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Appendices Reading makes a person knowledgeable, conversation - resourceful, and the habit of recording – accurate. Francis Bacon (1561–1626), an English philosopher. Twelve appendices contain diverse information about physicochemical properties of crude oils and petroleum products; physicochemical properties of sulfur com- pounds, acids, alkalis, and hydrogen used in refinery units; chemical composition of alloys; metallographic replication; fouling mechanism; chemical cleaning from fouling; recommended procedure for passivation of cooling water systems; and boil-out procedure (chemical cleaning and passivation of inner surfaces of boiler and steam pipelines). © Springer International Publishing Switzerland 2017 289 A. Groysman, Corrosion Problems and Solutions in Oil Refining and Petrochemical Industry, Topics in Safety, Risk, Reliability and Quality 32, DOI 10.1007/978-3-319-45256-2 Appendix A Schematic of a Typical Oil Refinery Sulfur Claus plant Fuel gas Gas plant LPG Deethanizer Blending Liquefied Depropanizer n-Butane petroleum Alkyla gas (LPG) Alkylation feed Catalytic te Light Alkylation Gasoline Naphtha Atmo- Catalytic Blending Iso-naphtha Automotive spheric Isomerization Heavy gasoline Desalted Distillation Platformate Crude oil naphtha Crude oil Hydrotreating/ Catalytic Cat cracked Desalting Desulfurization Reforming Kerosene naphtha Middle Jet fuels distillate SR kerosene Crude Oil HDS mid Storage Atmospheric Hydrotreating/ distillate residue Deslufurization Distillate Distillate fuel oils SR mid Blending distillate Diesel fuel oils Loading Cat cracked Crude distillate Catalytic Vacuum Heavy vacuum distillate Cracking Distillation Cat cracked clarified oil Heavy fuel oils Residual (burner oils) Coker/Visbreaker Distillate (Gas oil) Treating Vacuum And residue Green Coke Blending Bitumen Visbreaking Thermally Coke Drum cracked residue Bitumen Schematic of a Typical Oil Refinery © Springer International Publishing Switzerland 2017 291 A. Groysman, Corrosion Problems and Solutions in Oil Refining and Petrochemical Industry, Topics in Safety, Risk, Reliability and Quality 32, DOI 10.1007/978-3-319-45256-2 Appendix B Physicochemical Properties of Crude Oils and Petroleum Products Crude oil is a mixture of numerous distinct chemical compounds, mainly hydrocarbons. Crude oil classification. Crude oil is described by density (°API) and distillation curves (boiling point ranges). Classification of crude oils is usually made according to density (gravity), crude composition, sulfur content, and geographical origin. API gravity: Crude oil gravity may range from less than 10 °API to over 50 °API but most crudes are in the 20 to over 45 °API [1]. Crude oils are classified as light (>30 °API; density <870 kg/m3); intermediate or medium (20 < °API < 30; 870 < density < 920 kg/m3); and heavy crudes (<20 °API; 920 < density < 1000 kg/m3). Crude oils with API gravity less than 10 °API are referred to as extra heavy oil or bitumen. For instance, bitumen derived from the oil sands deposits in the Alberta (Canada) has an API gravity of *8 °API. Crude composition: paraffinic, naphthenic, and aromatic (see Table 2.1). Sulfur content: sweet and sour crudes. The term ʽsour’ crude initially related to crudes containing only dissolved hydrogen sulfide independent of total sulfur content. There is no sharp dividing line between sweet and sour crudes. A crude is considered ʽsourʼ if total sulfur content is ranged in 0.5–1.0 wt% S and more. A crude is considered ʽsweetʼ if total sulfur content is less than 0.5 wt%. Geographical origin: There are above 500 different crude oil types from different geographical regions. For instance, West Texas (USA), Maya (Mexico), Ras-Garib (Egypt), Ural (Russia), Azeri (Azerbaijan), etc. If refineries use different types of crudes and blends, this can lead to greater deterioration of equipment than when one type of crude oil is used. Conventional oil includes crude oil (from wells) and condensates (of natural gas sources). Opportunity crude oil refers to crude oils with a relatively high sulfur, salts and metals content, a high total acid number (TAN > 0.5 mg KOH/g), and density. These crudes give rise to problems related to corrosion, fouling, fuel quality, poison © Springer International Publishing Switzerland 2017 293 A. Groysman, Corrosion Problems and Solutions in Oil Refining and Petrochemical Industry, Topics in Safety, Risk, Reliability and Quality 32, DOI 10.1007/978-3-319-45256-2 294 Appendix B: Physicochemical Properties … of catalyst, and environmental protection. Therefore, opportunity crudes are con- sidered as ʽlow qualityʼ corrosive crudes with the price of about 80 % of the price of conventional crude oil [2]. The cost of crude accounts for about 90–95 % of the total running costs of