UOp INSPECTION TRAINING MANUAL Volume II TRAIN YOUR REFINERY INSPECTORS LIMITED DISTRIBUTION This material is UOP technical information of a confidential nature for use only by personnel within your organization requiring the information. The material shall not be reproduced in any manner or distributed for any purpose whatsoever except by written permission of UOP and except as authorized under agreements with UOP.THIS MANUAL IS INTENDED SOLELY FOR TRAINING PURPOSES AND Is” TO BE USED ONLY IN CONJUNCTION WITH AN INSTRUCTOR-BASED TRAINING PROGRAM. IT IS NOT INTENDED AS A SUBSTITUTE FOR A SPECIFIC OPERATING MANUAL RELATING TO THE OPERATION OF A UOP PROCESS UNIT OR AS THE BASIS FOR DEVELOPMENT OF SUCH A SPECIFIC MANUAL.Vil. VII. Xl. Xl. XIll. XIV. XV. TABLE OF CONTENTS VOLUME Il NATURE OF PETROLEUM UNITS OF MEASUREMENT CRUDE UNIT VACUUM UNIT RESIDUAL OIL PROCESSING HYDROTREATING PLATFORMING FLUID CATALYTIC CRACKING PROCESS VAPOR RECOVERY SYSTEMS AMINE TREATING UNIT VISBREAKING HF ALKYLATION SULFUR MANAGEMENT BOILERS REFRACTORYNATURE OF PETROLEUM 85040PETROLEUM The word petroleum is derived from two Latin words, “petra” (rock) and “oleum” (oil). The early pioneers of the oil industry frequently used the term “rock oil.” The use of this term, however, has long since been replaced with the derivative “petroleum” which, in turn, is simply referred to as “oil”. Petroleum in its natural, unrefined (crude) state, varies in appearance from a whitish, clear liquid of very light consistency through brownish or greenish color all the way to a black, heavy asphaltic, almost solid material. Petroleum is not an element or compound. It is a complex mixture of related chemical compounds called hydrocarbons. Hydrocarbons are so named because they mainly consist of the elements hydrogen and carbon. In addition, small variable amounts (normally less than 5%) of combined sulfur, oxygen, nitrogen, and metals are present in crude oil. HYDROCARBONS Hydrocarbons are the basic and most important group (series) of organic compounds in crude oil. Each series of hydrocarbons represents a specific type of compound and is reviewed later in this section. Series Type of Compound Normal Paraffins Straight saturated carbon chains lsoparaffins Branched saturated carbon chains Olefins Straight and branched unsaturated carbon chains with double bond(s) Acetylenes Straight and branched unsaturated carbon chains with triple bond(s) 85040 1-2Naphthenes Saturated cyclic hydrocarbons containing one or more rings Aromatics Unsaturated cyclic hydrocarbons containing one or more rings TYPES OF PETROLEUM (Crude Oil) The diversity of the hydrocarbon mixtures and variance of the combined trace elements determine the appearance, consistency, and type of crude oil. Initially, to differentiate the quality and potential products among the various crude oils, the oil industry used the concept of the “base” of a crude oil. The base method categorizes, after atmospheric distillation, the cooled residual wax content of crude oil into three main types; paraffin base (wax bearing), asphaltic base (wax free), and mixed or intermediate base (contains both). This method was later enlarged to include the hybrid “naphthenic crude”. The cooled residue of naphthenic crude is predominantly asphaltic with small amounts of paraffin wax. Although still widely used in the industry, the base method - was superseded by a classification index developed by Lane and Garton of the U.S. Bureau of Mines which uses as a basis the specific gravity of “key fractions” produced from a standardized method of fractionation. U.S. Bureau of Mines periodically publishes the results of its analysis so that the method and information are kept up to date. Types of petroleum (crude oil), in general, are associated with geographical locations of their source. For example, Saudi Arabian crude oil is classified as a mixed base crude whereas, Pennsylvanian crude might be classified as a paraffin base crude. 85040 1-3 4CHEMISTRY OF PETROLEUM Atom An atom is the smallest indivisible part of matter that is able to retain all the chemical properties of the element. It is also the smallest unit of matter that can take part ina chemical reaction. Molecule A molecule is the smallest particle of matter which exists independently and which retains all the properties of the compound. It contains atoms bonded together in a fixed whole number ratio. For example: Oxygen Oo Nitrogen No Carbon dioxide CO2 Sulfur Sg Hydrogen Ho Water H20 The subscript number represents the number of atoms of each element of the molecule. Chemical Compound A chemical compound is the result of chemically combining the atoms of two or more elements. The elements are combined in definite weight ratios, and the number of atoms of each element which are present in a molecule directly determine these ratios. An example of a chemically combined compound is common table salt NaCl. In this case, an atom of sodium (Na) has combined with an atom of chlorine (Cl) to form a molecule of sodium chloride (NaCl). Mixture A mixture is the combination of two or more substances in which each substance retains its individual properties and can be separated by physical means. A mixture has no unique set of properties, it possesses the properties of the substances of which it is composed. Air is an example of a gaseous mixture; it is composed principally of 85040 dG Yinitrogen, oxygen, argon, water vapor, and carbon dioxide each of which displays its own unique properties. Chemical Formula A chemical formula is the representation of a chemical compound using the element symbols to show exactly the number of atoms of each element combined in a molecule of that compound. This representation is generally shown either as an empirical formula or as a structural formula. An empirical formula is the simplest representation of a compound. It does not indicate the exact position of each atom; it merely states the elements and number of atoms of each element. A structural formula indicates the location of each atom in a graphic or symbolic format. Valence Valence refers to the combining power of an atom. Every atom of each element has a specific number of electrons, or electron spaces, available to be used in the chemical combination of a compound. We refer to these as “bonds.” For a compound to be stable, each of its bonds must be satisfied or more commonly referenced as being “saturated”. An example of this is methane, which has one (1) carbon atom and four (4) hydrogen atoms. The valence of carbon is four (4) and the valence of hydrogen is one (1). Therefore, it takes four hydrogen atoms to satisfy the carbon atom, and in doing so each hydrogen atom is also satisfied. In this instance we can state that methane is stabilized because it is a saturated compound. Atomic Weight The weight of an atom of hydrogen is 1.67 x 10-24 g, that of an atom of carbon is 1.99 x 10-23 g, and that of an atom of oxygen is 2.66 x 10-23 g. The use of such extremely small numbers is not practical, and as atoms are so minute it is difficult to compare them with any familiar object for comparable ratios. It is possible, however, to compare atoms with each other based on a predefined unit of weight. This unit is defined as atomic mass unit - amu. Using atomic mass units, the relative atomic weights of hydrogen, carbon, and oxygen are 1.0079 amu, 12.011 amu, and 15.999 amu, respectively. 85040 1-5 YiThese relative atomic weights are proportional to the actual weights of the atoms. One (1) atomic mass unit is equivalent to approximately 1.661 x 10-24 g. It requires about 602,200,000,000,000,000,000,000 (6.022 x 1023) amu to equal 1g. Molecular Weight The molecular weight of a substance is the sum of the weights of the atoms shown in the formula. The compound water, for example, has the chemical formula of H20 - this represents two (2) atoms of hydrogen and one (1) atom of oxygen. Based on the above definition of atomic weights, the molecular weight of water is the weight of two (2) hydrogen atoms (1.00079 x 2) plus the weight of one oxygen atom (15.999); this equals 18.00058 amu. In reality, water is usually referred to as having a molecular weight of 18 amu. In most industrial calculations, molecular weights are expressed to the nearest hundredth amu. Radical A radical is an atom or group of atoms that has one or more unpaired bonds (electrons). Because it is not saturated, it is very unstable and will readily react with other radicals to form covalent bonds. A covalent bond occurs when different atoms share each others bonds to attain the desired stable condition. In generalized chemical formulae, a hydrocarbon radical is denoted as R’. Radicals are differentiated by the superscript prime indicator (R’, R”). Normal Paraffins (Alkanes) A normal paraffin is a compound composed of carbon and hydrogen atoms with its carbon atoms linked together to form a “straight chain”. Each bond of the carbon atom is “saturated” by another carbon atom or a hydrogen atom and, therefore, the compound is stable. In the oil refining industry, normal paraffins are usually found in the range of one (1) to twenty-five (25) carbon atoms. As the number of carbon atoms increases, the compound becomes heavier; above seventeen (17) carbon atoms, the compound is solid at room temperature and atmospheric pressure. 85040 i-6 tyrTo distinguish a normal paraffin, the name and empirical formula are prefixed by the lower case letter “n.” In addition, the name of a normal paraffin ends in “ane” which is synonymous with the correct chemical terminology for normal paraffins which is “alkanes”. Examples representing the empirical and graphic structural formulae of normal paraffins follow on the next page. 85040 |-7 JMethane Ethane Propane Butane Pentane Empirical Formula Structural Formula 1 CH, HCH H I H—C—C—H CoHe | H H nh H—C—C—C—H C3Hg i | H H H maT H—C—-C—C—C—H C4Hi0 I ot Jo 4 H H H H nae H—C—C—C—C—C—H Cs5Hi2 ro tf -— yf H H H HH 85040 JHexane CeHi14 T =-o-2 a O- | | oOo- | | x isoparaffins (Alkanes) Compounds that have the same empirical composition but different structural formulae are called isomers. An isoparatfin has the same composition as a normal paraffin but a different structure and, therefore, is an isomer. For example, the compounds normal butane and isobutane both contain four (4) carbon atoms and ten (10) hydrogen atoms but, because of the different structures, they have different properties even though their molecular weights remain the same. lsoparaffins have “branched” carbon chains — carbon atoms linked together in a non-linear format. As the number of carbon atoms increases, so does the possible combination of different branched structures. Isohexane, for example, can exist in five different structures all with the same empirical : formula and, as described above, each will have different properties. The empirical formula for an isoparaffin should always be prefixed by the lowercase letter “i”. The following represents the different structures of normal butane and isobutane and two (2) of the different properties, i.e., specific gravities and boiling points: i Lid 1. Normal Butane C4H10 Specific Gravity 0.584 H Y 1 1 1 H Boiling Point -0.6°C (31.1°F) OOOH i H—-C-——-H 2. Isobutane i-C4H10 Specific Gravity 0.563 H Boiling Point -11.7°C (10.9°F) | H—O—C—C—H | | | H 85040 1-9*This same structured isomerization occurs in the other series, for example: Lo H—C=—-C—C—H Isobutene i-C4Hg | Specific Gravity 0.6002 H Boiling Point -6.9°C (19.6°F) no H Olefins (Alkenes & Alkadienes) Olefins are similar in structure to normal and isoparaffins except that one pair of carbon . atoms is linked together by a double bond (mono-olefin) instead of a single bond. Because of the double bond linkage, these compounds are unsaturated and, therefore, unstable. In this unsaturated state, it is easier to cause olefins to undergo chemical changes than saturated paraffins. When an olefin contains more than one double bond, it is classified as a polyalkene, a term that includes alkadienes (di-olefins). Another type of olefin which has two (2) carbon atoms linked together by three (3) bonds is classified in a series called alkynes which is usually referred to as the acetylene series. Some compounds contain both double and triple bonds; these are classified as alkenynes; the simplest example is a gas named butenyne or vinylacetylene. For ease of classification, in general, the names of mono-olefins end with “ene”, di- olefins end with “diene”, and alkynes end with “yne”. A representative structure of each of these olefins is shown below. ian 1. Propylene C3H6 OH H 85040 1-10H H H 2. Butadiene CaHe | | | | H—C==C—C==C—-H i 3. Propyne C3H4 eo H Cycloparaffins (Cycloalkanes) Cycloparaffin compounds are sometimes known as “naphthenes” or “cyclics”. These - are saturated, stable compounds which usually have five (5) or six (6) carbon atoms arranged in a ring structure. Rings of seven (7) or eight (8) carbon atoms are not very stable and are seldom found in crude oil. To differentiate these compounds from normal paraffins, the parent name of the compound is prefixed with “cyclo” such as, cyclopentane (Cs5Hi9) and cyclohexane (CgHi2). The structural formulae of these compounds are shown below: Cyclopentane (C5H10) Simplified Structure aN A C WNL HT [-H H—C———C—-H , | a Cyclohexane (CgH 12) Simplified Structure 85040 =H H H ocO oH ee HON UM ae Ss HH Cyclopentane and cyclohexane are found in crude oil in large amounts, particularly in naphthenic crudes. These cycloparaffins, when fractionated from the crude oil, are valuable because they can be converted to high octane gasoline stock. This stock is then used to make premium grade gasoline. Cycloparaftfins may also have branched chains; formed by radical(s) linking with one or _ more carbon atoms of the ring structure. Simplified ring structure examples are shown below: Methylcyclopentane (CgH 12) Methylcyclohexane (C7H14) In addition, ring compounds can combine with each other to form larger, more complex cycloparaffins. Aromatic Hydrocarbons The name aromatic is derived from the characteristic odors that these compounds usually have. The “parent” aromatic is benzene (CgH6) because all the aromatics in this series are derivatives of benzene. The “benzene ring” has six (6) carbon atoms linked together by three (3) single bonds and three (3) double bonds. Aromatics are 85040 I-12 Yiunsaturated, unstable compounds used extensively in the oil refining industry for the production of high octane automotive and aviation gasolines and the manufacture of chemicals. The simplified ring structures of benzene and some of its derivatives follow. The circle inside the hexagon symbol denotes three (3) alternate double bonds and is widely used in the industry to symbolize the benzene ring: 1. Benzene CgHe O 2. Methylbenzene C7He CH (Toluene) or ° 3. Ethylbenzene CsHi0 CO” H Pa 4. 1,4-Dimethylbenzene CsHi0 CH, (para-Xylene) CH, $5040. °5. 