is at atmospheric conditions. ; © Step 6 From a knowledge of the amount of hydrocarbon vapour moles, the moles of steam in the flash zone and the flash zone’s total pressure, calculate the partial pressure of hydrocarbons. This is moles HC Vapour ——__— =X total pressure ‘moles steam-+moles HC vapout ee © Step 7 Adjust the EFV curve to the calculated partial pressiire, ‘This is accomplished by selecting a temperature on the atmospheric EFV curve,02 ‘THE DISTILLATION PROCESSES ‘Then use the vapour pressure charts given in Appendix 1 (Figure A1.6). Take the selected temperature at atmospheric pressure. ‘and move along parallel to the vapour pressure line until the required partial pressure axis is intersected. Read off the new temperature, Plot this on the percentage volume axis on which the original temperature was selected. Draw the new EFV through this point parallel to the atmospheric EF'V, Locate the required cut point on this new EFV and read off the temperature. This will be the flash, zone temperature, The following example illustrates this procedure. Example calculation Using the following material balance and the TBP for Kuwait crude calculate the flash zone temperature and pressure. Use 3%, vol. overflash and 1.2 b/h steam per gallon for bottoms stripping. ‘ Material balance EEE EEE EE 4 Volume Yolune Weise Males ‘TAP ewt : : range Cun Stam) Gut nes GPM $0 */0al”Th/h “AW min Mesh Whole crude = — 100 3000) 52500 6.8685 7.23 379575, 100.0 225.3168 Ovetead —Gas—380 250 7500 19125 0702 $84 T6850 02-952 --sO51 Kero 480 100 30005250 0798 664 34860. 92 I6L6 ~ 2157 Lish sot 810 120 300 800 088 “7M 44216 17 ai56 Dost Heavy ws cil 6807.0 noo 3515075 72826784 70°22“ Residwm +850 460 13800 24150 0957 816 97085 S19. SATS. a9 Total =) 103000. $3500 oss 721. 379575 1000 ks NeRk Pout Flash zone material balance Overfash 650-725 30 $70. $00, 1STS OBL. 14 MESS 3.0 889 Product “ Gas~680 54.0 S40 16200 26350 0.78 618249 aR. 137713249. vapour Total —Gas-725 57.0 $7.0 7100 29925 OTR BAD. INHTKS SEA 142313644 vapour Liguid MS 48.0 “40° 12900 22515 0.988 R22 'IBS4ID 489 S787 aNd phase 7 Total 10010 30000,, 52500 sess, 7.23 a79575, 16, oes. not include liquid overflow from bottom wash ay Flash zone. calculations : (@) Total pressure at flash zone: : Establish overhead drum pressure at Spsig Establish ait condenser pressure drop at 5 psi Establish crude/overhead exchanger’ at 2 psi (shell side) Total ovethead pressure < Ppsig Assume 40 trays between flash zone and tower top. Let AP per tray be 0.25 psi Total tower pressure drop Then total flash zone pressure Opsi 2 psig Call it-25 psig for design’‘THB ATMOSPHERIC CRUDE DISTILLATION UNIT 63 (b) Calculate partial pressure of vapour in flash zone From Figure 6.3 we will take bottom stripping steam requirement at 1.21b/gal = 12x24 150= 28 980Ib/h steam = 1610 moles/h steam Partial pressure of vapour is Moles HC vapour Pressure Total moles vapour 1364.4 25 psig 1364.4 +1610 = 11.47 psig 26.17 psia (©) Calculate EFV of whole crude at atmospheric pressure Slope of whole crude ref line=11.8 °F/% vol. (Figure 6.5) (DRL) . Slope of flash ref line (FRL) (from Figure A1.2) =8.5°F/% ATs (DRL-FRL)=40°F Ts DRL 67°F FRL 50% 67-40 627 °F TBP Flash % Vol. Actual. DRL AT Ratio AT FRL — Flash 0 -ia7 15-202 0.24 48 200 152, 10 190 190, 0.04 0 285 285 30 420 430 -10 0.34 -3 450 447 50 645, 667 -22 0.34 -8 627 619 70 900 900 0 034 0 795 795 90. 1235 1140 95 0.34 32S 947 FBP 2192 1250 942, 0.34. 320, 1040. 1360 ‘The atmospheric BFV curve is plotted in Figure 6.6, The $0% volume temperature is 619 °F. Using the vapour pressure curves in Appendix 1 locate 619°F on the atmospheric pressure line. Then move parallel with the nearest sloped line to a pressure of 26.17 psia, Read off this temperature and plot it on Figure 6.6. Draw a line through this point and parallel to the atmospheric EFV curve. This is the EFV curve at 26.17 psia pressure. Read off the temperature for 579%’ volume distilled. This is the flash zone temperature and is 720°F. ‘ 6.5 Estimating Tower Draw-off Temperatures ‘TOWER BOTTOM TEMPERATURE ‘The tower bottom temperature (residue dray-off) i calculated by a simple heat balance when the flash zone conditions and the quantity of stripping steam are known. Using64 ‘THE DISTILLATION PROCESSES 1300 + 1200 +100 terre g Temp. CF) 0 o % 2% 0 4 om wm M0 ‘% vol. distiled Figure 6.6, Whole crude EFV curves, the material balance given, for example, in Section 6.4 and the calculated flash zone condition, the bottoms temperature can be calculated as follows: Consider the material on the top stripping tray. This will consist of product residue plus the stripout as liquid: Product residue is 197085 #/h Stripout will be 6% by vol. = 1449 gal/h Let stripout be 