Fatty acids from petroleum

Synthetic Routes to Fatty Acids from Petroleum... 

Hydrogenation of carbon oxides with iron, cobalt, or nickel catalysts (Fischer-Tropsch process). Hydrocarbons are the main products Recovery and separation of oxygenated products obtained from CO and H2 Partial oxidation of nonaromatic hydrocarbon mixtures, e.g., petroleum, paraffins, and natural gas, to produce a mixture of products, such as esters, acids, aldehydes, ketones, and alcohols. This also includes higher fatty acids from petroleum and patents on formaldehyde production... 

Fatty acid methyl ester (FAME), resin acid (RA) from esterified tall oil (FAME, RA and free fatty acid) NaX Petroleum naphtha [181]... 

Manganese(III) acetate is poorly reactive with saturated hydrocarbons.514 However, oxidation of adamantane by Mn(OAc)3 in trifluoroacetic acid gives relatively high yields of 1-adamantyl trifluoroacetate, showing a preferential attack at tertiary C—H bonds.515 Oxidation of n-alkanes by air in the presence of manganese catalysts constitutes the basis for an industrial process for the manufacture of synthetic fatty acids from n-alkanes of petroleum origin, which has been commercially developed in the Soviet Union.516... 

In order to separate the potassium salts of fatty acids from glycerol, the products of the saponification mixture must be acidified. Subsequently, the fatty acids can be extracted by petroleum ether. To identify the fatty acids that were isolated, they must be converted to their respective methyl ester by a perchloric acid catalyzed reaction ... 

The fatty acids of high molecular weight which are used commercially are obtained from animal and vegetable fats and oils. Recent attempts to prepare these acids from petroleum have been successful. When hydrocarbons which boil at a high temperature are heated with air in the presence of mercuric oxide, they are converted into acids. The process may prove of industrial significance. 

Nevertheless, many of the materials extracted in surfactant analysis are so insoluble in the solvent from which they are extracted that two extractions are sufficient, and the loss on washing is negligible even if the extracts are combined. An obvious example is the extraction of fatty acids with petroleum ether from acidified aqueous solution. 

Extraction of fatty acid from soap is similar, except that the solution is made acid at step 1. Extraction of fatty amine is as described, but if it is necessary to extract the NFM and the amine separately the extraction is done first from an alkaline medium (NFM and amine together), and the amine is then extracted with acidified aqueous ethanol, and re-extracted with petroleum ether after making the solution alkaline. 

The fatty acids from each fraction were transesterified with methanolic-HCl (Stoffel et al., 1959), extracted by light petroleum, evaporated and assayed for fatty acid radioactivity in a Packard Scintillation Spectrometer. 

A major kind of renewable fuel is made by hydrolyzing the long-chain fatty acids from triglycerides and attaching methyl groups to produce esters. This liquid product, commonly called biodiesel fuel, serves as a substitute for petroleum-derived liquids in diesel engines. The development and cultivation of plants that produce oils and other lipids is a mtgor possible route to the production of renewable resources. 

Xanthates and dithiophosphates dominate sulfide flotation usage, though several other collectors including more recently developed ones are gaining acceptance rapidly (43). As of this writing, this is an active area of research. Many of the sulfide collectors were first used ia the mbber iadustry as vulcanizers (16). Fatty acids, amines, and sulfonates dominate the nonsulfide flotation usage. The fatty acids are by-products from natural plant or animal fat sources (see Fats and fatty oils). Similarly petroleum sulfonates are by-products of the wood (qv) pulp (qv) iadustry, and amines are generally fatty amines derived from fatty acids. 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

To overcome these difficulties, drilling fluids are treated with a variety of mud lubricants available from various suppHers. They are mostly general-purpose, low toxicity, nonfluorescent types that are blends of several anionic or nonionic surfactants and products such as glycols and glycerols, fatty acid esters, synthetic hydrocarbons, and vegetable oil derivatives. Extreme pressure lubricants containing sulfurized or sulfonated derivatives of natural fatty acid products or petroleum-base hydrocarbons can be quite toxic to marine life and are rarely used for environmental reasons. Diesel and mineral oils were once used as lubricants at levels of 3 to 10 vol % but this practice has been curtailed significantly for environmental reasons. 