1,2,4-Trimethylbenzene CgH102 CH, (Pseudocumene) CH, CH3 6. lsopropylbenzene CoHi02 CH, (Cumene) CH3 CH, Like the cycloparaffins, aromatic ring compounds can combine with each other to form larger, more complex aromatic compounds. An example of this is naphthalene (C10Hs), the structure of which is shown below: 85040 1-14UNITS OF MEASUREMENT ‘65040 4TIME Refinery operations are usually based on hourly rates of flow, energy consumption, etc. For industry statistical reports, refinery crude runs are generally reported as barrels per day. Various accounting systems within a particular organization will refer to weekly or monthly basis. Hourly records may be run on the 12-hour clock basis, wherein midnight to noon times are reported as AM (e.g., 6:00 AM), and noon to midnight are PM times (e.g., 6:00 PM). The 24-hour system is finding worldwide favor, particularly in the transportation industries and in the manufacturing industries. This system eliminates possible confusion between AM and PM. In this system, the day ends at midnight (2400 hrs.). Noon is 1200 hrs. In the morning, 6:00 AM is 0600 hrs. and, in the evening, 6:00 PM is 1800 hrs. Clocks and timing equipment for the 24-hour system are widely available from commercial suppliers. TEMPERATURE The two most common temperature scales are the Fahrenheit and Centigrade scales. The Fahrenheit scale is older and based on 0° being the temperature of an equal weight of snow and common salt. From this point, the freezing point of water is 32° and the boiling point is 212°. The Centigrade scale is simpler in concept. The span between freezing point and boiling point of water is 100°. Therefore, the freezing point of water = o0°C and the boiling point = 100°C. Both systems are based on temperature measurements at one (1) atmosphere pressure (760 mmHg). The Fahrenheit scale is the one on which many of the petroleum industry’s standards and correlations have been based, principally because the preponderance of development has been done in U.S. and U.K. laboratories. The Centigrade scale is coming to use more as international use of the metric system increases. Studies of the fundamental principles of chemistry and physics have evolved the concept of an Absolute Zero. This is an extrapolated, theoretical point which has never been actually measured, but it does serve to correlate measurements and calculations a 85040 -2 Yiof phenomena encountered in chemical process design and engineering and, therefore, in the petroleum industry. This Absolute Zero, having been extrapolated, has two different values relative to the Fahrenheit and Centigrade scales. For the Fahrenheit scale, Absolute Zero = -460°F. For the Centigrade scale, Absolute Zero = -273°C. The Absolute Scales are named after the engineers (Glaswegians!) who first enunciated them. Accordingly, we have the Rankine scale ("R) devised by W. S. M. Rankine using the Fahrenheit scale and the Kelvin scale ("K) derived by William Thompson, Lord Kelvin. For comparison: O°R = 0°K = -460°F = - 273°C Water freezes at 492°R = 273°K = 32°F = 0°C Water boils at 672°R = 373°K = 212°F = 100°C Conversion formulae: Centigrade to Fahrenheit: 9/5(°C) +32 = °F Fahrenheit to Centigrade: 5/9(°F - 32) = °C Centigrade to Kelvin: °C +273 = °K Fahrenheit to Renkins: °F +460 = °R PRESSURE Pressure is the measure of the application of a force. In common usage, it is usually expressed as the force of a given mass over a specified area. The mass exerts its force due to the acceleration of gravity. Accordingly, we have units such as pounds per square inch or kilograms per square centimeter. “Standard” pressure is taken as the force exerted by the natural column of the atmosphere and is equal to 14.7 pounds per square inch or 1.033 kilograms per square centimeter. Normal atmospheric pressure will support a column of mercury 760mm (29.9 inches) high. This equals 33.6 feet of water. In most refineries, there are one or 85040 li-3 Yimore mercury barometers of standard configuration which are used for calibrating pressure measuring devices. A pressure measuring device is calibrated to measure a pressure relative to atmospheric pressure. To determine an absolute pressure, the prevailing atmospheric pressure value must be added to any pressure gauge reading. Pressure may, in some cases, be less than atmospheric. The term vacuum describes this situation. Vacuum pumps are capable of withdrawing air or other vapor from a system to create sub- atmospheric pressure. Many refinery applications require this be done. Following are some pressure measurement units in common oil refinery usage and some conversions. 1 kg/em2 = 14.22 Ib/in2 (psi) 760mm Hg = 14.7 Ib/in2 (psi) = 1 Standard Atmosphere 760mm Hg = 29.9 inches of mercury = 33.6 ft. of water Absolute Pressure = Gauge Pressure + Atmospheric Pressure DENSITY AND SPECIFIC GRAVITY Density is defined as the weight of a substance per unit volume. In the metric system, the cubic centimeter is the unit of volume and the gram the unit of weight. If a cubic centimeter each of iron, wood, lead, and water are weighed, they will be found to have widely different weights. A term is necessary to denote the weight of a unit-volume ofa substance. A cubic centimeter of water weighs 1 gram, so the density may also be expressed as 1 gram per cc. The weight of a large body may be calculated if the density of the material is known. Find the volume in cubic centimeters and multiply by the density in grams per cubic centimeter, and the result will be the weight of the object. 85040 Il-4The density of some solids in grams per cc: The density of some liquids: The density of some gases: 8 5040 Gold Mercury Lead Iron Aluminum Wood Ice *varies with species Sulfuric Acid Sea Water Fresh Water Kerosine Gasoline Air Oxygen Nitrogen Carbon Monoxide Hydrogen gice 19.3 13.5 11.4 7.7 2.6 0.8" 0.9 g/cc 2.00 1.03 1.00 0.80 0.75 g/cc 0.0012 0.00134 0.00118 0.00117 0.000085 N-5Specific gravity is the ratio between the weight of a body and the weight of an equal volume of water. For example, a cubic centimeter of a certain type of iron weighs 7.7 times as much as a cubic centimeter of water; the cubic centimeter of iron will weigh 1 x 7.7 =7.7 grams. The weight of any object may be found by multiplying the volume by the specific gravity by the density of water. Note that the specific gravity of water is 1.00 and that water weighs 1.00 g per cubic centimeter. As a result, the specific gravity any object is numerically equal to its density in grams per cubic centimeter. Densities of gases for practical purpose are compared with air at atmospheric pressure and 60°F (15.6°C) instead of with water, as in the case of liquids and solids. With air as a comparative reference, the “specific gravities” of the gases listed above are: Air 1.00 Oxygen 1.120 Nitrogen 0.983 Carbon Monoxide 0.975 Hydrogen 0.071 Baumé gravity is a scale using salt water as a reference instead of fresh water. It is used in refineries only in reference to acids and alkalies and that because the suppliers of these commodities use the Baumé scale. Degree Baumé = 140 Specific Gravity API gravity is used in most other instances in the petroleum industry. The API gravity uses water as a standard and calls its API gravity 10°. As the specific gravity increases, the API gravity decreases. Crude oil with a 42° API gravity has an actual specific gravity of 0.82. American crude oils commonly run from 0.768 to 0.996 specific gravity, which would be from 52.6° to 10.5° on the API scale. 85040 ll-6API gravity readings are standardized at a temperature of 60°F and, if taken at any other temperature, they must be converted to 60°F to be accurate. Tables for this conversion are found in the bulletin “API Standard 2500” and in many engineering handbooks. The formulas for conversions are as follows: 141.5 Degrees API = —————~>___ - 131.5 9 Specific Gravity sg: . 141.5 Specific Gravity = ————~_ Pecitic Gravity API+131.5 VOLUME AND MASS FLOW Material flows through oil refineries are described in terms of volume and in terms of | mass. The industry evolved in the U.S. in terms of barrels of crude oil and, from that, barrels of various products - gasoline, kerosine, etc. In other parts of the world, flows came be to measured in terms of mass flow, principally in terms of tonnes - usually referred to as metric tons (1 metric ton = 1000 kilograms) and cubic meters. For design engineering work and all calculations dealing with separations and conversions, the fundamental units are mass flow units (pounds or kilograms). Liquids are described as barrels per day, gallons per minute, cubic meters per hour, liters per hour. Vapors are described as cubic feet per second (ft3/sec), millions of standard cubic feet per day, normal cubic meters per hour. Some equivalents are: 6.29 barrels (bbl) 1 cubic meter (M3) 35.3 cubic feet (ft?) = 1 cubic meter (M3) 3.79 liters (I) 1 U.S. Gallon (gal) 28.3 liters (I) = 1ft3 85040 ll-7 tyrENERGY Refinery energy usage is generally described in terms of heat units and electrical units. The common heat units are the British Thermal Unit (BTU) and the calorie (cal.). A BTU is the energy required to raise the temperature of 1 pound of water 1°F. A gram-calorie is the energy required to raise the temperature of 1 gram of water 1°C. These units are the ones by which a fuel energy content is measured in a calorimeter. In view of the large energy usage in a refinery, we more commonly use millions of BTU’s (MMBTU/hr) and millions of kilograms calories (MMKCAL/hr). A major energy use in a refinery is raising temperatures, and this energy is mostly supplied by burning fuel in a tired heater. As a result, heaters and heat exchangers are described in terms of BTU’s and K-calories. Pumps and compressors are driven by electric motors and, in some cases, by steam - turbines. These devices are described in terms of electrical energy - the kilowatt hour - or kilowatt. As a carryover from electric power plant practice, fired heaters and other heat transfer equipment are rated in kilowatts or even megawatts. 85040 It-8CRUDE UNIT i $5040, WtCRUDE DISTILLATION The discussion of crude column operation that follows is of a somewhat general nature. Operating experience for the unit will decide the best choice of procedure where alternative operations are possible. Crude can be separated into gasoline, kerosine, diesel oil, gas oil, and other products by distillation at atmospheric pressure. Distillation is an operation in which vapors rising through fractionating decks in a tower are intimately contacted with liquid descending across the decks so that higher boiling components are condensed and concentrate at the bottom of the tower, while the lighter ones are concentrated at the top or pass overhead. Crude is generally pumped to the unit directly from a storage tank, and it is important that charge tanks be drained completely free from water before charging to the unit. If water is entrained in the charge, it will vaporize in the exchangers and heater and cause a high pressure drop through that equipment. If a slug of water should be - charged to the unit, the quantity of steam generated by its vaporization is so much greater than the quantity of vapor obtained from the same volume of oil that the decks in the fractionating column could be damaged. Water expands in volume 1600 times upon vaporization at 100°C at atmospheric pressure. HEAT EXCHANGE In order to reduce the cost of operating a crude unit, as much heat as possible is recovered from the hot streams by heat exchanging them with the cold crude charge. The number of heat exchangers within the crude unit that cross heat exchange with other units will vary with unit design. A record should be kept of heat exchanger outlet temperatures so that fouling can be detected and possibly corrected before the capacity of the unit is affected. Desalted crude is heat exchanged against whatever other heat sources are available to recover maximum heat before crude is charged to the heater, which ultimately supplies all the heat required for operation of the crude unit. Heat input is controlled by having the heater transfer temperature reset flow of fuel to the burners. The heater transfer temperature is merely a convenient control, and the actual temperature, which has no great significance, will vary from 585°F (325°C) to as 85040 il-2 Yihigh as 806°F (430°C), depending on the type of crude and the pressure at the bottom of the fractionating tower. It is noteworthy that, if the quantity of gasoline and kerosine in a crude is reduced, the transfer temperature required for the same operation will be increased even though the “lift” is less. CRUDE FLASHING Crude entering the flash zone of the fractionating column flashes into the vapor, which rises up the column, and the liquid residue, which drops downward. This flash is a very rough separation. The vapors contain appreciable quantities of heavy ends which must be rejected downward into reduced crude, while the liquid contains lighter products, which must be stripped out. FRACTIONATION Flashed vapors rise up the fractionating column counter-currently to the internal reflux flowing down the column. The lightest product, which is generally gasoline, passes overhead and is condensed in the overhead receiver. (Should the crude contain any non-condensable gas, it will leave the receiver as a gas and can be recovered by other equipment, which should be operated to obtain the minimum flash zone pressure.) The temperature at the top of the fractionator is a good measure of the end point of the gasoline, and this temperature is controlled by returning some of the condensed gasoline as reflux to the top of the column. Increasing the reflux rate lowers the top temperature and results in the net overhead product having a lower end point. The loss in net overhead product must be removed on the next lower draw tray. This will decrease the initial boiling point of material from this tray. Increasing the heater transfer temperature increases the heat input and demands more reflux to maintain the same top temperature. External! reflux which is returned to the top of the fractionator passes downward against the rising vapors. Lighter components of the reflux are revaporized and return to the top of the column while heavier components in the rising vapors are condensed and return down the column. There is an internal reflux stream flowing from the top of the 85040 ill-3 Yifractionator all the way back to the flash zone and becoming progressively heavier as it descends. Products heavier than the net overhead are obtained by withdrawing portions of the internal reflux stream. The end point of a side-cut will depend on the quantity withdrawn. If the side-cut withdrawal rate is increased, the extra product is material which was formerly flowing down the fractionator as internal reflux. Since the internal reflux below the drawoff is reduced, heavier vapors can now rise to that point and result in a heavier product. Changing the drawoff rate is the manner in which side-cuts are kept on end point specifications. Temperature of the drawoff decks is a fair indication of the end point of the product drawn at that point. An experienced operator may vary his drawoff rate to hold a constant deck temperature and, therefore, a specification product. The degree of fractionation between cuts is generally judged by measuring the number of degrees centigrade between the 95% point of the lighter product and the 5% point of - the heavier product. (Some people use IBP and FBP, but the IBP varies with stripping.) The gap between gasoline and kerosine should be approximately 41°F (5°C); between kerosine and light gas oil, 37°F (3°C) is normal. Fractionation can be improved by increasing the reflux in the fractionator, which is done by raising the transfer temperature. There may be occasions when the internal reflux necessary to achieve satisfactory fractionation between the heavier products is so great that, if it was supplied from the top of the fractionator, the upper decks would flood. An “Intermediate Circulating Reflux” solves this problem. Some internal reflux is withdrawn, pumped through a cooler or exchanger, and returned colder a few decks higher in the column. This cold oil return condenses extra vapors to liquid and increases the internal reflux below that point. If improved fractionation between light and heavy gas oil is desired, the heater transfer temperature is increased, which would cause the top reflux to increase, then restore the top reflux to its former rate by increasing the circulating reflux rate. It is to be noted that even though the heater transfer temperature is increased, the extra heat is recovered by exchange with crude and, as a result, the heater duty will only increase slightly. 