Lesson 11 Petroleum Refineries Lesson Goal and Objectives Goal To familiarize you with the general operation of a refinery, potential air pollution emission points, and the control equipment or procedures used to reduce these emissions. Objectives At the end of this lesson, you should be able « 1. describe the four basic procedures involved in the refining of crude oil: ‘© separating, * converting, * treating, and * blending. 2. list eight air pollution sources and the types of pollutants they emit. 3. describe the control equipment or procedures used to reduce emissions from sources of air pollution in a petroleum refinery. Introduction Crude oil is a mixture of hydrocarbon compounds and small amounts of sulfur. nitrogen, oxygen. and various metals. The chemical and physical characteristics of crude oils differ significantly; some crude oils are clear, volatile liquids, while others are heavy, viscous sludges. The exact chemical (pro- portions of the various organic compounds) and physical characteristics of a crude oil depend on its original geographic location. A petroleum refinery takes one or more crude oils and converts, oF refines, these oils into useful products such as gasoline, heating oils, lubricating oils, and a wide variety of chemicals and solvents. The refining process involves first separating the crude oil into its various components. The less desirable or usable components are then sent to treating processes to remove impurities such as sulfur and metals and/or to conversion processes to increase the yield (amount produced) of the more desirable products (i.e., gasoline). In discussing the emission sources at a refinery, an understanding of the entire refining process is important. A refinery is comprised of many individual process units, each designed and operated to process specific crude oils and produce specific products. The number and complexity of the process units at each refinery varies significantly. Therefore, it is impossible to label one flow diagram as “typical” of all refineries. Although each refinery is unique, the process units at any refinery can be categorized into four basic procedures: © separating, * converting, © treating, and © blending.The following discusses the important process units, not only in terms of production but also atmospheric emissions, for each of these refining procedures, Refining Process A refinery is made up of many interconnected process units. As we said, no single flow diagram can be used to show the relationship of the process units at all refineries. Figure 11-1 presents a simplified schematic of the layout of the basic refining operation. Most refineries are designed to maximize the production of gasoline (light distillates). Some small refineries may only perform crude separation and some limited treating. Large refineries, however, have converting and additional treating Processes. Although each process unit in a refinery performs a different function (separating, con- verting, etc.), the equipment used in any process unit is very similar. Process units generally consist of reaction vessels or towers. piping, pumps, compressors, valves, and heat exchangers. Therefore. the physical appearances of the different process units are similar, making any refinery look like incricace ‘masses of pipes and towers (see Figure 11-2). Separacing Treating couring} Blencing ‘Crude ditionSeparating The first step in the refining process is to separate the crude oil into its various components. Separating the components is accomplished by heating the crude oil and then removing the various components according to their boiling ranges. This separation process is referred to as distillation, or ‘fractionation. Figure 11-S illustrates a two-stage separation operation. This two-stage separation con- sists of a crude atmospheric distillation tower and a vacuum distillation tower Before entering the crude distillation tower, the crude oil is heated to approximately 400°C (750°F) in a furnace. The heated crude oil enters the distillation tower and the vapor (lighter hydrocarbons) begins to rise up through the tower. The tower consists of many trays spaced an equal distance apart. Components having a low molecular weight pass up through these trays, while the heavier components begin to condense on the lower trays. At various points in the cower, liquid is drawn off the trays. Components with the lowest boiling point (also low molecular weight) are drawn off the top of the tower while the liquid with the higher boiling point leaves the bottom of the tower. The liquid leaving the bottom of the tower is sent to the vacuum distillation tower for further separa- tion. The sidestreams can be sent to storage to await additional processing or