7.5 #/gal and have a mol..wt of 305 ‘The stripout percentage is read from the curves given in Section 6.2 and using the enthalpy data in terms of BtU/Ib the heat balance can be closed to give a value to the outlet temperature as shown below. Note that the enthalpy data used in this item have been taken from the author’s own files, It is recommended that engineers use enthalpy data that can be obtained in standard data books such as Maxwell's ‘Hydrocarbon Data ot the GPSA Engineering Data Book ot some other recognized ‘source,‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 65 eee Enthalpy : VIL APL —soK °F lbh BTU/Ib -BTU/hx 10-6 BTU BT Ux 10-6 In Residue L B ILS 720,197,085 396 78.046 Stripout Z WS LS 720 10.868 410 4,456 Steam 450 28.980 1290 37.384. Toral 236.933 119.886 Out Residue, 2 ILS T 197085 x. 197 085,.X Stripout ¥ an 10868 490) 5.325 Steam V oS 28980 1383, 40.079 Total 236933, 197 085-+45.404 eee At partial pressure of FZ= 13.53 psig 197 085.X+45,404 = 119.886 74.482.000 © 197 085 78 BTU/b 04°F (irom enthalpy) ‘The outlet temperature is 704 °F. SIDE-STREAM DRAW-OFF TEMPERATURE A method developed by J. W. Packie (5) has been used extensively for this Purpose. This’ method uses the partial pressure of the side-stream product FRL (flash reference line) initial temperature. The calculation to obtain the FRL has already been dealt with in Section’ 6,3. In arriving at the partial pressure on the tray all material lighter than the draw-off Product and the steam passing through the tray are considered inert, Carry out the calculation using the following steps: © Step 1 Fix the amount of steam passing through each draw-off. Use the curves in Section 6.2 © Step 2 Fix the total pressure for each draw-off tray (pressure profile). Again use the method given in Section 6.4 and an estimate of the tray location. © Step 3 Calculate the FRL and establish initial boiling points. Use the TBP cut point for this (not the TBP end-points). © Step4 To obtain the total moles of vapour passing through the tray an estimate of overflow from the draw-off tray must be made, For this purpose use a rule of thumb which gives the following ratio of overflow to product moles: HOO overflow 2.9 LGO overflow 1.2 Kero 0,9-1.0 © Step Calculate the partial pressure of side-stream draw-off at each tray. Using the vapour pressure curves in Appendix 1 relate the FRU. initial: boiling6 ‘THE DISTILLATION PROCESSES rer 3 ‘rae oF Tig ase cuave Basen oN metieacns a [at Ere g s & nore: UE Guy Wi PACA METHOD Theor ded ig temperate ~ Aca soda ope a7 8 ‘0200 300 00 20 ca 700 0 00 (0% Pointofcuton atmospherle TBPC of crudo *F Figure 6.7. Temperature correction for calculating side-stream draw-off temperature—crude distillation i Boint (which iat atmospheric) to that forthe pata pressure. This has been described in Section 6.4, © Step 6 Now the temperature at the partial pressures evaluated in Step 5 is corrected using Figure 6.8. The resulting temperature is the draw-off temperature from the main column, Consider the following example using the material balance given for Section 64 and the steam rates provided by Figure 6.3; ae Example calculation w © Sieam raies to be used in side-stream stripping Al strippets have four actual trays. HY gas oil will use 0.3 steam, per gal LT gas oil will use 0.5 #steam per gal Kero will use 0.65 # steam per gal Steam % Heavy gas oil - 3675x0,3 838 Ib/h Light gas oi] ~ 6300x0.5 =3150 Kero - 5250X0.65 =3413‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 67 © Pressure profile in tower ‘This will be 40 trays in the fractionating side. ‘Summary of tray locations and pressures ‘Tray no. Pressure (psig) HGO draw-off 32 234 Bottom PA return 29 2.7 LGO draw-off 2 19.5 LGO PA'return 9 18.8 Kero draw-off 2 15.5 © Calculate theoretical initial boiling points We will use the Packie method for this. From cut TBP produce the FRL for each cut. HGO 50% point TBP is 648 °F Slope of TBP is 0.6°F/M% Slope of FRL is 0.2 °F/%, 50 (DRL~ FRE) is 7 50% FRL is 641 From FRL curve IBP is 626 °F at atmospheric LGO 50% point TBP is 550°F Slope TBP is eet = Slope FRL is 0.3 °F/% 50% FRL is 550°F IBP is 527 °F at atmospheric Kero TBP 50% point is 420°F ‘TBP slope is ae =1.2°E/M% FRL slope is 0.5 °F/% FRL 50% is 420°F IBP FRL is 395 °F at atmospheric 16°F/% © Calculate approximate partial pressures and draw-off temperature Internal reflux is assumed as follows: toHGO tray 290 moles toLGO tray 250 moles To kero tray 200 moles HGO tray partial pressure ;68 THE DISTILLATION PROCESSES Moles HC xT re Total moles vapour rsteam * TO! Press _ 1614.9 “349 X38,1=19.1 psia ‘Theoretical temperature is 660°F (using vapour pressure curves) From Figure 6.7: ‘Theoretical temperature —actual temperatu actual