85040 Ie-4Sometimes a fractionator will be “pulled dry,” that is, the rate at which a product is being withdrawn is greater than the quantity of internal reflux in the fractionator. All internal reflux then flows to the stripper, the decks below the drawoff run dry and, therefore, no fractionation takes place. At the same time, there is insufficient material to maintain the level in the stripper, and the product pump will tend to lose suction. It is necessary, therefore, to either lower the product withdrawal rate or increase internal reflux in the tower by raising the transfer temperature or by reducing the rate at which the next lightest product is being withdrawn. PRODUCT STRIPPING The flashed residue in the bottom of the fractionator and the side-cut products have been in contact with lighter boiling vapors. These vapors must be removed to meet flash point specifications and to drive the light ends into lighter and more valuable products. Steam, usually superheated steam, is used to strip these light ends. - Generally, only enough steam is used to meet a flash point specification. While a further increase in the quantity of steam may raise the IBP of the product slightly, the only way to substantially increase the IBP of one product is to increase the yield of the next lighter product. (Provided, of course, the fractionator has enough internal reflux to make a good separation.) All stripping steam is condensed in the overhead receiver and must be drained off. Refluxing water will upset the fractionator. If the end point of the overhead product is very low, water may not pass overhead and will accumulate on the upper decks and cause the tower to flood. PRODUCT DISPOSAL All products are cooled before being sent to storage. Light products should be below 140°F (60°C) to reduce vapor losses in storage, but heavier products need not be as cold. If a product is being charged to another unit, there may be an advantage in sending it out hot. A product must never leave a unit at over 212°F (100°C) if there is any possibility of it entering a tank with water bottoms. The hot oil could readily boil the water and blow the roof off. | 85040 HI-SDESALTING Most crude oils contain traces of salt which can decompose in the heater to form hydrochloric acid and cause corrosion of the fractionator overhead equipment. In order to remove the salt, water is injected into the partially preheated crude and the stream is thoroughly mixed so that the water extracts practically all the salt from the oil. The mixture of oil and water is separated in a desalter, which is a large vessel in which the water settles out of the oil, a process which may be accelerated by the addition of chemicals or by electrical devices. The salt-laden water is automatically drained from the bottom of the desalter. If the oil entering the desalter is not hot enough, it may be too viscous to permit proper mixing and complete separation of the water and oil; some water, therefore, may be carried into the fractionator. On the other hand, if the oil is too hot, some vaporization may occur and the resulting turbulence can result in improper separation of oil and - water. The desalter temperature is, therefore, quite critical and normally a bypass is provided around at least one of the exchangers to that the temperature can be controlled. The optimum temperature depends upon the desalter pressure and the quantity of light material in the crude, but is normally about 248°F (120°C) + 50°F (10°C), being lower for low pressures and light crudes. The average water injection rate is 5% of the charge. Regular laboratory analyses will monitor the desalter performance, and the desalted crude should normally not contain more than two pounds of salt per 1,000 barrels of feed. Good desalter control is indicated by the chloride content of the overhead receiver water. This should be in the order of 10-30 ppm chlorides. If the desalter operation appears to be satisfactory but the chloride content in the overhead receiver water is greater than 30 ppm, then caustic should be injected at the rate of 1-3 Ibs. per 1,000 barrels of charge to reduce the chloride content to the range of 10-30 ppm. Salting out will occur below 10 and severe corrosion above 30 ppm. Another controlling factor on the overhead receiver water is pH. This should be controlled between pH 5.5 and 6.5. Ammonia injection into the tower top section can be used as a control for this. 85040 Iil-6 tyr,CRUDE UNIT Corrosion and Control in the Crude Distillation Area Corrosion by acidic water and inorganic salts in crude-distillation condensers is a major problem in petroleum refineries. As refineries become larger and must be kept on- stream continuously to be economically profitable, control of corrosion becomes an essential part of refinery operation. Crudes received at a refinery vary widely in potential corrosivity both because of differences in chemical composition and because of differences in pretreatment at the well and during transportation. Recovery operations using oxygen-containing water or gas, acidizing, solvent dewaxing, stripping with gases containing oxygen, adding corrosion inhibitors which increase the amount of water carried in the crude, and aeration during storage and handling can all increase corrosivity, particularly in refinery - condensers. Hydrogen chloride and hydrogen sulfide produced by thermal decomposition of impurities in the crude are the principal offenders, and their corrosivity is increased in the presence of oxygen and water. Hydrogen Chloride Because crudes are generally found in the presence of salt water, the water entrained in crude contains about 3-10% salts, mostly chlorides. Hydrogen chloride is formed when chloride salts, mainly Mg and Ca, are heated to approximately 250°F (121°C) in the presence of water. Although most water is separated from the crude at the wellhead, some water and dissolved salt reach the refinery. In the preheaters, temperatures are high enough to convert these salts to hydrochloric acid, which is the major corrodent in overhead condenser systems. —ooEEOEOEEEEEEEEEEEEEEeee ESS 85040 iNl-7 |Hydrogen Sulfide Most hydrogen sulfide is removed from crude before it reaches the refinery. However, crudes will frequently contain up to 6% (by weight) sulfur in organic sulfur compounds. In preheaters at temperatures above 450°F (232°C), these compounds decompose to form hydrogen sulfide. Both HCI and H2S are formed in other refinery units by thermal or catalytic decomposition in catalytic crackers and cokers, by hydrodechlorination and hydrodesulfurization with hot hydrogen in reformers, hydrodesulfurizers, hydrotreaters and hydrocrackers, and by decomposition of processing catalysts such as aluminum chloride, used in some isomerization and alkylation processes. In all units, HCl, H2S and possibly some volatile organic acids go overhead with the vapor from distillation towers and combine with condensed water to form a strongly acid solution (pH 1-2), particularly corrosive to carbon steel. Oxygen Oxygen accelerates corrosion by HCI and H2S and also minimizes the benefits of some corrosion inhibitors. Air can enter units by leaks in vacuum equipment or dissolved in the crude, in desalter or other wash water, and in distillation and gas stripping steam. Corrosion Controlling Technique The following discussion and Figure Ill-1 are related to controlling corrosion in primary or atmospheric stills. However, the principles involved are applicable to all refinery distillation corrosion problems. Desalting, neutralization, and inhibitor addition can be used alone or in combination to essentially stop corrosion in crude or other unit condensers provided the limitations are recognized and adequate control is exercised. Table Ill-1 summarizes the advantages and disadvantages of the common methods of corrosion control. 85040 il-8Air-free steam condensate, boiler blowdown or fully stripped sour water is preferred for desalting. Ammonia-rich refinery “sour” water from distillation tower condensers, if used for desalting, can cause plugging of distillation towers and condensers with ammonium salts and under-deposit corrosion. Although complete chloride removal is desirable to minimize corrosion in the overhead system of the distillation tower, it appears that chlorides may tend to inhibit high-temperature corrosion by sulfidic compounds. CRUDE NEUTRALIZER INHIBITOR CONDENSER 7 . PROBE WATER PRIMARY > PReHEATER TOWER NAPHTHA PREHEATER TO VACUUM DISTILLATION UOP 1324-2 Figure Ill-1 Typical Crude Distillation Unit 85040 Itl-9 Z|TABLE Ill-1 CORROSION CONTROL METHODS Treatment Advantages Disadvantages Desalting Minimizes HCI evolution Removes a sulfidic-corrosion inhibitor Removes solids May add oxygen May add volatile salts Adds water for salt hydrolysis Neutralizing Minimizes corrosivity Forms chloride salts Minimizes inhibitor usage Deposits chloride salts May add oxygen May stress-corrosion crack copper alloys Water washing Minimizes fouling May form highly corrosive salt Forms emulsions Adds water to product and to reflux May add oxygen Adding corrosion Essentially eliminates May accelerate corrosion at low inhibitors corrosion concentrations Emulsifies at high concentrations Corrosive above 250°F (121°C) at high concentrations 85040 Ill-10Neutralizers To minimize the corrosivity of the overhead condensate, neutralizers are added to contro! pH. Ammonia has been preferred because it is cheap and it is easy to handle as a liquid, gas, or as an aqueous solution. Its salts are very soluble in water and can be readily removed by water washing. In most units, the pH is controlled by manual adjustment of neutralizer feed rate on the basis of spot samples. Dilute ammonium hydroxide (about 10% by weight) is normally recommended by injection to maximize pH control and to minimize the possibility of stress-corrosion cracking of copper alloys. More concentrated NH4OH (28%) has been used, particularly in cold climates where dilute NH4OH freezes. Anhydrous ammonia in gas cylinders is used where pumps are not available. In some units, steam is used to carry the ammonia to the tower overhead. This prevents freezing and disperses the ammonia in the vapor for better utilization and more sensitive control. Two primary dangers in the use of ammonia are the possibilities of salt decomposition, mainly NH4OH and (NHa)2S, and stress-corrosion cracking of copper alloys commonly used in exchanger tubes. In refineries, cracking of copper alloys has occurred where ammonia was added above about pH 9 and in units using anhydrous ammonia, where there was a dead space for ammonia to collect. Ammonium chloride deposits also can induce cracking because they product ammonia in the presence of copper. 2NH4C! + Cu — CuClo + 2NH3 + Ho Deposits of salt can be controlled by using the minimum necessary amount of neutralizer or by injecting air-free water to wash out salt. However, insufficient water could result in more severe corrosion of carbon steel by moderately concentrated NH4ClI solutions above 200°F (93°C). 85040 Wit-11 3Operating the overhead system at pH 4-6 is another method used to minimize salt deposition and corrosion. This method can increase the potential corrosivity of the system for carbon steel. Therefore, to operate at a lower pH, the corrosion inhibitor must be reliable. If the inhibitor is not adequately dispersed to all parts of the system, severe localized corrosion could occur. Also, most inhibitors are active only in a specific pH range close to neutral. Thus, the low pH range approach required very close control. Ammonium sulfide, which can be formed in the system from NH4OH and H2S, reduces NH4CI corrosivity to carbon steel. Corrosion decreases with increased (NH4)oS concentration above a minimum, but is highly dependent on the absence of free sulfur. (NH4)2S solutions can oxidize to elemental sulfur or polysulfides which accelerate corrosion of carbon steel. Thus, while ammonium hydroxide can effectively neutralize acid corrosion, care must be - used in the rate of addition of NH4OH. Too little will not effectively prevent acid corrosion; too much can result in salt deposition and alkaline corrosion. Mono-, di-, and tri-ethanolamines (MEA, DEA, and TEA) morpholine, and diethylamine have also been used as neutralizers. These amines are more expensive than ammonia and can still cause Salt deposition and allow some corrosion of carbon steel. Dilute NaOH solutions can be injected alone or emulsified with an inhibitor, but precautions against caustic embrittlement of carbon steel must be taken. Separate injections of neutralizer and inhibitor are preferred for independent control, but single injections may be used if an existing unit cannot conveniently provide two separate systems. The use of judiciously controlled caustic injection has proven to be an excellent method of corrosion control in the crude unit. 85040 WW-12UOP GUIDELINES FOR CAUSTIC INJECTION Caustic Injection The caustic injection facilities should be provided in addition to ammonia injection facilities in those units wherein only single stage desalting is used. Where two stage desalting is used, no caustic injection should be provided, but the ammonia injection should be retained. Where caustic injection is provided, the following guidelines are recommended. * Use a solution of 10 wt-% sodium hydroxide. * Inject the caustic solution at a point in the crude stream between the desalter and heater, but where good mixing will take place ahead of the heater. ¢ Set the normal injection rate a 1 pound of sodium hydroxide per pound of salt per thousand barrels of desalted crude oil with an absolute maximum of 4 pounds of caustic per 1000 bbis of desalted crude. Normal control would be at a rate such that chlorides in the crude tower overhead would be in the range of 10-20 ppm. Final pH contro! of the overhead water should be done with ammonia injection. A typical crude desalter is shown schematically in Figure Ill-2. Crude from tankage is mixed thoroughly with 3-5% water in the feed pump. The mixture is then heated to approximately 250°F (121°C), and the resulting emulsion is broken chemically or electrostatically in the desalter. This treatment generally removes more than 95% of the salt and 50-75% of entrained solids. The amount of HCI liberated when the crude is heated in the furnace is reduced markedly by desalting so that the potential for corrosion in the condenser system is reduced. Some refineries now use two desalters in series to reduce salt content to only a trace. Solids removal minimizes fouling in subsequent equipment. 