blending as final product, The operation of the vacuum distillation tower is similar to the crude distillation tower, except that the pressure in the tower is lower (vacuum). The vacuum tower is used to separate the heavier por- tion of the crude (from the bottom of the atmospheric distillation tower) into fractions. Operating under a vacuum enables the heavier compounds to vaporize at lower temperatures. If heavy crude is distilled at high temperatures it tends to decompose or polymerize, possibly plugging operating equip- ment and reducing the percent yield of product produced. The vacuum is usually created by using a steam ejector.Figure 1-5. Separating: cwo-aage diillacion. Converting Conversion processes are used to increase the quantity and the quality of the end products at a refinery. Unlike the separation processes which merely separate the crude oil according to molecular weight, conversion processes change the chemical structure of the components. The less desirable components are converted to more salable products. For example, most crude oils contain only a small percentage of gasoline. To meet the high demand for gasoline, the heavy gas oils are converted to gasoline, increasing the average yield co over 40% gasoline from a barrel of crude.Various conversion processes are used in a refinery. Some of the more common ones are listed in Table 11-1. The most common process is to “crack” the high molecular-weight, high boiling-point compounds (heavy fuel oils) into smaller, low molecular-weight, low boiling-point compounds (gasoline). Several cracking processes have been used, including thermal cracking, catalytic cracking. and hydrocracking. Catalytic cracking is the most important (both from an environmental and end- product viewpoint). Of the several different catalytic cracking processes, fluid catalytic cracking (FCC) is by far the most widely used. ‘Table 1-1. Conversion proce. Cracking A. Thermal caching 1. Visbreaking oF vacancy breaking Used to reduce the visconry of some residual fractions #0 hae they ay be blended into fuel ot Visbreaking ss muld form of cracking that scarred ‘out in « heating furnace and disllason cower 2, Coking Severe form of thermal cracking. Convers low-value residual fuel ol w higher-value ‘gu oi pl preoleum coke, The coking proces is carried out a¢ high temperarures and low Pressres. B, Catalyse cracking Breaks down the heavier daillate fracons into the lighter. more valuable {fline. The catalyic cracking procem can be catagorand as 4 Guidised bed, momag bed, of fixed bed (once-dough). By far. the mow predominant isthe Ouidized bed denga. /— Used wo upgrade « wide vary of feedstocks into more valuable product. [a laydrocraching, the feedmocks are cracked ia the preemce of hydrogen. crusing the cracked produce to become sarurated with hydrogen. Because hydrogen i wed, hydrocracking aso ‘Eaproves the quar ofthe product by denufursing and denirfying the feedmocks. A wide vranery of catalua and ces designe are used in hydrocracking. (Catalsic reforming — Used to rearrange the srucrure of low-octane compounds to yield high-occane ‘compounds. The proce coavera arsight-chained naptha to ringed- or branched-arvctured guciine ‘components The reforming proces alo produces hydrogen which i used in other refinery procenes ‘Alkylason Joins together two different srucrared compounds, and some rythecc chemicals. One ofthe compounds made i branched or ringed molecule, while che other is 4 double-bonded ‘molecule Sulfuric or hydroluorc acid is wae to easly the reaction. Imerzasion Ui ssiar to catalytic reforming ia tha ti wed to rearrange the sructure of + com: pound. The iomerizacon proces is unally applied vo burane or misrure of peatane and hesane to ‘ereeee their one eating.Figure 11-4 illuscrates one design for a fluid catalytic cracking unit (FCCU). In this design. the feed seream (heavy gas oils) is heated and then mixed with the hot, regenerated powder-like catalyst. ‘The liquid gas oils begin to vaporize. crack into smaller compounds, and rise to the reactor carrying the catalyse with them. Seeam is added to the reactor to fluidize che catalyst and to strip the hydrocarbon products from the catalyst. The gaseous products rise through the reactor vessel, pass through cyclones to remove entrained catalyst particles, and are removed from the top of che reactor. Crone Liquid gus oi/eacalym Liguid (heavy gus ols) A Tigure 11-4. Simplified Msid caralyse cracking anit. During the reaction, coke deposits form on the finely-powdered catalyst particles. These coke deposits must be continually removed to maintain catalyst activity. The spent catalyst is withdrawn from the reactor and sent back to the regenerator. In the regenerator, a controlled amount of air is added to burn off the coke without harming the catalyst. The gases in the regenerator pass through cyclones that separate the regenerated catalyst dust from the combustion gases. This “cyclone” may be a single cyclone, dual cyclones, or multiple large diameter cyclones. (Chapter 2 covers operating principles of cyclones.) The exhaust gases from the cyclones contain particulate matter. carbon monoxide, sulfur oxides, nitrogen oxides, and hydrocarbon vapors. 