temperature= LGO draw-off temperature Steam to tray is: Bottoms stripping 1610 moles/h HGO stripping 102 moles Total 1712 moles/h Partial pressure of HC From Figure 6.7 actual temperature is 545-52 =493°F Kero draw-off temperature Steam to tray is: Total from HGO tray 1712 LGO stripping _175 Total 1887 Partial pressure of HC 1020.8 x 200 3107.8 30.2=11.9 psia : 0% FRL at 14.7 psia is 395 °F 0% FRL at 11.9 psia is 380°F Figure 6.7 at actual temperature is 380 °F -36 =444°P‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT Cs a5 08 a7 08 09 10 15 20 25 90 36 40 9.9) 99.9 @ 9 Reet tee eeEEEeeeEESL EeLEg 05 06 07 08 09 10 1S 20 25 30 35 40 Aor ‘Az Absorption factor = L/YK S= Stripping tactor = YK/L Figure 6.8, Absorption and stripping factors (Reproduced by permission of Fluor Daniel Inc) 6.6 | Calculating Tower-top Conditions Before proceeding with this section it is necessary to define and establish some fundamental thermodynamic definitions relating to fractionation-in general: © Bubble point This is the temperature and pressure conditions at which @ hydrocarbon liquid begins to vaporize. © Dew point This is the temperature and pressure conditions at which a hydrocarbon vapour begins to condense, © Flash vaporization This is the quantity and composition of a liquid and vapour in equilibrium at any given condition of temperature and pressure. Note that the composition of liquid and vapour in equilibrium will be different to one another.70 ‘THE DISTILLATION PROCESSES ‘The tower-top conditions relate to the temperature and pressure for the reflux drum and above the top tray of the tower. REFLUX DRUM CONDITIONS ‘The temperature condition for this drum is,set by ‘either ambient air conditions, if the tower overheads are air cooled, or, water temperature if water cooled, Normally the reflux drum in a crude unit handles totally condensed material (i.e. no vapour phase) and is usually cooled to a point below its boiling point (or bubble point), The pressure.at which the drum is operated is calculated from the bubble point of the overhead material. Because the drum is normally subcooled the pressure is maintained by a fuel gas stream: Consider the following example and calculation. Example calculation ‘The overhead from the material balance given in. Séction 6.5 has the following component: Mole fraction composition: G 0.008 G 0.054 iC, 0.021 nC, 0.084 Cs 0.143 Cs 0.155 G 0.175 Comp 1 0.124 Comp 2 0.124 Comp 3 0.075 Comp 4 0,037 Total 1,000 ‘The reflux drum temperature will be fixed at 100 °F. The pressure will be calculated at the bubble Point of this material at 100°F. Bubble point is defined as the sum of all. ¥s=sum of all KXs Kis the equilibrium constant. This can be read from the equilibrium curves or can be considered (rough and not be used for definitive design) as: Vapour pressure Total pressure This relationship will be used for this calculation. The calculation is iterative (trial and error) as follows: i j | j | | | 4THE ATMOSPHERIC CRUDE DISTILLATION UNIT a) At 100°R Ist trial at S psig 2nd trial at 1Opsig Mol fract. X K K ‘x G 0.008 40.6 0.325 32.40.59 G 0.084 «9.3. 0,502 7.420.401 icy oo = 3.550.075.0388 005 nC 0.08 = 2.540.213 0.03 OTL G 0.143 0.890.127 Ol .t02 G 0.155 0.254 0.039 0.200.081 CG 0,084 0,015 0.067 0.011 Comp 1 0.023 0,003 0.020 0.002 Comp 2 Neg Neg Comp 3 Neg Neg Comp 4 Neg Neg 1,299 For 2nd trial (estimate) ‘Take the K value of the highest ‘y’ fraction (in this case C3) where K=9.3. Kk Take tis A =7.16 (new K) Make the 2nd trial with KC; at 7.10 1.10 pC, at 100 °F =190 psia then total pressure ced 26.5 psia 2nd trial pressure=26.5 psia= 11.8 psig, Let us set it at 10psig ‘The second trial gives sum of Ys= 1.027 as this is considered close enough. Then drum will be operated at 100 °F and at 10 psig. TOWER-TOP CONDITIONS ‘The temperature and pressure conditions that will exist at the top of the tower will be the dew point of the overhead hydrocarbon product at its partial pressure with the steam. This can be calculated in a similar manner as that for the reflux drum, ‘This time, however, the relationship for the condensing phase will be used. This is sum of all xs= sum of all Y/K. ‘The total pressure in the top of the tower is fixed by the reflux drum pressure. ‘The resulting temperature is calculated using the steps given in the following example. ‘The quantities (moles/h) of hydrocarbons follow those given in the material balance ‘Section 6.5. The steam figures used are those previously used. Tower-top temperature conditions ‘The crude tower configuration in this example uses a pumparound to condense reflux overflow. Many crude units condense product and an external reflux stream using an overhead condenser (see Section 6.1).n ‘THE DISTILLATION