Refinery Overview

Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed 1. Introduction Oil refining is one of the most complex chemical industries, which involves many different aspects and complicated processes with various possible connections. The objective in refinery operations is to generate as much profit as possible by converting crude oils into valuable products such as gasoline, jet fuel, diesel, and so on [James et al., 2001; Zhang et al., 2000]. In recent years the requirements for large quantities of liquid hydrocarbons, particularly gasoline and diesel fuels, have increased and will continue to escalate, which will necessarily cause the steady rise in production volume of the refining industry. The International Energy Agency in its World Energy Outlook 2008 is predicting the increase in yearly oil use to be 1.3% until 2020 and 1.0% from 2020 to 2030 [Muzic et al., 2010]. 2. Refinery The typical fuels refinery has as a goal the conversion of as much of the barrel of crude oil into transportation fuels as is economically practical. These transportation fuels have boiling points between 0 and 345C (30 to 650F). The greater the densities will mean more of the crude oil will boil above 566C (1050F). Historically this high-boiling material or residua has been used as heavy fuel oil but the demand for these heavy fuel oils has been decreasing because of stricter environmental requirements. This will require refineries to process the entire barrel of crude rather than just the material boiling below 566C (1050F) [James et al., 2001]. In refineries some processes will take place depending on the complexity of the refinery (may be all) such as crude desalting and atmospheric and vacuum distillation; gasoline manufacturing processes, such as catalytic reforming, catalytic cracking, alkylation, and isomerization; hydrodesulfurization processes for naphtha, kerosene, diesel, and reduced crude; conversion processes such as distillate and resid hydrocracking; resid conversion processes such as delayed coking, visbreaking, solvent deasphalting, and bitumen manufacture; pollution control processes such as sulfur manufacture, sulfur plant tail gas treatment, and stack gas desulfurization.

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Refinery Overview
Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed 2.1. Crude desalting Crude desalting is the first processing step in a refinery. The objectives of crude desalting are the removal of salts and solids and the formation water from unrefined crude oil before the crude is introduced in the crude distillation unit of the refinery. 2.2. Refinery distillation Crude oil as produced in the oil field is a complex mixture of hydrocarbons ranging from methane to asphalt, with varying proportions of paraffins, naphthenes, and aromatics. The objective of crude distillation is to fractionate crude oil into light-end hydrocarbons (C1-C4), naphtha/gasoline, kerosene, diesel, and atmospheric resid. Some of these broad cuts can be marketed directly, while others require further processing in refinery downstream units to make them saleable. 2.3. Hydrotreating Hydrotreating processes aim at the removal of impurities such as sulfur and nitrogen from distillate fuels (naphtha, kerosene, and diesel) by treating the feed with hydrogen at elevated temperature and pressure in the presence of a catalyst. 2.4. Hydrocracking Distillate hydrocracking is a refining process for conversion of heavy gas oils and heavy diesels or similar boiling-range heavy distillates into light distillates (naphtha, kerosene, diesel, etc.) or base stocks for lubricating oil manufacture. The process consists of causing feed to react with hydrogen in the presence of a catalyst under specified operating conditions: temperature, pressure, and space velocity. 2.5. Thermal processes 2.5.1. Visbreaking Visbreaking is a mild thermal cracking process. The function of a visbreaking unit is to produce lower viscosity and low-pour resid for blending to fuel oil. In this cracking process, cracked gas, gasoline/ naphtha, gas oil, and thermal tar are produced. The gas oil is blended back into the thermal tar to yield fuel oil. Thermal cracking reduces the viscosity and pour point of the resid