11-6Treating ‘Treating, or “purification” processes are used to remove sulfur. nitrogen. and metal compounds from the intermediate feedstocks. Removing these compounds improves the quality of the products by eliminating odors, discoloration, and in some instances, producing a more stable finished compound. These compounds must also be removed to avoid damaging the catalysts used in the conversion proc: esses such as catalytic cracking and catalytic reforming. Numerous treating processes can be used. depending on the contaminant that must be removed. Presently, the most common treatment process for all types of petroleum products is hydrotreating. In hydrotreating, the petroleum products are passed over a catalyst and hydrogen gas is injected into the reactor. The hydrogen reacts with the sulfur in the oil and converts the sulfur into hydrogen sulfide. The hydrogen sulfide is then removed and may be recovered as elemental sulfur by further processing, In addition to removing sulfur. hydrotreating can also be used to saturate (add hydrogen to) many unstable double-bonded compounds; thereby reducing their tendency to polymerize (form gammy substances). When hydrotreating is used to remove sulfur, it is referred to as hydrodesulfurization. Many other treatment processes are available to remove undesirable contaminants. In general, the petroleum products can be washed with acids (such as HySO,) or caustic bases (such as NaOH) to remove sulfur compounds (especially mercaptans). Removing these compounds improves the quality and/or performance of the petroleum products. Filtration, absorption. and air blowing are other processes used to purify che petroleum products. Blending Blending involves mixing different fractions of the “refined” petroleum products to produce over 2000 finished products. Products are blended to meet specifications as to the vapor pressure, vis- cosity, sulfur content, boiling point, or octane number desired. Blending is a closed process that, occurs in pipelines or tanks that use pumps and valves to mix the various petroleum factions. Review Exercise 1. True or False? The chemical composition of crude oil is exactly the same for all geographic locations. 2. Four basic procedures involved in the refining of crude 1. False oil are: heating the crude and removing its components according to * treating their * converting 2. crpsal size. * blending b. boiling point 5. Separating the crude oil into its fractions is accomplished by 2. © separating €. octane number. 3. b. boiling point4, Two stage distillation usually occurs in and. distillation towers. 5. In a distillation tower, the components with the boiling point (_____ molecular weight) are drawn off at the top of the tower. a. lowest, lowest b. highest, lowest ¢. lowest, highest d. highest, highest — 4. atmospheric and vacuum 6. The feed stream into the vacuum distillation tower comes from the top/bottom of the atmospheric tower. 5. a. lowest, lowest 7. Operating a distillation tower under a vacuum causes the 6. bottom components to vaporize at temperatures. a. higher b. lower ¢. indeterminable 8. True or False? Conversion processes change the chemical 7. b. lower structure of the less desirable components to make them more salable. 9. The conversion process used to break high molecular-weight, 8. True high boiling-point compounds into smaller, low molecular- weight, low boiling-point compounds is a. thermal cracking. , catalytic cracking. ¢. hydrocracking. d. any of the above 10. By far, the most widely used of the catalytic cracking processes is ; 11. Im the fluid catalytic cracking process, the catalyst is continually regenerated by a. adding steam. b. burning off the coke which deposits on the catalyst. cc. cooling the catalyst. 4. washing the catalyst with a caustic solution of NaOH. 9. d. any of the above 10. fluid catalytic cracking 12. The exhaust gases from the catalyst regenerator may contain a. particulate matter. b. CO. ¢. hydrocarbons. d, all the above 11, b. burning off the coke which deposits on the catalyst. Processes are used to remove sulfur, nitrogen, or metal compounds from the intermediate petroleum products. 12. 