Petroleum Refining FOR THE NON-TECHNICAL PERSONFOR THE NON-TECHNICAL PERSON William L. Leffler Pennwell Books Division of PennWell Publishing Company 1421'S. Sheridan Tulsa, Oklanoma 74112Copyright © 1979 by PennWell Publishing Company 1421 South Sheridan Road/ P.O. Box 1260 Tulsa, Oklahoma 74101 All rights reserved. No part of this book may be reproduced, stored in a retrieval system, oF transcribed in any form or by any means, electronic ‘or mechanical, including photocopying and recording, ‘without the prior written permission of the publisher. ber, 97663 Library of Congress Catalog Card Number: 73 Treerdeonal Standard Book Number O-87816-1068 vant in the United States of Ameria Si ese e2 TABLE OF CONTENTS Foreword 1 Introduction Crude Oil Characteristics IL Distilling IV Flashing VY The Chemistry of Petroleum VI Cat Cracking VII Refinery Gas Plants VII Alkylation IX Catalytic Reforming X Residue Reduction XI Hydroeracking XII Gasoline Blending XIII Distillate Fuels XIV Asphalt and Residual Fuel XV Hydrogen, Hydrotreating, and Sulfur Plants XVI_ Isomerization XVIL_ Solvent Recovery of Aromatics XVIII Fuel Values—Heating Values XIX Ethylene Plants XX Crude Oil, Condensate, and Natural Gas Liquids Answers and Solutions Index 103 107 113 120 123 127 130 135, 139 187FOREWORD For as long as I have been associated with the oil industry, which is only | about 15 years, I have been aware of the lack of tools available to the non-engineers to permit self-improvement. Its asif there is a technocratic conspiracy: “Let's keep the technology in the technicians!" Or maybe there is a caste system in oil companies. Those with the engineering degrees don’t need a primer on technology; those without the technical |, degrees don't have a “need to know,” s0 no technician attempted to articulate the fundamentals. My experience is that both situations probably exist from time to time and in varying amounts, so I take pen and ruler in hand to combat the first and disprove the second. This book is intended to satisfy the needs of the ‘youn, astute, sspising industry entrant who has no degree in chemical or process engineering or one of the closely related disciplines. It will be useful to the many persons in financial work, supplies, transportation, distribution, public relations, advertising, sales, or purchasing in petro- eum based or related companies. ‘The format is designed to permit little gulps at a time, followed by some reinforcing exercises which often build on previous work. If nothing else, by the time the reader is finished with the book he will not be intimidated by technical jargon. At least he will be able to ask mere penetrating questions. And that's most of the self-improvement battle won.INTRODUCTION If you're reading this book, you don’t need an introduction to the subject. You're already into it. So this section will simply describe how to use this book. ‘The layout of the materials is designed to satisfy three different needs. It can be used as a reference book, because there's a good table of contents in the front and good index in the back. The book can be used as a text in a ‘course on refining processes. The combination of lectures, reading, and problem solving should be very reinforcing. But because most people will not have the Iuxury of listening to a lecturer, the layout is primarily designed for personal study. With that in mind, the rather dry material has been moistened with as much levity and practicality as could be precipi- tated. For personal study, the following work plan and comments might be helpful. Chapter If on crude is most important. Chapyer II on distilling has a lot of mechanical detail that’s not fundamentally important. Don't let it dismay you. The material on flashing (Chapter IV), cat cracking, alkylation, reforming, residue reduction, and hydrocracking are all impor- tant. Understanding the mechanics of the refinery gas plants is less 50. Be sure to study the chapter on gasoline blending thoroughly. Ithelps put the rest of the book in mental order. Chapters XIII through XIX are lagniappe, free giveaways. The information is useful, but not vital. So plan to keep your attention span through at least the first dozen chapters. ‘The only chapter that interjects economics into the subject matter in any explicit way is Chapter XVIII, Fuel Values—Heating Values. The tables and diagram are handy reference material, and the subject matter is vital to understanding interfuel competition. It will be a big self-help if you will do the exercises at the end of the chapters. The answers and solutions are in the back of the book.2 I Petroleum Refining for the Non-Technical Person ‘One final comment, This book should raise as many questions as you might have had before you started reading it . . . maybe more, That's not z meant as an apology, but as a statement of human behavior. So find a process engineer and ask as you go along. CRUDE OIL CHARACTERISTICS What is crude oil? The best way to describe it is to start by saying what itis not and what it doesn’t do. It is nota chemjcal compound; itis amixture of chemical compounds. The most important of its behavioral characteristics happens when its heated up. When itis warmed to its boiling temperature and held there, it will not all evaporate. Contrast that with water to make a point. Take a pot of water and heat it to 212°F. (Fahrenheit) and keep the heat on. What happens? The water Fig. 2-1 —Boiling Temperature of Water is 212° F.4 I Petroleum Refining for the Non-Technical Person starts to boil (to flash or vaporize). Eventually, if the heatis kept on, all the water will boil off. If you had a thermometer in the pot, you would notice that the temperature of the water just before the last bit boiled off would still be 212° F. That's because the chemical compound HzO boils at 212° F. At atmospheric pressure it boils at no more or no less. Crude Oil Composition Now back to crude, Unlike water, rude is not a chemical compound, but thousands of different compounds. Some are as simple as CHs (methane); some are as complex as CasHeo. CHa and CesHoo are the cchemist’s shorthand for certain chemical compounds. The nomenclature will be explained more fully in a later chapter. They are all generally combinations of hydrogen and carbon atoms, called hydrocarbons. The important characteristic is thateach of these compounds has its own boiling temperature, and therein lies the most useful and used physical phenome- rnon in the petroleum industry. Distillation Curves ‘To explain, take the same pot and fil it with a medium weight crude oil ut the flame to it and heat it up. As the temperature reaches 150° F, the ‘crude oil will start to boil. Now keep enough flame under the pot to ‘maintain the temperature at 150° F. After a while the crude stops boiling. Step two, raise the flame and heat the crude to 450° F. Again the crude starts boiling and after a while it stops. ‘You could repeat the steps on and on, and more and more crude would boil off. What is happening (you may have guessed) is that the compounds. that boil at a temperature below 150° F varporized in the first step, the compounds that boil ata temperature between 150° F and 450° F vaporized in the second step, and so on. What you are developing is called a distillation curve, a plot of temperature on one scale and the percent evaporated on the other. Each type of crude oil has a unique distillation curve that helps characterize what kinds of chemical compounds are in that crude. Generally the more carbon Crude Oil Characteristics 1 5 ‘cnUDE OWL Bons AT 1s0"F AND AS0"F... AND TS0°F AND 900F Fig. 2-2 —Boiling Temperatures of Crude Oil 1000] ~ ws ae _ Z| Bz BOILING TEMPERATURE *F ie 0 ee wo te cot 100 ‘CUMULATIVE PERCENT VOLUME Fig. 2-3 —Crude Oil Distiliation Curve6 J Petroleum Refining for the Non-Technical Person atoms in the compound, the higher the boiling temperature, as shown in the examples below: Boiling SS (Weight Compound Formal Temperature PoundstGallon propane SO 7 rs "tone 49 Secane 6 Fractions In further specifying the character of crude oil, ithas been useful tolump certain compounds into groups called fractions. Fractions of cuts are the fgeneric names for all the compounds that boil between any two tempera- tures, called cut points. "The typical crude oil has the following fractions Temperatures Fraction 99.220" F fmoline 220-315" F phe 315-480" F erosene 450-800" F pall 00" F and hier residue Subsequent chapters will spend a lot of time discussing the characteris- tics of each of those fractions, but some are already apparent from the names. Itis important to note that crude oil compositions vary widely. The light crudes tend to have more gasoline, naphtha and kerosene; the heavy erudes tend to have more gas oil and residue. You may deduce from this that there ig a relationship between the weight of the compounds and the temperature at which they boil. There is. Generally, the heavier the compound, the higher the boiling temperature. Conversely, the higher the cut points, the heavier the fraction. Cutting Crudes To pull together all this information on distillation curves, a Title arithmetic manipulation may be instructive. Take the curves for the two Crude Oil Characteristics. | 7 1000 soo resDUE 00 + _ =o 3 om 5 caso & 500 : | : x g 1 A= 3 x0 oo waPTaa 1 200 + onoune 100 | [ovtaneS sho uciren t 1B baba 60708008 CUMULATIVE PERCENT VOLUME Fig, 2-4 —Crude Oil Distillation Curve and Its Fractions crudes in the next figure and run through the steps to determine which crude has a higher kerosene content (a bigger kerosene cut), Kerosene has a boiling temperature range from 315° F to 450° F. Using Fig. 2-5 complete the following steps: 1, For the heavy crude, start from the vertical axis at 315° and intersect the distillation curve, going right, at point A. Point A is at 26% on the horizontal axis. 2. Now start at 450° and intersect the same distitlat i rsect the same distillation curve, goin right, at point B. Point B is at 42% on the horizontal axis. iad 3. Caleulate the cumulative percent volume: from the initial boiling8 I Petrolewn Refining for the Non-Technical Person 1000 |— - g 3 500 BOILING TEMPERATURES *F | fee aie i i H | 1020 304060 6070-80 90 100 (CUMULATIVE PERCENT VOLUME Fig. 2-5 —Kerosene Fraction in Two Types of Crude point of the kerosene to the end point: 42-26 = 16%. The heavy crude contains 16% kerosene. 4. Now do the same procedure for the light crude and find out that there is 48.5-66.5 = 18%. ‘Therefore the light crude has more kerosene in it than the heavy, Gravities Gravities measure the weight of « compound. Chemists always use a measure called specific gravity which relates everything to something universally familiar, water. Crude Oil Characterisies. | 9 ‘The specific gravity of any compound is equal to the weight of some volume of that compound divided by the weight of the same volume of water, wei compound Specific gravity =! ght + 7 compos ‘The chemists" approach must have been too simple for the chemical engineer because the popular measure of gravity in the oil industry is a diabolical measure called API gravity. For some forgotten reason, the formula for API gravity, which is measured in degrees, is: Ear 14.5 AS __ 31.5 specific gravity If you play with the formulae a little bit, you'll find the following relationships, which might be the mental hooks on which you can hang the concepts. 1. Water has a specific gravity of 1 and an API gravity of 10°. 2. The higher the API gravity, the lighter the compound. 3. The reverse is true for specific gravity. 50° API NAPHTHA "ASPHALT Fig. 2-6 —The Lower the API Gravity, The Heavier the Liquid10} Petroteunt Refining for the Non-Technical Person Typical gravities: ‘Specie Grainy API Gravy envy ode “O90 0 Ligh erode oe 6 Gatoline 074 oo ‘Asp 098 a Sulfur Content ‘A final divergence on the subject of crude oil quality is appropriate at this point—a discussion of sulfur content in crude. One of the annoying aspects Mother Nature endowed crude oils with is varying amounts of sulfur content in various types of crude oil. To complicate the endowment, the sulfur is not in the form of elemental sulfur, but is usually a sulfur compound. That is, it is chemically bonded to some of the more Complicated hydrocurbun molecules, so that itis not easily ceparated from the pure hydrogen/carbon compounds. "The parlance in discussing crude oils of varying sulfur content is to categorize them into sweet crudes and sour crudes. The quaintly oriental sweet and sour designations have no more to do with the human senses than. the terms dry and sweet have to do with the taste of wine. They simply refer to low sulfur content (sweet) or high sulfur content (sour), the former being typically 0.5% sulfur, o less; the latter 2.5% or more. The area in between is sometimes called intermediate sweet or intermediate sour. But the distinction between sweet and sour crudes is not clear; what may be sweet to some, may be sour to others. Review A clue to the varying interest by refiners and traders in the different crudes becomes apparent in Fig, 2-7. The distillation curves for five crudes, three domestic and two foreign, are shown. Some crudes hhave more light fractions, some more heavy. They all have different prices. Depending on product demands and the hardware in a refinery, some crudes will be more suitable and economically attractive than others. Crude Oil Characteristics 111 200 8 ALASKAN———p/” NoTH SLOPE 7 SONS TEMPERATURE -F § 812 1 Petrolewn Refining for the Non-Technical Person EXERCISES i TH 1. (@) Draw the distillation curves for the following crude oils (on the . ame graph ; oe = | DISTILLING a whan § Ottohoma sveet HeaeyCaliornia oie = s iio ze 32 = ‘A popular mistake by the casual passerby of a refinery is to refer to the eee 3 4a ‘many tall columns inside as “cracking towers.” In fact, most of them are 31510 390 a a distilling columns of one sort or another. Cracking towers, which are ov 500 Sa ts usually shorter and squatter, will be covered in a later chapter $500 to 380 a a Distilling units are the clever invention of process engineers which sore i ua exploit the important characteristic discussed in the last chapter, the $3010 900 85 roa distillation curve. The mechanism they use is not too complicated but, for 300 to 1000, 39 ia ver 1000 20 that matter, not that interesting. However, inthe interest of completeness and familiarity, the rudiments will be covered here. (b) How much naphtha (220%-315°) is there in each crude? 2. Suppose you had a beaker of asphalt (11 API) and a beaker of naphtha (50° API), both equal volumes. If you mixed them together, what would the resulting API gravity be? The answer is not “30.5° API. ‘The Simple Still ‘An analogy will be useful. The Kentucky moonshiner uses the simple still to separate the white lightning from the dregs. After the sour mash has fermented i.e., a portion of it has slowly undergone a chemical change to alcohol; itis heated to the boiling range of the alcohol. The white lightning vaporizes, moves through the condenser, where it is cooled and tumed back to liquid. What's left in the still is discarded. What goes overhead is bottled. This is simple batch process distillation. If a moonshiner wanted to sell a better-than-average product, he might run his product through a second barch still much like the first, separate the best part of the liquor from some of the non-alcoholic impurities that inevitably flow along with the overhead in the first still. They might have gone overhead because of his inability to control the temperature of the sour mash boil, or because he wants to be sure he gets all he can and purposely sets the temperature a litle high on the first batch. Such a two-step operation could be made into the continuous operation shown on page 15. In fact, many early commercial distilling operations looked like that B14 1 Petrolewn Refining for the Non-Technical Person WET RAGS FOR COOLING au . Fig. 3-1 —The Moonshiner’s Still ‘The Distilling Column ‘The batch distilling operation above is obviously not suitable for handling 100-200,000 barrels/day of crude oil with five or six different ‘components being separated. The distilling column can do it ona sustained basis with much less labor, facilites, and energy consumption in the form of fuel/heat From afar, what happens at a crude distilling column is shown in Figure 3-3. Crude goes in, and the products going out are the gases (butane and lighter), gasoline, naphtha, kerosene, light gas oil, heavy gas oil, and residue. ‘What goes on inside the distilling column is more subtle. The first clement important to the operation is the charge pump, which moves the Distilling | 15 poo Fig. 3-2 —Two Stage Batch Still STRAIGHT AUN GASOLINE —— kenosene CRUDEOR _ HEAVY Gas Om _STRAGHT AUN RESIOUE [3 —Distilling16 J Petroleum Refining for the Non-Technical Person crude from the storage tank through the system. (See Figure 3-4) The crude is first pumped through a furnace where it is heated to a temperature of perhaps 750° F. From the knowledge developed in the last chapter, you can see that over half ofthe crude oil changes to the vapor form as itis heated to this temperature. This combination of liquid and vapor is then introduced to the distilling column Inside the distilling column there is a set of trays with perforations in them. The perforations permit the vapors to rise through the column, When the crude liquid/vapor charge hits the inside of the distilling column, ravity causes the liquid to drop toward the column bottom, but the vapors start moving through the trays toward the top. (Figure 3-5) ‘The perforations in the trays are fited with a device called bubble caps > CHARGE PUMP Ss ehey FURNACE osTILUNG ‘COLUMN Fig, 3-4 —Crude Oil Feed to Distilling Distilling 147 HEATED ‘CRUDE, Fig. 3-5 —Crude Entering the Distilling Column (Figure 3-6) Their purpose is to force the vapor coming up through the trays to bubble through the liquid standing several inches deep on that tray. This bubbling is the essence of the distilling