Handbook of petroleum refining processes
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However, distillation processes produced only a certain amount of gasoline from crude oil. In , the thermal cracking process was developed, which subjected heavy fuels to both pressure and intense heat, physically breaking the large molecules into smaller ones to produce additional gasoline and distillate fuels. Visbreaking, another form of thermal cracking, was developed in the late 's to produce more desirable and valuable products. Catalytic Processes.
Higher-compression gasoline engines required higher-octane gasoline with better antiknock characteristics. The introduction of catalytic cracking and polymerization processes in the mid-to late 's met the demand by providing improved gasoline yields and higher octane numbers.
Alkylation, another catalytic process developed in the early 's, produced more high-octane aviation gasoline and petrochemical feedstock for explosives and synthetic rubber. Subsequently, catalytic isomerization was developed to convert hydrocarbons to produce increased quantities of alkylation feedstock. Improved catalysts and process methods such as hydrocracking and reforming were developed throughout the 's to increase gasoline yields and improve antiknock characteristics.
These catalytic processes also produced hydrocarbon molecules with a double bond alkenes and formed the basis of the modern petrochemical industry. Treatment Processes. Throughout the history of refining, various treatment methods have been used to remove nonhydrocarbons, impurities, and other constituents that adversely affect the properties of finished products or reduce the efficiency of the conversion processes. Typical examples of treating are chemical sweetening, acid treating, clay contacting, caustic washing, hydrotreating, drying, solvent extraction, and solvent dewaxing.
Sweetening compounds and acids desulfurize crude oil before processing and treat products during and after processing. Following the Second World War, various reforming processes improved gasoline quality and yield and produced higher-quality products. A number of the more commonly used treating and reforming processes are described in this chapter of the manual. Crude oils are complex mixtures containing many different hydrocarbon compounds that vary in appearance and composition from one oil field to another.
Crude oils range in consistency from water to tar-like solids, and in color from clear to black. Crude oils are generally classified as paraffinic, naphthenic, or aromatic, based on the predominant proportion of similar hydrocarbon molecules.
Mixed-base crudes have varying amounts of each type of hydrocarbon. Refinery crude base stocks usually consist of mixtures of two or more different crude oils. Relatively simple crude oil assays are used to classify crude oils as paraffinic, naphthenic, aromatic, or mixed.
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More comprehensive crude assays determine the value of the crude i. Crude oils are usually grouped according to yield structure. The higher the API gravity, the lighter the crude. For example, light crude oils have high API gravities and low specific gravities.
Handbook of Petroleum Refining Processes / Edition 3
Crude oils with low carbon, high hydrogen, and high API gravity are usually rich in paraffins and tend to yield greater proportions of gasoline and light petroleum products; those with high carbon, low hydrogen, and low API gravities are usually rich in aromatics. Crude oils that contain appreciable quantities of hydrogen sulfide or other reactive sulfur compounds are called "sour.
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Basics of Hydrocarbon Chemistry. Crude oil is a mixture of hydrocarbon molecules, which are organic compounds of carbon and hydrogen atoms that may include from one to 60 carbon atoms. The properties of hydrocarbons depend on the number and arrangement of the carbon and hydrogen atoms in the molecules. The simplest hydrocarbon molecule is one carbon atom linked with four hydrogen atoms: methane. All other variations of petroleum hydrocarbons evolve from this molecule. Hydrocarbons containing up to four carbon atoms are usually gases, those with 5 to 19 carbon atoms are usually liquids, and those with 20 or more are solids.
The refining process uses chemicals, catalysts, heat, and pressure to separate and combine the basic types of hydrocarbon molecules naturally found in crude oil into groups of similar molecules. The refining process also rearranges their structures and bonding patterns into different hydrocarbon molecules and compounds. Therefore it is the type of hydrocarbon paraffinic, naphthenic, or aromatic rather than its specific chemical compounds that is significant in the refining process.
Methane CH 4. Butane C 4 H Isobutane C 4 H Benzene C 6 H 6.
Refining Processes Handbook - 1st Edition
Napthalene C 10 H 8. Cyclohexane C 6 H Methyl Cyclopentane C 6 H Ethylene C 2 H 4. Isobutene C 4 H 8. Acetylene C 2 H 2. Sulfur Compounds. Sulfur may be present in crude oil as hydrogen sulfide H 2 S , as compounds e. Each crude oil has different amounts and types of sulfur compounds, but as a rule the proportion, stability, and complexity of the compounds are greater in heavier crude-oil fractions.