PROCESSES In this example only the product vapour and total steam need to be considered for partial pressure conditions at the tower top. Assume that total pressure is 15 psig at the top of the tower: Total vapour moles =805.1 moles/h Total moles steam =2076 805.1 29.7 psia 2881.1 =8.3 psia Partial pressure= The following dew point caleulation will be carried out at 8.3 psia. 1st tit at 220° And teal at 225 °F Mole Mol Weight Vol. Comp fay K X=¥/K KK XeV/K wt factor —SG__ factor Lui prop. G ma Neg Neg G 0.084 84.3 0001 93.9 OO 4.04508 008 iQ 0.02 38.6 0001 39.8 000158008 0.863 G10 mol, =1307 nc, 0.084 2952 0.003 30.1 0003-58084 0.80 G 0.18 12.53 O01 1265 OO OR 0629126 166 G 0.185 4.10 0033 4.94 Om] BS 28S ATS 0.300 ¢, 0.175 2.17 O08! 219 0080 100800 aT IO *API=53 MidBP 260 0.124 1.00 0.24 1.160.107 114.198 1.602 Mid-BP 300 0.124 0.506 0245 OSI8 0.259 126. “BO.114. 765396 Kea MidBP 340 0.675 0.229 0328 0.253 0293136 39.848 0.765.135 MidBP 352 0.037 0.108 0389 0.126 0294 182 44.668 O78 Ser Totals 1.000 Li7e 1.06 130.7 138551 0.767 18.059 Vapour press at selected temperature Total systems pressure 2nd trial=0,108X 1.170 (K from mid-BPT 362 component) New K=0.126 then VP =8.3 psia x 0.126= 1.05 psia=225 °F 2nd trial is close enough actual temperature: 0.126 1.060.134 VP=1,11=229 °F Notes (a) In estimating for the 2nd trial and final temperature the K of the highest X component is multiplied by.the total value.of the X function. Then vapour Pressure curves are used to give the component temperature corresponding to this new vapour pressure. (b) The molal composition of the final X is the composition of the liquid in equilibrium with the product vapour. In other words, the composition of the pumpatound liquid and the internal reflux. ‘The tower-top conditions are 229 °F at 15 psig.‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 2B 6.1 Fractionation and Internal Reflux at the Tower-top Section This crude tower condenses internal reflux using a pumparound section at the very top of the tower, This is a four-tray section and these trays are used for heat transfer only. However, actedit of one tray can be taken for separation. Consequently, the total number of trays between tower top and kero draw-off for mass transfer is nine. Using the procedure described in Section 6.2, internal overflow is established by the family of curves given in Figure 6.2 for max. steam and the overhead to first side-stream. This is illustrated in the following example. Example calculation ‘The material balance given in Section 6.5 is used as the basis. An ASTM Gap of 30°F is required between the 5% point for kero and the 95% point for naphtha. ‘The 50% TBP difference between overhead and Ist side-stream is approximately 420 — 265 = 155 °F Fractionation factor is 17.4 (read from the curves in Figure 6.2) ‘The total number of trays between kero and the tower top is nine. ‘Therefore refx rato is 74 1.933 Gals of hot overflow Soe Reflux ratio is Cr OF total product vapours. ‘Then gals of hot overflow required = 1,933x 13 125 =25271 gal/h 5371 fh op 253 Gal/h overflow at 60 °F = 755 isis expansion factor) 222314 From the dew point calculation item 1,7 Ib/gal for overflow is 6.36 (53° API) overflow 141917 Ib/h 6.8: Calculating the Top (Naphtha) Pumparound Duty to Meet an Internal Reflux Requirement ‘This is a heat balance over the tower-top configuration using tower-top conditions and knowledge of the required internal reflux between naphtha and kero. The following example to illustrate this uses the material balance from Section 6.4, the tower conditions developed in Section 6.6 and the internal reflux calculated.4 ‘THE DISTILLATION PROCESSES Consider the heat balance over the envelope shown in the diagram: Heat in with © Product vapour from tray 5 © Overflow vapour from tray 5 @ Steam from tray 5 Heat out with © Naphtha product vapour © Steam from tower top © Overflow liquid to tray 5 © Pumparound The heat balance is as follows: es : Enthalpy York API? K °F Ib/h__ BTU/Ib ~ BTU/hx 108 In Product yap. = WV 7012245 76650 266 20.389 Overflow vap. Vo = 5312 245-4917 25 35.763 Steam v 245373811194 44.633 Total in 255.948 100.785 Out Product vo 1 12 229 76650 (258 19.776 Steam v 29° 373811188 44.409 Overflow L 533 12-234 1at9IT 114 16.179 Pumparound Cc Total out 255.958 80.3644-C (2) Estimated fromi tower profile @) Role of thamb—top tay temperature is tower top +5 °F Heat in = Heat out Then 100.785 = 80,3644-C Pumparound duty = 20.421 10° BTU/h‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 15 6.9 Calculating the Required External Reflux to the Top of the Tower Fi (Note that this calculation is applicable to the more conventional overhead configuration where the total product, reflux and steam are