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Refinery Overview
Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed and hence the cutter stock requirement for blending this resid to fuel oil. Thus, the overall production of fuel oil is reduced. A second consideration is the removal of some feed sulfur. Although visbreaking is an inefficient process in this respect, sulfur removal does occur to some extent. 2.5.2. Delayed coking Delayed coking is a thermal process in which the vacuum residue from crude distillation is heated in a furnace then confined in a reaction zone or coke drum under proper operating conditions of temperature and pressure until the unvaporized portion of the furnace effluent is converted to vapor and coke. Delayed coking is an endothermic reaction, with the furnace supplying the necessary heat for the coking reactions. The reactions in the delayed coking are complex. In the initial phase, the feed is partially vaporized and cracked as it passes through the furnace. In the next step, cracking of the vapor occurs as it passes through the drum. In the final step, successive cracking and polymerization of the liquid confined in the drum takes place at high temperatures, until the liquid is converted into vapor and coke. The coke produced in the delayed coker is almost pure carbon containing some of the impurities of the feed, such as sulfur and metals. 2.6. Gasoline manufacturing processes 2.6.1. Catalytic reforming Catalytic reforming of heavy naphtha is a key process in the production of gasoline. The aim of catalytic reforming is to transform, as much as possible, hydrocarbons with low octane to hydrocarbons with high octane. The chemical reactions that lead to these changes are guided by a catalyst under well-defined operating conditions. 2.6.2. Fluid catalytic cracking Fluid catalytic cracking (FCC) is an effective refinery process for conversion of heavy gas oils into gasoline blend components. Cracking is achieved at high temperatures in contact with powdered catalyst without the use of hydrogen. After separation of the catalyst, the hydrocarbons are separated into the desired products by fractionation. The main products of the FCC process are gasoline, distillate fuel oil, and olefinic C3/C4 liquefied petroleum gas (LPG). By-product

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Refinery Overview
Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed coke, which is deposited on the catalyst during the reaction, is burned off in the regenerator. The heat liberated during the combustion of coke supplies the heat required to vaporize the feedstock and heat of reaction. 2.6.3. Alkylation Alkylation is important refining processes for the production of alkylate a high-octane gasoline blending component. Alkylate product is a mixture of branched hydrocarbons of gasoline boiling range. 2.6.4. Isomerization Most gasoline formulations require inclusion of some light naphtha to meet the front-end distillation and octane specs. However, C5/C6 normal paraffins in this boiling range have low octane, which make them very difficult to include in the gasoline formulation. Branched chain C5 and C6 hydrocarbons have higher octane, making them more suitable for inclusion in gasoline. The isomerization process is designed for continuous catalytic isomerization of pentanes, hexanes, and their mixtures. The process is conducted in an atmosphere of hydrogen over a fixed bed of catalyst and at operating conditions that promote isomerization and minimize hydrocracking. 3. General properties of petroleum fractions Most petroleum distillates, especially those from the atmospheric distillation, are usually defined in term of their ASTM boiling ranges. The following general class of distillates is obtained from petroleum: liquefied petroleum gas, naphtha, kerosene, diesel, vacuum gas oil, and residual fuel oil. 3.1. Distillates 3.1.1. Liquefied Petroleum Gas The gases obtained from crude oil distillation are ethane, propane, and n-butane isobutene. These products cannot be produced directly from the crude distillation and require high-pressure distillation of overhead gases from the crude column. C3 and C4 particularly are recovered and sold as liquefied petroleum gas (LPG), while C1 and C2 are generally used as refinery fuel.

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Refinery Overview
Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed 3.1.2. Naphtha C5-400F ASTM cut is generally termed naphtha. There are many grades and boiling ranges of naphtha. Many refineries produce 400 F end-point naphtha as an overhead distillate from the crude column, then fractionate it as required in separate facilities. Naphtha is used as feedstock for petrochemicals either by thermal cracking to olefins or by reforming and extraction of aromatics. Also some naphtha is used in the manufacture of gasoline by a catalytic reforming process. 3.1.3. Kerosene The most important use of kerosene is as aviation turbine fuel. This product has the most stringent specifications, which must be met to ensure the safety standards of the various categories of aircraft. The most important specifications are the flash and freeze points of this fuel. The initial boiling point (IBP) is adjusted to meet the minimum flash requirements of approximately 100F. The final boiling point (FBP) is adjusted to meet the maximum freeze point requirement of the jet fuel grade, approximately -52F. Full-range kerosene may have an ASTM boiling range between 310 and 550F Basic civil jet fuels are 1. Jet A, a kerosene-type fuel having a maximum freeze point of -40F Jet A-type fuel is used by mainly domestic airlines of various countries, where a higher freeze point imposes no operating limitations. 2. Jet A-1, a kerosene-type fuel identical with Jet A but with a maximum freeze point of -47F. This type of fuel is used by most international airlines. Jet A and Jet A-1 generally have a flash point of 38F. 3. Jet B is a wide-cut gasoline-type fuel with a maximum freeze point of -50 to -58F. The fuel is of a wider cut, comprising heavy naphtha and kerosene, and is meant mainly for military aircraft. 3.1.4. Diesel Diesel grades have an ASTM end point of 650-700F Diesel fuel is a blend of light and heavy distillates and has an ASTM boiling range of approximately 350-675F Marine diesels are a little heavier, having an ASTM boiling end point approximately 775F. The most important specifications of diesel fuels are cetane number, sulfur, and pour or cloud point. Cetane number is related to the burning quality of the fuel in an engine. The permissible sulfur content of diesel Page 5 of 8

