Paraffins paraffin oxidation process

Probably because of the rate problem, the very active and highly specific copper-ion reactions apparently have not yet found useful application in paraffin oxidation processes. This further illustrates the requirement that a viable catalyst... 

Acetic acid, as noted above, is rather resistant toward oxidation in a paraffin oxidation process. It is not, however, completely inert it can be attacked by the higher valence states of catalyst ions and by the free radicals in solution. In the case of Co , an acetoxy radical is produced (eq. (34)) ... 

The 1929 contract eliminated the concerns of the earlier contract, but within a year it, too, appeared inadequate. The difficulty was in defining borderline processes and products as either chemical or petroleum. In October 1930, Standard and I.G. Farben, therefore, organized another company, the Joint American Study Company or JASCO Incorporated, to which each assigned its borderline processes for examination on a case by case basis. I.G. Farben assigned JASCO its world rights, outside of Germany, to its paraffin oxidation process, acetylene arc process, and Buna process. Standard had none to contribute in 1930. ... 

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). 

The raw materials for the manufacture of soap, the alkali salts of saturated and unsaturated C10-C20 carboxylic acids, are natural fats and fatty oils, especially tallow oil and other animal fats (lard), coconut oil, palm kernel oil, peanut oil, and even olive oil. In addition, the tall oil fatty acids, which are obtained in the kraft pulping process, are used for soap production. A typical formulation of fats for the manufacture of soap contains 80-90% tallow oil and 10-20% coconut oil [2]. For the manufacture of soft soaps, the potassium salts of fatty acids are used, as are linseed oil, soybean oil, and cottonseed oil acids. High-quality soap can only be produced by high-quality fats, independent of the soap being produced by saponification of the natural fat with caustic soda solution or by neutralization of distilled fatty acids, obtained by hydrolysis of fats, with soda or caustic soda solutions. Fatty acids produced by paraffin wax oxidation are of inferior quality due to a high content of unwanted byproducts. Therefore in industrially developed countries these fatty acids are not used for the manufacture of soap. This now seems to be true as well for the developing countries. 

Par-Isom [Paraffin isomerization] A process for isomerizing light naphtha in order to improve the octane number. The proprietary catalyst was developed by Cosmo Oil Company and Mitsubishi Heavy Industries, and the process was developed by UOP. The oxide catalyst is claimed to be more efficient than zeolite catalysts currently used for this process. 

The direct sulfation of wax olefins has been perfected in Europe but has not been commercialized to any extent in the United States. More work has been done in this country on alcohols that have been prepared by Fischer-Tropsch syntheses, oxo process reactions, and reduction of the fatty acid mixtures obtained by paraffin wax oxidation. In most instances these alcohols as well as the olefins have been branched chain or secondary products, both of which have been reported to give inferior detergent and sudsing properties (13, 2Jf). 

The statements of the possible role of HO radicals in saturated hydrocarbon oxidation processes is proved by experimentally determined formation of sufficient amounts of hydrogen peroxide and HO radicals during oxidation of propane [27] and paraffin dehydrogenation products [28-30],... 

Following the discussion from the preceding section, consideration will be given to the oxidation of ethene and propene (when a radical pool already exists) and, since acetylene is a product of this oxidation process, to acetylene as well. These small olefins and acetylene form in the oxidation of a paraffin or any large olefin. Thus, the detailed oxidation mechanisms for ethane, propane, and other paraffins necessarily include the oxidation steps for the olefins [28]. 

Aliphatic gem-dinitro compounds can be prepared by anodic oxidation of a nitro-paraffin in aqueous alkaline solution in the presence of an excess of N02 [201]. Yields are considerably better when Ag" is the oxidizing agent [202], so that an indirect oxidation process involving the generation of Ag" " at an Ag anode was found to give excellent results [203]. 