Petroleum and Goal. The alkanolarnines have found wide use in the petroleum industry. The ethanolamines are used as lubricants and stabilizers in drilling muds. Reaction products of the ethan olamines and fatty acids are used as emulsion stabilizers, chemical washes, and bore cleaners (168). Oil recovery has been enhanced through the use of ethan olamine petroleum sulfonates (169—174). OH—water emulsions pumped from wells have been demulsifted through the addition of triethanolarnine derivatives. Alkanolarnines have been used in recovering coal in aqueous slurries and as coal—oil mix stabilizers (175—177). 

To improve processing and to plasticize the mbber compound, numerous processing agents have been used over the years, eg, petroleum and ester plasticizers, resins and tars, Hquid mbber peptizers, peptizers, fatty acids and derivatives from vegetable oils, and polyethylene and hydrocarbon waxes. 

Other processing aids utilized in tires are vegetable oils (fatty acids, fatty acid esters/alcohols, and metal salts of these oils), naturally occurring resins such as pine tar, hydrocarbon resins from petroleum stUlbottoms, and vulcanized vegetable oils (WOs). WOs were utilized heavily in the early 1900s, but are no longer used extensively in tires. 

Carboxylic acids having 6—24 carbon atoms are commonly known as fatty acids. Shorter-chain acids, such as formic, acetic, and propionic acid, are not classified as fatty acids and are produced synthetically from petroleum sources (see Acetic acid Formic acid and derivatives Oxo process). Fatty acids are produced primarily from natural fats and oils through a series of unit operations. Clay bleaching and acid washing are sometimes also included with the above operations in the manufacture of fatty acids for the removal of impurities prior to subsequent processing. 

Caustic soda by reaction of sodium amalgam and water Nitration of organic compounds with aqueous nitric acid Formation of soaps by action of aqueous alkahes on fats or fatty acids Sulfur removal from petroleum fractious by aqueous ethauolamiues Treating of petroleum products with sulfuric acid... 

Acids that are solids can be purified in this way, except that distillation is replaced by repeated crystallisation (preferable from at least two different solvents such as water, alcohol or aqueous alcohol, toluene, toluene/petroleum ether or acetic acid.) Water-insoluble acids can be partially purified by dissolution in N sodium hydroxide solution and precipitation with dilute mineral acid. If the acid is required to be free from sodium ions, then it is better to dissolve the acid in hot N ammonia, heat to ca 80°, adding slightly more than an equal volume of N formic acid and allowing to cool slowly for crystallisation. Any ammonia, formic acid or ammonium formate that adhere to the acid are removed when the acid is dried in a vacuum — they are volatile. The separation and purification of naturally occurring fatty acids, based on distillation, salt solubility and low temperature crystallisation, are described by K.S.Markley (Ed.), Fatty Acids, 2nd Edn, part 3, Chap. 20, Interscience, New York, 1964. 

Most of the inhibitors in use are organic nitrogen compounds and these have been classified by Bregman as (a) aliphatic fatty acid derivatives, b) imidazolines, (c) quaternaries, (d) rosin derivatives (complex amine mixtures based on abietic acid) all of these will tend to have long-chain hydrocarbons, e.g. CigH, as part of the structure, (e) petroleum sulphonic acid salts of long-chain diamines (preferred to the diamines), (/) other salts of diamines and (g) fatty amides of aliphatic diamines. Actual compounds in use in classes (a) to d) include oleic and naphthenic acid salts of n-tallowpropylenediamine diamines RNH(CH2) NH2 in which R is a carbon chain of 8-22 atoms and x = 2-10 and reaction products of diamines with acids from the partial oxidation of liquid hydrocarbons. Attention has also been drawn to polyethoxylated compounds in which the water solubility can be controlled by the amount of ethylene oxide added to the molecule. 

Higher molecular primary unbranched or low-branched alcohols are used not only for the synthesis of nonionic but also of anionic surfactants, like fatty alcohol sulfates or ether sulfates. These alcohols are produced by catalytic high-pressure hydrogenation of the methyl esters of fatty acids, obtained by a transesterification reaction of fats or fatty oils with methanol or by different procedures, like hydroformylation or the Alfol process, starting from petroleum chemical raw materials. 

For a further separation of the sulfonated surfactants the latter are heated for 4 h with 2 N HC1. The methyl ester sulfonates are split into methanol and a-sulfo fatty acids, which form disodium salts after neutralization with NaOH. The product mixture from acid hydrolysis can be separated by extraction with petroleum ether. For example, the fatty alcohols formed from fatty alcohol sulfo-... 

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