refineries, so it is very attractive for refineries to process opportunity crudes, especially high TAN crudes. Opportunity crudes use is expected to grow up to 20 % to 2025 [3]. Unconventional oils include oil sands, synthetic crudes, heavy and extra-heavy oil, coal-to-liquids, biomass-based liquid supplies, gas to liquid (hydrocarbon liq- uids arising from chemical processing of natural gas). Unconventional oil is crude oil produced or extracted using techniques other than the conventional (oil well) method. Oil industries and governments across the globe are investing in uncon- ventional oil sources due to the increasing scarcity of conventional oil reserves. Conventional oil is easier and cheaper to produce than unconventional oil. However, the categories “conventional” and “unconventional” do not remain fixed, and over time, as economic and technological conditions evolve, resources hitherto considered unconventional can migrate into the conventional category. Oil sands (named also bituminous sands or heavy oil sands) consist of natural bitumen or extra-heavy crude oil trapped in unconsolidated sandstone. These hydrocarbons are forms of crude oil that are extremely dense and viscous, with a consistency ranging from that of molasses for some extra-heavy oil to as solid as peanut butter for some bitumen at ambient temperature, making extraction difficult. As a result of their high viscosity, they cannot be produced by conventional methods, transported without heating or dilution with lighter hydrocarbons, or refined by older oil refineries without major modifications. Such heavy crude oils often contain high concentrations of naphthenic acids, sulfur and heavy metals (particularly nickel and vanadium), which interfere with refining processes, although lighter crude oils can also suffer from these contaminants. Synthetic crude (syncrude or upgraded crude) is an intermediate product pro- duced when unconventional oil (usually oil sands) is upgraded into a transportable form. Synthetic crude may also refer to shale oil (an output from an oil shale pyrolysis). The properties of the synthetic crude depend on the processes used in the upgrading. Usually, it is low in sulfur and has *30 °API gravity. Synthetic crude is transported to oil refineries where it is treated into finished products. Synthetic crude may also be mixed, as a diluent, with heavy oil to create synbit. Synbit is more viscous than synthetic crude, but can be a less expensive alternative for transporting heavy oil to a conventional oil refinery. Synthetic crude should not be confused with synthetic oil, synthetic fuel,orbiocrude. Tight oil is crude oil contained in crude oil-bearing formations of low perme- ability, often shale or tight sandstone. It should not be confused with oil shale which is an organic-rich fine-grained sedimentary rock rich in kerogen (a solid mixture of organic compounds). The kerogen in oil shale can be converted to shale oil through the chemical processes of pyrolysis, hydrogenation, or thermal dissolution. Appendix B: Physicochemical Properties … 295 Table B.1 Major kinds of hydrocarbons in one reference crude oil [4] Type Percent in crude oil Alkanes: Normal 14 Iso (Branched) 18 Cycloparaffins (Naphthenes): Alky Cyclopentanes 10 Alky Cyclohexanes 6 Bicycloparaffins 5 Aromatics: Alkylbenzenes 18 Aromatic-cycloparaffins 5 Fluorenes 3 Binuclear Aromatics 17 Polynuclear Aromatics 4 Table B.2 Petroleum products obtaining from crude oil in atmospheric distillation column [5] Petroleum product Hydrocarbonsa Boiling temperature range (°C) b Gas C1 to C4 c Naphtha C5 to C12 20–210 Gasoline C5 to C12 20–210 d Kerosene C9 to C16 150–290 e Light gas oil C12 to C20 180–320 e Heavy gas oil C12 to C24 190–370 Fuel oil >C20 >340 Bitumen (Asphalt) >C40 >540 aA shorthand method of listing hydrocarbons is used for characterizing compounds by number of carbon atoms in the molecule, e.g., C1 and C4 are related to methane (CH4) and butane (C4H10) bLiquefied Petroleum Gas (LPG, propane-butane) is obtained from this gas mixture cFull-range naphtha. The naphtha obtained directly from the atmospheric crude distillation column is named straight-run naphtha. Naphtha is also produced during processing of heavier parts of the crude oil: catalytic cracker naphtha, visbreaker naphtha, cocker naphtha. As opposed to the straight- run naphtha, these naphthas contain olefinic hydrocarbons. Light naphtha is the fraction boiling from 30 to 90 °C, containing the C5 and C6 hydrocarbons. Heavy naphtha is the fraction boiling from 90 to 200 °C, containing the C7 to C12 hydrocarbons. Medium naphtha is the fraction of the heavy naphtha that boils below 150 °C and contains mostly C7 to C9 hydrocarbons dJet fuel and aviation turbine fuel are obtained then from this kerosene eDiesel fuel
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