85040 I-13—$—_—_________} ; Electrodes ; TRUE UUE ERD O UD CEP EE ers Try Cocks z . i Brine i Out i é Mixing : 4 , Valve 8 5 1 eeonennnconncsoneetssanceneresrectscocrecessccrsenusenesssuewensene DEMUISI fier Alternate Water Water Injection Injection Point Injection iRP-ROO-17 Figure Ill-2 Typical Low Velocity Desalter Without adequate control, desalting can cause additional corrosion problems. Desalting water should be as pure as possible for maximum efficiency. In particular, the water should be air-free to prevent additional oxygen pick-up by the crude. Generally crudes are slightly acidic, so it is often advantageous to add some caustic to the desalter water. This extracts acids and leaves the crude slightly alkaline, thus minimizing subsequent hydrolysis of residual salts to HCI. Also, the alkaline (pH 8.0-8.5) desalter effluent water, which contains about 8% salt, is less corrosive to disposal equipment than is an acidic effluent. Corrosion Inhibitors Injection of the proper amount of corrosion inhibitors into the crude column overhead, along with a neutralizer for pH control and water injection, can essentially eliminate corrosion of carbon steel. Too little inhibitor may result in accelerated local corrosion and too much may cause emulsification problems. Injection, typical dosage of approximately 3 pounds per 1000 barrels of gross liquid throughput, is made into a —EEIIIoIIoIoI~“~))=— >] [> SS __S____aSS ss 85040 Wil-14 Yihorizontal or downward flowing section of the vapor line ahead of the first exchanger. At the above dosage, pH should be controlled to 6.5-7.5. Evatuation of Corrosion Control The long-range effectiveness of a corrosion control program can be determined by use of several testing methods. Periodic analyses of crudes, before and after desalting, and of effluent waters from both the desalters and the condensing systems, are essential to determine the methods and efficiency of corrosion control. Additional information on salt deposition and fouling must be obtained by regular evaluations of process conditions such as heat transfer coefficients and distillation efficiency. The degree and rate of corrosion can be determined by careful unit inspection during shutdowns, on- stream non-destructive testing techniques, analyses of process streams for metals, and corrosion probe and corrosion coupon exposures at carefully selected locations. Determination of dissolved iron and copper should be made on the process water. With good inhibition, about 0-10 ppm of each metal will be found, whereas corrosive conditions are indicated by 50-500 ppm of these metals. Occasional upsets that remove scale may give misleading results. However, similar consecutive analyses can indicate how fast metal is being lost because of corrosion. On-stream inspection of selected equipment by radiographic and ultrasonic techniques give more definite indications of corrosion damage without shutting the unit down. However, these methods are not sensitive enough for day-to-day evaluations. Llke visual inspection during shutdowns, non-destructive testing determines the long-term efficiency of the corrosion contro! program. Corrosion probes in the outlet of overhead condensers appear to correlate best with actual corrosion rates. Probes are also valuable in the vapor space of towers and exchanger inlets where temperatures may fall below the dew point. Retractable corrosion probes are preferred because, with suitable safety precautions, they can be replaced without shutting down the unit. 85040 I-15 YiCorrosion probes operate on the principle that electrical resistivity is dependent on the cross-section of the conductor. As corrosion removes metal from a probe, its resistance increases. Measurement of the current passing through the probe (a wire of the same material as the reactor) can be easily converted to mils (0.001 inch) of metal lost to corrosion. By plotting these measurements along a time scale, corrosion rates can be determined and correlated with desalter, neutralizer and inhibitor control as well as other operating variables that affect corrosion. Corrosion rates of 500-1000 mils per year can exist on carbon steel with no corrosion control program. If either neutralization or an inhibitor is used, this rate will drop to 10- 200 mpy. With use of both inhibition and neutralization corrosion rates of 0.5 mpy can be expected on carbon steel. SUMMARY Control of crude pretreatment, neutralization, wash water injection and both selection and injection of inhibitor are essential to prevent or minimize corrosion of carbon steel and alloys in the highly corrosive environments of refinery operation. Alloying with Admiralty metal, Monel, and even Hastelloys B and C can reduce the rate of corrosion of the process equipment but cannot stop the attack as completely as the process treatment approach. The cost of alloying all equipment exposed to process waters is prohibitive. Usually only some critical equipment is alloyed and a process treatment system is devised. Complete desalting will minimize chloride corrosion of crude condensers and fouling by suspended solids, but may accelerate sulfidic corrosion of furnace tubes. The use of ammonia-rich water in the desalter can cause additional corrosion in distillation towers by ammonium salt deposition. The same type of salt corrosion can occur when the crude tower overhead is neutralized with ammonia solutions to minimize stream corrosivity and inhibitor dosage. Ammonia solutions can cause stress-corrosion cracking of copper alloys often used in condenser equipment. Water washing can remove salts and sufficiently dilute corrodents, but may increase corrosion by forming a moderately concentrated NH4Cl solution and by adding oxygen to the system. The corrosion of carbon steel by NH4Cl solution is inhibited by the presence of oxygen-free 85040 I-16 Yisulfide, but is accelerated if the sulfide has oxidized. Monoethanolamine and diethanolamine form less corrosive neutralization products than ammonia. Corrosion inhibitors can give essentially complete protection under specific conditions; however, low concentrations can accelerate corrosion and high concentrations can cause emulsification with resulting loss of product or product quality. The activity of some inhibitors is reduced markedly at both high and low pH. Adequate dilution and dispersion of the high-boiling inhibitors in the process stream are essential, not only to insure complete protection, but also to avoid corrosion by concentrated inhibitor solutions at the hot injection point. Rapid and, on occasion, major changes in these corrosion-control techniques may be required. Since the variables are highly interdependent, consultation with competent corrosion engineers is advisable. Since each crude unit is unique, the methods used to control corrosion must be combined in the most economical manner with a clear ~ understanding of the corresponding limitations and risks. CRUDE HEATER INSPECTION Direct fired heaters in a refinery are used to add heat to the system and may use either oil or gas for fuel. A large number of heaters are equipped with burners to use either oil or gas. Heaters used in crude and vacuum units are used for heating the oil. The ideal conditions in this type of heater (Figure Ill-3) is to operate at conditions at which no cracking occurs. Cracking of oil produces coke. Ideal conditions are rarely obtained and there will usually be some coke formed. Heaters used as reboilers on light oil systems, such as strippers and stabilizers, are usually operated at conditions below cracking temperatures for the material being heated and rarely form coke in the tubes. Inspection of heaters should be a thorough inspection of all components. Casing, breeching, buckstays, stack, foundation, burners, linings, tubes and supports should be checked each down period. 85040 1-17 tyr8 5040 SHOCK TUBE SUPPORTS HIP TUBES, NH HIP oo) LabONS HIP TUBE SUPPORTS Se rey THERMOWELLS Ly Yo™. HIP THERMOWELL RS 7 || - RADIANT TUBES REFRACTORY RADIANT TUBE SUPPORT PRR Poooerim ri PEEP DOOR if FIREBRICK | FIRE BOX SHELL CENTER WALL ACCESS DOOR OUTLET ¢ | INLET DG TT DG 7 => SNUFFING STEAM ANGLE BURNER Figure Ill-3 Crude Charge Heater (End View) lit-18 VT;When inspecting any heater, certain things should be done before entering the heater. Check the fuel system to make certain that all burners are disconnected and that there has been a blind installed in the main fuel line. The closing of a block valve in the main fuel line is not acceptable. This is a safety measure and is for the protection of the inspector and any other personnel who may be entering the heater. Make certain all steam valves to the heater are blinded off or disconnected. Check ladders and platforms for broken or missing bolts, broken welds, holes in the platforms, missing hand rails and missing kick bars. If moveable platforms are overloaded with plugs, headers, and clean out equipment, the removal of equipment before platforms are used by personnel is recommended. It is a good practice to walk around the heater and check the foundation for cracks and settling, check the structural steel for warpage, broken welds and loose and missing bolts. Check the casing for hot spots, cracks, corrosion, loose and missing bolts. The stack should be checked for wrinkles, hot spots, corrosion on the stack and loose, missing and corroded bolts. A large amount of information can be obtained as to the condition of the inside of the heater by the - information obtained from inspection of the outside of the heater. Inside the heater, the damper should be checked for freedom of movement and for position, both opened and closed, as the indicator on the outside shows. Make sure that the control device for the damper works freely and the controls are located in an accessible and safe area for the operator. Check the steam snuffing lines to be sure all lines are open and that the snuffing line control valves are accessible and in a safe area. After the inspection on the outside has been completed, enter the heater and check the refractory walls, roof and floor. Bulges in the walls may be caused by the brick being set too closely, not enough room in the expansion joints, dirt accumulation in the expansion joints, settling of foundation, vibration due to pumps and burner firing, and explosions in the fire box. Evidence of refractory troubles usually shows up as cracks in the walls, loose brick, refractory on the floor or bulges in the wails. 85040 lil-19 trTube sheets should be inspected for cracks, broken or missing bolts; oxidation or corrosion is sometimes found. The intermediate tube hangers support the tubes along the length of the tubes. Check for cracks, oxidation, missing, broken or oxidized bolts and missing sections. Radiant tube hangers, or those attached to the walls with hooks on them, can usually be replaced with no large amount of work. Tube hangers which have to have the tubes inserted through holes in the hangers present a more serious problem in replacement. This entails the replacement of all tubes. Fortunately, this type of hanger is usually used in a cooler environment, such as convection sections, and rarely have to be completely replaced. The tubes being in a cooler zone do not sag and warp as badly. In the UOP Center Wall Updraft-type heaters, the shock tubes (those directly below the convection section) are most apt to cause trouble because they operate at a very high temperature since they receive both radiant and convection heat. These hangers oxidize badly. They are usually easy to replace, as they are bolted on to the bottom of - the convection tube supports. They are usually designed for easy replacement without loss of tubes. Tubes, supports, buckstays, insulation, burners and other internal equipment should be itemized and records maintained. Tubes should be inspected for wall thickness, oxidation, bulging, and warping. Hammer testing of tubes will give an answer to the dead tubes in the heater. Heaters should be inspected early in shutdown period as major work can be found in heaters and could create delay in shutdown schedule. Tubes and headers should have thickness measurements recorded, metal loss plotted with records for length of runs, hours fired and renewal of tubes and recommendations made. Sulfur between 600-800°F (316-427°C) is very corrosive. This range of temperature is found in hip and radiant wall tubes. The changing of charge stock to crude units can accelerate corrosion and the tubes are usually the first failure. Tubes wall thickness should be measured at more than one point (number of measurements taken on each tube will vary depending on length and condition of tube) as wall thickness can vary over the length of a tube and are also usually thinner on the fireside of the tube. Figure IIl-4 shows examples of this variation of wall thickness. 85040 {11-20 YiLT OEE Ne ee pes I ef TS tm. 7 Bhan ; i ete gia Ba. . i as) Rear as 49 0G Oks SLE oe TS é ; i Ba Se EAE mre aS Aaa ah Lae ae ie Pein Red meee ten chs Pee aes i paver e0 Ae fee Oe ate ae 8 ek A No Figure Ill-4 lures Heater Tube Fa Wl-21 85040INSPECTION OF HEATER TUBES Preparation of Surface The internal surface of tubes can usually be cleaned by turbining. Loose coke should be blown out with air or steam. External surfaces may be prepared by scraping, sandblasting, wire brushing, washing or wiping. Visual Inspection of Heater Tubes External Prior to conducting the preliminary external inspection, the inspector shall question the fireman or operator regarding any “hot spots” observed during the run. He shall also make a rapid survey of the severity of coke and/or salt deposits in the tubes as soon as - the headers have been unplugged. An inspection of the external tube surfaces shall then be made for burned spots, bulges and severely oxidized areas. Check the tubes where they contact the tube supports to be sure the tubes are not losing meta! from rubbing against the supports. Tubes which fail to pass this examination shall be marked for replacement so they will not be turbined. Figure Iil-5 shows a heavily coked and moderately bulged tube. Notice the checking of the scale in the bulged areas. Severe overheating of carbon steel and low chromium alloy tubes will result in scaling. Moderate and heavy scale may be knocked off with a hammer and the tube examined for cracks and longitudinal grooves. Figure Ill-6 shows a bulged and heavily scaled 6° OK carbon steel tube. Note the checks and cracks in the scale indicative of swelling and bulging. Conditions as severe as these would be cause for rejection. Figure IlIl-7 shows a moderately scaled 6° OD carbon steel tube with a typical groove pattern. This tube failed at two points, both of them in grooves. 85040 II-22Tea. are Bi iinet’ eye eae peta Figure Ill-7 Heater Tube Failures Due to Coke Buildups 85040 {ll-23 YiThere are many borderline scaling cases in which the decision to replace or continue the tube in service will depend on the inspector's judgment. Among the factors to be considered in such cases are severity of operating conditions, anticipated length of next run and relation of other processing units to the heater in question. In case of doubt, replace the tube. The inspector shall not lose sight of the fact that heavy scaling means loss of tube wail thickness. The loss of tube metal will be approximately 1/3 to 1/2 of the scale thickness. Therefore, in measuring OD’s, scale should be completely removed. Severe bulges (over 1/8") are readily observable and shall be cause for rejection in all cases. Bulges may completely encircle a tube or may be on one side only. Normally, bulges will be found only on the side exposed to fire box flames unless the bulge has been caused by internal mechanical damage. Measurement of a bulge shall be made by placing a straight-edge on the highest point of the bulge, with the edge parallel to the longitudinal axis of the tube, and measuring the gap between the Straight-edge and the unaffected portion of the tube. Minor bulges can be determined by OD measurements .