operation: the hot vapor (starting out at 750° F) bubbles through the liquid. Heat transfers from the vapor to the liquid during the bubbling. So as the vapor bubbles cool a litle, some of the hydrocarbons in them will chenge from the vapor to the liquid state, As heat transfers to the liquid, the temperature of the vapor drops below the boiling point of some of the hydrocarbons in the vapor and, they condense (liquefy). After passing through the liquid and shedding some of the heavier18 | Petroleum Refining for the Non-Technical Person Fig. 3-6 —Bubble Cap on a distilling colurnn tray hydrocarbons, the vapor then moves up to the next tray where the same process takes place. Simultaneously on each tray, as heat is transferred from the vapor to the liquid, the lightest part ofthe liquid turns to vapor and moves up the column. Meanwhile, the amount of liquid on each tray is growing as some of the hydrocarbons from the vapor are stripped out. So a device called a downcomer is installed to permit excess liquid to overflow to the nextlower tray. Every so many trays, the liquid is drawn off to keep the amount of product going out of the distilling column equal to the crude coming in. ‘What happens as this process continues on a steady state is that the boiling temperatures of the liquids on each tray will be lower, the higher up the column. The sidedraws taking product off the top trays will capture lighter products. At the bottom of the column, the sidedraws will handle the heavies Reflux and Reboit ‘There are several things that go on outside the distilling column that facilitate the operation. To assure that some of the heavies don’t get out the Distilling 1 19 i i Lows PRODUCT SOEORAW Fig. 3-7 —Downcomers and Side-Draws top of the column, sometimes some of the vapor will be run through a cooler. Whatever is condensedis reintroduced to a lower tray. Whatever is still vapor is sent off as product. The process is a form of refluxing. Conversely, some of the light hydrocarbon could be entrained on the bottom of the column where the liquid part of the crude oil ended up. So a sidedraw may be used to recirculate the liquid through a heater to drive off any lighter hydrocarbons for reintroduction inte the distilling column as a vapor. This is called reboiling. The advantage of a reboiler is that only a small fraction of the crude stream has to be worked on to accomplish the additional recovery. The whole crude volume doesn’t have to be heated, saving energy and money Reboiling or refluxing can be used effectively in the middle of the column as well facilitating good separation. The advantage of the reboiler is that it gives a heat input to help push lighter molecules up the column. Similarly, refluxing can give a last shot at condensing some heavy molecules that may have gotten too high in the column20 | Petroleum Refining for the Non-Technical Person os yocrm| -G Zecumiston REFLUX = eBOILER ccumutsron uo srmacir ae ‘Sour Fig. 3-8 —Reboil and Reflux ‘Sometimes the crude composition is such that there would not be enough liquid/vapor flow on some of the trays of the column. In that case, using reflux and reboil can regulate the flows to keep the distilling (separating) ‘operation going. Cut Points, ‘To someone analyzing distilling operations, the key parameters are the cut points. The temperatures at which the various distilling products are separated are called the cut points. Specifically, the temperature at which a product (or cut or fraction) begins to boil is called the initial boiling point Distilling {21 (IBP). The temperature at which it is 100% vaporized is called the end point (EP). So every cut has two cut points, the IBP and the EP. By referring to the diagram in Fig. 3-3 agein, it becomes readily apparent that the end point of naphtha is the IBP of kerosene. At a cut point, the EP and the IBP of the two cuts are the same, at least nominally. Depending on how good a separation job the distilling operation does, the IBP and the EP might not be the same. You may have wondered, looking at the mechanics of trays and bubble caps, how well the process works. In fact, the operation is a litle sloppy, resulting in what is referred to as, pardon the expression, rail ends. For instance, if the naphtha and kerosene were enalyzed in a lab, the two distillation curves would look like the curves below. Looking closely, the end point of naphtha is about 325; the IBP of the kerosene is about 305 ‘TEMPERATURE °F 303030 ~40~«80 8070 (CUMULATIVE PERCENT VOLUME 30 00 Fig. 3-9 —Overlapping Distillation Curves ‘A better way of visualizing the tail ends is in Fig. 3-10, which plots femperature against not cumulative percent vaporized, but percent being vaporized at that temperature (the first derivative of the above diagram, if jou know calculus).22. I Petroleum Refining for the Non-Technical Person PERCENT VOLUME VAPORIZED 265 318. 10 TEMPERATURE ~ °F Fig. 3-10 —Tail Ends in Distillation Cuts Almost all refining operations have the phenomenon of tail ends. Itis so common it is taken for granted. However, to simplify analysis, an accommodation is made. The usual cut temperatures in any distilling operations are generally the effective cut points. These represent the compromise temperature at which the cuts can be considered cleanly cut The balance of this book will implicitly mean effective cut point when the term cut point is used. Setting Cut Points ‘The cut points in the last chapter and in the discussions above may have been taken asa given for each fraction, but there is some latitude in setting the cut points on a distilling column. Changing the cut point between naphtha and kerosene has several implications. If the cut point were changed from 315 to 325, several things would happen. First, the volumes coming out of the distilling column change—more naphtha, less kerosene. ‘That's because the fraction between 315 and 325 now comes out the naphtha spigot instead of the kerosene spigot. & Fig. 3-17 —Distiling Crude and Product Disposition Distilling | 23 ‘Atthe same time the gravities of both naphtha and kerosene get heavier. How can that be? The cut moving into naphtha is heavier than the average naphtha gravity. Itis also lighter than the average kerosene gravity. So both cuts get heavier! ‘Some of the other properties also change, but gravity is the only one that has been discussed so far and can be handled. As the downstream operations are discussed in later chapters, the further implications of changing cut points on the distilling unit will be appreciated ‘A listing of the destinations of all the distilling unit cuts will help set up future chapters. The light ends from the top of the column (the overhead) {0 to the gas plant for fractionation. The straight run gasoline goes to motor gasoline blending. Naphtha goes to the reformer for processing. Kerosene goes to a hydrotreater for cleanup. Light gas oil goes to distillate fuel blending. Heavy gas oil goes to the cat cracker as feed. Straightrun residue is feed to the flasher. 520" __eutane 480 ye cas process eet moronoacoune NAPHTHA. > CAT REFORMING ars KEROSENE p= HvonOTREATING pa caso, © PF vet Btenons CE em car enscrne RMGHT AUN oe rLaASHING24 1 Petroleum Refining for the Non-Technical Person EXERCISES 1, Fill in the blanks below with nomenclature from the following list: tailends downcomer overhead IBP EP cooler furnace straight run gasoline continuous crude oil fractionator batch bubble cap increases decreases a. After moonshine comes out the top of a still, ithas to be run through a before it can be bottled. b._____ processing is not very practical in a modern refinery. Today all crude distillation is a operation, c. The device that facilitates the essential job of scrubbing in a distilling unit is the 4d. The holes in the distilling column trays are fitted with either a ora ‘i . Tail ends occur because the of one cut overlaps the of another. £. As vapor moves up the distilling column, its temperature g. Lowering the end point of a distilling column cut — volume of that cut and the API gravity. the 2. The refinery Operations Manager is told he must produce 33 MB/D of furnace oil this winter. He is also told he will be supplied with 200 MB/D of crude—30 MB/D of Louisiana crude and 170 MB/D of West ‘Texas. The distillation curves for those crudes are shown below. Another premise in the operation is that he must maximize jet fuel. That is, he must squeeze as much out of the crude as possible. He knows that the boiling range for jet fuel is 300-525° F, so he will have to set the cut points on his distilling units at these two temperatures. Finally, in order to meet the specifications for the 33 MB/D of furnace oil, 20 MB/D of straight run light gas oil (SRLGO) will have to be cut from the crude on the distilling units and provided to the furnace oil blending operation. Distilling | 25 Problem: At what temperatures will the Operations Manager have to cut SRLGO to make 20 MB/D? DISTILLATION DATA, Wee Terae Louisiana “% Volume BVolume Tera 20 113.260 ie 280.15 i 315-300 & 500-750 i 780.1000 i 10 Hints: Calculate a composite crude oil distillation curve, The turbine fuel EPis the SRLGO IBP. Socalculate the SRLGO EP that gives 20 MB/D.* Save the answer to this problem. Problems in subsequent chapters wil build on this exerciFlashing 27 W as¢ FLASHING When distillation curves and distilling columns were discussed in the last two chapters, the shape of the curve at temperatures around and above 900° F was purposely left vague. There is a phenomenon that happens at these temperatures called cracking. To accommodate this phenomenon and remedy its bad symptoms, the process of vacuum flashing was developed. Ethylene ‘The Cracking Phenomenon (CaH9) Suppose a laboratory technician were going to develop a crude distilla- tion curve. He would heat the crude oil; note and record the temperature; capture the vapor and condense (Iiquify) it; and record and cumulate the volume of the liquid. If he permitted the temperature of the crude to rise to about 900° F, a sudden change in the shape of the distillation curve would take place. As the temperature went from 900 to 1100° F, the cumulative volume recovered would exceed 100%, and crude would still be boiling in the pot, This may be an exaggeration of what can be observed easily with the naked eye, but it makes the point, As the complicated hydrocarbon molecules that have not yet vaporized at 900° F are heated to higher temperatures, the energy transfer from the heat is enough to crack the molecules into two or more smaller molecules. For example, a molecule of CiaHs« may crack into three pieces —CsHl1s, CeHiiz, and C2Hs as shown in Fig. 4-1, (A fuller discussion of the chemical reaction in cracking will be covered in the chapter on cat cracking.) Recalling the discussion on boiling points, it becomes apparent why the 4 shape of the distillation curve changes so abruptly. The smaller molecules boil at much lower temperatures than the larger ones. As they are created 4 by cracking, they leap out of the boiling crude. But that is only half the octane (Cotta) Bx" story. Why does more volume get created? In simplest terms, the small molecules take up more room per pound than the large ones. Again tecall the discussion on hydrocarbon properties and specific ravites. The compound CisHae weighs 7.2 Ib/gal, but CaHis, CeHis ind CaHs weigh 5.9, 5.6, and 3.1 Ib/gal, respectively. Take a gallon of ‘CisHa« and suppose you could crack it completely into these three components. (It never happens that way; combinations of different B compounds turn up, too.) The chemistry of it says that there would be 50% Coie, 38% Collis, and 12% CHa. But the percentages are by weight, 2628 | Petrolewn Refining for the Non-Technical Person not by volume. If you start with 7.2 Ib, you end up with 7.2 1b. How many gallons? Calculate them as follows: 7.2 pounds of Crctlss = 7.2 Ibs + 7.2 Ib/gal = 1.00 gal '50% yield of Collis = 3.6 Ibs + 5.9 Ib/gal = 0.61 38% yield of CoHiz = 2.7 Ibs + 5.6 Ib/gal = 0.48 12% yield of C2He = 0.9 tbs + 3-1 Ib/gal = 0.29 _ 100% 7.2 1bs 1.38 gal So, 7.2 Ib of CisHs« take up I gal, but 7.2 Ib of the components take up 1.38 gal. The simple reason this phenomenon exists is that the larger molecules tend to have the atoms packed closer together than the smaller molecules. So they take up less space per Ib. Fig. 4.2 —Cie Has and its Cracked Components Weigh the Same Cracking is an interesting and lucrative process, but only when it is controlled, The distilling unit is not designed to control it, so temperatures that cause it are avoided in distilling. The heaviest cut points on the distilling column are around 750° F. There are, nonetheless, lots of hydrocarbons that need to be separated inthe straight run residue cut, and the technique used is vacuum flashing. Flashing | 29 Effects of Low Pressure Suppose you had the hot dog concessions in both the Astrodome and Mile High stadiums. Do you know that, on the average, to boil water to cook hot dogs you'd heat the water to 212° F in Houston but only 210° in Denver? This temperature gradient represents the effect of different atmospheric pressures caused by change in altitude. When people refer to the air in the mountains being thinner, they really mean less dense, which is because the pressure is less. ‘The relationship between pressure and boiling temperature is simple. ‘The process of heating only helps the molecules to absorb enough energy to escape from the liquid form. The rate at which they escape depends on the rate at which heat is delivered to them and the pressure of the air above them. The lower the pressure, the less energy has to be transmitted, and the lower the temperature at which vapor will start forming in the liquid i.e., boiling ‘The point is—the lower the pressure, the lower the boiling temperature. ‘Vacuum Flashing Apply the pressure-boiling temperature relationship to the crude oil cracking problem. The straight run residue will crack if the temperature {goes too high; the straight run residue still needs to be separated into more cuts. The solution is to do the fractionation at reduced pressure Straight run residue is pumped directly from the distilling column to the flasher. Because of the way distilling works, the temperature of the residue is equal to the IBP, with a couple of degrees to allow for cooling. The straight run residue is taken into a squat, large diameter column where the pressure has been lowered. Atmospheric pressure is 1¢.7 Ib per square inch (psi), and that is about what distilling columns have inside. The pressure in, vacuum flasher is about 4.5 t0 5.5 psi. At that reduced pressure, the lighter fractions of the residue will begin to boil (flash). Flashing is a cooling process. That is why you stick your forefinger in ‘your mouth then hold it up in the air to find the wind direction. The breeze30 | Petroleum Refining for the Non-Technical Person ‘vacuum ‘CRUDE. DISTILLING COLUMN FLASHER yACUUM -— PUMP cH +—— FLASHED | > pstiate -— |} ——>eavy FLASHED DISTILLATE STRAIGHT RUN, eee RESIOUE steam > BOTTOMS Fig. 4-3 —Vacuum Flashing vessel. Heat is transferred from the steam to the residue, maintaining the temperature and the flashing. The other function of the steam is vacuum control. Pressure in the vessel is Kept very low by a vacuum pump at the top the vessel or JNoom inthe diagram, several streams can be drawn off the flasher. Light flashed distillate and heavy flashed distillate are sometimes kept segregated. Either can sometimes be used as lubricating oil feedstocks. Often they are not segregated but drawn off together and called flasher (—Ptie heavy material from the bottom ofthe flasher is called, appropri ately enough, flasher. bottoms, and it used as feed to an asphalt plant or a thermal cracker, or as a blending component for residual fuel Flashing is the equivalent of distilling the straight run residue at a cut point in the neighborhood of 1000-1 100°F. Most distillation curves are depicted as if the theoretical distillation took place. Flashing | 31 Because even vacuum flashing has its practical limitations, the end point of the straight run residue i.e., the end point of the crude oil, is never ascertained, Vacuum distillation is not run that high. This lack of knowledge is of no consequence, however, because the products using the bottom of the barrel are not sensitive to end point, per se. Other measures, such as gravity and viscosity, are the properties used to control the quality of the flasher bottoms EXERCISES 1, Fill in the blanks: a. Vacuum Flashing is a technique to continue ____of crude oil at high temperatures without encountering —__ b. The lower the pressure around a liquid, the ______ (lower, higher) the boiling temperature. . The higher the pressure in a vacuum flasher, the (lower, higher) the end point of the flasher tops. assut rate and feed temperature don’t change. 