Hydrocarbons fatty acids products

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. 

A microsomal FAS was implicated in the biosynthesis of methyl-branched fatty acids and methyl-branched hydrocarbon precursors of the German cockroach contact sex pheromone (Juarez et al., 1992 Gu et al., 1993). A microsomal FAS present in the epidermal tissues of the housefly is responsible for methyl-branched fatty acid production (Blomquist et al., 1994). The housefly microsomal and soluble FASs were purified to homogeneity (Gu et al., 1997) and the microsomal FAS was shown to preferentially use methylmalonyl-CoA in comparison to the soluble FAS. GC-MS analyses showed that the methyl-branching positions of the methyl-branched fatty acids of the housefly were in positions consistent with their role as precursors of the methyl-branched hydrocarbons. 

Victorian brown coal occurs in five major lithotypes distinguishable by color index and petrography. Advantage has been taken of a rare 100 m continuous core to compare and contrast chemical variations occurring as a function of lithotype classification. For many parameters there is a much greater contrast between the different lithotypes than there is across the depth profile of (nearly) identical lithotypes. Molecular parameters, such as the distributions of hydrocarbons, fatty acids, triterpenoids and pertrifluoroacetic acid oxidation products, together with gross structural parameters derived from IR and C-NMR spectroscopic data, Rock-Eval and elemental analyses and the yields of specific extractable fractions are compared. 

Currently, branched fatty acids are commercially produced as a by-product from dimer fatty acid production using clay catalysts. However, this process suffers from a rather poor selectivity, yielding complex mixtures of both alkyl-branched and dimeric fatty acids [331]. Although skeletal isomerization of linear hydrocarbons has been a common practice in the petrochemical industry, the direct catalytic isomerization of fatty acids or esters has mrned out much more challenging. Most commercial solid acids fail to produce branched products... 

Hydrogenolysis Process. Patty alcohols are produced by hydrogenolysis of methyl esters or fatty acids ia the presence of a heterogeneous catalyst at 20,700—31,000 kPa (3000—4500 psi) and 250—300°C ia conversions of 90—98%. A higher conversion can be achieved using more rigorous reaction conditions, but it is accompanied by a significant amount of hydrocarbon production. 

Secondary alcohols (C q—for surfactant iatermediates are produced by hydrolysis of secondary alkyl borate or boroxiae esters formed when paraffin hydrocarbons are air-oxidized ia the presence of boric acid [10043-35-3] (19,20). Union Carbide Corporation operated a plant ia the United States from 1964 until 1977. A plant built by Nippon Shokubai (Japan Catalytic Chemical) ia 1972 ia Kawasaki, Japan was expanded to 30,000 t/yr capacity ia 1980 (20). The process has been operated iadustriaHy ia the USSR siace 1959 (21). Also, predominantiy primary alcohols are produced ia large volumes ia the USSR by reduction of fatty acids, or their methyl esters, from permanganate-catalyzed air oxidation of paraffin hydrocarbons (22). The paraffin oxidation is carried out ia the temperature range 150—180°C at a paraffin conversion generally below 20% to a mixture of trialkyl borate, (RO)2B, and trialkyl boroxiae, (ROBO). Unconverted paraffin is separated from the product mixture by flash distillation. After hydrolysis of residual borate esters, the boric acid is recovered for recycle and the alcohols are purified by washing and distillation (19,20). 

Interest in synthetic naphthenic acid has grown as the supply of natural product has fluctuated. Oxidation of naphthene-based hydrocarbons has been studied extensively (35—37), but no commercially viable processes are known. Extensive purification schemes must be employed to maximize naphthene content in the feedstock and remove hydroxy acids and nonacidic by-products from the oxidation product. Free-radical addition of carboxylic acids to olefins (38,39) and addition of unsaturated fatty acids to cycloparaffins (40) have also been studied but have not been commercialized. 