- or, more rapidly, by holding a strong light several feet from the tube bank and to the side and rear of the inspector while glancing rapidly along the lighted tube profiles. The contrast with the dark background will disclose most bulges. Tubes which are warped to the extent that their interior surfaces cannot be visually examined throughout their lengths for cleaning tool grooves shall be calipered with a mechanical tube caliper. Tubes shall be carefully examined biannually for general corrosion and for localized Corrosion at the points resting on the tube support casting. External corrosion is most apt to occur in the convection section where it is difficult, if not impossible, to thoroughly clean or inspect. External corrosion is normally more severe in the convection tubes adjacent to the heater breeching, where the lowest flue gas temperatures occur. Where it is impossible to inspect certain tubes, the inspector shall make it a point to examine the exterior surface of such tubes when they are removed for other reasons, such as internal corrosion. Tubes shall be examined behind the rear faces of the headers for signs of leaking rolls. 85040 Hl-24Internal Internal visual inspection shall be made to check pitting, mechanical damage to the tube as a result of turbining and condition of the roll and flared tube ends. Inspection shall be conducted from each end of the tube. Figure Ill-8 shows several examples of tubes removed due to damage by turbines. A strong flashlight or extension light shall be placed in the opposite end of the tube from the inspector to assist in discovering defects or coke deposits remaining in the tube due to insufficient turbining. Examination of the ends of flared tubes shall be made to determine the condition of the flare and whether coke is building up in the roll. A gradual buildup of coke between the tube and the header, in which case the flare must be of sufficient OD and thickness to keep the header from slipping off the tube. Frequency External and internal visual inspection of heater tubes shall be made in accordance with conditions and shutdown schedule. 85040 Hi-25UOP 132H-7 Figure Ill-8 Turbine Damage to Tubes 85040 VT;. ° oe . . + ae ’ 4 2M, “ . . at , . J “4 Ad fo we sti, VOT ay eta Figure Ill-9 Crude Heater Tube Crude Heater Tube (4°) showing complete failure due to high sulfur charge stock. This tube is carbon steel and service lift was approximately six months. Figure Ill-10 Carbon Steel Tube Failure tn High Sulfur Crude Service ar \l-27 OTCRUDE UNIT FRACTIONATING COLUMNS This vessel (Figure Ill-11) is subjected to sulfur, salt, naphthenic acid, hydrogen sulfide, Stress, pit and erosion type corrosion. Internal inspection from top head to bottom through all trays, drawoffs and side pans should be made each down period if past records have stated corrosion in the various sections of the tower. Fractionators are protected with various liners and different types of materials for corrosion protection. The upper shell, top head and trays are usually Monel for protection against HCI. Lower section of tower shell and trays can have 11-13% Cr stainless steel lining and internals for protection from sulfur corrosion. In unlined areas, corrosion can usually be found on the shell and areas where condensate liquid can be formed, such as areas under projected lines or nozzles. Corrosion can be found anywhere in these columns. The location of the corrosion depends on the charge stock and its contaminants, service, arrangement of flow, type of - tower, materials of construction, temperatures and pressures at which the column operates. In very general terms, corrosion in crude fractionating columns can be put into two classifications. 1. Low Temperature — where the temperature is low enough to cause condensation of water vapors to the liquid state. Water as liquid dissolves acids and other corrosive substances and increases the tendency to cause corrosion. This type of corrosion is found in the upper portion of the columns and at points where reflux and other cold liquids enter the column. 2. High Temperature — where the temperature is high enough that water does not condense to the liquid state. Corrosive substances are considered dry and attack the materials directly. This type of corrosion is found in the lower portion of the columns and where incoming streams are hot. 85040 (Il-28Vent Vapor Out Reflux Naphtha Draw Naphtha Internal Reflux hie Ip: E Wis Kerosene Stripper Vapor Return Kerosene Pump Around Inlet Kerosene Draw Diesel Internal Reflux Diesel Stripper reo Vapor Return tr Lia . Diesel Pump es O Diesel Draw Around Inlet wf wt Feed Inlet me Stripping Steam ( th Bottoms Outlet IRP-ROO-19 Figure Ill-11 Crude Fractionator I-29 85040 4INSPECTION OF CRUDE FRACTIONATING COLUMNS Upper Portion Check for corrosion on the top head, at the weld seams, and on the shell. Check the bubble caps, risers, holding devices, floor plates, support members and support rings for corrosion. If cast iron trays are used, dig out the tray packing at the shell. This packing becomes saturated with water causing corrosion to occur in the form of a ring around the shell. Check below the reflux nozzle inlet on the shell and tray for corrosion. Check the shell where the liquid overflows the downcomer weirs for corrosion. Check the weirs and any spots that may form a water trap for corrosion. If dirt has accumulated in one area, check under the dirt on the shell and tray floors as corrosion sometimes becomes very severe in these areas. The type of corrosion described above usually extends downward about eight trays becoming less severe further down the tower. The best protection against corrosion in the upper portion of a crude tower is to. - use Monel lining and Monel trays. Center Portion of the Column This is a transition area from low temperature to high temperature corrosion. Monel or Type 410 alloy may or may not be used in this area. Most crude fractionating columns have carbon steel. Corrosion in this area is not usually severe, but instances have occurred where corrosion has been quite severe due to organic acids being present. For this reason, one should always inspect this area unless previous experience indicates otherwise. Area About 5 Trays Above Inlet or Feed Tray Including Feed Tray The highest temperatures in the column will be found in this area. In most cases, corrosion will be found in the form of general metal loss over all surfaces. Points of high turbulence and impingement will show a much higher rate of corrosion. Iniet extensions corrode severely. In this area, upset trays are not uncommon due to operation mishaps. The material for combating corrosion in this area is Type 410 alloy for corrosion from sulfur, or TP 316L S.S. for naphthenic acid corrosion. 85040 HI-30 YiBelow Feed Tray Including Trays, Side Pans and Bottom Well This section, if lined, is usually lined with Type 410 alloy. Corrosion diminishes going downward from the feed tray. Trays and side-to-side pans usually show little corrosion. They may be upset and are usually driven downward due to water in the charge stock. This, of course, depends on the origin of the explosion. The bottom well usually shows little evidence of corrosion. OVERHEAD RECEIVERS AND REFLUX ACCUMULATORS Overhead receivers (Figure Ill-12) and reflux accumulators ordinarily operate at temperatures in the range of 150°F (65°C) or below. The pressure at which they operate is dependent upon the fractionating column with which they are associated. Because of the low temperature, water is almost always present. For this reason, corrosion is usually found along the very bottom of the vessel, although it may be found - on the upper portions of the shell. This is sometimes caused by condensation of water vapor on the cooler surface or it may be due to corrosive substances in a gaseous state which accumulate in the atmosphere above the liquid level in the vessel. Check for corrosion along the weld seams, on the bottom (especially where a water trap may be formed), and on the upper shell. Vessels which do not have complete drainage of water, or in which water is present, can be very severely corroded if the water is not removed. This is because the water dissolves corrosive material and holds it in contact with the shell. The best material for combating corrosion in most receivers is Monel but, quite often, a concrete lining reinforced with hex mesh is used because of the cost of Monel and time. When recommending a concrete lining, it is imperative that an acid cement with a silica sand be used. Portland Cement is an alkaline cement and is consumed by any acid present and should never be used as a lining. Carbon steel strips are sometimes used to a good advantage, but it must be understood that the carbon steel will be corroded and this type of lining merely moves the corrosion from the shell to the lining and, in time, the lining will have to be replaced. ———_C_CC—————————==_=_[_¥_—¥_=_—¥_£_=_¥_=_=_=_====—=<=*={¥=={@<*<>*<=>@*<*_*_*c_*C*_*= <<< <—<—[_“_$_==$${_$_<*{=*_*{<=_<—<*{=_[{__<_«c—aX i —_x«[]][[=—“LS=>ppES|]»)90h™_——_—___=== 85040 Wl-31 trHOT-VAPOR BY-PASS INLET GAS OUTLET VORTEX BREAKER STAND PIPE SUPPORT HC OUT SADDLE WATER OUT UOP 132H-12 Figure Ili-12 Overhead Receiver With Water Boot Recommendations as to liners in any equipment should be discussed with the Operation Manager as to charge stock involved, process restrictions, use of inhibitors and specific materials to be used to arrest corrosion. COOLERS, CONDENSERS, HEAT EXCHANGERS, ETC. Many types of tubular equipment are used in crude and vacuum unit processes. During scheduled turnarounds, these items are routinely checked. Corrosion of various tubes and shells is common. Water with oxygen entrapment creates serious corrosion to shells and heads. Anodes are used extensively in these items to arrest galvanic-type corrosion. Inspection of tubular items should be thorough and all parts inspected with good records maintained. Renewal of any portion of any item should be recorded with service life plotted. Changes to tubes are important as to materials selected. In particular, service 85040 Mi-32 tiand recommendations should be approved by the Engineering Department to insure proper selection of materials. PIPING Corrosion can be found in a majority of the process lines. Chrome and alloy piping, usually 5 Cr-1/2 Mo, have been the solution to the corrosive medias in particular lines in a process. 85040 Mi-33VACUUM UNIT ‘85040 WV-1INTRODUCTION In order to examine the production of gas oil and lighter components from the bottoms material of an atmospheric distillation unit, these bottoms (reduced crude) can be further distilled in a vacuum distillation unit. The distillation of heavy oils is conducted at a low pressure in order to avoid thermal decomposition or cracking at high temperatures. In the vacuum unit, almost no attempt is made to fractionate the products. It is only desired to vaporize the gas oil, remove the entrained pitch, and condense the liquid product as efficiently as possible. Vacuum units which prepare lubricating oil fractions are completely different in both design and operation. REDUCED CRUDE FLASHING The reduced crude is charged through a heater into the vacuum column in the same manner as whole crude is charged to an atmospheric distillation unit. However, whereas the flash zone of an atmospheric column may be at 1-1.3 kg/cm2, the pressure in a vacuum column is very much lower. The vacuum heater transfer temperature is generally used for control, even though the pressure drop along the transfer line makes the temperature at that point somewhat meaningless. The flash zone temperature has much greater significance. The heat transfer and flash zone temperatures are generally varied to meet the vacuum bottoms specification, which is probably either a gravity (or viscosity) specification for fuel oil or a “penetration” specification for asphalt. Very heavy pitches are called asphalts. If the flash zone temperature is too high, the crude can start to crack and produce gases which overload the ejectors and break the vacuum. When this occurs, it is necessary to lower the temperature and, if a heavier bottoms product is still required, an attempt should be made to obtain a better vacuum instead. Slight cracking may occur without breaking the vacuum. This is sometimes indicated by a positive result from the Oliensis Spot Test. The Oliensis Spot Test is a simple laboratory test which purports to indicate the presence of cracked components by the separation of these components when a 20% solution of asphalt in naphtha is dropped on a filter paper. The flash zone temperature will vary widely depending upon the crude 85040 IV-2 Vitsource, pitch specifications, quantity of product taken overhead, and flash zone pressure. Temperatures from below 599°F (315°C) to over 797°F (425°C) have been used in commercial operations. Some vacuum units are provided with facilities to strip the pitch with steam. This will tend to lower the temperature necessary to meet an asphalt specification, but an excessive quantity of steam will overload the jets. VACUUM BOTTOMS FLASHING Pitch must be handled more carefully than most refinery products. The pitch pumps which handle very hot, heavy material have a tendency to lose suction. This problem can be minimized by recycling some cooled pitch to the column bottom, thus reducing the tendency of vapor to form in the suction line. It is also important that the pitch pump glands be sealed in such a manner so as to prevent the entry of air. Since most pitches are solid at atmospheric temperatures, all pitch handling equipment must either be kept active or flushed out with gas oil when it is shut down. Steam tracing alone is - sometimes inadequate to keep the pitch fluid, but where this is done, the highest pressure steam available should be used. Pitch is sometimes cooled in open box units, as shell-and-tube units are not efficient in this service. It is often desirable to send pitch to storage at high temperature to facilitate blending. When pitch is sent to storage at over 212°F (100°C), care should be taken to ensure that the tank is absolutely free from water. Pitch coolers should always be flushed out with gas oil immediately once the pitch flow stops, since melting the contents of a cooler is a slow job. 85040 IV-3i Nvili aon Would Ivsoasia VHLLHGWN Hy aNaSOW4M 128310 yosvo ‘muy OLM—LYM = Bano ( Y bs yz 2uvsnzanoo ananure | IV IIE 2 wNuO 0224 ¥aziINVEneZa AuaAoogu NNW AHOIVMss § Svo0L-%D MOLOEFE HANI Suaddiuis wvals 4noaais ULES «6 MBZINVINGTG «= NBN IOD OWA NNNIOS FaneD gure IV-1 Fi Crude and Vacuum Distillation Unit “W-4ENTRAINMENT CONTROL The vapor rising above the flash zone will entrain pitch, which cannot be tolerated in cracking unit charge. The vapor is generally washed with gas oil product sprayed into the “slop wax” section. The mixture of gas oil and entrained pitch is known as slop wax, and it is often circulated over the decks to improve contact though the circulation rate is not critical. The final stage of entrainment removal is obtained by passing the rising vapors through a metallic mesh demister blanket through which the fresh gas oil is sprayed. Most of the gas oil spray is revaporized by the hot, rising vapors and returned up the column. Some slop wax must be yielded in order to reject the captured entrainment. Variation in the color of the gas oil product is a valuable indication of the effectiveness of entrainment control. Slop wax is a mixture of gas oil and pitch and can be recirculated through the heater to the flash zone and reflashed if the plant has the capacity to do so. However, ifacrude - contains volatile metal compounds, these will be recycled with the slop wax and can finally rise into the gas oil. Where volatile metals are a problem, it is necessary either to yield slop wax as a product or to make a lighter asphalt which will contain the metal compounds returned with the slop wax. PRODUCT CONDENSATION The scrubbed vapor rising above the demister blanket is the product and no further fractionation is required. It is only desired to condense these vapors as efficiently as possible. This could be done ina shell-and-tube condenser, but these are inefficient at low pressures and the high pressure drop through such a condenser would raise the flash zone pressure. The most efficient method is to contact the hot vapors with liquid product which has been cooled by pumping through heat exchangers. It is further desired to usefully recover the heat of the rising vapors by heat exchange against crude oil, so we must arrange to have the circulating liquid at a high enough temperature to permit efficient heat exchange. Therefore, a compromise must be made. if the gas oil circulation is high enough to condense all the vapors, the gas oil pan temperature will be so low that we will have inefficient heat exchange. In order to obtain 85040 IV-5 Yia Suitable high pan temperature, we are forced to reduce the circulation rate until some of the vapors escape uncondensed. The problem of uncondensed vapors is easily solved by adding a small, circulating light vacuum gas oil section to catch these vapors by condensation against light vacuum gas oil from a water cooler. The heavy vacuum gas oil circulation rate is chosen to maximize crude heat exchange. Sometimes it is impossible to remove enough heat with crude exchange alone, and some HVGO from the outlet of the HVGO cooler is returned to the circulating line. This should only be done when necessary, since both heat and cooling water are wasted. The HVGO product is cooled and pumped to storage on HVGO pan level control. The LVGO section is a final contact condenser and normally the circulation rate should be adequate to keep the vapor to the jets within about 5°C of cooling water temperature. A high circulation rate will provide a cushion against upsets. VACUUM PRESSURE MEASUREMENT Confusion often arises because of the different scales used to measure vacuum. Positive pressures are commonly measured as kilograms per square centimeter gauge, which are kilograms per square centimeter above atmospheric pressure. Atmospheric pressure is 1.035 kg/cm2. Another means of measurement is to measure in millimeters of mercury. Atmospheric pressure (sea level) is 760 millimeters of mercury absolute, while a perfect vacuum is 0 millimeters absolute. When vacua are measured, we can more conveniently do it by using millimeters of mercury absolute. 