4. Products from a flasher are called 1g the feed and €. Toreduce the volume of flasher tops, holding the feed rate constant, you either _____ the pressure in the flasher or temperature of the flasher feed. 2. Use the data given to the Operations Manager in the previous chapter. - Inorder to satisfy the need for feed tothe asphalt plant, 35 MB/D of flasher botioms must be made available. (a) What is the maximum cut point at Which the flasher must operate to assure supply to the asphalt plant? Use the distillation curve temperatures, not the internal flasher pressures and temperatures. (b) If the straight run residue was cut from the distilling BS column at 800° F, what would be the volume of flasher tops?THE CHEMISTRY OF PETROLEUM So far, in most of the discussion of crude oil and refining you have been able to avoid the basics of chemistry; but the good times have come to an end, ‘The rest of the refining processes, for the most part, are chemical reactions. While you don’t have to have taken Chemistry [and have gotten at least a CC in Physical Chemistry, you will have to know something about hydrocarbons to go on from here. Don't skip this chapter! You will have to keep a figurative thumb in these ation of the subsequent seven chapters. Atoms and Molecules Physicists are continually surprising the scientific world by breaking matter into smaller and smaller particles, even more esoteric than neutrons and electrons. Luckily, the smallest notion in petroleum refining is the ‘atom. Examples are carbon, hydrogen, sulfur or oxygen, whose chemical symbols are C, H, S and O. ‘The characteristics of matter depend on the types of atoms that make up and how they are attached to each other in groups called molecules. ‘There are rules by which atoms can be arranged into molecules, The most important rules have to do with valences and bonds. Valences. Each type of atom (element) has an affinity for other elements according to its atomic structure. For example, carbon atoms would always like to attach themselves to four other atoms. Hydrogen atoms would always like to attach themselves to only one other atom. Definition: the valence of an atom of any element is equal to the number of hydrogen atoms (or their equivalent) that the atom can combine with. 32. The Chemistry of Petroleum | 33 Bonds. The connection between two atoms is called a bond. You can think of it as an electrical force that ties the two atoms together. Hydrocarbons, The simplest example of valence, bonds and hydrocarbons is methane, which has one carbon and four hydrogens, CHa. Looking at the structure, you can see all the valence rules are satisfied. Fig. 5-1 —Methane If the next simplest hydrocarbon, ethane, is chosen, some further complications can be introduced. Ethane is CoH. You can check that each carbon has four attaches; each hydrogen has one. Note that one carbon atom is attached to another one. That is okay. As amatter of fact, whenever you see hydrogen referred to as a separate compound, it will always be called He because that is how itexists—one hydrogen attached toa second satisfying the valence rule of both atoms. . HOW Ethane (CoH)34 1 Petroleum Refining for the Non-Technical Person ‘A whole class of hydrocarbons can be defined by extending the relationship between methane and ethane. These molecules are prafins or straight chain compounds and have the formula CoHa+2. Examples are propane, normal butane and normal pentane. ‘Normal Butane (cs (Catto) HH HH ieee H-c-G-c-c-c-# rae es ease HHH WH [Normal Pertane (Catto) Fig. 5-3 —Propane, Normal Butane, Normal Pentane Why the prefix “normal” before butane and pentane? Well. there are several ways to arrange the carbon atoms in C+Hie and CsHis. One 0 themis shown inthe figure above. Another is to put abranch off one of the inside carbons. In that case, the compounds C«Hie and CsHiz are calle isobutane and isopentane. The Chenistry of Petroleum | 35 Even though normal butane and isobutane have the same formula, they behave differently. They boil at different temperatures; they have different gravities (since they are packed differently); and they cause different chemical reactions which will be important in a later chapter on alkylation, Naphthenes ‘Once you get more than four carbons in a molecule, another class of hydrocarbons is possible, the ring or cyclo compounds. When five carbons are bent around to aring, the compounds cyclopentane (CsHi0). Note that there are fewer hydrogens in cyclopentane than in normal or isopentane. Larger rings, starting with cyclohexane, are possible, too. This class of compounds is called naphthenes. Cydohoxane (Cota) Fig. 5-5 —Naphthenes Beyond the simple paraffins and cyclic hydrocarbons are an infinite variety of possibilities by connecting the two types of compounds. The simplest example is methyl cyclopentane, which is the connection of CHs, called a methyl radical, and a cyclopentane where a hydrogen ought to be, : forming CeHia HHH ‘ it ————<$—___ W-G-¢-G-H ryt w[a i wooo 4 te mat ral 7 Isopentane Sco E— 4 Methy! Cycopentane Cony Caer od eur Fig. 5-4 —Isobutane, Isopentane36 1 Petroleum Refining for the Non-Technical Person Olefins and Aromatics It is possible to have a compound with two carbons and only four hydrogens. That would seem to violate the valence rules you ust spent six tuinutes learning. But in the chemical compound ethylene, C2Hs, there is a Touble bond between the two carbon atoms to make up forthe deficiency of hydrogen atoms. Ironically, the double bond holding the two carbons together is weaker than a single bond—not stronger. You could think of it as two bonds sharing the spot of one bond. Therefore, the compound is tunstable and can be chemically reacted with some other compound or ‘Element with relative ease to forma new compound, eliminating the double bond. That is why ethylene is such a popular compound for making more complicated compounds. For example, sticking a lot of ethylenes to each ‘other makes polyethylene. The Chemistry of Petroleum 137 ompound cyclohexane. Each carbon has two hydrogens attached and is tached 1 two other carbons Ifyou removed one hydrogen from each carbon, you could bring the valence ules back to being satisfied by puting insome doube bonds between the carbons. A double bond between every peercralaal The resulting molecule is CsHe, benzene. Saying tha ev nd around the benzene ring is a double bond is a gross iplification. The real description has to do with a resonatin, and hopping bonds. Jee fone of the hydrogens of the benzene molecule is removed and CH: oat ine lic, he Col ane (The Called a mety radical. Ae ethyl radical would be CsH. The radical names are similar to ¥e paraffins they look like, methane and ethane.) If two methyl radicals are substituted for two, not one, hy not one, hydrogens on the benzene ring, the resu is CaHlso, xylene (pronounced zi-leen). 3 ny ‘ ua i be Eg aaa a ¥ aa haw hn no by on Etyene Propylene Bayona ars era ‘era en il c Fig. 57 —Olefins wenn ‘The key characteristic of the olefins is the absence of two hydrogens _ from an otherwise saturated paraffin i.e., a paraffin that has a full complement of hydrogens. The formula, therefore, is CH» oa lefins are unnatural. It may be that only ‘God can make a tree, but He KC) could not handle olefins. They are not found in crude oil but are man-made in one of the several cracking processes that will be covered in later Chapters. This seemingly irrelevant fact has implications inthe design of refinery gas plants and will be discussed in Chapter VII. ‘The other olefins that will be of primary interest in petroleum refining will be propylene (CaHe) and butylene (C+Hs). Like ethylene, these Compounds can be reacted with other chemicals relatively easily and so fare suitable for a number of both chemical and refinery processes. “Aromatics ate another exception to the valence rules. Take the ring Fig. 5-8 —Aromatics ‘The double bonds in rect double bonds in the benzene ring ae very unstable and chemically fee eee hey popular building block in the chemical ind iene and xylene are also important, a BE ith aromatics recovery nrefineieg ne Chaps XE eas fags aromatic include any compounds that have the benzene ring in fs hem. But in practice, many people use the term aromatics to refer to the 'BTX's, the benzene, toluene, and xylenes. The name aromatics, by theRefining for the Non-Technical Person 38 | Petroleum way, comes from the characteristic smell of most aromatic compounds, ich i i arbonish odor. which is sort of sickly sweet hydroc: ve tne mu ‘You can see that once the numberof carbons gets above six, the number of different variations in stctore explodes, For that reason, very i ymetimes, the n ‘tention is paid to the individual compounds. Someti fm at nuptbenes an arratis might beset usally the physi properties (gravity, viscosity, boiling temperatures, etc.) are used as expedient. EXERCISES 1. Isobutane is the isomer of normal butane. Why isn't there an isomer of propane? : 2. How many different ways can isobut Isobutylene? a 3. Name the four types of structures 4, There are three different kinds of xylene. Can you draw t shown in this chapter? ; 5. Why is there only one type of toluene’ lane be structured? Isopentane? generally referred toas the PONA’S. he two not WI CAT CRACKING In the adolescent years of the petroleum industry, the p:oportion of the ‘crude oil barrel that consumers wanted in the form of gasoline increased faster than fuel oil. It became apparent to oil men that the production of enough straight-run gasoline to satisfy the market would result in a glut of heavy fuel oils. The economic symptoms of this problem were increasing prices of gasoline and declining prices of the heavier cuts. To.cope with this physical and economic problem, the inventive process ‘engineers developed a number of cracking techniques, the most popular of ich was cat crac Process In the last two chapters, the process of cracking was discussed and the chemistry involved was explained. To put it in the context of a controlled process, incat cracking straight-run heavy gas oils are subjected to heat and pressure and are contacted with a caralyst to promote cracking. First, a catalyst is a substance added to a chemical reaction which facilitates or causes the reaction; but when the reaction is complete the catalyst comes out just like it went in, In other words, the catalyst does not £* change chemically. Itcauses reactions between other chemicals. Catalysts are like some ten-year-olds you know. They never get into trouble; it’s just that wherever they go, trouble happens. Next, the feed to the cat cracking process is usually a straight-run heavy {25 oil as well as the tops from the flasher. The boiling point for cat feed can be anywhere in the 650-1 100° F range. g., Heat is required to make the process go; temperatures in the cat cracker where the cracking takes place are about 900° F. Finally, the process is designed to promote cracking in a specific way 3940 | Petroleum Refining for the Non-Technical Person The object isto convert the heavy cuts to gasoline. Ydeally, all the product would be in the gasoline range, but the technology is not that good. During the cracking process, several phenomena occur. As the large molecules crack, the lack of sufficient hydrogen.to saturate all the carbons causes some small amount of carbons to form coke, which is virtually pure carbon Stome stuck together. As the large molecules break up, a full range of Smaller molecules from methane on up are formed. Due to the deficiency ‘of hydrogen, many of the molecules are olefins. Where the large molecules fn the feed are made up of several aromatic or naphthene rings stuck together, smaller aromatic or naphthenic compounds plus some olefins result. Finally, the large molecules, made up of several aromatic or naphthenic rings plus long side chains, are likely to erack where the side Chains are attached. The resulting molecules, though lower in carbon count, are more dense or heavier; that is, their specific gravity is higher. ‘They also tend to have higher boiling temperatures. The irony ofthis is that 'm a product which is heavier than the feed. The products of cat cracking are the full range of hydrocarbons, from methane through to the residue range. ‘There are three sections to the cat cracking hardware, the reaction chamber, the regenerator, and the fractionator. Reaction Chamber “The guts of the cat cracker is the reaction chamber. The cat feed is pumped through a heater, mixed with catalyst being pumped into the line, then introduced into a large vessel that looks like a water tank called a reaction chamber. By the time the feed reaches the vessel, the cracking process is well underway, so the residence time in the vessel is only Seconds. Then the catalyst and hydrocarbon are separated and drawn off. “The catalyst is generally one of two types: beads or particles, The beads are Ys to % inch in diameter. The particles are much smaller and look like baby powder. Beads, however, are pretty much out of vogue now. The particles have two unusual characteristics. Ifa container of them is shaken br tilted, the powder reacts just like a fluid. Hence, the process is sometimes called Fluid Cat Cracking “The second characteristic is common toboth the beads and the particles Cat Cracking | 41 ‘CRAG! PRODUST ——> REACTION CHAMBER spent a CATALYST. { FEED: FLASHER TOPS TF HEAVY Gas oi] FRESH GAIALYSI Fig. 6-1 —Cat Cracker Reaction Chamber bus not apparento the naked eye. Under a microscope itcan be seen that psa hs lege number of pores an, ata soneequetce, a tremendous area. Because the influence of the catalyst depends on contact with ‘The Regenerator f During the cracking process, the cracked hydrocarbon that i42 1 Petroleum Refining for the Non-Technical Perst © + 02> CO and COz / is similar to burning coal or briquets in this process, oxidation of coke, i si olor bgutin Boas oxygen ad ives aff erbon monoige (CO), Mfexide (CO), anda large amount of heat The heat, inthe form ofthe hot Co and COn is generally used in some other part ofthe process such a8 cing the ea feed temperature in a heat exchanger. Then the vented to the atmosphere. SPENT ‘CATALYST 3—> FRESH CATALYST Fig. 62 —Catalyst Regenerator rom the bottom of the regenerator comes freshly regenerates exts¥E ready to be mixed with cat feed on its way to the re the catalyst is in continuous motion going thr regeneration cycle. ‘The Fractionator Meanwhile, back on the hydrocarbs eaves the reaction chamber, it is charg column dedicated to the cat cracker product g Fig. 6.3 —Fractionation generated catalyst, rough the cracking/ on side, when the cracked produet into) to a fractionating 4 ced (pumped into) to a fractionat yout, ‘The products separated Cor Cracking | 43 generally are the gases (Cs and lighter), cat cracked gasoline, cat cracked light gas oil, cat cracked heavy gas oil, and the fractionator bottoms, called eyele oil. A variety of things can be done with the cycle oil, but the most popular is to mix it with the fresh cat feed and run it through the reaction again. Since only a small proportion makes it all the way through the reaction under a steady state, this is called recycling to extinction. [+2 CAT CRACKED GASOLINE REACTION CHAMBER [= car CRACKED LIGHT GAs On. PRooUCT | = oar onackeo Heavy ans oi TOFEED Pum ~<“Syelz OL ‘The cat cracked heavy gas oil can be used as feed to a thermal cracker or a5 a residual fuel component. The light gas oil makes a good blending stock for distillate fuel and the cat cracked gasoline a good motor gasoline blending component. There is quite a bit of latitude in the cut point between the gasoline and ight gas oil stream. This is one way to regulate the balance between wsoline and distillate as the seasons change. As the winter heating oil son comes on, many refineries go into a max distillate mode. One of the rations that changes is cat cracked gasoline end point, in order to drop44 1 Petroleum Refining for the Non-Technical Person Cat Cracking | 45 more volume into the cat light gas oil. In the summer, during & max gasoline mode, the shift isin the other direction. “The ight ends from the fractionator are different in composition (han those from the crude distilling column light ends. The eracking proce aoste in the creation of olefins, so the Cs and the lighter stream not only wutanes; but also hydrogen, contain methane, ethane, propane, and b coreo, Sthylene, propylene, and butylenes. Because of these extra componctl's i oa this stream is sent to be separated at the cracked gas plant. This is fn Lo uchTer aentrast tothe gas from operations like distilling (and, as discussed Je" cat former, and others) where the gases Reaction | easoune the hydrotreater, hydrocracker, re “is, These are sent to the sats gas plant for lene, and butylenes from the cat cracker a process that contain only saturated compoun: separation, The isobutane, propyl J» cariao ‘will be of special interest when discussing alkylation, Converts these olefins into gasoline blending components TAl the pieces fit together as shown in the figure below. You can se there are two circular flows going on. On the left side, the catalyst Boes through the reaction, is regenerated and gets charged back to the reach ante On the right side, hydrocarbon comes in and goss out, butte cycle ‘il causes continuous circulation of some components. FRAC. tionaton| [CAT HGO eA t CYCLE OL, FRESH CATALYST Yields “the object of the cat eracking process is to convert heavy gas oll (0 gasoline and lighter. A set of typical yields will demonstrate how successful the process is. —_ Tolan Since the cycle oil i eee —_—- —— asiaa ae oil is recycled to extinction, a simple diagram for cat Hen G0 ea Bese sn't even show it as entering or leaving th nae cour more important does show up, however, the pheromeronot gan Ta a ger ut only with the gravities of th i on Coan aH s \¢ products coming out compare: scent weight instea Cat-Cracked Light Gas Oi (Cu-Cracked Heavy Gas Oi! Gyete O11 Of percent volume, th Recycle seam nt Tsuen fed oF yield ds show a substantial gain.46 | Petroleum Refining for the Non-Technical Person Cat Cracking | 47 Process Variables ‘Some of the things that have an effect on the way a cat cracker operates ace the quality of the feed, the reactor temperatures, the feed rate, the recycle rate and, curiously, the time of day and temperature outside the ‘control room. ee SA.GASO SRNAPH KERO. ‘SFLGO ‘SBHGO Feed Quality. The cracking reaction is very complex, and lots of data fare available to predict yields from different feed characteristics. The gravity of the feed and its paraffin, naphthene, and aromatic content are important. Reactor Temperature. The higher the temperature, the more cracking will occur; but at some point, the amount of gases created will really take ff, at the expense of the cat gasoline or cat light gas oil. The optimum reactor temperature is a function of economic incentive. FLgortows Feed Rate and Recycle Rate, ‘The yields will sufferat higher feed rates, so the trade-off with the volume of fractionator bottoms being recycled or left in the cat heavy gas oil is watched. Time of Dayand Temperature. Inorderto regenerate the spent catalyst