In recent years, especially in the USSR and Europe, synthetic fatty acids, prepared via hydrocarbon oxidation, have been used to prepare fatty amines (2,9). In 1978 Eastern Europeans produced an estimated 0.55 biUion kg of synthetic fatty acids with odd and even numbers of carbon atoms, whereas in the United States, production of natural fatty acids with even carbon atom chain-length acids was 435 million kg. To date, there has been no significant production of synthetic fatty acids in the United States. 

Wood is the raw material of the naval stores iadustry (77). Naval stores, so named because of their importance to the wooden ships of past centuries, consist of rosin (diterpene resin acids), turpentine (monoterpene hydrocarbons), and associated chemicals derived from pine (see Terpenoids). These were obtained by wounding the tree to yield pine gum, but the high labor costs have substantially reduced this production in the United States. Another source of rosin and turpentine is through extraction of old pine stumps, but this is a nonrenewable resource and this iadustry is in decline. The most important source of naval stores is spent sulfate pulpiag Hquors from kraft pulpiag of pine. In 1995, U.S. production of rosin from all sources was estimated at under 300,000 metric tons and of turpentine at 70,000 metric tons. Distillation of tall oil provides, in addition to rosin, nearly 128,000 metric tons of tall oil fatty acids annually (78). 

Catalytic Oxidation for Straight-Chain Paraffinic Hydrocarbons. Synthetic fatty acids (SFA) are produced by Eastern European countries, Russia, and China using a manganese-catalyzed oxidation of selected paraffinic streams. The technology is based on German developments that were in use during World War II. The production volume in 1984 was estimated to be about 5.5 x ICf t/yr. The oxidation is highly exothermic and is carried out at about 105—125°C, mostly in continuous equipment. 

Hydrolysis using aqueous alkaH has been found to remove ash material including pyrite. A small pilot plant for studying this process was built at the BatteUe Memorial Institute in Columbus, Ohio (74) and subsequentiy discontinued. Other studies have produced a variety of gases and organic compounds such as phenols, nitrogen bases, Hquid hydrocarbons, and fatty acids totaling as much as 13 wt % of the coal. The products indicate that oxidation and other reactions as weU as hydrolysis take place. 

Many of the surfactants made from ethyleneamines contain the imidazoline stmcture or are prepared through an imidazoline intermediate. Various 2-alkyl-imidazolines and their salts prepared mainly from EDA or monoethoxylated EDA are reported to have good foaming properties (292—295). Ethyleneamine-based imida zolines are also important intermediates for surfactants used in shampoos by virtue of their mildness and good foaming characteristics. 2- Alkyl imidazolines made from DETA or monoethoxylated EDA and fatty acids or their methyl esters are the principal commercial intermediates (296—298). They are converted into shampoo surfactants commonly by reaction with one or two moles of sodium chloroacetate to yield amphoteric surfactants (299—301). The ease with which the imidazoline intermediates are hydrolyzed leads to arnidoamine-type stmctures when these derivatives are prepared under aqueous alkaline conditions. However, reaction of the imidazoline under anhydrous conditions with acryflc acid [79-10-7] to make salt-free, amphoteric products, leaves the imidazoline stmcture essentially intact. Certain polyamine derivatives also function as water-in-oil or od-in-water emulsifiers. These include the products of a reaction between DETA, TETA, or TEPA and fatty acids (302) or oxidized hydrocarbon wax (303). The amidoamine made from lauric acid [143-07-7] and DETA mono- and bis(2-ethylhexyl) phosphate is a very effective water-in-od emulsifier (304). 

Trees, especially conifers, contain tall oils. Tall oil is not isolated dkecfly tall oil fatty acids are isolated from the soaps generated as a by-product of the sulfate pulping process for making paper. Refined tall oil fatty acids are obtained by acidification of the soaps, followed by fractional distillation to separate the fatty acids from the rosin acids and terpene hydrocarbons that also are present in the cmde tall oil fatty acids (see Carboxylic acids Fatty ACIDS FROMTALL OIL). 