Hydrogen sulfide is a primary contributor to corrosion in refinery processing units. Other corrosive substances are elemental sulfur and mercaptans. Moreover, the corrosive sulfur compounds have an obnoxious odor. Pyrophoric iron sulfide results from the corrosive action of sulfur compounds on the iron and steel used in refinery process equipment, piping, and tanks. The combustion of petroleum products containing sulfur compounds produces undesirables such as sulfuric acid and sulfur dioxide. Catalytic hydrotreating processes such as hydrodesulfurization remove sulfur compounds from refinery product streams.
Sweetening processes either remove the obnoxious sulfur compounds or convert them to odorless disulfides, as in the case of mercaptans. Other Refining Operations include: light-ends recovery; sour-water stripping; solid waste and wastewater treatment; process-water treatment and cooling; storage and handling; product movement; hydrogen production; acid and tail-gas treatment; and sulfur recovery. Auxiliary operations and facilities include: steam and power generation; process and fire water systems; flares and relief systems; furnaces and heaters; pumps and valves; supply of steam, air, nitrogen, and other plant gases; alarms and sensors; noise and pollution controls; sampling, testing, and inspecting; and laboratory, control room, maintenance, and administrative facilities.
Because this is a closed process, there is little potential for exposure to crude oil unless a leak or release occurs.
Where elevated operating temperatures are used when desalting sour crudes, hydrogen sulfide will be present. Depending on the crude feedstock and the treatment chemicals used, the wastewater will contain varying amounts of chlorides, sulfides, bicarbonates, ammonia, hydrocarbons, phenol, and suspended solids. If diatomaceous earth is used in filtration, exposures should be minimized or controlled. Diatomaceous earth can contain silica in very fine particle size, making this a potential respiratory hazard.
An excursion in pressure, temperature, or liquid levels may occur if automatic control devices fail.
Control of temperature, pressure, and reflux within operating parameters is needed to prevent thermal cracking within the distillation towers. Relief systems should be provided for overpressure and operations monitored to prevent crude from entering the reformer charge. The sections of the process susceptible to corrosion include but may not be limited to preheat exchanger HCl and H 2 S , preheat furnace and bottoms exchanger H 2 S and sulfur compounds , atmospheric tower and vacuum furnace H 2 S, sulfur compounds, and organic acids , vacuum tower H 2 S and organic acids , and overhead H 2 S, HCl, and water.
Wet H 2 S also will cause cracks in steel. When processing high-nitrogen crudes, nitrogen oxides can form in the flue gases of furnaces. Nitrogen oxides are corrosive to steel when cooled to low temperatures in the presence of water. Chemicals are used to control corrosion by hydrochloric acid produced in distillation units. If sufficient wash-water is not injected, deposits of ammonium chloride can form and cause serious corrosion.
Crude feedstock may contain appreciable amounts of water in suspension which can separate during startup and, along with water remaining in the tower from steam purging, settle in the bottom of the tower. This water can be heated to the boiling point and create an instantaneous vaporization explosion upon contact with the oil in the unit. Solvent Dewaxing. Solvent dewaxing is used to remove wax from either distillate or residual basestocks at any stage in the refining process. There are several processes in use for solvent dewaxing, but all have the same general steps, which are: 1 mixing the feedstock with a solvent, 2 precipitating the wax from the mixture by chilling, and 3 recovering the solvent from the wax and dewaxed oil for recycling by distillation and steam stripping.
Usually two solvents are used: toluene, which dissolves the oil and maintains fluidity at low temperatures, and methyl ethyl ketone MEK , which dissolves little wax at low temperatures and acts as a wax precipitating agent. Other solvents that are sometimes used include benzene, methyl isobutyl ketone, propane, petroleum naphtha, ethylene dichloride, methylene chloride, and sulfur dioxide. In addition, there is a catalytic process used as an alternate to solvent dewaxing.
Delayed Coking. Isobutene C 4 H 8. Acetylene C 2 H 2.
http://webdisk.builttospill.reclaim.hosting/la-importancia-de-comer-sano-y-saludable.php Sulfur Compounds. Sulfur may be present in crude oil as hydrogen sulfide H 2 S , as compounds e.
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Each crude oil has different amounts and types of sulfur compounds, but as a rule the proportion, stability, and complexity of the compounds are greater in heavier crude-oil fractions.