fresh air is pumped into the regenerator continuously. As the temperature ofthe air outside goes down, the air gets more dense. Since the blowers that pump the ait operate at fixed speed, more oxygen is actually pumped ito fhe regenerator when it's cold than when i's hot. The more oxygen, the note coke bumed off the catalyst. The fresher the catalyst, the better the ‘eaction, The better the reaction, the more gasoline produced. From the deposited on i ; Gperator’s data logs, the swings can actually be plotted, and as night comes f, plocess removes itby reatng itwith ome ong the temperature drops, the yield gets better. With the heat of the to form afternoon, the yield falls off. Gc. The purpose of cat cracking is to convert 1, Cat cracker feed usually comes from the Review Fromaprocess point of view, the cat cracker can be sketched a — = ‘a feed-in/product-out box in the refinery flow diagram. Thus far, you" Covered distilling, flashing, and cat cracking. The way in which thes come together is shown in Fig. 6-5. This diagram introduces the shorthand notation that will be used from here on and the are found in the cra‘ ‘Streams. the cracked gas stream but not in the sats gas ya The cat-cracker fractionator bottoms, calle: : foms, called. by injecting them inthe feed.48 J Petroleum Refining for the Non-Technical Person Use the data and answers from the previous chapters and the ence from this chapter. Assume feeds to the cat cracker are al 3 avy ga ol the cut between the oilis Sxerserye comet Ae fuser tops and all he sagen sts aoe ant asc and laser fed.) How much cat ight es produced? - yan idiatr of how compli ccm a efter armas to make a downstream volume change. N Mle increase the von of et ight B95 refining operations can get is the me six REFINERY GAS PLANTS Almost all the refinery processing units generate some volumes of butane and lighter gas. Gas processing is not a very colorful operation, but maybe that's why the engineers gave such exotic names to the parts. There's lean oil, fat oil, sponge oil, rectified absorbers, to mention a few; all are in the central location called the gas plant, SATS GAS PLANT ‘The gas streams from most of the refinery process units have only E: saturates in them: methane, ethane, propane, butanes, and maybe hydro- B gen, The word saturates is a synonym for hydrocarbons with no double E bonds; that is, all the carbon atoms are ‘‘saturated with hydrogen atoms. BE These streams are usually handled in a facility called the sats gas plant. g, This is in contrast to the streams that also contain olefins, ethylene, B; Propylene, and butylenes that are handled in the cracked gas plant. By. The separation of the paraffins is alot harder than the separations in the B crude distilling unit. Remember that each of the paraffins boils at a single femperature. That doesn't leave much tolerance for tail ends or any kind of loppy separation. As a result, the separation columns have lots of trays fend lots of reboiling and refluxing F Another complication is the pressure/temperature relationships. The gas Poanis are just the inverse ofthe flasher. In order to get part of the streamn to Pivity—an essential step in distllation—the mixture has to be either super fsooled (see the table below) or put under a lot of pressure. Usually both ods are used in combination. fe sats gas coming from the processing units cen go through the Bollowing typical steps: 4950. | Petroleum Refining for the Non-Technical Person Refinery Gas Plants | 51 Gaseous LIGHT ENDS -ETHANE 8 LIGHTER ‘COMPRESSOR PHASE SEPARATOR LEAN OWL, 20s ( ‘GAS FROM PROGESS UNIT Lawn UGHT ENDS GASEOUS LIGHT ENDS Fig. 7-1 —Compression and Phase Separation RECTIFIED ABSORBER 1. Compression. Low pressure gases are compressed to about 200 psi 2. Phase separation, Because of the high pressure, some of the heavier gases liquify, allowing them to be drawn off. 3. Absorbtion. The remaining high pressure gases are introduced tu the middle of the rectified absorber. (Rectified is a synonym for distiling.) Into the top tray of the absorber is pumped a naphtha, which trickles dow? the column. As it does, it picks up most of the remaining propane and butane in the gas. The naphtha laden withthe propane and butane is called fat oil; logically the naphtha introduced to the top of the column, ready (© ‘absorb the propane and butanes, is called lean oil. (Figure 7-2) 4. Debutanizing. The fat oil is charged to a column, called a de- butenizer, which separates the butanes and propane from the naphtha. 4 Because the boiling range of the naphtha starts about 150° higher than butane, the split is relatively easy. (Figure 7-3) “The liquid portion of the phase separation is charged to the debutanize also. 4 'S, Depropanizing. The Cs/Ce stream is separated in a tall column tha takes the propane overhead. 6. Deisobutanizing. Splitting the butanes is done in this column. Since the boiling temperatures of normal and isobutane are so close, many trays are needed to get good separation. The deisobutanizer is usually the tales column in the gas plant. 3 Bi Fig. 7-2 —Absorption 7. Sponge absorbtion. One complication occurs ‘ ion wen the lean oil i cdrecord aren, Some he ean sully eptane [Cru or can (Ca, vaporizes and goes out the overhead withthe fan and lighter (Cs). To recover he lean ol the overhead is charged Ey tom of another absorter color and another beaver lan ol led sponge ol, charged tothe top. The overhead is almost ll C— the almost al ean ol as shown in Figure 7-4 : eth Ces usally not split inarefinery since its primary use is efnery FE Sometimes, however, the ethane might be needed for feed to a : Plant, and the C2~ is then de-ethanized in another absorberRefinery Gas Plants 52. | Petroleum Refining for the Non-Technical Person ee 2 i 1 ! cf SPONGE Meee z tt 4 i cascous | | e UGHT | 1 | I | peIso- SPONGE i on ]DEBUTANIZER St oan a : os FFlg. 7-4 —Sponge Absorption Fig. 73 —Debutanizing, Depropanizing, and Deisobutanizing Disposition ‘ams? Because each of the different compo- in the refining business, and the highest sition 10] formal butane. Used almost entirely as a motor gasoline blending Beomponent. Due to its volatility, it is good for starting cold engines, yet Bil stay dissolved in the gasotine with minimal evaporation. Some normal Bitane is also used as a chemical feedstock and as a fuel Why separate all these stre nents has found a unique home value can be attained only when the stream is separated for dispos pane. In the U.S., most LPG (Liquified Petroleum Gas) is pro- About 10% of the LPG sales are butane or butane-propane mixes. pane as a fuel has some unique characteristics that have found favor in ¥ applications. It can be liquified at reasonable temperatures and this use. : Used almost entirely as one of the feedstocks to th aityain Occasionally used as a motor gasoline blending alkylation process. ‘component,54 J Petroleum Refining for the Non-Technical Person a oc Some Properties of Light Enés Bolg Fenpeae SPONGE Compound ae SEONGE comet kee Cbaaon) Tptogen ‘ten Mebane (COMPRESSION Ethane 25 bye ao area Propane aan Propylene. 423 PHASE, ‘ Isobutane an ‘SEPARATION Ce Normal Butane 46 ie | ampere w i Normal Butylenes o | ay sat ] Sop “ABSORBER DEPROPANIZER il Re atmosphere presse "There are hee forms of oral {2B ae oes fort soma bees, eco em ithe omnla aca wih Lo DDEBUTANIZER peISOBUTANZER| Fig. 7-5 —Sats Gas Plant CRACKED GAS PLANT pt fas surams from the eat cracker and the other crackers contain ifn, ethylene, propylene, and buylees, Usually the ethylene isnot thee were aed in th chemical pam frst Neo Fn a refinery, the propylene and butylenes are usually sent to an lation plant. For convenience, the paraffins, propane and butane at plete Separation in the same fashion as inthe sats gas plant. pressures for ease of transport, particularly in trucks. Yet at ambien temperatures, it will readily vaporize, making it easy to burn in stoves home furnaces, ete. Propane has also widely been used as a chemical feedstock. Ethane. The only application that gives rise to separating ethane in 4 refinery is its use as a chemical feedstock. (See Chapter XIX, “Ethyleng Plants.) Otherwise, the ethane is left with the methane Hydrogen r hee are several processes in refineries that require hydrogen: hydro- king and a variety of hydrotreating units. Some of the gas streams, in Methane, Refineries have a voracious appetite for fuel. Methane find a ready home in all the process furnaces and steam boiler furnaces around the refinery.a 56.1 Petroleum Refining for the Non-Technical Person from the reformer, have higher concentrations of from the reformer are kept segregated through and the compression permits separation of @ ‘ich can be used in the hydrogen particular the stream hydrogen. Often the gases the compression stage, hydrogen concentrate, an HalCs mix whi applications Supplementary supply of hydrogen canbe made specially ifthe refer hha a eydrogen plant, otherwise called a stean-ethane reformer, which will be discussed in a later chapter. Storage Facilities talk about the rather specialized facilities needed ‘This is a good place to to siore the refinery gases. Because of the volatility and boiling temper tainers are needed to store the tures of these streams, high pressure cont streams in the liquid form: Methane (and ethane 0: never stored in a refinery but is produced. ‘There are some surge way to the refinery fuel system) is usually sent drums in the system which can accum- ie some of the gaseous methane for short periods of time during opera'n changes. Also those tall flares so characteristic of refineries are used 0 take the momentary surge in gas made by burning the excess. ‘Propane and butanes (and sometimes ethane) can be stored in steel storage or in underground storage. 1d butane storage is the spherical “The characteristic of the propane an shape. Steel storage is ether inthe form of bullets (cylinders on their sides with rounded ends) or large spheres ‘ptimization of structural strength to accommodate the hi the cost of the steel. ‘Underground storage generally takes one of in rock, shale, of limestone; of jugs leached out of domes as shown in Fig. 7-6. eso case, mined storage, the propane or butane is pumped i and out of the cavern in the liquid form, with the difference in the amos a ont od made-up by more oF less vapor being formed above the igi Ina salt dome, the ins and outs are b 8 “The ug contains a combination of propane and salt water (brine). THEW gh pressure and f salt in underground sal t directly to the fuel system as itis g s. The round shape is due to an wo forms: caverns mined] handled in a more unusual fashions Refinery Gas Plas | $7 TOIFROM LPG SHIPPING <> { FACILITY TOIFROM, <> BRINE Pir GROUND LeveL aun PROPANE, isis, i ike any ther ailwater combing ce any oe ston, do not mix. To pump the Bopanc out, is pumped in, fri rs . the propane out To seen pumped orig te rine ot alo bie pi Qoe advan fat done gsi expnalyBysbsiang BE wer the rn, oreo he a te ‘ os ing the: of the jug at no cost. There is, of course pea io the size—the risk of collapse : Ss apractical limit—— 58 1 Petroleum Refining for the Non-Technical Person “The other advantage is the original construction cost. Salt dome juss af mach cheaper than mined storage, which is much cheaper than ste! Morage. Unfortunately, Mother Nature limits the availability of salt STomes, suitable rock, shale, and limestone to a few areas around the country. EXERCISES 1. Fill in the blanks ver The two sections of the ges plant are called the ___— gas plant and the gs plant heavier gases in the rectified b. The naphtha used to strip out the “The liquids-laden lean oil is absorber is called called cc. Aste stream is called a 2, Match up the following streams with the usnal uses. “4 to absorb a lot of some parts of another Methane Ethane Hydrotreating Propane Blended to motor gasoline Normal Butane Refinery fuel Isobutane Alkylation feed Propylene Chemical Feed Butylenes. Commercial fuel Ethylene Hydrogen 3, Draw a set of distillation col ‘cracker gases into C2 and lighter, propane, propylene, norm: isobutane, and butylenes. Use tl teach compound, Assume each column has onl draws, What special problem does the butane/butylenes split pr 4. Make a flow diagram of t covered, the crude distilling column, the fl gas plant. resent? Jumns that could be used to separate the cat, al butane, he table that has the boiling temperatures o ly tops and bottoms, no side fhe streams in and out of the units already; jasher, the cat cracker, and the y ALKYLATION After the engineers were so were so clever about the inve a © invention of eat crac atuckedthe roblemofl heightens th proses create, The bts maximize the volume of gasoline being produced, but ind Paper wer oo ve say dated he tesoline blends, Soa process was devised which was he inverse af ercking, llarion a small molecules and ends up with large ones a ‘The Chemical Reaction To achemist, alkylation, (Fig. 8-1) can cover to ety engine ali fn Ge eeain af promos lene wit isobutane to form an iso-parafin, called alkylaies seks Yolumetic effect on refining operation is the inverse of cracking because there isa significant amount of shrinkage. With propylene as th el of propylene and I-6 bares of scbutane goes fn and 21 bbl of product come ot ar ie 2 bbl of isobutane me out; one barrel of butylene and is yield 1.8 bbl of product. As in cracking, the weight in equals the weight ‘out. Only the densities change. The Process The chemical react ical reaction can be made to take place by subjecting the isobutane and olefin i i olefins to very high pressures. But the equipment would be pery expensive to handle this route to alkylation, Like a lot of other cy Like processes, catalysts have been developed to facilitate the process and 59Alkylation {61 60 J Petroleum Refining for the Non-Technical Pers age 4 scp _lpmooucr,| caer i tso-urane | CMLER REACTOR T+) separator} =] “WASH, 4 n-con ; " 4 eee with sci gee ee bn oo a 4 wegen e H=E-M gohepane 5 5 - Prop 4 (crs) i : i i i i 4 2 i a " 1S0-BUTANE, T Fig. 8-2 —Alkylation Plant teooctane (Cote) f pumped through a chiller. All the steams are in ligu Be the chilling is done right in the reactor. teobut form. Sometimes lsobutane (Cate) B The Reactors. ‘The reaction time for the alkylation process is relatively f:s1ow, from 15 to 20 minutes, so the mixture is pumped into a battery of Blsrge reactors. The reactors hold so much total volume that by the time they all tum over once, the residence time of any one molecule is quite long H(about 15 to 20 minutes). As the liquid passes through the reactors, it counters mixers to assure that the olefins come in good contact with the igsbutane in the presence of the acid, permitting the reaction to occur. Fig. 8-1 —Alkylation of Propylene and Alkylation of Butylene -yen main parts; the chiller, the reactors, the y plant consists of se a Trea pe caustic wash, and three ditiling columns as shown i acid separator, the caustic wast Figure 8-2. works best af ion with sulfuric acid catalysts wor Shborhood of about 40° F. So the olefin feed ( im from the cracked g idand The Chiller. Alkyle ", ig temperatures in the oe “ rapanelpropylene andlor butnebtyene cet ao eined witha seam of soutae anda steam of sure a ld Separator. The mixture then moves to a vessel where no mixing fiskes place, and the acid and hydrocarbon separate like oil and water. The Bidrocarbon is drawn off the top; the acid is drawn off the bottom. The acida 62 | Petrolewm Refining for the Non-Technical Pers also referred to then recycled back tothe feed side. The acid separator is also refere as the acid settler. : ivhavesome from the ai separator wil ave ust Wash. Thebydrocarbon panna sone = sof .cid in it, so it is treated with caustic soda inavessel. Cat ee (foes tn th ° at baking soda does to acid indigest the hydrocarbon what B Lae oe as The tnd effects csapear. Wha’ et is amin hydrocarbons ready to be separated. ‘Three standard distillation columns separate the alky- Cae "The iso-butane is recycled to the feed. late and the saturated gas. Yields sn process, a number of side re¢ Darin oe undesirable. Because there area Jot of motecules one a e, butane, and formi ting are small amounts of propane, # forming ad reset pent too a, but asa amount of ar a thek rar gang complex byércarvon mixtures fom aswel roe cles out withthe acid and disappears when te acid the supplier for eprocessing “ine volumeti balances for prop sactions occur, some of yylene and butylene feed are as follows: Feeds Propylene Butylene Taobuiane Products Propane ‘Normal Blane ligt fields don’t sh What the feeds and the yiel butane that just passes through the plant unt alky plant provides significant capaci jormal g .ow is the propane and norm: jouched, Asa matter of fact, the ity to the refinery for making} Alkylation 1 63 segregated propane and butane. When the alky plant is down for one reason ‘or another, the propane/propylene stream is usually routed to the refinery fuel system and LPG production is cut significantly Process Variables ‘The alky plant manager has to watch a number of key variables to keep too many side reactions from occurring, causing the quality of the alkylate to deteriorate. Reaction temperature. Low temperatures cause the sulfuric acid to get syrupy and not to mix well. The olefins do not completely react. High temperatures cause compounds other than isoheptene and isooctane to occur, lowering the alkylate quality. Acid strength. As the acid circulates through the process, it gets iluated with water and picks up tar. As the acid concentration goes from 99% down to about 89, itis drawn off and sent back to the acid supplier for refottification. Isobutane concentration. By having an excess amount of isobutane, the process goes better. Isobutane recirculation systems are generally built ; in, The ratio of isobutane to olefin varies from 5:1 to 15:1. Olefin space velocity. The amount of time the fresh olefin feed is resident in the reactor causes the quality of the alkylate to vary. ‘Review — What's so important about