condensed in the overhead condenser.) ‘There is a telationship between the quantity of reflux pumped back to the tower from the reflux drum and the internal reflux. As the external reflux flow can be measured and the internal reflux cannot, it is desirable to calculate the relationship between the two reflux streams, This will be necessary because it is the internal reflux that establishes the amount of fractionation between the adjacent cuts (ASTM gap). ‘The steps to establish this are as follows: © Step 1 From the product naphtha lab analysis calculate tower-top, conditions using the steam input to the tower (Section 6.6). ; © Step 2. Establish the internal reflux using ASTM gap required (Section 6.7). © Step 3. Calculate the condenser duty required to generate the internal reflux (Section 6.8). Adjust the. calculation to that for total overhead condenser, © Step 4. Using the condition at the tower top and reflux drum calculate a heat balance over the top of the tower. ‘The unknown in this'case will be the flow of external reflux, Equate and solve for the unknown. Steps 1 to 3 have already been described and using the example provided in these. steps the heat balance for Step 4 is given in’ the following’ example. Example caleulation Enthalpy Vork APIo KF BTU BTU/hx 106 In Naphtha product = Y= 7012-2460 76650” 266 20.389 Reflux yo 1% 2 M60 x 266 266.X ‘Steam v 246 37381 1197 44,745 Total in 140314X 65.134-4266.X Out Naphtha product = 7 12 10 766506 Reflux L 0: 1210-0 46 Water: L 100. 37381, 100 Condenser Total out 114031 +¥ _ 65 134000-+ 266% =78 624000 446 X “13.490 000 External reflux =61 318 Ib/h ; Note: . The tower-top temperature.is now-that calculated in Section 6,7 at a slighty higher partial pressure equivalent to a Moles Prod, +moles reflux (essumed) Total moles HG + steam 29.7 psia16 ‘THE DISTILLATION PROCESSES 6.10 Establishing the Internal Reflux between Side-streams This procedure utilizes the curve relationship between ASTM gaps, reflux ratios and number of trays developed by Packie (5) and described in Section 6.2. These steps are: © ‘Step 1 Establish the'degre¢ of fractionation required, Remember there are limits to this. For example, it is very unlikely that an ASTM gap will be'attained ini tthe heavier end of the tower (i.e. LGO to HGO). © Step 2 Evaluate the 50% vol. temperature difference between the TBP of the two adjacent cuts. © Step3 Using the side-stream-to-side-stream family of curves for max, steam tead off the factor corresponding to the ASTM gap (or overlap) on the 450% TBP temperature curve, _® Step 4. The factor is the number of trays between the cuts multiplied by the reflux ratio. The reflux ratio is Hot overflow (gal/h) Total-product gal/h entering the highest tray © Step 5 From this the hot overflow can be calculated and will be uscd to predict pumparound requirements and tower performance. ‘These steps are illustrated by the following example. Example calculation Using the quantities given in the material balance (Section 6.4) and the TBP curves given in Section 6.3, predict the overflow required to obtain a 30°F ASTM overlap between LGO and HGO, © Number of trays between LGO and HGO draw-offs are 11 (two pumparound trays are equal to one fractionating tray). @ The temperature difference between the 50% of otal product passing through the LGO tray and the HGO product is 300 °F: @. Using 30°F overlap and the 300 °F curve in the side-streant to-side- stream mak. steam curve gives a factor of 10.2. @ = The reflux ratio‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT n Hot gallons of overflo Gal of product vapour Gal of product vapour=24 675 (from material balance). ‘The hot gallons of overflow=22701 gal/h 6.11 Calculation to Establish Pumparound and Overflash that will meet Internal Reflux Requirements Internal reflux throughout the tower is generated by heat input through overflash and its removal by pumparound or external reflux streams. All other heat to maintain heat balance is removed by the product streams. Thus, if the percentage overflash is increased there must bea comparable incréase in pumparound duties. Otherwise the only effect of increase overflash will be to change the cut point. t ‘Overflash, as described earlier, is that portion of the crude feed that is vaporized over and above that amount vaporized to provide the distillate products. Normally overflash is between 3% and 5% volume on crude. Pumparound is the method of removing this heat by an external stream drawing off a quantity of liquid from the tower. This is cooled and returned to the tower some trays (usually two to three) above the draw-off. This area in the towet acts as an internal condenser, and condenses. vapours that are not removed: as the product