85040 IV-6VENT tvco _——~ Pav REFLUX ~ DEMISTER Lc & LG MANWAY - Tt \ ro OL - HV GAS OIL “———. tv Ga O11 OUT REFLUX TLPRV teats _.—HV GAS OIL out HVGO SPRAY — rprV ST E —_— ., DEMISTER ™~ SLOP WAX RETURN « TLPRV ~ ™ GRID ““~. SLOP WAX OUT FEED TANGENTIAL CASTRIBUTOR STEAM INLET PUMP VENT RETURN __--— QUENCH VORTEX BREAKER uc ~ ——~ gorToms ouT UYOP 1374-2 Figure IV-2 Vacuum Column 85040 = YiSTEAM JET EJECTORS Operating Principle Figure !IV-3 illustrates a typical two-stage ejector system. In an ejector, steam is injected at high velocity through a specially designed nozzle and transfers sufficient energy to the gases from the suction header to entrain them through the diffuser into the first-stage discharge header. The pressure in the first-stage discharge header is, of course, higher than the pressure in the suction header but, if the velocity of the steam through the diffuser throat is high enough, gas cannot back into the suction header. Ifa single ejector is incapable of raising the gases to atmospheric pressure at which they can be vented, the steam is condensed and a second ejector taking suction on the non- condensable gases raises them to a higher pressure. The dimensions of an ejector are quite critical so that any given ejector will only operate . over a relatively limited range. A substantial change in suction or discharge conditions will probably demand a change in the dimensions of the nozzle or diffuser, or both. The effect of changes in operating conditions can be summarized as follows: Steam Pressure Steam pressure must be maintained quite close to that for which the equipment was designed. If steam pressure greatly exceeds that for which the nozzle was designed, the quantity of steam discharging into the diffuser will be greater than can pass through the diffuser and steam will back into the suction header. Too low a steam pressure will mean a drastic loss in performance of the ejector. It should be noted that wet steam will cause random fluctuations in ejector performance and, in addition, will erode the nozzle and diffuser. 85040 IV-8Discharge Pressure if the discharge pressure rises above design, there is an increasing probability of reverse flow. An increase in discharge pressure on an ejector discharging to atmosphere is only possible if the discharge is obstructed. On multi-stage units, however, an increase in inter-stage pressure due to high condensate temperatures or failure of a second- or third-stage ejector will immediately affect the performance of the first-stage unit. NOZZLE INSPECTION PLUG NL NS [Fy Cate RSS STEAM STRAINER STEAM INLET NOZZLE HEAD SUCTION HEAD NOZZLE SUCTION UOP 1374U-3 Figure IV-3 Cutaway View of Steam Jet Ejector 85040 IV-9 YrLoad A decrease in load (kgs/hour of vapor to ejector) will result in a somewhat higher vacuum being obtained. If the load is increased above design, however, the vacuum obtained will fall off quite suddenly and dramatically. Cooling Water Temperature The temperature at which steam is condensed in the inner and final condensers will have a relatively minor effect on the vacuum obtained, but will substantially reduce the load at which the ejector system breaks down, since an increase in condensate temperature increases the inter-stage pressure. In order to ensure flexibility, a refinery ejector system for a vacuum unit will generally be constructed using two parallel sets. The minimum combination of equipment which will - achieve a satisfactory vacuum is normally used. Vapors drawn from the top of a typical vacuum unit to the jets consists of air from leaks, steam entrained from the bottom of the crude distillation tower, light hydrocarbons, sulfur and nitrogen compounds from thermal decomposition in the heater, and any hydrocarbons lighter than gasoline which have not been stripped from the charge. Steam and light hydrocarbons will condense in the inter-condenser so that the first-stage ejectors can be heavily loaded under conditions which only lightly load the second-stage ejectors. Any actual cracking in the furnace will produce light gases which will very rapidly overload the second-stage ejectors. Both condensable and non-condensable vapors handled by a typical vacuum unit ejector set are highly odoriferous so that the condensate must be stripped and the non-condensable vapors incinerated. 85040 IV-10 J— Lite NOZZLES NS DIFFUSER ‘\ Fi THROAT % \. T1 2ND STAGE JETS = NON-CONDEN- SABLES TO INCINERATION (OR SRD STAGE) 1ST STAGE DISCHARGE HEADER FINAL ~~ CONDENSER STEAM 2ND LU STAGE SUCTION HEADER CONDENSATE OILY DRAIN CONDENSATE — } Tap UOP 1374U-4 To 4 DISPOSAL INTER- CONDENSER j.~~~"~"~"" P| Figure IV-4 Typical Arrangement — Vacuum Unit Two-Stage Jets 85040 IV-11 YiINSPECTION OF VACUUM UNITS The inspection of a vacuum unit includes several steps. There are several areas where severe corrosion can occur including the vacuum unit charge heater, vacuum tower, heat exchangers, and associated piping. All piping in the vacuum unit should be ultrasonically inspected for thickness while on- stream. The reason for on-stream inspection is two-fold: first, any thin lines that could rupture will be found; and second, any lines that are at retirement can be fabricated before the scheduled maintenance turnaround. The area where most corrosion is expected in the piping circuit is the heater transfer line. The temperature at which sulfur starts to corrode is approximately 500°F (260°C). Since the heater transfer line runs above this temperature, there is a distinct possibility of corrosion. Also, the intermediate reflux circuit has a possibility of heavy corrosion due to the high temperature. Piping from the vacuum tower bottoms is also susceptible to severe corrosion due to high temperature sulfur attack. Any other lines in the charge circuit or vacuum tower outlets that are in excess of 500°F (260°C) should be closely monitored for high temperature sulfur corrosion. The proper metallurgy and corrosion allowances should be used in the areas mentioned above. The next area of major concern is the vacuum unit charge heater. There are two major areas of concern. These areas are the tubes (internal corrosion) and failure of heater internals (i.e., tube hangers). The internals tend to fail more often in a vacuum charge heater due to the high temperatures. Since the temperature is so high, an AISI 300 series steel is used for the tube supports and hangers so severe oxidation and corrosion do not occur. The hangers and supports should be carefully watched so failure does not occur. A failed hanger or support could cause a sagged tube. The other area of major concern in a vacuum unit charge heater is the tube I.D. Due to the high temperature, severe sulfur corrosion is possible. The condition would be most noticeable in highly turbulent areas such as the return bends in heater tubes. The reason that the corrosion is most noticeable in the turbulent areas is because the loose sulfide scale is washed away, exposing fresh steel to corrosion. The return bends and 85040 IV-12 Yijust past the return bend should be monitored closely since that is the area where failure is most likely to occur. When specifying the material to be used in a vacuum unit charge heater for the tubes, the sulfur content of the charge stock should be taken into account. The vacuum column has several areas where corrosion and/or erosion can be present. The corrosion and erosion sections can be dealt with separately. Erosion occurs mainly in the venturi’s (ejectors) and at the feed inlet to the vacuum tower. In several cases, the liner has been washed out in the area of the tangential inlet due to the high velocity of the incoming material; therefore, s wear plate is sometimes installed. This plate is usually made of the same material as the liner. Also, erosion has occurred in ejectors downstream of the injection steam nozzle. This erosion can be caused by the use of wet steam in the ejectors. Most corrosion occurs at temperatures above 500°F (260°C) due to high temperature ~ sulfur corrosion. A vacuum tower is usually lined from the 500°F (260°C) area down. This liner is usually made of AIS! 405 and is considered the corrosion allowance. The liner should be checked thoroughly each downtime for corrosion. If severe corrosion is present on the liner, that is an indication that there is naphthenic corrosion occurring in the tower. AISI 405 is not sufficient in this case and AISI 316 type should be used. There also have been several corrosion problems in vacuum units in the slop wax draw trays. The trays usually have holes corroded through, believed to be caused by some small amounts of naphthenic acid. This acid is the reason for the use of AISI 300 series steel. The exchangers generally do not have severe corrosion. The only time that corrosion generally occurs is if the temperature is over 500°F (260°C), resulting in high temperature sulfur corrosion. The condition usually occurs on the tube side. When this occurs, the tubes are usually made of AISI 410 and the carbon steel channel is lined with AISI 410. Another problem that generally occurs is fouling between the tubes. If serious fouling occurs under deposit, corrosion should be looked for very carefully. The exchanger equipment should be hydroblasted clean each turnaround. 85040 IV-13 YiRESIDUAL OIL PROCESSING ‘$5040,INTRODUCTION The oldest refinery conversion process is thermal cracking, which some say originated as far back as 1860, and even then provided extra low-boiling products from the lower valued residue stocks. Modern thermal cracking is attributed to Dubbs & Son, who obtained patents on the process in 1913. They demonstrated the first commercial unit in 1919. For many years, this was the principal refining unit after the crude distillation operation. It processed atmospheric residue and produced cracked gasoline plus distillates, and a reduced amount of residual material which went into heavy fuel oil. Over the years of thermal cracking operation, variations evolved, such as visbreaking—a mild cracking operation, and coking-the extreme in cracking severity. THERMAL CRACKING Application Thermal cracking is the earliest known petroleum conversion process. It dates back to the beginning of the industry, and probably was the serendipitous outcome of a misoperation of some kind! In any event, as the market requirement for motor fuel increased, the cracked gasoline was a welcome addition to the refiner’s gasoline pool, especially because of its superior anti-knock characteristic. Also, thermal cracking reduced the amount of low value heavy fuel produced per barrel of crude oil. As first demonstrated commercially in 1919, the process was of single coil design, small capacity, and with limitations imposed by equipment available at that time. Through the 1920's, through necessity, progress in equipment technology made available hot-oil pumps and larger reaction chambers, allowing the design of larger units. With this, the two-coil design was evolved and first operated in 1932. This was the process that prevailed until the advent of fluid catalyst cracking in the early 1940’s. By the 1940's, thermal cracking accounted for nearly haif the production of automobile motor fuel. This fraction has now been reduced with the advent of fluid catalytic cracking (FCC). However, thermal crackers continue operating in some refineries, and a large new one was constructed in England as recently as 1975. 85040 V-2 YiProcess Flow A simplified flow scheme of a two-coil thermal cracking unit is shown in Figure V-1. Feed to the unit is atmospheric reduced crude and is introduced just above the flash zone of the fractionator, where vapors from the flash separator enter the column. Overhead product is an endpoint gasoline which is stabilized before sending to storage. A light gas-oil is withdrawn as a side-cut, stripped to a fuel oil specification, and sent to storage. From a lower tray, a higher boiling distillate containing the lower boiling constituents of both feed and recycle, is withdrawn and sent to the light-oil heater. Feed to the heavy-oil heater is taken from the bottom of the fractionator and contains the higher boiling portions of both recycle and feedstock. Light Oi! Heater © Gas . wesstesliy Propane Fractionator/~ \ Separator & ) Butane Reaction Flash Chamber ti Side-cut ve Separal oe od Stripper Stabilizer {N ; § | 5 J Distillate Fuel Oil Feed Atmospheric Reduced Crude eayy Oil Gasoline eater Fuel Oil Residuum IRP-ROO-04 Figure V-1 Two-Coil Thermal Cracking Unit 85040 V-3 YiHeater effluent streams enter the top of the reactor chamber from which all products are withdrawn through a pressure control valve. The mixture leaving the reaction chamber enters the flash separator, in which a residual fuel oil of the desired properties is separated. Typical conditions would be 900°F (482°C) from the heavy oil heater and 1000°F (538°C) from the light oil heater, with pressure in the soaking drum controlled at 200-300 psig (14-21 Kg/Cm2g) with the separator and fractionator at 60-130 psig (4-9 Kg/Cm2g). Process Chemistry Under conditions of thermal cracking, hydrocarbons decompose into smaller hydrocarbon molecules including gases (H2S, C1-C4 hydrocarbons), light and heavy distillates, and tar. Thermal cracking theory is that the decomposition products are free radicals, which enter into a series of reactions resulting in a broad range of products because they: * react with other hydrocarbons * react with other free radicals * decompose to olefins e react with metal surfaces in the heater and reactor chamber In theory, small free radicals can react with a larger molecule and capture a hydrogen atom, resulting in a small molecule, e.g., ethane, and a large unsaturated molecule which, being more unstable, can decompose to form olefins and smaller radicals. Free radicals can combine, and these then create the larger species that form products in the middle distillate range. Condensation reactions can proceed to the extent of forming ring compounds, polynuclear aromatics and tars. Coke and bitumen are the ultimate polymerization products. These molecules become very large with considerable cross linkage. 