Oxidation of C12-C14 n-paraffms using boron trioxide catalysts was extensively studied for the production of fatty alcohols.Typical reaction conditions are 120-130°C at atmospheric pressure. ter-Butyl hydroperoxide (0.5 %) was used to initiate the reaction. The yield of the alcohols was 76.2 wt% at 30.5% conversion. Fatty acids (8.9 wt%) were also obtained. Product alcohols were essentially secondary with the same number of carbons and the same structure per molecule as the parent paraffin hydrocarbon. This shows that no cracking has occurred under the conditions used. The oxidation reaction could be represented as ... 

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. 

Faraday, in 1834, was the first to encounter Kolbe-electrolysis, when he studied the electrolysis of an aqueous acetate solution [1], However, it was Kolbe, in 1849, who recognized the reaction and applied it to the synthesis of a number of hydrocarbons [2]. Thereby the name of the reaction originated. Later on Wurtz demonstrated that unsymmetrical coupling products could be prepared by coelectrolysis of two different alkanoates [3]. Difficulties in the coupling of dicarboxylic acids were overcome by Crum-Brown and Walker, when they electrolysed the half esters of the diacids instead [4]. This way a simple route to useful long chain l,n-dicarboxylic acids was developed. In some cases the Kolbe dimerization failed and alkenes, alcohols or esters became the main products. The formation of alcohols by anodic oxidation of carboxylates in water was called the Hofer-Moest reaction [5]. Further applications and limitations were afterwards foimd by Fichter [6]. Weedon extensively applied the Kolbe reaction to the synthesis of rare fatty acids and similar natural products [7]. Later on key features of the mechanism were worked out by Eberson [8] and Utley [9] from the point of view of organic chemists and by Conway [10] from the point of view of a physical chemist. In Germany [11], Russia [12], and Japan [13] Kolbe electrolysis of adipic halfesters has been scaled up to a technical process. 

Fatty Acid Esters. Defoamers that are more environmentally acceptable than convential products are based on fatty acid esters of hydroxy alcohols, such as sorbitan monooleate [1908] or sorbitan monolaurate in combination with diethylene glycol monobutyl ether as a cosolvent [451]. These defoamer compositions are as effective as conventional materials, for example, those based on acetylenic alcohols are less toxic, especially to marine organisms, and are readily biodegradable. The defoamer compositions are used in water-based hydrocarbon well fluids during oil/gas well drilling, completion, and workover, especially in marine conditions. 

In addition to hydrocarbons, other products have also been found, especially in the reactions of the higher fatty acids. In steady state, the current density obeys the Tafel equation with a high value of constant b 0.5. At a constant potential the current usually does not depend very much on the sort of acid. The fact that the evolution of oxygen ceases in the... 

Oxidative damage to membrane polyunsaturated fatty acids leads to the formation of numerous lipid peroxidation products, some of which can be measured as index of oxidative stress, including hydrocarbons, aldehydes, alcohols, ketones, and short carboxylic acids. 

Pentane and ethane (end products of n-6 and n-3 polyunsaturated fatty acid peroxidation, respectively) in expired air are useful markers of in vivo lipid peroxidation. Nevertheless, when gas chromatography is used to measure hydrocarbons, some technical difficulties may be experienced because chromatographic resolution of pentane from isoprene and isopentane is extremely difficult to achieve. Another possible problem could be the presence of these gases as contaminants in atmosphere. Furthermore, the production of hydrocarbon gases depends on the presence of metal ions to decompose lipid peroxides. If such ions are only available in limited amounts, this index may be inaccurate. 

When variable-valence metals are used as catalysts in the oxidation of hydrocarbons, the chain termination via such reactions manifests itself later in the process. This case has specially been studied in relation to the oxidation of paraffins to fatty acids in the presence of the K Mn catalyst [57], which ensures a high oxidation rate and a high selectivity of formation of the target product (carboxylic acids). As the reaction occurs, alcohols are accumulated in the reaction mixture, and their oxidation is accompanied by the formation of hydroxyperoxyl radicals. The more extensively the oxidation occurs, the higher the concentration of alcohols in the oxidized paraffin, and, hence, the higher is the kinetic... 

Alkaloids, amines, drugs, fatty acid methyl esters, hydrocarbons, petroleum products, phenols, solvents, waxes, general purposes... 

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