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CHAPTER THREE
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include hydrogen consumption that may be 20 to 100 percent higher than that for fixed bed resid desulfurization process, and loss of liquid and hydrogen to high gas yields The distillate products require further hydrotreating and conversion to produce transportation fuels Thus, the options for refiners processing heavy high sulfur will be a combination of upgrading schemes and by-product utilization Other heavy oil upgrading options include: (a) deep cut vacuum distillation, (b) solvent deasphalting prior to conversion, and (c) hydrogenation prior to conversion For the present, using a schematic refinery operation (Fig 31), new processes for the conversion of residua and heavy oils will probably be used in concert with visbreaking with some degree of hydroprocessing as a primary conversion step Other processes may replace or augment the deasphalting units in many refineries Depending on the properties, an option for heavy oil, like tar sand bitumen, is to subject the feedstock to either delayed coking or fluid coking as the primary upgrading step with some prior distillation or topping (Speight, 2007) After primary upgrading, the product streams are hydrotreated and combined to form a synthetic crude oil that is shipped to a conventional refinery for further processing to liquid fuels The product qualities resulting from the various heavy oil upgrading technologies are quite variable and are strongly dependent on feed type, process type, and processing conditions However, producing fuels of acceptable properties is possible (in all cases) with existing petroleum processing technology, although the economics vary with a given refinery However, there is not one single heavy-oil-upgrading solution that will fit all refineries Heavy feedstock properties, existing refinery configuration, and desired product slate all can have a significant effect on the final configuration Furthermore, a proper evaluation however is not a simple undertaking for an existing refinery The evaluation starts with an accurate understanding of the nature of the feedstock; along with corresponding conversion chemistry need to be assessed Once the options have been defined, development of the optimal configuration for refining the incoming feedstocks can be designed
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35 PETROLEUM PRODUCTS AND FUELS
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Petroleum products and fuels, in contrast to petrochemicals, are bulk fractions that are derived from petroleum and have commercial value as a bulk product (Speight, 2007) In the strictest sense, petrochemicals are also petroleum products but they are individual chemicals that are used as the basic building blocks of the chemical industry The constant demand for fuels is the main driving force behind the petroleum industry Other products, such as lubricating oils, waxes, and asphalt, have also added to the popularity of petroleum as a national resource Indeed, fuel products derived from petroleum supply more than half of the world s total supply of energy Gasoline, kerosene, and diesel oil provide fuel for automobiles, tractors, trucks, aircraft, and ships Fuel oil and natural gas are used to heat homes and commercial buildings, as well as to generate electricity Petroleum products are the basic materials used for the manufacture of synthetic fibers for clothing and in plastics, paints, fertilizers, insecticides, soaps, and synthetic rubber The uses of petroleum as a source of raw material in manufacturing are central to the functioning of modern industry 351 Gaseous Fuels Natural Gas Natural gas, which is predominantly methane, occurs in underground reservoirs separately or in association with crude oil (Speight, 2007) The principal types of gaseous fuels are oil (distillation) gas, reformed natural gas, and reformed propane or liquefied petroleum gas (LPG)
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FUELS FROM PETROLEUM AND HEAVY OIL
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The principal constituent of natural gas is methane (CH4) Other constituents are paraffinic hydrocarbons such as ethane (CH3CH3), propane (CH3CH2CH3), and the butanes [CH3CH2CH2CH3 and/or (CH3)3CH] Many natural gases contain nitrogen (N2) as well as carbon dioxide (CO2) and hydrogen sulfide (H2S) Trace quantities of argon, hydrogen, and helium may also be present Generally, the hydrocarbons having a higher molecular weight than methane, carbon dioxide, and hydrogen sulfide are removed from natural gas prior to its use as a fuel Gases produced in a refinery contain methane, ethane, ethylene, propylene, hydrogen, carbon monoxide, carbon dioxide, and nitrogen, with low concentrations of water vapor, oxygen, and other gases Liquefied Petroleum Gas Liquefied petroleum gas (LPG) is the term applied to certain specific hydrocarbons and their mixtures, which exist in the gaseous state under atmospheric ambient conditions but can be converted to the liquid state under conditions of moderate pressure at ambient temperature These are the light hydrocarbons fraction of the paraffin series, derived from refinery processes, crude oil stabilization plants and natural gas processing plants comprising propane (CH3CH2CH3), butane (CH3CH2CH2CH3), isobutane [CH3CH(CH3)CH3] and to a lesser extent propylene (CH3CH=CH2), or butylene (CH3CH2CH=CH2) The most common commercial products are propane, butane, or some mixture of the two and are generally extracted from natural gas or crude petroleum Propylene and butylenes result from cracking other hydrocarbons in a petroleum refinery and are two important chemical feedstocks Mixed gas is a gas prepared by adding natural gas or liquefied petroleum gas to a manufactured gas, giving a product of better utility and higher heat content or Btu value The compositions of natural, manufactured, and mixed gases can vary so widely, no single set of specifications could cover all situations The requirements are usually based on performances in burners and equipment, on minimum heat content, and on maximum sulfur content Gas utilities in most states come under the supervision of state commissions or regulatory bodies and the utilities must provide a gas that is acceptable to all types of consumers and that will give satisfactory performance in all kinds of consuming equipment However, there are specifications for liquefied petroleum gas (ASTM D1835) which depend upon the required volatility Since natural gas as delivered to pipelines has practically no odor, the addition of an odorant is required by most regulations in order that the presence of the gas can be detected readily in case of accidents and leaks This odorization is provided by the addition of trace amounts of some organic sulfur compounds to the gas before it reaches the consumer The standard requirement is that a user will be able to detect the presence of the gas by odor when the concentration reaches 1 percent of gas in air Since the lower limit of flammability of natural gas is approximately 5 percent, this 1 percent requirement is essentially equivalent to one-fifth the lower limit of flammability The combustion of these trace amounts of odorant does not create any serious problems of sulfur content or toxicity The different methods for gas analysis include absorption, distillation, combustion, mass spectroscopy, infrared spectroscopy, and gas chromatography (ASTM D2163, ASTM D2650, and ASTM D4424) Absorption methods involve absorbing individual constituents one at a time in suitable solvents and recording of contraction in volume measured Distillation methods depend on the separation of constituents by fractional distillation and measurement of the volumes distilled In combustion methods, certain combustible elements are caused to burn to carbon dioxide and water, and the volume changes are used to calculate composition Infrared spectroscopy is useful in particular applications For the most accurate analyses, mass spectroscopy, and gas chromatography are the preferred methods The specific gravity of product gases, including liquefied petroleum gas, may be determined conveniently by a number of methods and a variety of instruments (ASTM D1070, ASTM D4891)
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