alkylate? For one thing, it has a high g, octane number. For another, it has a low vapor pressure. Since gasoline Bending has not been discussed yet, octane numbers and vapor pressure Beprobably don’t mean anything to you. Suffice it to say that those are desirable qualities of gasoline blending components aad that’s the value of Ikylation: low valued cracked gas components are tumed into high valued oline components. Bi The alky plant can be represented by a box with propylene, butylene and Bsobutane in, along with propane and normal butane, and alkylate out,Alkylation | 65 Ga 1 Protea Refcng forthe Non Tchncl Person —— withthe pope and oral butane. To put alkylation in epee: thenthe refinery processing units covered so far, plus a yt au a show in Fig. 8-3. It's surprising how complicated it quickly g 1. Fill in the blanks a. Alkylation is the inverse of b. The catalyst in alkylation is either _____ or depending on the process chosen. ©. The five main parts of an alky plant are: 4. Alkylate is made up mostly of two isoparaffins called and = e. Because of the high _. alkylate makes a good oa 2. The cracked gas stream coming to an alky plant has the following shown it and low. composition Propane a5 Propylene 25 Isobutane 10 Normai butane 20 Butylenes 30 cou foo a liSes Ifthe volume is 3000 B/D and the alky plant yields are those shown in Ee this chapter, how much isobutane is needed from the sats gas plant? What are the alky plant outtums? ioc uso FLASHER SA RESOU! Lesorrows_ Fig, 83 —Refinery Processing OperationsWw sss CATALYTIC REFORMING ‘The thd generation of refinery processes came asa result of the market requirement for increasing the quality of gasoline. Quality wes generally seared by octane number which will be discussed in Chapter XU MGavoline Blending.” In the 1950's and 60's, the octane race was # prevalent factor in gasoline marketing. One method introduced to improve rrevaatane number of gasoline was catalytic reforming. It is important for this discussion to keep a mental finger on Chapter V, Petroleum.” ‘The Chemical Reactions Unlike the previous processe: the boiling range of the feed an does change is the chemical composition Feed to a cat reformer is usually straight run naphtha some other processes, such as hydrocracking, are sometimes is a high concentration of paraffins and napht reformer causes many compounds, which have much higher octane numbers cee watovming typically results in the following change inthe naphhe volume Pacafins Otetas “The Chemistry of 1s discussed, there is very little difference in id the product of a catalytic reformer. What Naphthas from thermal cracking, coking, and especially fed to the cat reformer also. Typically there henes inthis fraction. The eat lof these components to be reformed into aromatics Catalytic Reforming | 67 The good reaction: we 6 that take place in the cat refor 1) aaffins are converted to isoparaffins 2, Paraffin ae converted to naphthenes laphthenes are converted to aromatics. 1B Process are ‘Some not-so-good reacti ions take place: 4, Some of the paraffin: _ ee ea and naphthenes crack end form butanes and 5. Some of the side chai ide chains get broken off slo bas nigh us ‘the naphthenes and aromatics ie important thing to remember is paraffins and napth ind napthenes get converted t0 aromatic compou nes ipounds and some isomers, as shown in the Normat hexane Isohexane Parattins to soparattins 4 Hoda Woe-H Ke W-e-m aN i oy ie wo tte Hogan os Ho e-n wee \ Fy Hoeon Nomal heptane ao 4 Motiyleydohexane Parattins to Nephthenes68 | Petroleum Refining for the Non-Technical Perso CoH 4 Toluene [Naphthenes fo Aromatics butane (yclohoxane Naphthenes crack to Butanes and tighter Benzeno Side chains crack off aromatics orming light ends + Methane Fig. 9-1 —Reformer Reactions rs Catalytic Reforming 1 69 ‘The Hardware mn dollars taken to keep track of it ‘ reactors. The product is then run he purpose of liquitying at this point|-Technical Person 30. | Petroleum Refining for the Non-Technical cycling. This to permit separation of the hydrogen rich ges stream for recycling ee importa sw sentences. see mptant enough 0 warrant 2 ew sent ortant by-product of cat reforming. Look back at the ‘Most of them result in the production of exit Mrogen because aromatics don’t need as many hydrogens as naPhONe® acreeratfins, But reforming is also a user of hydrogen in the teas, Teeten mat be mine wit he elt ep gD conceialon i .ctors. This prevents carbon ator deposit tydropen apo ine peat cracking, sea, the aon reacts wh Trrogen and forms a hydrocarbon £85. snwhile back at the hardware, part o ae ees js sent to a fractionator called a stabi! from the bation of sr a debutanizer It makes a botiom product Bea id lighter go overhead and are sent (0 the Hydrogen is an imp chemical reactions. called reformate; butanes an gas plant. Regeneration atalyst cause @ s, coke deposits on the cataly 1 an interval of operations, coke d ly nue 8 ea iy: Symptoms ofthe decline ar regoed octane ‘eaettatomate yield per bare of fed, or bot. __—— Teds Voie aed conrad ; "Ean __cuayt OT i : 3 Cics 3 3 G 3 ‘ fe 3 % & “ efor é He (Getane number) Jnut down to regenerate the catalyst, but @ Early eformets ie was devised by adding another reactor. At any one continuous flow design was Catalytic Reforming {71 time three of the reactors are in operation, the fourth reactor being in the egeneraton mode. Regeneration is accomplished by admitting hot air to Femove the carbon from the catalyst, forming carbon monoxide and dioxide. The cycle time for a reactor to be off line is only about 30 hours, so the catalyst is kept fresti virtually all the time. Despite the continuous regeneration, over a long period of time the activity of the catalyst will decay. The high temperatures required for regeneration cause the catalyst’s pores to collapse. Consequently, every 2-3 years the entire reformer must be shutdown for catalyst change out. Process Variables ‘The dials and buttons that the engineers play with are the temperature, Pressure, and residence time. The game is really a balance between the volume of the reformate and its quality. Fig. 9-3 shows the relationship: as the octane number goes up, the percent volume reformate goes down. Correspondingly, the yield of butanes and lighter goes up. So the operation of the catreformer must be tuned in very closely withthe gasoline blending operations and the gasoline component yields ofthe o:her processing units, ‘The properties of the naphtha feed, as measured by the paraffin, olefin, hnaphthene, and aromatic content, affect the yields and quality, also. The PONA analysis of naphtha is an important component in the analysis of a crude oil's value. Aromatics. Cat reforming is a primary source for benzene, toluene, and. g xylenes. The process for recovery of the BTX’s will be covered separately ina later chapter. Bi Review. Catalytic reforming is an important process for upgrading low Boctane naphthas to a high octane blending component, reformate. The {PON content of the feed is shifted from the P and N towards the A, to fepitalize on the high octane numbers of aromatics. Unfortunately, the higher the octane number of the reformate, the lower te yield and the more light ends produced.Technical Person 721 Petroleum Refining for the Non-Techt 78 t 7 REFORMATE VIELD % VOL. & [REFORMATE OGTANE NUMBER Fig 5.3 —Cat Reformer Yields vs. Octane Number | ao. a Ac ett - 2 8 Catalytic Reforming | 73 EXERCISES Fill in the blanks: a. The basic purpose of catalytic reforming is to increase the _. of naphtha. b. The expensive component of the reforming catalyst is ¢. Reformate has a much higher concentration of ______ than the reformer feed. d. An important by-product of cat reforming is €. The other by-products of cat reforming are = and £, To keep the catalyst from getting coked up, the reactors are kept filled with &: Symptoms of aging catalyst are the decline of the reformate ———— or ______, and the increase yield of the ____. 2, Suppose the reformer feed is 15 MB/D and the operating conditions are setto produce 91 octane reformate. The 91 octane reformate is worth 2.0 times as much per barrel as the Cs and lighter produced. Each increase in z..octane number increases the value of the reformate 0.5% (92 octane is 2.0, X 1.005 as valuable; 93 is 2.0 x 1.005 x 1.005; ete.). Does it make sense fo increase the severity of the reformer, that is, run it to produce higher octane reformate? Use the yield versus octane number chart in this chapter. E (Hint: check the economics at 91, 95, and 100 octane). B3. Draw an additional example of each of the five types of reactions that lake place in the catalytic reformer. 4. In the 1960's, Shell Oil Company advertised the use of “Platformate”” in its premium gasoline. What is platformate a contraction of? ; Draw the refinery configuration covered so far, including the cat freformer in its place.X. RESIDUE REDUCTION High rates of crude runs inevitably produce large volumes of the bottom of the barrel. In the U.S. economy, the large growth rate in the demand for gasoline was not matched by the growth rate for residual fuel. Even the reduction of straight-run residue volumes by flashing could not balance residual fuel supplies with demands, so refiners resorted to several types of process units to convert residue to light products. As early as 1920, large volumes of pitch were being processed in thermal crackers, greatly ameliorating the gasoline/residual imbalance. In recent years, advanced technology has favored construction of cokers. These processes are very similar to each other and will be covered here as the most popular methods of residue reduction ‘Thermal Cracking In the chapter on vacuum flashing, you leamed about a process unt designed to avoid cracking of molecules due to high temperature, In this chapter, you will learn about promoting cracking due to high temperatures ‘The difference is in the controlled conditions ‘Remember, thermal cracking is the breaking of hydrocarbon molecules into smaller compounds, usually olefinic due to the absence of ext hydrogen. Long chain paraffins can rupture anywhere. For the cycl compounds, the break tends to be at the point where astraight chain, ifan js attached. As a consequence, the heavier products tend to have high olefin, naphthene, and aromatic contents. Feed to the thermal cracker is usually flasher bottoms, but sometimes cl cracked heavy gas oil and cat cracked cycle oil are used for feed: Ifthe broader range of streams is fed to the thermal cracker, the ight distillate range hydrocarbons are kept separate from the heavier siocl "4 Residue Reduction | 75 be is fed to a separate furnace Severity) are higher for the lig rity gh the lighter , since the temperature requirements products. The furnaces heat the feed to as ors FLASH FEDS ‘cHAMBER, nesoue | X FURNACES RESIDUE ae ‘ Product is mixed with a recycle stream Ps the cracking. Both streams are charged to a Products go ovechead because the lighter products from the top ofthe flash chamber are charged to a ighter pr from the top of the fi imber re96 1 Petroleum Refining for the Non-Technical Person Residue Reduction | 77 1 Ce and lighter streams are sent o the cracked gas plant. sntha are used for gasoline blending or ls can be used as a distillate fuel or, ‘fractionator. Th "The thermal cracked gasoline and nap! ccan be sent to the reformer. The gas oil Tike the fractionator bottoms, can be recycled to extinction [——>¢. austen [—> casoune |_casoune oss § [> naPuTia os 8 § Lomo [> | FRAC. CRRCKATE KEROSENE _ FERTER cro FIRST STAGE REACTOR He HEATER SECOND ‘STAGE REACTOR, Hydrocracking | 83 the catalyst causes cracking, but the cracking process needs heat to keep it going. That is, it is an endothermic process. On the other hand, as the ‘cracking takes place, the hydrogen saturates (fills cut) the molecules, a Process that gives off heat. This process, called hydrogenation, isexother- ‘mic. Thus, hydrogenation gives off the heat necessary to keep the cracking going. Another way in which they are complementary is in the formation of isoparaffins. Cracking forms olefins, which could join together to form normal paraffins. Hydrogenation rapidly fills out all the double bonds, often forming isoparaffins, preventing reversion to less desirable mole cules. (The isoparaffins have higher octane numbers.) After the hydrocarbon leaves the first stage, itis cooled and liquified and ‘un through a hydrogen separator. The hydrogen is recycled to the feed. ‘The liquid is charged to a fractionator. Depending on the products desired (gasoline components, jet fuel, and gas oil), the fractionator is run to cut out some portion of the first stage reactor. Kerosene range material could je taken as a separate side draw product or could be included in the fractionator bottoms with the gas oil. ‘The fractionator bottoms are again mixed with a hydrogen stream and charged to the second stage. Since this material has already been subjected {0 some hydrogenation, cracking, and reforming in the first stage, the p operations of the second stage are more severe (higher temperatures and Bi pressures). Like the outturn of the first stage, the second stage product is E separated from the hydrogen and charged to the fractionator. Imagine the kind of vessels necessary to handle the operating conditions, 2000 psi and 750° F. The steel reactor walls are sometimes 6 in. thick. A critical worry is the possibility of runaway cracking. Since the overall Process is ettlothermic, rapid temperature increases are possible, ac- fclerating the cracking rates dangerously. Elaborate quench systems are Fig. 1]-1 —Two Stage Hydrocracker YF, pressut Feed is mixed with hydrogen vapor, a to oa re 2000 psi, and charged to the frst stage reactor, AS it Ba ee ria abut 4 to 0% ofthe feeds vsked 0 range material (below 400° F end point) in several ways. Fi “The hydrogen and the catalyst are complementary inseveral way! ‘As it pes Pbuilt into most hydrocrackers to control runaway. Another excellent feature of the hydrocracker is @ 25% gain in Polume. The cracking/hydrogenation combination results in products Febose average gravity is a lot higher than the feed. A typical set of pi/trocracker yields, using coker gas oil and cat cracker light gas ola feed ‘shown below. The primary products, gasoline blending components, called hydrocrackate.84 1 Petrolewn Refining for the Non-Technical Person Hydrocracking | 85 important are the feed rates an Fates and operating con: =— the cokee, Ia addhion, the alky plat asd element Cote gus dages for economical dispositgn of the ack ae ee esey PPE “Cat rached ight 05 i position of the cracker products. . Penduet E Propane XERCISES Isobutane 1. Contrast hyd Normal buase wydrocracking, cat cracking, an. , Ligm iydoeacete 2. How isa hydrocracker complementary scerema cracking ackate hydrocracker? toacatcracker? A reformertoa 3. Draw the refine tefinery flow diagram with the hydrocracker added Not shown is the hydrogen requirement, which is measured in standard ccubie feet per barrel of feed. Net consumption of 2,500 sef/bbl is typical. Because the heavy hydrocrackate has a lot of (compounds that easily convert to aromatics) itis often fed to the reformes. for upgrading. The kerosene range material makes a good jet fucl or distillate blending stock. Residue Hydrocracking. There are a few hydrocrackers that have been Constructed to handle straight run residue ot flasher bottoms as feed. Mos, Gf them are operated as hydrotreaters, as described in Chapter XV. The Yields ate over 90% residual fuel. The purpose of the operation is serove sulfur by the catalytic reaction of the hydrogen and the sulfur ‘Compounds, forming H2S, hydrogen sulfide. Residue witha sulfur conegy oP about 4% of less can be converted to heavy fuel oil with less than 0.3% sulfur. ‘ Review With the addition of the hydrocracker to the refinery processing scher the absolute requirement for integrated operations becomes apparent. fone sense, the hydrocracker is the pivotal unit since it can swing 0 fefinery yields between gasoline, distillate fuel, and jet fuel. But jstGasoline Blending | 87 GASOLINE BLENDING ‘The best known hydrocarbon is gasoline, but itis astounding how little is known about the characteristics of this product. The explanation for this public naivete probably lies in the competitive pressures which force producers to make a product which performs. Andif the product performs: the buying public loses interest (or never has any) in what makes it good ‘This chapter will cover several areas: 1. The two most important variables in gasoline blending: vapor pressure and octane number. 2. The effect of tetraethyl lead in gasol 3, Procedures for blending gasoline. “£, The impact of gasoline blending requirements on refinery operations. ‘There is a small chance that you'll be lost from the beginning if you don't have some idea how an automobile engine works, so a couple of paragraphs and illustrations will precede the discussion. P COMPRESSION: IGNITION Power Gasoline Engines. ‘The essential parts of a gasoline engine, atleast fo this discussion, are the gas tank, fuel pump, carburetor, cylinder, find the spark plug. Engines without the last item (spark plugs) will by discussed in the next chapter, because they're diesels “The process flow in a gasoline engine stars in the gas tank when you" it at the service station. When you start the engine, the fuel pump sue gasoline out of the tank and sends it to the carburetor. The carburci Sapotizes the gasoline, mixes it with air, and sends it to the cylinder, ini point, the sequence of events is essential, as ilustrated in Fig, 2:4 “The gasoline/air vapor mixture is sucked into the cylinder asthe pis} moves towards the bottom of the stroke and the space in the cylinder to its largest. The inlet valve closes and the piston then moves up f Cylinder, compressing the vapor. When the piston reaches the top of Toe Bout Biroke, the spark i ne bara cPi ves off powerful spark, igniting he gasoline. Ths ively, causing a hu, ine. The Essure on the pis ige expansion of the con epson. Poncrisuammited wie crak satasc ay ylinder in a power stroke. At the botiom ofthe, rf ae ofthe power 688 Petroleum Refining for the Non-Technical Person stroke, the exhaust valve atthe top of the cylinder opens and the burnt fuel is pushed out as the piston moves up the cylinder. At the top of the stoke, 1d the process is ready to be repeated. Note the inlet valve opens again an that each cycle requires two trips ofthe piston up and down the cylinder. Vapor Pressure One of the crucial steps in the engine cycle is the vaporization of the gasoline. When the engine is warmed up, there is no problem: the engine hreat assures that 100% of the gasoline will enter the cylinder in vapor form, But when the engine is being started from cold, the conditions are much more difficult. “The trick in handling cold stars is to have enough volatile hydrocarbon in the gasoline to get a vapor-air mixture that will ignite. ‘The measure of volatility is vapor pressure, and more specifically Reid Vapor Pressure (RVP), named after the man who designed the test apparatus, Definition. to keep a liquid from vaporizing. A light hydrocarbon like propane will have a very high vapor pressure, since it is very volatile, A heavier hydrocarbon like ga ol will ave nearly a zero vapor pressure, since it wil waporize very slowly . «. at normal temperatures. 