85040 V-4Process Variables The most important variables in thermal cracking or in any thermal operation are: e Feedstock properties ¢ Temperature ¢ Residence time e Pressure Feedstock Properties The most difficult chemical species to degrade thermally are the polynuclear aromatics; the easiest are paraffins. On this basis, feedstock properties can be summarized as follows to indicate the order in which ease of cracking occurs. Paraffins iso-Paraffins Cyclo-Paraffins Aromatics Polynuclear aromatics Therefore, a crude oil that is paraffinic in nature will have an atmospheric reduced crude that will be easy to crack. Similarly, an aromatic crude would produce a difficulty cracked, or refractory resid. Temperature Cracking starts to occur in the range 600-700°F (315-371°C), depending on the character of the feedstock. Temperature is often controlled by introducing a quench stream, such as fresh feed or recycle stock, into the heater transfer line ahead of the reactor. 85040 V-5 YTResidence Time In general, the longer the residence time, the lower is the temperature required for a given level of conversion to light hydrocarbons. The longer residence time also provides an opportunity for larger molecules to condense, producing tars and coke. Reactors are usually sized on the basis of an allowable time for maximizing gasoline — up to 200 seconds. Pressure Pressure determines the phase prevailing in the reactor, whether the system is in vapor or liquid phase. At pressures around 100 psig (7 Kg/Cm2g), reactions occur in the vapor phase and tend to yield more lighter hydrocarbons (C2-C4 range). Higher pressures (200 psig (14 Kg/Cm2g) and higher) bring out mixed phase or even total liquid regimes favoring production of hydrocarbons ranging from gasoline to diesel oil and - heavier distillates. 85040 V-6 JVISBREAKING Application Visbreaking is a mild thermal cracking process which upgrades the viscosity and pour point of atmospheric or vacuum reduced crudes while yielding some light products. It is a proven, inexpensive method for producing more valuable products from heavy crude residues. The objective of the visbreaking process is to reduce the viscosity as much as possible without significantly affecting fuel stability. If the operation were carried out at too severe conditions, the resulting product becomes unstable. This results in the formation of polymerization products during storage which forms sludge and causes filter plugging. The high viscosities of paraffinic-based residues are caused by the presence of highly complex ring compounds having long paraffinic side chains. Visbreaking - operation is carried at conditions to thermally crack these paraffinic side chains into lower boiling hydrocarbons. Feed is heated and mildly cracked in the visbreaking heater. The heater effluent is immediately quenched in order to stop the thermal reaction at the desired conversion and to prevent coke formation. This effluent is directed to a flash fractionator where gas, gasoline, gas oil and residue are separated. Visbreaking yields depend on feed properties, cracking temperature, pressure and residence time. In general, an increase in either temperature, pressure or residence time increases visbreaking severity. Higher severity increases the gas and gasoline yield and, at the same time, reduces the yield and viscosity of the cracked residue. Visbreaking severity is limited by the stability of the residue or fuel oil product. Visbreaking is used for the following types of operation: ¢ Fuel oil production e Gas oil recovery * Gas oil cracking for maximum diesel FS 85040 V-7 YiVisbreaking for Fuel Oil Figure V-2 represents the flow scheme of this type of visbreaking operation. The feed is heated and cracked in a fired heater. Heater effluent is quickly quenched to prevent overcracking, then flashed in a fractionator for removal of light ends and recovery of the desired flash point residuum. The primary objective of this visbreaking operation is to decrease heavy fuel oil production through a reduction of viscosity of the feed. This enables the refiner to produce fuel oil to viscosity specifications with little or no addition of lighter and more valuable cutter stocks. In this operation, gasoline and gas yields generally do not exceed 10 wt-% of the feed. Gas + Gasoline Flash Fractionator Steam Feed Light Gas Oil Quench Residual Oil or Fuel Oil IRP-RO0-05 Figure V-2 Visbreaking For Fuel Oil 85040 V-8 YiVisbreaking for Gas Oil Recovery Figure V-3 represents the flow scheme for this type of visbreaking operation. Fresh feed is heated to the desired visbreaking temperature. Heater effluent is quenched with a liquid recycle stream of gas oil and directed to a flash fractionation column. Gas and gasoline are taken overhead from the fractionator and can be routed to a gas concentration unit for recovery of C3-C4 olefinic gases and stabilized gasoline fractions. Alternatively, the flash fractionator net overhead liquid can be charged to a stabilizer column with light gases being directed to the fuel gas system. Light gas oil (LGO) is recovered as a side-cut of the flash fractionator. A portion of the flashed LGO may be used as quench to the bottom of the flash fractionator and to the heater outlet. The net LGO produced may be blended into diesel fuel after appropriate treating. Flash fractionator bottoms are then charged to a vacuum fractionator where heavy vacuum gas oil (HVGO) and visbreaker vacuum residue are recovered. HVGO may be charged to a fluid catalytic cracker, hydrocracker or thermal cracker. Most of the visbreaker ~ vacuum residuum is usually burned in the refinery as fuel, with the rest blended into No. 6 fuel oil. Depending on the specific feedstock, it is possible to convert from 25-40 vol- % of the nondistillables present in the charge to distillable products. Gas + Gasoline Flash Fractionator Light Gas Residual Oil Oil IRP-ROO-06 Figure V-3 Visbreaking For Gas Oil Recovery 85040 V-9 YiVisbreaking Plus Gas Oil Cracking for Maximum Diesel Figure V-4 represents the flow scheme for this type of visbreaking operation. This visbreaking operation is usually applied to atmospheric-reduced crude feedstocks. The feed is heated and cracked in a heater. Heater effluent is quenched and then flashed in a fractionator. Fractionator bottoms are then charged to a vacuum fractionator where visbreaker vacuum residue is recovered, while heavy vacuum gas oil is recycled and Cracked in a separate heater coil into LGO and lighter fractions. The primary objective is to maximize LGO suitable for diesel oil. An alternate objective may be to produce a low pour point No. 6 fuel oil from high pour point reduced crudes. This can be achieved by blending some of the LGO produced into the visbreaker vacuum residue until No. 6 fuel oil pour point and viscosity objectives are met. To save on precious cutter stocks, refiners try to use as much of the visbreaker vacuum residue as boiler plant fuel as possible. Gas + a pansenonnnsaanat 5 Gasoline 5 Jets Flash Reaction Fractionator Vacuum Chamber Flash Miers Steam a, myx xX Feed rT Quench Recycle Lignt vas Residual il IRP-RO00-07 Figure V-4 Visbreaking Plus Gas Oil Cracking For Maximum Diesel 85040 V-10 YiProcess Variables The objective of visbreaking is not necessarily the production of gasoline, but a minimum yield of fuel oil having a specified viscosity. The most important variables are feedstock properties, cracking temperature, and residence time. in general, an increase in either temperature or residence time results in an increase in visbreaking severity. Increasing the severity of cracking increases the gas and gasoline yield and, at the same time, reduces the viscosity of the cracked residual oil. Too severe cracking conditions may result in an unstable fuel oil; that is, a fuel oil that is too high in sediment and water content or whose sediment content increases in hot storage. Transfer Temperature and Residence Time Transfer temperature, which is the temperature of the feed as it leaves the heater, determines the degree of cracking effected, along with the residence time of the oil in ~ the heater. The higher the temperature and the longer the residence time, the greater will be the degree of conversions. In addition, the quantity and viscosity of the cracked residuum will be lower. Transfer temperature is controlled by the rate of heater firing. Residence time depends on the total volumetric flow of oil and injected steam through the heater. To produce a given degree of conversion to gas plus gasoline, either the temperature or time may be adjusted. Experiments have shown, however, that the cracked residual oil becomes decreasingly stable as severity is increased, particularly with high K charge stocks (UOP K of 12). This increases the rate of coking in the plant and the rate of formation of solid precipitate in storage. The rate of coking and the likelihood of producing unstable fuel oil are reduced by using temperature, rather than residence time, to produce the desired conversion. As severity is increased, more steam should be injected into the heater tubes to decrease the residence time and the temperature raised to attain conversion. The increased steam and fue! consumption will, however, increase utility costs. 85040 waThe proper balance between time and temperature can be attained through analysis of the cracked residual oil for its tendency to form precipitate in storage. The rate of coke deposition in the heater is also an indication of this balance. Coke deposition can be assessed by inspection of the tubes or by the rate of firing necessary to produce a given transfer temperature for a given flow rate through the tubes. During good operation, the flashed residuum should have a sediment and water level of 0.1-0.4%. During poor operation, it can be as high as 3%. Quench Rate Light gas oil is recirculated and injected into the heater outlet to quench the charge stream to stop the cracking reactions that take place in the heater. If the heater effluent is not quenched, it will continue to crack en route to the flash chamber and in the chamber itself, thereby rapidly coking the equipment. As quench flow is increased, ~ however, the amount of material flashed off in the flash chamber decreases and more light material is carried out with the flashed resid and is carried overhead in the vacuum column. The quench rate should, therefore, be just enough to reduce the temperature of the feed to the visbreaker flash chamber to about 800°F (427°C). Operating Stock The operating conditions and expected product yields are set by the properties of the feedstock. Low K factor feeds are easier to visbreak than high K factor feeds. The higher the K, the lower the yield of gas plus gasoline; the higher the residuum viscosity, the higher the fuel oil sediment and water content is at a given cracking temperature and residence time. 85040 V-12 JCOKING Introduction Petroleum coke is a bottom-of-the-barrel product from the refining of crude oil. Production of petroleum coke has had a considerable growth in volume in the past decade. In 1959, total feed rate to delayed coking units was approximately 360,000 barrels per stream day (BPSD), producing 10,500 tons per day of coke. In 1965, the corresponding figures were 530,000 BPSD and 17,000 tons of coke. Petroleum coking capacity world-wide is currently estimated to exceed 1,100,000 BPSD and 62,000 tons of coke per day. Of this, about 85% is in the USA. In earlier years, the economic incentive to the refiner for installation of coking facilities lay mainly in the reduction of heavy fuel oil yield by upgrading heavy residuals and bottom-of-the-barre! materials into more valuable distillate products. In addition to - coking, this end can be achieved through application of other processes such as thermal cracking, visbreaking, deasphalting or vacuum fractionation. All but coking, however, produce a heavy, refractory liquid bottoms which requires tankage and cutter stock. In many instances, the economic justification for coking assumed that coke either had zero value or, because it represented a disposal problem, a negative value. In recent years, intensive cultivation of non-fuel markets for coke has made it a petroleum product in its own right. At the present time in the USA, the use of coke for fuel purposes has decreased to less than 15% of total coke production, the largest end use being in the making of carbon anodes required in aluminum manufacture. Other established coke uses are for producing silicon carbide, titanium, calcium carbide, electrodes for arc furnaces in making stainless steels, as a recarburizing agent in iron and steel, and in the cement industry. More recent developments have included the use of high purity graphite for aerospace components and as a moderator in nuclear reactors. Large potential markets are anticipated for converting coke into regenerable activated carbon to be used for purifying air and water. 