but are allowed to flow downwards from tray to tray. as reflux, Normally the amount of overflash is fixed by the coil outlet température. The variable then is the pumparound duty at any of the relevant sections. Remember, when you change one pumparound then the other pumparounds also change to mect heat balance requirements. Consider the following example. It is required’ to. calculate the bottom pumparound duty to meet the internal reflux calculated in Section 6.10. Mass balances will be as given in Section 6.4. ‘Temperatures, flash zone conditions and steam rates will be as used previously in this chapter. In this calculation side-stream stripper:bottom temperatures are. going to be used instead of the calculated side-stream draw-off-as a rule of thumb these. ; are about 10°F lower than draw off. However, they can be calculated)-as,will be shown later. : ag or Overflow from tray 22 to meet fractionation of the 30,°F gap between 95% vol, ASTM of LGO and 5% vol. ASTM of HGO is 22701 gal/h at 498 °F, or 17487 gal/h at 60°F. The SG at 60 is 0.843, then Ib/h is 122412. The heat balance is condiicted over the envelope shown below: : Streams into the envelope Crude feed Overflow to tray 21 Steam to HGO stripper Steam to bottom stripper we ;8 ‘THE DISTILLATION PROCESSES 4 [etal = 4 4 Co ‘teem ote L. Lt Hao Fan. 4 1 ; ; te Steet Lam este’ Enthalpy Ib/h’— BTUAb BTU/hx 106 In Crude feed vapour Vo 50) 11S 720" 194145528 102.509 Critde feed liquid LO US ALS 720° 185430»: 396 73.430 v L Steam (total) ‘ 450308181290,» 39.755 Overflow to tray 21 366115. 498. 122412 263... 32.194 Total in 532 805 247.888 Out i i 7 ‘Prodt, distillates v.35) nS 500185796 304 61.360. Overflow v 6.6 1S 500 122.412 365 44.680, HGO product Lo 30 1S. 587. 26754298. 7919, Residue L138 ANS 704 197085, 378 74,498 Steam to LGO vo- 500 308181318 40.618 Bottom pumparound c Total out 532.805 29.01 +C C= Pumparound duty As heat in = heat out ‘Then 247.888% 10! BTU/h= 229.075 x 1054-C BTU/h Pumparound daity = 18.813 x 106 BTU/A‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 9 Streams out of envelope Product vapour plus overflow vapour (produet vapour =naphtha, kero and 1LGO) Steam to tray 22 HGO product (stripped) Residue product Pumparound duty - 6.12 Overall Tower Heat Balance ‘When the flash zone conditions, the product draw-off temperatures, and total stream input are established it is now necessary to predict side-stream stripper product temperature to construct an overall heat balance. The purpose of the overall heat balance will be to check the total pumparound duties and establish any of those not already fixed for specific fractionation requirements, In estimating side-stream stripper bottoms temperature the rule of thumb given in Section 6.11 can be used. However, for this exercise a heat balance over a side- stream stripper is given as an example of a temperature calculation method. The steps for preparing the overall heat balance are as follows: © Step 1 Establish total heat in with crude. © Step2 Calculate stripper bottoms temperature for distillate products (an. example for one product outlet is given). © Siep 3 Calculate bottoms temperature outlet (this has been done in Section 6.35). © Step 4 Show total steam input—this will be as in the curves, in Section 6.2. © Step 5 Commence the heat balance as shown in the example that follows on page 81. STRIPPER PRODUCT TEMPERATURE The example provided in this section will be for the heavy gas oil stream using the quantities given in the material balance in Section 6.4. Steam rates and stripout will be fixed as per the curves given in Figure 6.2. HGO stripper outlet temperature : Steam rate will be 0.51b/h per gal/h of product. = 1838 b/h Stripout is 5% vol. of feed stream (Figure 6.2). Let mol.wt of stripout be 230 (estimated average of distillates) and SG be 0.865 (again estimated). Consider the following heat balances.: & A & a - 80 “9°9 woRseg UY poremoTes eH sy amMrEreduiay Ke OOH x poy SUL :s10N de 855 = ODH “dua ag AVI L67=X 000 £56 L=X PSL OZ ooy mojoq do ¢ 78 pareurnss (1) Bisd grog JO smssord rented 3. X SLIT HLET 786 62 Mo TOL zs ewe Sete 8681 2 >= - a meas X ¥SL 9% X PSL9t o str of 4 OOH sss°0 68 O6ET ws sit tw 4 anoding m0 12601 86 62 Ur OL, £0 vos O6ET ws Stl ee anoding uez osc 8€8.1 ost -— = 4 ‘WENg eer's wOE HSL OT iS SIE Of «= "T- OD ¥a PRE ur WALL WA avaia wat do NX IdVs WA ures, Adem,THE ATMOSPHERIC CRUDE DISTILLATION UNIT a1 en Enthalpy E Bt VorL ‘APL K ‘Temp SF —__“Ib/a__ BTU MAb BTU/x 10 ‘Section In Crude fed = VL = 20 319575) 195.939. 6.12 Steam v 450 3738). 1290 48221 6.9 Total in 416936 224.160 out Residum LIB) WS OE, 19708537 HDB 6S HO LW, WS $8 2674) 1977946 6.12 L900 L %3 1S 488 44655 LT 6S Keto LSS 2 3 3 1 BAI 5 Naphtba yo 2 29 16650 158. 