1f you think for & moment you'll realize that vapor pressure is a function of temperature.3 Reid vapor pressure (RVP) is measured at 60° F. 3 Engine Conditions, _ Definitions out of the way, go back to the car: buretor problem. The RVP of gasoline must meet two extreme conditions ‘On cold starts, enough gasoline (maybe 10%) must vaporize to provide # ignitable mixture. Once ignition occurs, the rest ofthe gasoline that cide vaporize will burn too. The other extreme is when the engine is runnin winile completely warmed up, or even more extreme, is being restated When it’s hot. At that point, the gasoline vapor must not expand so muey that no ait can be mixed in on the way to the cylinder. Again the mixtu must be ignitable. j Refiners have found that there is a direct correlation between gasoline's ability to meet these conditions and the RVP. Furthermore, Vapor pressure is a measure of the surface pressure it takes a B Blending for Vapor Pressure. refiners get there? If you look atthe mentioned above, The am E sed a the pressuring gen Gasoline Blenl lending | 89 have found th aster nis hen RVP for gasoline varies with the seasons. I dead of winer in pace like Bemidji, Minnesota, col stats ned fusoline with a 13 psi RVP. During the dog days of August in ae sar psi. Vapor Lock. On ; \e other constr Paper ack 0 int on vagor pressure is w mentoring vapor lack A combination of high tide and hgh lmpercs ci cute bens At gh aes, te mp ea 7 : ‘gasoline will tend to vapori iw i te tm High enprscsaggmte he poem he fe un Exes pan coninion of por andi when tiene “onsequently, the carburetor will be nd wil be starved and the ‘engine will quit, and won't start agai the temperature of the gasoline /on’t start again unt igain until the temperature of the gasolis To avoid vapor lock, cvitonnen te dOcks gasoline RVP is localized to accommodate the prevailing in the area, includi a including seaso barometric conditions. See Hye list of gasoline bien: eee = nC 3 ; 70 Reforma 94 RON Feormate 100 KON Ligh ydoeecae Heey Hydrctche lorie Sle tan Castine Stig Ron Napa a Cached Coates ‘ Coker Gasoline ‘ ‘ iif you sat down to design the scheme for an indi id gasoline, - stty to blend gasoline,90 I Petroleum Refining for the Non-Technical Person ‘around to be the marginal component used for all vapor pressure control. But amazingly, that’s the way it turned out. Butanes are made in refineries as a by-product of conversion processes. They also are recovered from natural gas in gas processing plants. Somehow these two rather inelastic Supplies end up providing all the butane that’s needed for gasoline blending Getting down to nuts and bolts, the procedure for calculating the amount of butane needed to pressure up the gasoline involves only algebra and weighted averages. Vapor pressure calculations are not exactly related 10 the volumetric weighted averages, but for the purposes of this exposition, they're close enough. Suppose the RVP specification is 10 psi and you have a blend of five components. How much normal butane is needed? Component ‘Siaigh rn esol ~ Li Hydrocrackate Cav erncked gasoline Nonna tene For 10 psi RVP 10(19,000 + x) = 60,600 + 52x 190,000, + 10x = 60,600 + 52x 2x + Oe = 129,400 2 3081 barrels of normal butane equred ‘Total gasoline production is 19,000 + 3,081 = 22,081 bbl ‘So the calculation is pretty simple, but some of the implicati mentioned. Since the speci Volume made. Unfortunately, in most markets, except those like Miam Beach, the demand for gasoline is lower in the winter than the summer owever, give some flexibility 1 ‘The additional gasoline capacity does, h maximize distillate production. Normal versus Iso-butane. isobutane to pressure gasoline? There are sever Y to demystify the subject , Goaine. That's a fine definition, but i {Universally obscure phenomenon, knocking. Knocking. jons mightbel fication for RVP is higher in the winter than ing the summer, the capacity to produce gasoline is higher in the winter. The higher the RVP spec, the more butane can be blended in and the more tv Why use normal butane instead off ral good reasons. First of al Gasoline Blending | 91 dl e a ually the price of the butanes are such aaa ome Ear ariee -nd as much butane as allowed. Secondly fe another iene es wane alkylation. Very often, there isn't oq parico poee intrecting ae eae is often a little less than isobutane. i hoa vapors in the winter than 1 rasa Octane Number Everybody who bi uys gasoline knows ‘more expensive. Hardl wo a igh octane gas 'yone knows why. This section is an attempt Octane numbers ers are measures of whether a gasoline will knock in an requires an explanation of another Ill be helpful to refer i fe cyele, Ate ae Pett refer back to Fig. 12-1, the diagram ofthe it not only works © power, but it’s also tou cal 0 tough on the mechan sages of engine development twas dseovered ‘ine components behaved differently. The key i. At the very early st iat the various types of p:92 | Petroleum Refining for the Non-Technical Person Compression Ratio Equals Vi: Va characteristic is the compression ratio at which knocking occurred. The compression ratio in Fig. 12-2 isthe cylinder volume when the gesoline/ir Vapor was injected, Vi, divided by the volume when ignition occurred, Vi A series of guide numbers was devised to measure the compression rtig at which a gasoline knocked. Iso-octane, CsHis, was defined as 100 botane gasoline. Normal heptane, CrHie, which knocks at a much lowet Compression ratio was defined as zero octane gasoline. By using a tf engine, any gasoline component can be matched with blends of iso-ociateg sna normal heptane. ‘The octane number equals the percent ofiso-octaneit the blend that knocks at the same compression ratio, ‘An explanation of the test procedure might help. 4 has a top which can be screwed up or down to van] is fed into the engine while the head being tumed down. Atsome point, knocking will occur, as detected elie by ear or by the use ofa detonation meter. After noting the compress ratio, the cylinder head is backed off. Two blends of iso-octane and norm heptane are prepared. From familiarity with the apparatus, blends that Testing for Knock. test engine is used that the compression ratio. The gasoline knock with a higher and a lower comy octane numbers of these blends are known by d wn by det octane number of == the gasoline component can be ‘COMPRESSION 8.2 ‘RATIO FOR GASOLINE > ‘COMPONENT @.0| ral 18, r 7a Gasoline Blending | 93 ipression ratio can be concocted. The finition (the percent € read off the graph in Fig comb Ratio ron °*> FASE Beto OGTANE NoMBER 70! orrrsreteno) | 41] t For example, compression ratio of 8:1 so-octane (88 ON), Benzine they knock at fctane number of the EOciane Requirements. 7 <8 05 8m os oe on a test engi 'st engine a gasoline component knocks at a Two test blends are are mate up, one i th other with 968 is-ectane (96 ON) Inthe tee 7.2:1 and 8.4:1, respectively, From the chart, the J ively. From the chart, oe You know what octane numbers meas ? The design of an engine demands that the94 | Petrolewn Refining forthe Non-Technical Person Gasoline Blendi fuel behave in a certain way. The compression ratio of an engine line Blending | 95 determines the amount of power it can deliver. The higher the compression ‘atio, the longer the power stroke, the more powerful the engine. So different size cars have different engine designs, and therefore require- ‘ments for gasolines of different octane numbers. Bending for Octane leather, Tae bend ot guaine nt ein a ee jin inthe previous example onthe us of butane to achieve ‘0 achieve vapor pressure. Calculate the RON and MON. ‘Straight run gasoline faa ri a Types of Octane Numbers. You need to know two more sets of Reforma 4000 eho ee nomenclature about octane numbers, the different kinds and their uses. Et Hydrate Sm a Sto First of all, the tests for octane numbers are run under two sets of Necu ions ees) ne aco 6923 ‘conditions. The Research Octane Number (RON) test simulates driving ‘Under mitd conditions; the Motor Octane Number (MON) testis run under nore severe conditions and simulates operations under load or at high speeds, The two measures, RON and MON, give an indication of performance under the full range of conditions. nthe late 1960's there was a controversy between the FTC and the U.S. ted average octane nu: MON andl 67 Regge Octane numbers forthe 22,081 barrels are 78.1 Now calculate how much alkylate would have to be added to meet a ‘minimum specification of 80.0 MON and 89.0 RON. Alkylate has octane iinimum specifi yl refiners about posting octane numbers on gasoline pumps. The FTC @ ‘numbers of 95.9 MON and 97.3 RON. waited RON'S posted. The refiners objected that RON didn’t teli die ge: ~~ nn Whole story. The FTC considered posting RON and MON. “Too rz Confusing,” said the refiners. The FTC finally arrived at a compromise by oe Yates ON ERO ordering the following be posted on gasoline pumps: Session iain vgs are RON + MON #20 0_ ON + MO! eee for the 22,081 bbl of blended gasoli & the following alkylate must be added ine to meet the MON spec, “That measure doesn’t have any particular meaning other than the fact tha Cian the controversy was over. a 081) (78.1) + ¥ (95.9) = (22,081 + ¥) (80.0) i “The second piece of information about octane numbers is how they behave. When two gasoline components are mixed together, the RON’ and MON’s do not blend linearly. That is, the resulting RON and MON not the volume averaged octane. However, and most fortunately, there is such a thing as ablending octane number for the RON and MON of eve Somponent which does blend linearly. The blending octane number i related to the true (test engine) number in a constant way, and is develop by experience. When references are made to RON's or MON's 9 components, they can mean either the true or blending octane numb Hersinafter, all references to octane numbers will mean the blending ‘octane number, not the true number. a +195 bbl Ba" The same kind of calculation is a alculation is done for the alkylate to meet the RON (22,081) (87.4) + ¥ (97. 3) = (22,081 Y = 12,241 bbl ae More barrels are needed to m RON spec, so ides the ls are needed to meet the RON spec, so that de: + $0 that decides pyolume, because both the MON TI piolume, because both the ye en and the RON specs are minimums. The sub problem has be lkylate are added to meet tl aa ; this example. If 12,241 bbl of he minimum octane specifications, the RVP tane ‘on is no longer met. By the use of two equations and wo96 | Petroleum Refining for the Non-Technical Person Gasoline Blending | 97 unknowns, the volume of butane and the volume of alkylate, the corect blend can be figured out. Leaded Gasoline ‘The addition of lead to gasoline used to greatly simplify blending for octane number, Lead, in the form of tetraethyl lead (TEL) or tetramethyl Jead (ML) increases the octane numberof gasoline, without affecting any other properties, including vapor pressure. "TEL ica very toxic chemical, and in low concentration in the vapor form can induce violent illness or death. Because of this hazard, as late as the T960"s the Surgeon General of the United States (then part of the Executive Branch) set the maximum amount of TEL allowed in gasoline at tO ml per gal. The Environmental Protection Agency succeeded to fhe uthoritative position of the Surgeon General. Because of more intensive ° ie quality, in 1974 the EPA mandated a gradual phase SJown of the lead content in gasoline, starting in 1975. Nonetheless, ead thetormof TEL or TML is tll permitted in atleast one grade of gasoline produced by a refiner, and is sill an important economic tool, albeit somewhat blunted. Tt sounds contradictory, but lead is added to gasoline to suppress ignition, Remember thatthe lower the octane number, the more Tks #4 ‘Esoling isto knock, or self-ignite. Lead helps prevent the selignitin se Ngomplicating factor in the use of lead, is that the higher the conventration of lead additive, the less effective the last increment, In ott id lead content is svords. the relationship between octane number an non-linear—it bends over 4 oo Th Fig, 12-4, you can see that the effect of lead is unique for each Pe of __Blering Component _ a ating component. Some components are more susceptible to condi, Geet 15 FT Bear rina eae pent than others. Furthermore, when the components ar mie tema 94 ton 20 Wea 3010432” ASPHALT. fe oN ee NAN eH LI asouaer ro of | oto | ‘pe ae c £ c ASLAN Zn b FS y of Se walen i | il 4 emulsiricn NAW Po s2%5 W NF " S 4 ‘Asphalt Options i i sali nk wih 4050p asphalt. Operttngcondions onthe fasher wu, can then be changed to make a 250 pnsaton gre, nang ne ier tank, By blending these two grades directly into trucks, tank cars, ships, or barges, any grade in between 40 and 250 penetr Fig. 14-1 —An Asphaltene mean most popular test method uses a steel ball. Commercial grades of asphalt have softening points somewhere around 80-340° F. F ‘The hardness of an asphalt, once it’s applied, is measured by its penetration, The test apparatus for penetration has a long needle with a ‘weight on top. The depth to which the needle penetrates the asphalt over a standard period of time at a given temperature is the measure of penetration. Very hard asphalts are zero penetration, while the softer one range up to 250 a A wide variety of grades of asphalt can be dispensed at a refinery byj making blocked out runs: for a period of time, the flasher can be run to fill Blown Asphalt An alternative to producing asphalt via high temperature flashing is to E chemically change the consistency of the softer grades in a blower. In this Bunit hot air is blown into the asphalt, causing a chemical reaction. Either ie oxygen bonds to the asphalt or hydrogen combines with the oxygen to ake water which evaporates. A harder, more rubbery asphalt results. The Bower penetration asphalts can be achieved via this route, which is ponelimes cheaper because ofthe composition of the pitch content of the le.110 1 Petroleum Refining for the Non-Technical Person Cutbacks ‘The application of asphalt requires that the materials flow. In road construction, for example, the asphalt must completely surround the aggregate (gravel) and sand with which it is mixed. Normally asphalt is mixed and applied at heated temperatures. To reduce the severe equipment requirements due to temperature at the construction sites and at the same time achieve a hard durable product, sometimes a thinner is added to the asphalt. The thinner, or diluent, will soften the asphalt and permit lower application temperatures. After the asphalt has been applied, the diluent will evaporate, leaving the hard, durable asphalt behind. ‘The rate at which the diluent evaporates, usually in terms of days, will depend on the diluent used to cut the asphalt back. An asphalt that needsto ‘cure (achieve its final, stable state) rapidly can be cut with a very light diluent, like naphtha. Ifa longer curing time is acceptable, kerosene can be used. The terms RC Cutback and MC Cutback (Rapid Curing and 4 Medium Curing Cutbacks) generally denote the type of diluent used ‘The use of cutbacks has always been somewhat problematic. Some of the hydrocarbon, the diluent, just passes through the system and doesn't end up in the finished product. Secondly, the evaporation of the dilventis Emulsions E cuter stock added to meet the maximum visci » loaconversion unit (cracker) Asphalt and Residual Fuel J 111 RESIDUAL FUELS The usual disposition of flasher tion of flasher bottoms is residual fuel, or residu Resi! as avy onimanded lover shan thee or reasons, one physical and the other commercial, Movit ing reasons, on physical rcial. Moving and consumin; (ead geass special equipment. The pipelines, transportation, and {iorake must be heated so tha the residual fuel doesn't solidify. Second! more importantly, amos al residisaleftover from producing th ther Products. Its supply elasticity is nearly zero. a Blending Resid te ae resid is a by-product, the specs for marketable product are ver roots Fe most important speci viscosity, ameasureofhow mucha fia esists flowing as shown in Fig. 14-3. (Maple syrup is sists owing: : syrup is more viscous th water.) Flasher bottoms generally need to have some kind of a diluent or spec. Typically, the ely low value as feed Cat cracked heavy gas oil is usually used, if diluent is a heavy stream of low viscosity and a relativ available. Another specification is sulfur content, The allowable sulfur emissions from industrial fueling vary widely by geographic area and by the tequrements ofthe consumer, Resid! het a idual fuels are either hig sur, with the break somewhere around 0.3 to 1.0% by weigh sali, ‘To achieve