4. all the above 11-8 18. Treating14. True oF False? In addition to removing sulfur, hydroueaung can also be used to saturate many unstable double-bonded compounds, reducing their tendency to polymerize, 18. Washing petroleum products with acids or bases removes 14. True 16. ____ involves mixing the different petroleum fractions to produce a finished product. Air Pollution Emissions 15. sulfur compounds 16. Blending Refineries can emit particulate matter, hydrocarbons (volatile organic compounds), sulfur oxides, nitrogen oxides, and carbon monoxide. The type and quantity of pollutants emitted from a refinery depends on many factors such as type of crude. capacity, complesity of the processing. air pollution control equipment, and the degree of maintenance and housekeeping practices used in the plant. Only a few processes emit pollutants directly into the atmosphere through exhaust stacks. Unfor tunately, there are a large sumber of potential fugitive emission sources in the refinery. Table 11-2 lists, by type of emission, the potential emission sources in a typical refinery ‘Table 11-2, Poesndal waren of stmowpheric enimions within refinerin Type ol enimion ‘Saree Pardculare maar Suufur oxides Nierogen oxides Hidrocarboas Carbon monoxide Odors ‘Gatlyaic cracker. fad coking, cata regeneracon, procea heater. bolle, decoking operations, icinerstory Slfarrecorery unit, catalyde cracking, procem heater, toler. decoking opersions, uns regeneration easing ‘ic, aree Proces beaten boiler. catalyt regenera, Hare caulyee racking Storage tanks. loading operations, wate water teatng, ‘aalya regeneration, baromeic condenses, process heaere, Dole. cooling towers, vacuum joa, equipment leais (pumps, valves, blind changing) (Catalpe regenerason, decking, comprenor engines, Source: EPA, March 1979,Particulate Matter ‘The potential sources of particulate matter at a refinery are catalyst regenerators, boilers, process heaters, fluid cokers, decoking operations and incinerators. The major potential source of particulate matter is from catalyst regenerators used in the catalytic cracking units. Coke, which forms on the surface of the catalyst during the cracking process, must be burned off in regenerating units. Since flue gas from the regenerator contains heavy concentrations of catalyst dust, it must be sent to a con- trol device. Carbon Monoxide Of the sources listed in Table 11-2 the major emitter of CO is the regenerator for the catalytic crack- ing unit. In the regenerator. a controlled amount of air is used to burn off the coke from the catalyst, resulting in CO formation. Other sources of CO emissions include any combustion process that is operated improperly. Sulfur Oxides Crude oils from different parts of the world vary significantly in their sulfur content. Sulfur exists in crude oils in many forms, such as HS or attached to organic compounds (mercaptans). The major sulfur compound generated by refining is hydrogen sulfide. Nearly all refinery processes generate some gases which contain hydrogen sulfide or other low molecular weight sulfur compounds. The largest potential sources of these gases are from hydrotreating, cracking, and reforming processes. The exhaust gases from these processes are used as fuel in process heaters and boilers, and would result in sulfur oxide emissions if the sulfur compounds are not removed, ‘Another potential source of sulfur emissions is from the sour water strippers. Aqueous solutions from many refinery processes are contaminated with hydrogen sulfide. (In a refinery, streams containing HS are referred to as sour.) The hydrogen sulfide is removed from the water by steam stripping in sour water strippers. The stripped hydrogen sulfide can then be sent to a sulfur recovery unit, which reduces the potential SO; emissions resulting from the combustion of H,S. In addition, refineries also emit SO; emissions from the burning of residual fuel oil in boilers and process heaters. The quantity of SO, emissions depends on the percent of sulfur contained in the fuel. Nitrogen Oxide Nitrogen oxide emissions result from the combustion of fuel in process heaters and boilers, internal combustion engines used to drive compressors, and catalyst regenerators. For nitrogen oxide emis- sions, the amount emitted depends more on the design of the combustion unit than on the type of fuel. Hydrocarbons or Volatile Organic Compounds ‘As can be seen from Table 11-2, most of the equipment in a refinery has the potential to emit hydrocarbon vapors. Hydrocarbon vapors are released into the atmosphere in two ways. The vapors can be entrained in the exhaust gas and released through a stack, or they can be emitted from equi ment whenever the oils being processed are exposed to the atmosphere —either intentionally or by leaks. The amount of emissions depends on the volatility (vapor pressure) of the oils being processed. 11-10