19.776: 6.9 Steam Kor me me 373811188 A409 6.9 Purmparounds (by difference) 59.839 Total out 415956 224,160" | Set pumparoynd duties as: “Top pumparound (iaiphtha) © 20.421 BTU/h» 10% Mid pumparound (LGO) 20,605 BTU/hx 10" Bottom pumparound (GO) 18.813 BTU/hx 10° ‘Total 59.839 .82 ‘THE DISTILLATION PROCESSES: 6.13 Side-stream Stripper Performance Side-streams from the crude distillation tower contain light material in solution. To meet most product specifications the light material will require to be stripped out. Normally, steam stripping is used for this purpose. There are some rule-of-thumb methods of predicting the amount of steam and stripout from such a process. Indeed, these rules of thumb are quite reliable and very well proven. One such method is given in Section 6.2 Steam stripping takes place in a side-stream stripping column outside the main crude distillation column, These columns contain four or five stripping trays. The unstripped oil, which is at its bubble point, enters the top of tower and onto the top tray. Steam. is introduced into the tower below the bottom tray. Steam and the liquid move counter- ‘currently in the tower. The steam moves upwards zind the liquid stream downwards, Heat and mass transfer occur on the trays, taking out the light material into the steam and leaving the heavier material in the liquid phase. The amount of mass transfer that occurs depends on the ratio of vapour and liquid flow and also on the thermodynamic equilibria function of the components in both phases. ‘The performance of the unit may be equated to the efficiency of the trays in effecting the steamout required. Generally, stripping trays are never very efficient. In fact, usually they are below 50% even in reboiled strippers, which are more efficient than simple steam stripping. In evaluating the efficiency of the stripper or stripping trays in the steam stripping unit, the number of theoretical trays for the same amount of stripping can be calculated, The following are the steps to make such a calculation: © Step 1 Obtain the ASTM distillation (lab test) for the unstripped material and the stripped product, As our. example is based on LGO the unstripped sample could be that for the LGO pumparound. © Step 2, From plant data determine the quantity of product flow and the feed to the stripper, © Step 3 Using the method of converting ASTM to TBP, split the TBP into pseudo- mid. boiling point components, By using assay data assign specific gravity and mol wt values to the pseudo-components. Determine total moles per hour of each ‘component in the feed. © Step 4 From plant data obtain the steam rate to the strippér. From Figure 6.3 determine percentage stripout. © Step 5» Establish the vapour/liquid ratio for the top and bottom of the tower. Assume that all the stripout and steam enters the top tray: Assume negligible hydrocarbon in the vapour to the bottom tray. Assuine all the liquid feed enters the top tray and only the product leaves the bottom tray. © Step 6 If available, use plant data for the temperature of feed and any stréams leaving. If data are not available develop the profile by heat balance as shown in Section 6.12. : © Step 7 Calculate the equilibrium constants K for each component in the feed at the mean temperature of the tower. The XK in this case may be taken'as the ‘vapour pressure of the components divided by the total Presse, ‘Use the vapour pressure curves in Appendix 1 for this.‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 83 © Siep8 Calculate the stripping factor S for each component. Sis equal to. VK/L. Using Figure 6.8 determine the percentage stripped for each component for one theoretical plate, two theoretical plates and, if necessary, for more theoretical plates. © Step9 Proceed and determine the total stripped for each case of theoretical trays under consideration, By interpolation, match the number of theoretical plates (or fractions of theoretical trays) that will give the closest to the stripout and composition based on plant data. © Step 10 The theoretical trays calculated divided by actual trays in the column multiplied by 100 gives the tray efficiency (overall), ‘The following example illustrates this calculation procedure, Example calculation Steam stripping Feed rate and composition (unstripped LGO) ‘The basis is 6300 gal/h+472.5 gal/h light material = 6772.5 gal/h The composition of this material is as follows, Pa la er chs Pseudo- component mid- — % SG at Mole boiling point (°F) vol. gal/h_ 60°F Ib/h_ Mol. wt Moles/h—_fract. 180 12 813 10.705 52393 616 0.022 280 3.0 208.2 0.754 1832121 12.65 0.045 360 2.0 1355 0.780 1087150 7.03 0.025 410 128 866.9 0.793 6875 169 40.68 0.146 460 15.3 1036.2 0.801 $300. 