the same flexibility in field equipment but avoid the cutback } problems, emulsions have been developed. Emulsions are a mixture of about 50-70% asphalt and 30-$0% water. To keep the asphalt and water mixed, an emulsifying agent which is something like soap is added. The ‘agent, though much more expensive per gallon than the asphalt, comprised only about one percent. : ‘After application, the water evaporates just like the cutback diluent leaving the hard asphalt behind. Emulsions are generally applied at lowe temperatures than any of the grades mentioned before, since the additionof water to facilitate handling is pretty cheap. cost of desulfurization, as ell as the increasing demand for lower sulfur residual fuels. eatin Baliy, like distillate fuels, the flash point of residual fuels sometimes Fai sats fesidual fuels have to be heated to be pumped, the flash Fa ead mote ertcal than for distillates. At the same time, residual ! to be @ sump where a lot of miscellaneous streams can be112 J Petroleum Refining for the Non-Technical Person YW HYDROGEN, HYDROTREATING AND SULFUR PLANTS MAPLE SYRUP WATER All sorts of contaminants are found in crude oil. As the petroleum fractions travel through the refinery processing units, these impurities can have detrimental effects on the equipment, the catalysts, and the quality of the finished product. Furthermore, there may be legalor paralegal limits on the content of some impurities, like sulfur. Hydrotreating does an effective job in removing many of the contami= nants from many of the streams. Hydrogen is a vital input to the hydrotreating process. Low viscosmy HGH viscosrrY Fig. 14-3 —Viscosity is Resistance to Flow Hydrotreating Refinery streams that have Cs and heavier hydrocarbons in them are likely to have some sulfur compounds as well. The sulfur can be attached orimbedded anywhere in the molecule and therefore is chemically apart of & the stream, Hydrotreating has been used successfully to break the sulfur away. 3 In the hydrotreating process, the stream is mixed with hydrogen and B stted 10 500-800° F. The oil combined with the hydrogen is then charged 0 a vessel filled with a catalyst in pellet form. In the presence of the catalyst, several reactions take place: fi. The hydrogen combines with the sulfur atoms to form hydrogen ulfide (HS), Bs; b. Some nitrogen compounds are converted to ammonia pric: Any metals entrained in the oil are deposited on the catalyst g: ¢. Some of the olefins, aromatics, or naphthenes get hydrogen saturated find some cracking takes place, causing the creation of some methane, ethane, propane, and butanes B The stream coming from the reactor is sent to a flash tank where most of dumped. Flash poitis usually the limiting factor for what can be hidenin gl "A technique for incresng the sls of residual fst made from high sulfur eae became fashionable in the Carribbean refineries. The wg canbe remove fom the gs ge seas by lately inexesng Pyrcening process, described nth next chp. By Deng Pah fur ase tos ih he dese as he es residual ean meet alow sulfur spec. In some cieles thi Geseriped as “solution fo polio is dilution 113Hydrogen, Hydrotreating, and Sulfur Plants 1115 114 J Petroleum Refining for the Non-Technical Person The yield from hydrotreating residuals has higher light end production. In those large molecules, especially the “timethy! chickenwire” com, Pounds, sulfur, nitrogen, and metals cannot be removed without literally destroying the molecule to spring the imbedded pollutant. In the process the smaller molecules result HYDROGEN RECYCLE HyoROGEN Jet Fuel Hydrotreating. Hydrotreating can be used to improve the buming characteristics of distillates, especially jet fuel. ‘The Kerosene fraction can contain a large percentage of aromatic compounds which have higher carbon-to-hydrogen ratios. When these compounds burn, the deficiency of hydrogen can cause smoke. As a matter of fact, one of the specifications on jet fuel is the smoke point ‘The apparatus used to measure smoke point is similar to a kerosene lantern. A reservoir of fuel is fitted with a wick that can be cranked up or down to vary the length and the flame size. The smoke point is a measure of tow far the wick can be cranked up before smoke is visible above the flame. The smoke point is equal to the wick length, in millimeters. A kerosene with a low emoke point can be improved by hydrotreating uring the process, the aromatic rings get saturated with hydrogen, Converting them to naphthenes which are cleaner burning compounds | STABILIZER HEATER Hypnocen REACTOR OPARATOR HYDROTREATES PRODUCT Fig. 15-1 —Hydrotreater th propane adie, inn the HS an thes it of moni fo Overhead. To completly sip out these Hight ends, small act generally tacked onto the tll end ofthe process ‘The importance of hydrotreating hasbesn grad Years fortwo reasons ually increasing for many Hydrogen Plant ge, The normal source of hydrogen in a refinery is the cat reformer. ‘The g light ends of the reformer column contain a high ratio of hydrogen to a. Removal of sulfur and meta ° in reformers, cat crackers, and hydrocrackers. methane, so the stream is de-ethanized or depropanized to get a high concentration hydrogen stream. E ns are continually lowering the allowable sulfu ent eel et alng for desulfurization of distillates and jet fuel Bf. Some times the reformer hydrogen cannot satisfy all the hydrogen oe 4 quirements in a refinery. This might be true if there is a hydrocracker in eration. Hydrogen can be produced on purpose in a plant called a Steam ethane Reformer (SMR) as shown in Fig. 15-2. p.When the design engineers were searching for ways to make hydrogen, fetemical compounds with a high proportion of hydrogen were considered order to waste as little as possible ofthe remaining material or the energy sed 0 process it. The two compounds that were finally used were almost 0 obvious, methane (CH) and water (H20). ls is important protection for the catalysts ir i are likewise coming undedj sidual drotreating. Residual fuels ‘ fuel i though the flow eal uch lower hydrogen-to-carbon I116 1 Petroleum Refining for the Non-Technical Person Fig. 15-2 —Steam Methane Reformer ‘The trick in the SMR is to spring as much of the hydrogen from methane ‘and water as possible, but with a minimum amount of energy (fuel) ‘consumed in the process. With the aid of some very useful catalysts, the SMR operaies in four stags 1. Reforming. Methane and steam (the HzO) are mixed and passed over fa catalyst at 1500° F, resulting in the formation of carbon monoxide and hydrogen: CHi + H20 > CO + 3H: 2. Shift Conversion. Not content with the hydrogen already formed, the process exploits the carbon monoxide. More steam is added ove another catalyst at 650° F to form carbon dioxide and hydrogen: * CO +H20— CO2 + Hr 3. Gas Purification. In order to provide a concentrated hydrogel stream, the carbon dioxide is separated from the hydrogen by a solveai extraction process. 4. Methanation. Since the presence of any carbon monoxide or dioxidy in the hydrogen stream can mess up some of the applications, a clea step converts them fo methane. A catalyst at 800° F is used: CO + 3H: CHa + H20 CO2 + 4H2—> CHa + 2H20 j | 3S + HO co ba O: ‘The sulfur drops out of the reaction vessel in the molten (melted) form: CO SOz Most refineries store and ship sulfur in the molten state, although some, companies store sulfur by pouring it on the ground (in forms), letting i solidify. Sulfur can be stored indefinitely in this dry state, called a pile. i Claus plants convert about 90% to 93% of the HeS to sulfur. Lo environmental conditions may permit the balance of the H2S, known as hig tail gas, to be burned in the refinery fuel system. Alternatively, the til ge could be processed for high percentage H2S removal in more elabor processes like Sulfreen, Stretford, or SCOT (Shell Claus Offgas Trea ing). aIsomerization | 124 XWUI a= me MAKE Up Hs + chloride ieee ISOMERIZATION Isom plants are molecule rearrangers somewhat like the cat reformer ‘except that they only convert normal paraffins to isoparaffins. Curiously, the Ce isomerization unit is built for very different reasons than the Cs/Cs isomerization unit BUTANE ISOMERIZATION A refinery that has an alkylation plant is not likely to have exactly enough isobutane to match the propylene and butylene needs. If there isa hydrocracker in the refinery, there is likely to be surplus isobutane whichis probably blended off to gasoline. If there is not, there is a need to supplement the supply. The choices are usually two—buy it or make itona butane isomerization (BI) plant. fractionator, the latter are spit out and sent tothe fuel afore latter are split out and sent to the fuel syst tem; i the butan tionator so that the normal butaneean bese nbe rerun, The Process ° When the yields are fi i is are figured on a net basis, the i lihtly exceeds the normal butane feed the volurcnn goon noua ‘The feed to the BI plant is normal butane or mixed butanes (iso and, ssence, it’s normal JCS normal butane in, isobutane out, and that's it normal), which are sometimes called field grade butanes if they come from; ‘a gas processing plant. The butanes should not have any trace of olefins which would deactivate the catalyst. q ‘The butanes are fed to a feed preparation column where isobutane i removed; the high purty normal butane is then mixed with a small amount of hydrogen and chloride and charged to a reactor containing a platin catalyst. The catalyst causes the normal butane to reform itself into ig id has a lot of straight run gasolin: isomer, isobutane. ound “The stream coming from the reactor contains about 60% isobutane, normal butane, and a minor amount: of propane and lighter. In34y 120122 | Petroleum Refining for the Non-Technical Person ‘The Process Like the BI plant, the Cs/Cs Isom plant may have a feed fractionator that concentrates the normal pentanes and hexanes, rejecting the isomers. The normal paraffins are mixed with a small amount of hydrogen and organic chlorides and charged to a reactor. The catalyst will cause conversion of about half the feed to isomers (isomerate), $0 the reactor product can be fractionated to recycle the normal pentanes to extinction. Since the hexanes boil at a higher temperature than the normal pentane, but the isopentane boils at a lower temperature, the cost of the additional hexane splitter sometimes precludes recycling the normal hexane. Yields, Because the feed molecules are a little more complicated, the, reactions are somewhat more complex and the light end creation a litle higher, about 2-3%. Depending on the amount of recycle, the octane number of the isomerate can be varied from 80 t0 91 RON, with the cost of energy (fractionation, pumps) increasing with the octane number. Review. alkylation by converting normal butane to isobutane. Cs/Cs isomerization is a method of increasing the octane number of the light gasoline components normal pentane and normal hexane, which are found in abundance in light straight run gasoline. Ha ence et low 7 wxeo,| eer g rise Fig. 16-2 —CsICe Isom Plant Butane Isomerization is used to satisfy the feed needs of ame SOLVENT RECOVERY OF AROMATICS In 1907 a man named Edeleanu devel compounds could be The process worked loped a process by which aro1 Lean matic Preferentially removed from a hydrocarbon mixture. he on eases Where the boiling point of the aromatic as the other compounds in the mixture. Distillation under those conditions wouldn't work, so le le i in ms wouldn't work, so the Edeleanu Applications Removal of aromat *matic compounds can be desirabl Srey = lesirable for two differen eto range the aromatics have detrimental effects on the quality ofthe Tein orthe aromatics ate worth more hey te ooaothen ifthey're not. There are a . There are a numberof i been touched on. mber of examples, some of which have already @, Aromatic compounds in a kerosene can cause unacceptable smoke b. Kerosene ranj 'sene range solvents that are aromatic have various industrial applications OT Somaticsladen ©. Separated benzene, xylene. B asicern » xylene, and toluene have numerous chemical d. Removal of aromatics from heavy gas oil lubricating oil characterise 'Y Ba8 oil stocks can improve the124 J Petroleum Refining for the Non-Technical Person Solvent Recovery of Aromatics | 125 naphthenes. The reasons the process works are complex and not worth ‘examining here. The other key feature of the solvents is that the solvent, with the aromatics dissolved in it, readily separates itself from the rest of the compounds. Take kerosene as an example and assume it has a lot of aromatic compounds in it, To half a beaker of kerosene add half a beaker of a solvent—in this case, liquid sulfurdioxide. After mixing, the liquid will separate into two phases with the kerosene on the bottom and the sulfur SOLVENT RECYCLE dioxide on top. The kerosene on the bottom will fill less than half the beaker. The sulfur dioxide, because the aromatic compounds have en dissolved init, will take up more than half the beaker. >| gue If the sulfur dioxide is poured off, the aromatic compounds can be ‘SOLVENT -— —] “sprung” by simple distillation. This two step process is batch solvent atl processing. — “Toimseenare Knowing how a simple batch process works, a continuous flow process feo > = a is easy to conceptualize. In Fig. 17-1, athree column system is shown, The —— feed is introduced into the lower part of a —— of mixers inside. (Sometimes the mixers are mechanically moved, such as L in a rotating disc contactor.) The sulvent is intuoduced near the top. EXTRAGT-LADEN SOLENT STRACT ‘Almost all the solvent works its way towards the bottom of the vessel, Ce dissolving the extract as it goes along. The rest of the hydrocarbon, which rises to the top, is called raffinate. EXTRACT men Two columns are used to handle the streams coming out of the mixer. ‘One column just cleans up any solvent that may have followed along with: the raffinate. The solvent is recycled to the mixer. The other column separates the solvent and the extract. The solvent from this column is also recycled to the mixer. é ‘Some of the solvents used in various applications are listed below. ‘a, Kerosene treating: liquid $2, Furfural b. Lubricating oil treating: liquid SOz mixed with benzene, Furfural, phenol, propane (separates paraffins from asphaltenes). c. Gasoline: Sulfolane, phenol, acetonitrile, liquid Oz SPUTTERS the extraction proc F iction process more efficier {One bit of nomenclature is often m Ro benzene. It is the leftover of Benzene Recovery (benzene) are removed. As a “The most widespread application of solvent extraction is wsed in BTY] recovery, especially for benzene. To make the process efficient, the feed126 J Petroleum Refining for the Non-Technical Person BONY meant cur" acowancs 2 Mees os ‘GASOLINE L»] Recover or a RAFFINATE. HEAVIER __ L ae Fig. 17-2 —BTX Recovery Indeed, the choice of which streams to use as refinery fuel must eke into account the market value of the streams and the heating value, Thermal Content When a hydrocarbon is bumed, two things happen. A chemical reaction . Typically, the chemical reaction is a CHs + 202 COs + 220 + Heat 2CsHe + 1502 12COz + 6H20 + Heat BTU, which stands for British thermal unit. Definition: The amount of heat required to raise the temperature of one Pound of water one degree Fahrenheit is equal to one BTU, (able of the heating values for some commercial petroleum products is E given below. Waker Heating Value Nawal Ga 1000-1050 BTUISC Ethane 66,000 BTU/Gat Propane 91,600 BTU/Gal Botane 103,300 BTTUrGat Dislite Pet 140,000 BTU/Gal No.6 Fuel (2.5% Sufi) No, 6 Fel (0.35 Sultu) 153,000 BTUIGat 127128 Petrolewm Refining for the Non-Technical Person ‘There are two types of heating values. The so-called higher heating value represents the gross amount of heat given off by the chemical reaction (the heat of combustion). The lower heating value takes into account what happens to the water created. A portion of the heat of combustion is absorbed to vaporize the water. Not all that heat isrecovered ‘or usable as the heat goes through a furnace and out a stack. As a general rule: the heavier the fuel, the lower the ratio of hydrogen to carbon, so the less water is formed during combustion. Typical results of this inability to recapture the heat of vaporization are measured by the thermal efficiency: the recoverable heat divided by the gross heating value. Thermel Eficency Naural Gas ee Propane 5%, Distt Fue 388 Coal ‘Competitive Fuel Value Nomogram_ ‘A handy way to relate the values of the various products and their heating value is shown in the nomogram as shown in Fig. 18-1. ‘That peephole diagram first appeared in the Oil and Gas Journal in 1972 and ‘was updated to put higher scales on it in 1977. ‘As an example of nomogram use, assume you wish to find the fuel values equivalent to $2/MMBTU natural gas. First, go to the vertical scale ‘on the right and find the horizontal line that intersects it at $2. Next, read along that horizontal line, right to left, the intersections on the other fuels scales: 13.2 epg for ethane, 18.3 epg for propane, 20.8 epg for butane, ete Similarly, the value of any fuel can be equated to any other fuel by extending a straight line from the vertex on the left through the first fuel’s value until it intersects the second fuel’s scale. For example, by laying a straight edge from the vertex through the high sulfur No. 6 fuel oil scale at $10/bbI, you can see the equivalent values are 3 $34/ton for lignite, 22 cpg for Distillate fuel, 14 epg for propane, and $1.57/MMBTU for natural gas. Fuel Values—Heating Values | 129 re ose 088 Ea ‘it ‘ite at este 181 —Equivalent Fuel Values for selected hydrocarbonssme mS ETHYLENE PLANT The closest chemical companies come to being petroleum refiners is in ‘ethylene plants. That’s the reason why so many large ethylene plants are built by integrated oil/chemical companies: they bridge the gap between the two. Ethylene plants are better called olefins plants, but are variously referred to as ethylene