Even though methanol carbonylation is the favored process for new acetic acid capacity today, existing paraffin oxidation plants remain quite competitive where coproducts can be marketed successfully [2, 3]. Over half the original capacity of acetic acid plants based on paraffin oxidation remains in use today. In North America, Hoechst Celanese operates two facilities using the butane oxidation process to make acetic acid. The reported 1994 capacity at Pampa, Texas, is 250000 metric tons/year, while that at monton, Alberta, is 75 000 metric tons/year [4]. There are two plants believed to be using the naphtha oxidation process to make acetic acid BP Chemicals in Hull, England, with a capacity of 210000 metric tons/year [5] and a state complex in Armenia (in the former USSR) with a capacity reported to be 35 000 metric tons/year [6]. 

The significant reductions in acetic acid capacity based on paraffin oxidation that have occurred include those at (1) the butane oxidation plant operated by Union Carbide at Brownsville, Texas, (2) butane oxidation processes in the Netherlands and Germany, and (3) a Russian naphtha oxidation plant. 

Multitubular reactors are mainly used in gas-phase partial oxidation processes, such as the air oxidation of light olefins, paraffins, and aromatics. Examples of chemistries where these reactors are used include the partial oxidation of methanol to formaldehyde, ethylene to ethylene oxide, ethylene and acetic acid to vinyl acetate, propylene to acrolein and acrylic acid, butane to maleic anhydride, isobutylene to methacrolein and methacrylic acid, and o-xylene to phthalic anhydride. An overview of the multitubular reactor process for the partial oxidation of n-butane to maleic anhydride is given here. 

Among numerous compounds formed in vanadium-phosphorus-oxide system, vanadyl pyrophosphate is known to be an efficient catalyst for C4-C5 paraffins partial oxidation [1]. Typical process of its synthesis can be represented by a following scheme ... 

Data on the nature and yield of the hydrocarbon product are not available, although the process has been stated to have operated successfully on a semiplant scale with paraffin-base oils. That it has not yet been superlatively successful may be deduced from the lack of its widespread use. The possibility of sulfur removal from high sulfur crudes, such as the West Texas crudes, by such a process has probably been investigated but no authoritative information is available. It is probable that such an oxidation process will not greatly reduce the sulfur content in the product unless it is allowed to occur to an excessive extent. 

Iron-zeolite catalysts present an important type of materials with broad application for selective oxidations (i.e. benzene hydroxylation) and environmentally important processes, like SCR reduction of NOx or N2O decomposition. In the case of SCR reaction they could provide a convenient substitution of the vanadia-based system using environmentally problematic ammonia, by more convenient paraffin as a reducing agent. Unfortunately, the efficiency in utilization of paraffin is inferior in comparison to ammonia, namely due to paraffin nonselective oxidation by oxygen catalyzed by unspecified iron-oxide type species typically present in the iron-zeolite catalysts. The mostly used preparation processes include impregnation from water solutions, ion exchange procedures, both in water solution or solid state, as well as gas phase CVD. 

Among such oxidations, note that liquid-phase oxidations of solid paraffins in the presence of heterogeneous and colloidal forms of manganese are accompanied by a substantial increase (compared with homogeneous catalysis) in acid yield [3]. The effectiveness of n-paraffin oxidations by Co(III) macrocomplexes is high, but the selectivity is low the ratio between fatty acids, esters, ketones and alcohols is 3 3 3 1. Liquid-phase oxidations of paraffins proceed in the presence of Cu(II) and Mn(II) complexes boimd with copolymers of vinyl ether, P-pinene and maleic anhydride (Amberlite IRS-50) [130]. Oxidations of both linear and cyclic olefins have been studied more intensively. Oxidations of linear olefins proceed by a free-radical mechanism the accumulation of epoxides, ROOH, RCHO, ketones and RCOOH in the course of the reaction testifies to the chain character of these reactions. The main requirement for these processes is selectivity non-catalytic oxidation of propylene (at 423 K) results in the formation of more than 20 products. Acrylic acid is obtained by oxidation of propylene (in water at 338 K) in the presence of catalyst by two steps at first to acrolein, then to the acid with a selectivity up to 91%. Oxidation of ethylene by oxygen at 383 K in acetic acid in... 

The said study has paved the way for realizing an artificial system which resembles a natural enzymatic reaction process and which is needed for conditioning the existence of biomaterials. It is expected to be applied to the industrial-use oxidation process in which benzene and paraffin are transformed into phenol and alcohol, respectively. ... 

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