194 42.78... 0153 490 195 1320.6 0.836 11035 199 5545 0.199 520 167 1131.0 O84 9545 215 440 0,159 550 114 1178.4 0.846 9969 230 43.34 0.155 so 121 819.4 0.850 6963254 26.89 0.096 ‘Totals 100.0 6772.5 0.825 55852 200 -m9.41—1.000 OO The amount of steam to be used will be 0.5 Ib/h per gal of product = 6300x0.5 =3150 Ib/h steam =175 moles/h steam ‘The Kremser equation will be used for calculations of percentage stripped. This is given in Figure 6.8,84 ‘THE DISTILLATION PROCESSES. Establish the V/L ratio Consider the top plate Steam =175 moles/h HC vapour at the top tray. =7.5% vol. stripout All material lighter than 410 °F mid-BPT is stripped out and 2.36 moles/h of 410 °F Then total moles of HC as vapour = 28.23 ‘The liquid to the tray will be total moles of feed. Top Total vapour V_ =175 428.23 moles/h Liquid L =279.4= 219.41 moles/h At the bottom of the stripper The residual-amount of HC vapour is 0% ‘The vapour is steam =175 moles/h. Liquid is total moles- 28.23 =251.17 moles/h V/L top "294 V/L bottom Ave V/L =0.715 The stripping factor for each component is VK/L. Where K is the equilibrium constant. Vapour pressure In this case it will b roan cena ee “Total pressure Assume the total pressure for the stripper is 19.5 psig=34.2 psia (see Section 6.6) Then using Figure 6.8 first estimate will be based on two theoretical plates and the percentage of each component stripped out calculated thus:‘THE ATMOSPHERIC CRUDE DISTILLATION UNIT 85 2 Theor. piates 1 Theor. plate K493°R % Moles % Mid-BPT (°F) Moles/h_34.2psi_-VK/L— strip strip strip. Moles/h 180 616 12.99.22 1006.16 100 6.16 280 12.66 497 358° 94.8 12.00 78 9.87 360 7.05 187 134 75.05.2954 3.81 410 40.68 1.08 0,77 59.0 240 4217.09 460 42.18 0.58 = 0.41 30.0 12.805 6.42 490 55.45 0.43 0.31 NEG NEG NEG NEG 520 44.40 0.32 0.23 «NEG NEG NEG NEG 350 B.34 0.20 0.14 ~NEG NEG NEG NEG 591 26,89. 0.12 0.09 NEG NEG NEG = NEG Totals 279.4 60,25 43.35 ‘Temperature for K is taken a8 mean in the tower and is based on the heat balance and estimate method given in Section 6.2, ‘The amount of stripout that was achieved at the steam ratés given waé 28,23 nioles/h, ‘This should have been achieved by 1 theoretical tray (interpolating), The tower had four actual trays, therefore tray efficiency was only Sx 100=12.59% 6.14 Prediction of Tray and Tower Performance ‘This section deals with analysing tray performance in terms of flood and entrainment under calculated vapour and liquid loads. This can be carried out using test run data on the plant and referring to the manfacturers’ data for the tray geometry. In this case the analysis is based on percentage of critical vapour velocity as a criterion to detect possible entrainment problems. Downcomer yelocities are used to detect any possible excessive downcomer back-up. A more rigotous calculation can be used to determine actual downcomer back-up. ‘The calculation steps used for this tray analysis, which are based on valve trays, are as follows: : © Step 1 From plant data, lab data and calculations described in Sections 6.8, 6.9. and 6.11, summarize tray vapour and liquid traffic and tray conditions for critical trays. Critical trays may be defined as the top tray and side-stream and pumparound draw-off trays, ‘ © Step 2. Obtain the certified manufacturers’ drawings relating to tray geometry and downcomer details. Make sure that this represents the actual tray installed and no modifications have been done to the tray. These drawings should also provide details of tray spacing. © Step 3 Compute the liquid loading on thé tray using actual GPM divi to give CFS,Table 6.1 Valve tray design pris ‘THE DISTILLATION PROCESSES Design feature 1. Valve size and layout @) Valve diameter (©) Percentage hole area A/Ay (© Valve/pitch/diam, ratio (@) Valve distribution (©) Bubble area A, (f) Plate efficiency (g) Valve blanking 2. ‘Tray spacing (inches) 3,, Number of liquid passes 4, Downcomers and weirs (@) Allowable downcomer inlet velocity, ft/s of clear liquid Suggested Alternate valu values 2 BS - 12-36 1 12 0.3-0.4 ‘Comment Valve diameter is fixed by the vendor Open arca should be set by the designer. In general, the lower the open area, the higher the efficiency and flexibility and the lower the capacity (due to increased pressure drop). At values of open area toward the upper end of the range (say, 15%), the flexibility and efficiency are approaching sieve tray values. At the lower end of the range, capacity and downcomer filling becomes limited Valve pitch is normally triangular. However, this variable is usually fixed ‘by the vendor On trays with flow path length >5ft, and for liquid rates>5000 gal/h/ft (diameter) on trays with flow path Iength

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