crackers (a misnomer), steam crackers (because steam is mixed with the feed) or crackers, with a suffix denoting the feed (ethane cracker, etc.). Olefins plants can be designed to crack almost any kind of feedstock, but the types usually fall into the following categories: Ethane Ethane/ Propane Mix Propane Butane Naphtha Gas Oil ‘The original olefins plants were built to produce ethylene, primarily, to “3 supply the growing appetite of the chemical industry for this basic building block. Of slightly less interest was propylene, but there was a large pool of that hydrocarbon that could be stolen away from refineries if necessary. : So, many of the early olefins plants were designed to crack ethane or ethane, and propane because the yield of ethylene from ethane is very high. (See 3 the table opposite.) Later development of technology led to the use of the heavier feedstocks: because of the larger availability of the feeds and because olefin plants cracking naphtha and gas oils produce a high octane gasoline blending component. A number of huge olefins plants as large as medium-sizedy refineries now are integrated into refineries and produce a significant amount of the gasoline. Ethylene Plans 1131 Overy PLawr Yieus Pounds Per Pound of Feed ret ie Fp ae rn Yield: 7 Propylene 020 mr oe te SR lt oS Bee Fuel Oil = = oe Gi Reiner Interaction rine olefins plants provide a home for a number of junk streams in a ty. For example, the dry gas stream froma cat cracker is ‘1 a cat cracker is usually se tothe fuel system, even though it contains ethan, ethylene mee aud propylene. But atthe olefins plant, these components ean be separated and put to higher value uses. “panied am of the naphthas in the gasoline pool are low octane and of litle ue as blending component. Benzene raffinate isan example. These Streams can make an attractive feedstock for olefins plant reams ak ins plants, not oF because of their ow alternate value, but because they yield « high octane component as a by-product. eee nine other side ofthe ethylene plant there are some complementary things, too. The butylenes and heavier feed ean generally find a home in finery processes. By themselves they f te sie procests, By es they ate not readily marketable, Process The ethane/propane crackers are th ms 5 are the simplest design, but they demon- sete andamentals. The tan nd propanecan be fd separtly ras cern ths cracking fumaces where the short esidene time and high ture, followed by a sudden quench, yield a hi rae ; ch, yield a high volume of cthylene. But for the operating conditions and feeds, olefins plants are just fe plain old thermal crackers.132. J Petroleum Refining for the Non-Technical Person Ethylene Plans ETHANE RECYCLE THANE: >} auench |—>} PROPANE CRACKING. FURNACES FRAGTIONATOR ‘PROPANE RECYCLE t 133 Fig. 19-1 —Olefins Plant: Ethane-Propane Cracker In one pass through the cracking fumace, not all the ethane and propane disappears. So downstream, in the product fractionator, the ethane and propane are split out and recycled to the feed. Generally, the ethane is recycled to extinction, but some of the propane goes with the propylene. ‘There are three commercial grades of propylene, depending on the amount of propane mixed in. Polymer grade propylene is 97-99% propylene; chemical grade is 92-95%; refinery grade is 50-65%. ‘The plants that crack the heavier liquids, naphtha, and gas oil create ethane on a once through basis too. So, those olefins plants often have @ furnace which is designed to handle the recycled ethane. Yields are usually shown as if the recycling took place, not the once-through basis: Fig. 19-2 —Olefins Plant: Heavy Liquids Cracker ETHANE RECYCLE THANE FURNACE >| >| NAPHTHA on sor] Quench - oa | L_} Cec, SGASOUNE L+| [cAs ou oracKiG FURNACES erroH FRACTIONATOR134 [Petroleum Refining for the Non-Technical Person not in the refinery sector, is A chemical stream that tums up here, but not in t butadiene (Fig. 19-3). This chemical is in the diolefin family and has two double bonds and the formula CsHs. The two double bonds make it particularly reactive and it is used in creating plastics and rubber com- pounds. Fig. 19-3 —Butadiene EXERCISES 1. How much feed, in barrels per day, is required to run a typical olefins plant producing a billion pounds per year of ethylene from the following, feeds: Ethane (3.2 Ib/gal) Propane (4.24 Ibigal) Naphtha (6.4 Ib/gal) Gas Oil (7.3 Ib/gal) 2A eacey has an ethane/propane cracker with capacity of S00 MM pounds per year of ethylene. Presenly itis cracking a mixture of 70% (by ‘olume) ethane and 30% propane running the plant at capacity. Suddenly the propylene market tums sour, and the company wishes to produce only 20 MM Ib per year of propylene. How much feed were they cracking, how much propylene were they producing, and how much ethane should they substitute for propane. CRUDE OIL, CONDENSATE, AND NATURAL GAS LIQUIDS ‘The raw materials coming into a refinery from the oil patch have some ‘ames that are not too descriptive. Sometimes they sound all alike. What's the difference between crude and condensate; between natural gasoline and natural gas liquids? Oil Patch Operations A simplistic look at what goes on ina producing oil fieldis shown in Fig 20-1. The underground accumulations of hydrocarbon can be in several states. The well on the left has tapped a reserve that has a gas cap at the top. Production from that well is gas well gas. This hydrocarbon mixture is Predominantly methane, but 15-20% of the material could be heavier hydrocarbons, ranging up to the gas oils. As the gas comes out of the well and is transported, it cools down and ‘more of the heavier hydrocarbons liquify. The mixture is introduced into a vessel called a field separator. This vessel is sometimes referred to as a “wide spot in the line." What happens is that in the larger space the pressure drops, and whatever light ends have dissolved in the heavier liquids flash. Natural gas is drawn off the top of the separator. ‘The bottoms are condensate. The well in the middle has tapped the same formation, but the Production is crude oil with some dissolved netural gas. At the surface, another field separator will separate this mixture into natural gas and crude oil. ‘The well on the right has tapped another formation in which there is only crude oil. No separator facilities are necessary. Further Processing The crude oil, condensate, and natural gas are ‘almost always collected by pipeline gathering systems. Usually, a number 135136 1 Petroleum Refining for the Non-Technical Person Fig. 20-1 —Oit Pate f jons are brought of different grades of crude oil from different come ie cought Topeher ina single mix Iitis convenient, condensate <; — oe cea | toe Cotter [ov ance pact Nore L__» nor 145 Piagram 1—Disillaion Column set-up to segregate cracked gasca146 Petrolewm Refining for the Non-Technical Person Answers and Solutions | 147 FL_BOTTOMS Diagram 2—Crude Distilling column, flasher, cat cracker and gas plant CHAPTER VIII I. a. cracking, ‘esta b. sulfuric acid or hydrofluoric acis ¢. cooler, reactor, acid separator, caustic wash, and fractionators 4, isoheptane and isooctane e. octane number. . . vapor pressure . . . gasoline blending compo- nent shrinkage 2. iCe for Ca: 3000 x .25 x 1.6 = 1200 B/D ce \ for Ce: 3000 x 30x 1.2 = 1080 B/D ce i 2280 less the 300 B/D in the feed is 1980 B/D os [Joo °. punt Py i B/D) Material Balance BID 0. 450 Cs Cs 675 ice 750 C3 . 3001C. ALKY [na 690 SR GASO. gs 600 nCs. ~ 0c, [sana 900 Cu alkylate 2880 ° lens e ———__—F + |sntco Paes 1980 iCs (from the Sats Gas Plant) a HGO cou fo =a jecuco Yields [bes lec co (3000 x0. 15)+(3000%0.25 0.3) = 615 B/D (3000 0.20) +(3000x0.30x0. 1) 690 B/D [SR AESIDUE S| 5 pseeH (3000 0.25x1.8)+(3000%0.30% 1.7) = 2880 B/D Feed = 4980 B/D Outtum = 4245 B/D CHAPTER IX octane platinum . aromatics hydrogen ‘methane, ethane, propane, and butanes hydrogen yield... octane number butanes and lighter1481 Petroleum Refining for the Non-Technical Person 2. The values of the yield are computed as follows. 95 Oat 108 Oe. wos 252 Reformat Yield 867 750 ‘Reformat value ‘ealealation 88.0%20 ur20 15x20 = x(.005)¢ x(.005 Reformat value 1760 178 1569 Chand hemiervalue 2 10.5 252 Total value a7 ie 182, The value keeps going down, only slightly, as the octane number is raised and the yield of reformate falls. So it doesn't make sense to increase severity. 3. Parafins to Isoparaffins: 4 nob Hocnw Hoc-H Heb-w Hogan nid bn ee ede eee H-e-4 H-G-H ow i i Hod HaG-4 H-e-n H-G-# i ; Hoa 4 Normal heptane G lsohoptane Paraffins to Naphthenes: 5 Cyclohexane Answers and Solutions | 149 Naphthenes to Aromatics oH ed bey ney =| L,— l A cy Ben wing fn wey i Ordchoxane ae Naphthenes Crack to Butanes and Lighter How Methane Motnane\ | ) 150. | Petroleum Refining for the Non-Technical Person Answers and Solutions. | 151 4. Platinum plus reformate gives platformate 2. Flasher bottoms are 35 MB/D Coke Yield = _ 35,000 x 350 x 0, 1837.5 Tons/Day drum 5. Diag. 3 B 2000 3. Diag. 4 es Lesene [a | of cru S| sn co L us = oye eo aos ese ax L fos |! [reese A suey Diagram 3—Refinery Operation wth Catalytic Reformer coi0o ecrod retort |p CHAPTER X 7 Suc ‘sorTows” Eu 1. a, Catalyst fica b. Coke and Residue pic iso c. Cooled with a recycle stream frerao d. “Cooked” until it cokes HIS AESIOUE e. Low or poor f. Sponge .. . needle g. Cracked . . . olefins nh Diagram 4—Thermal Cracker added to Refinery Process . Furnace, distillation column152 Petrolewm Refining for the Non-Technical Person CHAPTER XI a Hyd Thermal cracking ___Coahing a ole eany aah ecnico Ks . nageal fuser Sotoms Proce c cata neat promone Sydrogen __ Product paras, aphiben atin, al iphtenic Somatic aphtheni, “ ‘letine somatic cktaie 2. Cat cracker gas oils make good feed to hydrocrackers. Hydrocrackate makes good feed to reformers. 3. Diagram 5 snaaso jsanar oy cru rer F] auxy }4 m| cou axe iors. Diagram 5—Refinery Flow Diagram with Hydrocracker Answers and Solutions | 153 CHAPTER XII 1. Vapor pressure is a measure of the surface pressure necessary to keep a liquid from vaporizing. RVP stands for Reid Vapor Pressure and is the numerical result of measuring vapor pressure using Reid's method. Power stroke is the downward motion of a piston that occurs after ignition, Vapor lock is the phenomenon of insufficient gasoline flow from a fuel pump due to its inability to pump liquid-gas mixtures, Pressuring agent is the hydrocarbon, usually normal butane, used to bring gasoline blends up to an acceptable vapor pressure. Knocking is the preignition of gasoline in a cylinder during the compression stroke RON and MON are measures of octane numbers under conditions simulating mild and severe conditions, respectively. Leaded gasoline is gasoline that has TEL or TML added to boost the octane number. Octane enhancement is the reaction to the addition of lead as measured by MON or RON __ BurelsRVP__RON-D_RON.17 SR Garoline 230 Lt 664 aS Reformate 240 28 9401008 Huy Hydroerackate 610 17 790 922 CC Gasotine ad 44 395.8 Sebiota 14920 4.25 Normal butane xX 20 9.0 102s (14,920,4.25) + $2.0X = (14,920 + x)C12.8) X= 3,116 Blend, including the butane 10s 2s ar 6154 J Petroleum Refining for the Non-Technical Person Ans | nswers and Solutions 1 155 Plotting 84.2 and 94.6 on the octane number versus Jead chart (Diagram 6) indicates that 4.8 g/gal need to be added, which exceeds the EPA limit of | a) LEAD ALKYL ANTIKNOCK SUSCEPTIBILITY CHART 3.17 peal If the heavy hydrocrackate is reformed, a low octane gasoline blending stock is replaced by a high octane component. Assuming the yield of 85%, the reformate volume goes up to 7,675, the hydrocrackate yield goes to | zero. SR Gasoline Reformat CC Gasoline Subtotal Normal butane ‘Blend, including the b “The lead requirement in Diagram 6 for the new blend is only 2.2 g/gal, below the legal limit. CHAPTER XV Hydroueating DEA Removal RP P-Product, Feet ners Seam Diagram 6-—Octane Enhancement Chart156 | Petroleum Refining for the Non-Technical Person CHAPTER XIX 1X 10 + (0.77 X 3.2 X 42 X 365) = 26 MB/D 50 MB/D Naphtha: 44 MB/D Gas Oil: 50 MB/D 2. Let X equal the feed in bid of the 70/30 mix. To make SOOMM Ib of ethylene, the feed rate is as follows: Calculate the weighted average ethylene yield from the ethane and propane. The yield from ethane is X times the percent ethane times the pounds per gallon ethane times the yield of ethylene from ethane times 42 gal per barrel times 365 days per year. Same for ethylene from propane. Enh 500x108 ‘rom ethane From propane _ (CLOVE. 29ED}BESHOOH + _ORHO.BONE 240.40,42}65) = 146 mb Gusfy wable) The propylene production was: rom ethane. From propane Propylene (14 6H0.793.2442(9650.1) + (14 6HO.314.2442)(365),0.18) = 96.5 106 To find out how much ethane and propane must be cracked to make 500 MM tb of ethylene but only 20 MM Ib of propylene, use simultaneous equations: Let ¥ equal the ethane feed rate in b/d Z equal the propane feed rate in b/d Then: __ rom hae From propane wo X10" = 20 X 10 = (¥}_3.2)42)368)0.01) + (Zy(4.24x42(365)0.18) 500 X 108 = 37.793 ¥ + 26,000 2 ‘20X10 = 490 ¥ + 11.700 2 Y= 124 MB/D ethane 1.2 MBID propane MB/O of 919 mix wilene propylene ze CEG. 2YADYBESHO.T) + (ZA 74} 42} 3HS}0.40) INI DEX (taliczed page numbers are the primary references) Absorber 49, 509, 137 Absorption 49, ff, 137 ‘Adsorption 137 Alky (See alkylate) Alkylate 599, 95ff Alkylation 35, 44, 52, $5, 597, 81, 101, 120 Avomatics 36f, 38, 40, 66fF, 74, 84, 104, 107,113, 115, 12397 Aromatics concentrate 123 Asphalt 10, 107° ‘Asphaltene 107 Batch sit 13 Benzene 37, 71, 12347 Benzene rafinate. (See raffinate) BI plant See Butane Isomerization) boiling poit. (See boiling temperature) boiting range. (See boiling temperature) Boiling temperature 47,26, 38, 40, 55 bonds 324, 36, 37 branch 34 British Thermal Unit. (See BTU) BTU 27g BIX37, 71, 1247 Bubble caps 76, 2/ Bulles 56 Butadiene 134 Butane 6, 34, 44, 49, 50, 53f, 70, tt, 113, 1200, 127, 130, 13697 Butane Isomerization 91, 1204 Buiylene 36, 44, 49, 55, 59ff, 101, 131 bon 32, 37, 40, 70, 107, 128 Carbon dionide 424, 11611, 127 Catalyst 399, 44, 46, 59, 69, 70ff,81, 8217, 101, 113, 120 Caustic soda 62 Cavern 56, Cetane number 1044 Chiller 609° Claus unit 178 Coke, 40, 41, 42, 70, 76, 114 sponge 79 needle 79 drum 7697 Coking 747° ‘Compression ratio 9247 Condensate 135/7 Condenser 13 Cracker, 130 cat 23, 39fF, 81, 114 thermal 43, 67, 75/7, 131 Cracking 13, 26,f 39ff, 74, 83 Crude of, 37, 26, 39, 101, 109, 111, 1354/6 sweet JO sour 10 Cryogenic 137 Cutpoints 6, 20, 22, 43 ‘Curbacks 107, 110 Cutter steck 177 Cycle oil a3, 44, 45,74 Cyclohexane 35, 37 Cyclopenane 35 Cylinder sop 187158 / Index DEA. (See diethanolamine) Desulfurization 1/1 Diesel 10347 Diesel fuel 1037 Diethanolamine 18/7 Distillate, 43, 74, 81, 84, 114, 127 fuel 43, 103ff Distillation curve 4, 6, 10 Distilling 134, 26, 44, 46, 63 Di-olefin 134 Downeomer 18 4, 26, 28 Edelaneau 123 Effective cut point 22 Emulsion 107 End point 2, 43, E.P. (See end point) Ethane 33, 37, 44, 49, 51, 53, 113, 127, 1B0rr, 1367 Ethylene 36, 44, 49, 55, 1307 Extract [24 Fat oil 49, SOft Flare 56 Flash chamber 75/f Flesh point 05, 111 Flasher, 23, 24ff, 39, 46, 49, 74, 107 tops 307, 39 bottoms 30ff, 74, 107, 111, 112 Fractionator 40, 42ff, 46, 62, 76, 83, 121 Fractions 6 Fumace 16, 131 Fumace Oil 101, 10347 Gain 45 Gas olf, 6, 44, 81, 83, 123, 130 catcracked 43, 46,74, 83, 101, 104, 111 coker 78, 83 straight run 39) Gas plant 44, 4997, 70, 1367 Gasoline, 6, 10, 43, 44, 2, 53, 66,75, 81, a6ff, 101, 124 cat cracked 43, 46, 954 ‘coker 74ff, 97 hydrocracked 83, 9Stf straight run 23, 39, 95ff, 122 thermal cracked 78, 95fT Gasoline blending 71, 86 9517 Gravities, Af, 23, 31, 35, 38, 45 APLOF specific 9f Hydrocrackate 83 Hydrocracking 44, 55, 81ff, 101, 114, 120, Hydroftouric acid 59 Hydrogen32, 36, 40, 44, 49, 557 70, 74, 81, 82ff, 107, 109, 1130, 128 Hydrogen concentrate 56 Hydrogen sulfide 113, 1177 Hydrogenation 83 Hydrotreating 23, 44, 95, 1134 ABP (See intial boiling point Initial boiling point 20/7 Iorbutane 34, 44, $2,.53, SOFT, 81, 90ff, 120 Isomerization 1207 Tsopentane 34, 121 Iso-paraffin 34 Jet fuel 83, 84, 114, 115 dogs 56 Kerosene 6, 7, 23, 83, 101, 104, 105, 123, Knocking 917 Lean oil 49, SOff, 137 Light ends 23, 44, 55, LPG 53, 63, 105 MC cutback 110 Metals 173 ‘Methanation 116 Methane 33, 37, 40, 44, 49, 55f, 113, 115, MON (See motor cetane number) Motor gasoline (See gasoline) Motor octane number 94/7 ee Naphtha 6, 23,50, 66ff,78, 101, 105, 110, 130 Naphthene 35, 38, 40, 666,74, 113, 123 latural gas 127, 13597 Natural gas liquids 13597 Natural gasoline 13597 NGL 13597 Nitrogen 1/3, Number 2 fuel See distillate fel) Octane $1, 63, 66, 70, 71, 86, 9197, 97 Olefin 36f7 40, 44, 49, 59, 63, 74, 113, 120, 123, Overhead 23 Oxygen 32, 109, 118, 127 Paraffin 34, 36, 38, 49, 55, 664,74, 104, 123) Pentane 34, 121 Platinum 65, 120 Pour point 05 PONA 142 Precursor 84 Propane 34. 44, 49, $0,539, 113, 120, 127, 130ff, 136ff Propylene 36, 4, 49,55, sor, 13097, 1329p Ratfinate 124, 131 Raw make 138 RC eutback 110 Reaction chamber 40, 74 Reactor 46, 60ff, 69, 71, 82, 113, 114 Reboil 13g, 49 Rectified absorber 49, Sor Refinery fuel $4, 55, 63, 118, 127 Reflux 18ff, 49 Reformate 70, 95¢F Reformer, 44, 83, 101, 114, 120 cat Off. 78, 81 steam methane $6, 1/596 Index 1159 Regeestor 0, 417 Reid 88 oe eid Vapor Pressure 7 Reser Octane Numb 93, 121 Resienes tine 6 Residual fal 2,74, 75,105,111, 114 sie, 640, 7478 14 sg ran 39 ROW (er Reseach Octne Numer VP (Se Reid Vapor ree) Salt dome sor Saturates 49 Shrinkage 59 Side-draws 18 ‘Smoke point 115, 123 SMR (See reformer, steam methane) Softening aoint 107 Sponge oil 49, 5147 Steam methane reformer (See reformer, steam methane) Sulfur 10, 32, 111, 113, 11760 Sulfur dioxide 11747. 124 Sulfuric acia Soup Tail ends 21, 49 Tall gas 178) Tetraethyl lead 86, 9677 ‘Thermal cracking (See eracking, thermal) Toluene 37,71, 1234 Trays 16, 21 fuel (See jet fuel) Vacuum Mashing 267 Valence 325, 36 Vapor lock aaj Vapor pressure 63, 86, 8877 Viscosity 31, 38, 117 Water 31, 10, 1150f Xylene 37, 71, 12397