Refinery Overview
Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed is being lowered worldwide due to the environmental pollution concerns resulting from combustion of this fuel. Pour point or cloud point of diesel is related to the storage and handling properties of diesel and depends on the climatic conditions in which the fuel is being used. 3.1.5. Vacuum Gas Oil Vacuum gas oil is the distillate boiling between 700 and 1000F. This is not a saleable product and is used as feed to secondary processing units, such as fluid catalytic cracking units, and hydrocrackers, for conversion to light and middle distillates. 3.1.6. Residual Fuel Oil Hydrocarbon material boiling above I000 F is not distillable and consists mostly of resins and asphaltenes. This is blended with cutter stock, usually kerosene and diesel, to meet the viscosity and sulfur specifications of various fuel oil grades. 3.2. Vacuum distillation products In an atmospheric distillation tower, the maximum flash zone temperature without cracking is 700-800F. The atmospheric residuum, commonly known as reduced crude, contains a large volume of distillable oils that can be recovered by vacuum distillation at the maximum permissible flash zone temperature. The TBP cut point between vacuum gas oil and vacuum resid is approximately 1075-1125F. The cut point is generally optimized, depending on the objectives of the vacuum distillation, into asphalt operation and pitch operation. 3.2.1. Asphalt Operation Given the specification of the asphalt (penetration) to be produced, the corresponding residuum yield can be determined from the crude assay data. In case a number of lubricating oil distillates is to be produced, the distillation range of each has to be specified, and the corresponding yields can be determined from the crude assay data. Lube cuts are produced as sidestreams from the vacuum column. In asphalt operation, some gas oil must remain in the pitch to provide the proper degree of plasticity. The gravity of an asphalt stream is usually between 5 and 8 oF API. Not all crudes can be used to make asphalt.

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Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed Experimental data for asphalt operation are necessary to relate asphalt penetration to residual volume. The penetration range between 85 and 10, are possible and the units are generally designed to produce more than one grade of asphalt. The principal criteria for producing lube oil fractions are viscosity, color, and rejection to residuum the heavy impurities and metals. These oils are further refined by solvent extraction, dewaxing, and other types of finishing treatment, such as hydrotreating.

References James H. Gary and Glenn E. Handwerk, Petroleum Refining Technology and Economics, 4th edition, Marcel Dekker Inc., ISBN: 0-8247-0482-7, 2001. Muzic M., K. Sertic-Bionda, T. Adzamic, The Application of Theoretical Solutions to the Differential Mass Balance Equation for Modelling of Adsorptive Desulfurization in a Packed Bed Adsorber, Chemical Engineering and Processing, doi:10.1016/j.cep.2011. 02 .009, 2010. Refinery process handbook Rober A. Meyers, Handbook of petroleum refining processes, 3rd edition, McGraw-Hill handbooks. Zhang N., Zhu X.X., A novel modelling and decomposition strategy for overall refinery optimization, Computers and Chemical Engineering, vol. 24, pp. 1543- 1548, 2000.

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Report No.1 (11-2011) Dalia Mamoun Beshir Mohamed Appendix A A typical diagram of oil refinery

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