85040 V-13 JProcess Description Coking units may be grouped into three classes: ultimate, partial recycle and delayed coking. Ultimate coking refers to a relatively high-pressure operation (above 175 psig (12 Kg/Cm2qg) and up to 1000°F (538°C) with recycling of coker gas oil to extinction. Normally two separate coil heaters are employed. Delayed coking refers to a low- pressure operation (about 30 psig (2 Kg/Cm2g)) and employs a minimum recycle consistent with coker gas oil endpoint requirement. The partial recycle coking operation is intermediate between ultimate and delayed coking. The operating pressure is normally about 60 psig (28 Kg/Cm2g), and maximum recycle is employed consistent with one coil operation. The use of ultimate coking was largely phased out in the 1940’s with the development and rapid commercial application of fluid catalytic cracking, which was capable of yielding a superior product slate. Except for a special application, it is not expected that - a modern refiner will even consider the ultimate coking process. The main source of coker feedstock is reduced crude from either atmospheric or vacuum distillation. Clarified oils from fluid catalytic operations and thermal cracking tars have assumed a more recent importance as improvements in coke quality are necessitated by more sophisticated market applications. Coking units will normally produce gas, gasoline and distillates in addition to coke product. These products may require treating or additional processing due to the unsaturated nature or other contaminants present in the feedstock. Their use and treatment are not covered here, but it should be noted that the hydrocracking process may be employed to produce additional distillate products and to reduce the sulfur content of the coker feedstock, thus resulting in recovery of lower sulfur content coke and co-products. Coking yields and product properties are dependent on feedstock characteristics and source as well as the operating conditions employed. By judicious selection of feedstocks and processing conditions, the refiner can produce high quality coke for many specialty end uses. Properties that contribute to a superior coke are low sulfur, 85040 V-14 Yilow volatile material, low metals and ash content, low porosity, low coefficient of thermal expansion (CTE) and good conductivity. The latter three properties are measured after calcination of the green coke. A high sulfur content in coke is objectionable for manufacturing of electrochemical anodes. During the graphitization process, evolution of sulfur from the carbon-sulfur complex can lead to fracturing of the anodes. High metals content of the coke is detrimental to both its electrical and mechanical properties. Volatile material, ash content, and porosity are related mainly to the mechanical properties of the coke. The Conradson carbon content of the feedstock is the predominant property affecting the yield of coke. The carbon residue from the test is a carbonaceous material formed during evaporation and pyrolysis of the residuum feedstock sample and is a direct measure of the coke-forming potential of a given feedstock. As related to coking operations, the most common classification used to describe the ~ constituents of residua are asphaltenes, resins and aromatics. The asphaltene fraction is a non-volatile, high-molecular weight, amorphous substance which exists as highly dispersed colloid in the oil. Asphaltenes are mainly composed of carbon, hydrogen, nitrogen, oxygen, sulfur, and molecules arranged in complex clusters or layers. The resin fraction of the residual is similar in structure to asphaltenes. However, resins are viscous, tacky materials of very low volatility. They are slightly lower in molecular weight than asphaltenes and have more concentrated amounts of nitrogen and sulfur. Compared to resins and asphaltenes, aromatics are simple structures composed of polycyclic six carbon aromatics. In the delayed coking process, feed is heated to 900-950°F (482-510°C) over a short time interval. High tube velocity rates are necessary to prevent the deposition of coke in the heater tubes. The thermally-cracked effluent leaving the heater discharges into a coke chamber. Under heat and delayed time conditions, coke is slowly formed. Two different reaction mechanisms form coke at these time-temperature conditions. In one, the colloidal suspension of the asphaltene and resin compounds is distorted resulting in the precipitation of the compounds to form a highly cross-linked structure of amorphous coke. The compounds are also subjected to a cleavage of the aliphatic 85040 V-15 Yi,groups. Due to its amorphous nature and high impurities concentration, coke produced from the resin-asphaltene compounds is undesirable for manufacturing high grade carbon anodes. The second reaction mechanism involves the polymerization and condensation of aromatics, grouping a large number of these compounds to such a degree that coke is eventually formed. Coke produced in this manner contains few cross-linkages and has a more Crystalline appearance than resin-asphaltene type coke. Petroleum cokes formed from feedstocks containing a high concentration of aromatics and low concentration of impurities, as characterized by thermal tar, decant oil, and residue having low concentrations of resin-asphaltene compounds, possess the crystallographic structure most desirable for carbon and graphite manufacture. A choice of feeds from among a multitude of stocks is usually available to the refiner for charging to a coker, either by mixing charge stocks in varying combinations, changing - the selection of crude oils or varying the crude oil blends. Consequently, the feeds will exhibit varying properties resulting in different yields and coke characteristics. Depending on the design limitations of the coker, the refiner, to some extent, can also vary the coke yields and characteristics by changing the operating conditions. The three general classifications of product coke are sponge, honeycomb and needle. Sponge coke is produced from high resin-asphaltene feedstock. Due to its impurities and low electrical conductivity, sponge coke is not suitable for manufacturing anodes. In physical appearance, the coke contains small pores separated by thick walls. Honeycomb coke is produced from low resin-asphaltene feeds and, upon calcining and graphitization, can produce satisfactory quality anodes. The ellipsoidal pores are uniformly distributed. These pores are unidirectional and, when cut across the minor diameter, show a honeycomb structure. Needle coke is produced from highly aromatic thermal tar or decanted oil stocks. The graphitized product yields a premium grade anode. In appearance, the unidirectional pores are very slender, elliptical in shape and connected at the major diameter. The coke surrounding the voids is fragile and, upon fracturing, breaks into splintery or needle-shaped pieces. 85040 V-16 tyr,To improve coke quality, high resin-asphaltene feedstock can be blended with large quantities of thermal tar or decanted oil to yield more desirable honeycomb coke. Ina typical refinery, however, production of cracked stocks would not be sufficient for this requirement. Consequently, cracked stocks are effective only in upgrading the total quality of coke if the basic feedstock did not have a high resin-asphaltene content. intermediate resin-asphaltene stocks, which produce sponge coke at lower operating severities, can also yield honeycomb coke by increasing the recycle rate or operating pressure. Since the resin-asphaltene compounds are completely precipitated from the effluent, even at low operating severities, an increase in severity causes all additional coke — through the condensation of aromatics — to be formed by the most desirable reaction. Therefore, when a feed yields a coke having a quality near the transition region of sponge and honeycomb-type coke, a slight increase in recycle or drum pressure can promote the change to produce the better quality, honeycomb-type coke. The economics for increasing the pressure or recycle rate generally depend on the incremental profitability of producing an improved quality coke. For increased pressure, there is an additional capital investment cost attributed to the increased pressure rating of equipment. For added recycle, there is an incremental capital investment cost attributed to the additional heater duty rating and increased fuel consumption. However, operating at the higher severity also results in destruction of coker gas oil and additional production of gas (butanes and lighter) and naphtha. To perform a meaningful economic analysis, it is necessary to study the delayed coking unit with respect to the entire refinery operation. Sulfur generally exists in larger amounts in the sponge coke produced from the high resin-asphaltene stocks than in honeycomb coke produced from the low resin- asphaltene stocks. Asphaltene sulfur atoms are distributed in the interior of the aromatic sheets and also on the surface of the cluster of molecules. As these compounds are precipitated to coke in the coking reactions, few sulfur atoms are fragmented from the surface and all interior atoms are retained in the coke. Therefore, for two equal sulfur-bearing stocks, sulfur content in coke increases with the concentration of asphaltenes and Conradson carbon content of the feed. 85040 V-17 ieThe coke chamber temperature effect is governed by the degree of heavy oils vaporized off the coke. The heavy oils contain lesser amounts of sulfur than the coke mass. Consequently, an increase in the drum temperature vaporizes the lower sulfur bearing oils from the coke, leaving a more concentrated sulfur bearing residue. Besides sulfur and ash (metals) contents, organic volatile matter is another coke property which influences the price of green coke to the electrode manufacturing industry. This material consists of very heavy hydrocarbons deposited in the coke matrix. During the coke calcining step, these heavy hydrocarbons are almost completely volatilized, resulting in a dense calcined coke product with fixed carbon exceeding 98%. This makes it very suitable for finishing into graphite electrodes (current conductor) and graphite anodes (e.g., when graphite is part of an electrochemical cell, like in the electrolysis of brine, or is providing a source of electrons at a surface as in cells, batteries, vacuum tubes). Drum temperature is the primary variable affecting the volatile carbon matter content in the coke. Increasing the drum temperature enhances the vaporization of heavy hydrocarbons, in turn reducing the volatile carbon matter. Consequently, as the volatile matter is removed from the coke, a harder coke is produced. The ease of handling and removing the coke from the drum or the grindability characteristics required in preparing the coke for calcining would dictate the maximum coke drum temperature at which the unit would operate. 85040 V-18Process Flow Generally speaking, a coking unit will consist of the following sections (Figure V-5). * Coke Chamber Section — Contains the coker heater and coke chambers where coke is formed and recovered. * Fractionation Section — Distillate products formed in the coking reaction are recovered. The fractionator may contain several product side draws dependent on the desired product split. * Vapor Recovery Section — Co-product light gases and stabilized gasoline range material are recovered in this section of the unit. Rb . FI High Pressure Debutanizer Fractionator are Compressors Separator at Vapor | servercerwuecevcerect bey rrrecrennnannae 2 re Recovery pibrecceerervererees “5 i = 2 _f Coker 4 Off Gas CS Heater Water j to Fuel rN Absorber | 8 10 Coke Chambers A LCGO to (NL Hydrotreater 20 = “a VS KS 3 25 HVGO HVGO Stripper —_— to J HC Unibon Jc a Feed IRP-A00-08 Figure V-5 Coker Process Flow 85040 V-19 YrCoker charge is fed to the lower section of the fractionator where material lighter than the desired endpoint of the heavy gas oil is flashed off. The remainder combines with recycle and is pumped from the bottom of the fractionator to the coking heater where it is heated to about 900°F (482°C). This scheme is true for both delayed coking and single-coil partial recycling coking. The design of the coking heater must be done carefully to prevent premature coking in the heater tubes which limits the length of the run. Liquid-vapor mixture leaving the coking heater passes to a coke chamber. A unit usually has two coke chambers, one being filled while the other is being decoked. Large units may have more than two chambers. These chambers are most often sized so that each chamber operates on a 48-hour cycle. This arrangement permits decoking of one drum to be scheduled at the same time each day on a 24-hour coking, 24-hour decoking cycle. Under time-temperature conditions in the chamber, coke is formed and allowed to accumulate in the vessel. The overhead vapors pass into the lower section of the fractionating tower for separation into gas, gasoline, gas oils and recycle stock. Gas oils are yielded as side-cut products from the fractionator. The recycle stock is either passed into the fractionator bottoms for charging to the heater in the case of a single- coil design or taken as a separate fractionator cut and charged through a separate coil to the heater in a two-coil heater design. Fractionator overhead vapors are condensed and flow to an overhead receiver. Both unstabilized gasoline and uncondensed light co- products are directed to the vapor recovery section. Although variations are possible depending on customer requirements, the vapor recovery section is normally designed to recover separately a light gas stream which is usually sent to fuel, an olefin-rich C3/C4 product which can be directed to polymerization or alkylation operations, and a stabilized gasoline for direct blending into gasoline poo! or for further processing as required. Essentially the same process flow is used in the case of the ultimate coking process unit with the following exceptions. 85040 V-20* Use of a two-coil heater for more efficient conversion required for recycling gas oils to extinction Addition of a reaction chamber to provide the necessary coking time-temperature relationship Since gas oil is recycled to extinction, this is essentially the maximum coke process. The only products are coke and 400°F (204°C) minus material. The 400°F (204°C) minus products are considerably more than that produced in the delayed and partial recycle coking process and, consequently, will require a correspondingly larger vapor recovery unit. Where the refiner has a vapor recovery facility such as that used for thermal or catalytic cracking units, it is common practice to recover coker light products in that unit. Process Variables Crude Sources and Type of Charge Stock A coking unit can be operated either to produce high quality coke or to maximize the yield of gas, gasoline, and distillate products. The crude source and type of feedstock have a major effect on coke yield and quality. The Conradson carbon content of the feedstock is the predominant property determining the yield of coke; the higher the concarbon content of the feed, the higher the coke yield. The nature of the feedstock, that is, its relative proportions of asphaltenes, resins, and aromatics and its impurities levels, affect the quality of the coke. Coke Chamber Temperature The coke chamber temperature, adjusted by varying the coking heater transfer temperature, has an important effect on both the yield and quality of coke. Heater transfer temperatures should be maintained between 875-925°F (468-496°C). At lower temperatures, a tarry coke is produced; at higher temperatures, the rate of coke formation in the heater is greatly increased. Within the temperature range discussed for 85040 V-21 Yia given feedstock, an increase in temperature will decrease the yield of coke and gas plus gasoline. An increase in temperature generally results in an improvement in coke quality. Increasing the drum temperature increases the vaporization of heavy hydrocarbon, thus reducing the coke volatile carbon matter content. As the volatile matter is removed, a harder coke is produced. The material vaporized, however, contains less metals and sulfur than the bulk of the coke, so as these materials are removed, the impurities level of the coke tends to increase. Harder coke makes coke removal more difficult. The ease of handling and the grindability characteristics which affect the preparation of the green coke for calcining will determine the maximum coke drum temperature at which the unit can operate. Coke Chamber Pressure The thermal cracking reactions upon which the process is based are a function of time and temperature. The effect of the two variables is related. The drum pressure, which determines the degree of vaporization and, therefore, the velocity through the heater and coke chamber, can be used to vary the residence time. The effect of increased residence time is that the yield of coke is increased. The pressure is controlled by the fractionator overhead receiver pressure controller. During normal operation, the pressure is maintained constant and the temperature is varied to adjust coke yield. Combined Feed Ratio The combined feed ratio is the volume of fractionator bottoms (fresh feed plus recycle) divided by the volume of fresh feed. As the combined feed ratio is decreased, the heavy gas oil product rate increases at the expense of all other products. The coke produced will be softer and have a higher volatile combustible material (VCM) and impurities level. The combined feed ratio can be varied by altering the gas oil draw rate. An increase in the gas oil draw will decrease the ratio. 85040 V-22