Methanol from petroleum oils

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. 

Unused wood residues as a by-product of current forest operations in Canada are estimated to be of the order of 0.14 billion cubic metres ( ). Apart from what is presently being utilized, there exists an estimated annual roundwood surplus of some 0.2 billion cubic metres. Associated with this surplus would be a further 0.2 billion cubic metres of wood residues. If this wood were easily accessible and available at reasonable cost, it could be converted to methanol or fuel oil equivalent to about two-thirds of Canada s annual petroleum products production. In Ontario, Hall and Lambert (3 ) have estimated available quantities of surplus wood in several categories. 

Coal liquefaction Fischer-Tropsch synthesis Synthesis of methanol Hydrogenation of oils Alkylation of methanol and benzene Polymerization of olefins Hydrogenation of coal oils, heavy oil fractions, and unsaturated fatty acids Adsorption of S02 in an aqueous slurry of magnesium oxide and calcium carbonate S02 or removal from tail gas Wet oxidation of waste sludge Catalytic desulfurization of petroleum fractions Wastewater treatment... 

Twenty-five years ago the only oxygenated aliphatics produced in important quantities were ethyl and n-butyl alcohols and acetone made by the fermentation of molasses and grain, glycerol made from fats and oils, and methanol and acetic acid made by the pyrolysis of wood. In 1927 the production of acetic acid (from acetylene) and methanol (from synthesis gas) was begun, both made fundamentally from coal. All these oxygenated products are still made from the old raw materials by the same or similar processes, but the amount so made has changed very little in the past quarter century. Nearly all the tremendous growth in the production of this class of compounds has come from petroleum hydrocarbons. 

Ryania. The root and stem of the plant Ryania speciosa, family Flacourtiaceae, native to South America, contain from 0.16—0.2% of insecticidal components, the most important of which is the alkaloid ryanodine [15662-33-9], C25H3509N (8) (mp 219-220°C). This compound is effective as both a contact and a stomach poison. Ryanodine is soluble in water, methyl alcohol, and most organic solvents but not in petroleum oils. It is more stable to the action of air and light than pyrethrum or rotenone and has considerable residual action. Ryania has an oral LD5Q to the rat of 750 mg/kg. The material has shown considerable promise in the control of the European com borer and codling moth and is used as a wettable powder of ground stems or as a methanolic extract. Ryanodine uncouples the ATP—AD P actomyosin cycle of striated muscle. 

Sauer and Fitzgerald [9] have described thin layer chromatographic technique for the identification of water-borne petroleum oils. Aromatic and polar compounds are removed from the sample by liquid-liquid extraction with acidified methanol, the extract is chromatographed on a silica gel thin layer plate, and the separated components are detected by their fluorescence under long- and short-wave ultraviolet light. Unsaturated non-fluorescing compounds are detected by iodine staining. 

The key words to the future of methanol/gasoline blends for automotive use are need and availability. Technically, the operation of methanol/gasoline blends in automotive engines is feasible with some associated problems. Economically, methanol is not yet competitive with gasoline produced from petroleum, hence the need has not been strongly established. Since the need or market is not established, the capital expenses involved in producing methanol from coal or garbage are not presently justified. However, if 40-60% of the crude oil used in the U.S. to produce petroleum products should suddenly become unavailable, the need would be very real. The necessity of compete evaluation of methanol and other alternate fuels is evident. 

The 1973 oil embargo and the ensuing petroleum and natural gas shortages forced the chemical industry to seek new resources for petrochemicals manufacture. About 86% of our domestic carbonaceous fossil fuel resources are coal and only about 2% each are petroleum and natural gas. Thus it is imminent to resort to a coal base for organic chemical products at this time. The manufacture of methanol from natural gas-based synthesis gas is a well-established technology and has been steadily improved over the years. Methanol also can be produced from coal-based synthesis gas in high yield at a... 

Alcohol Production. Studies to assess the costs of alcohol fuels and to compare the costs to those of conventional fuels contain significant uncertainties. In general, the low cost estimates iadicate that methanol produced on a large scale from low cost natural gas could compete with gasoline when oil prices are around 140/L ( 27/bbl). This comparison does not give methanol any credits for environmental or energy diversification benefits. Ethanol does not become competitive until petroleum prices are much higher. 

The MTG process was developed for synfuel production in response to the 1973 oil crisis and the steep rise in crude prices that followed. Because methanol can be made from any gasiftable carbonaceous source, including coal, natural gas, and biomass, the MTG process provided a new alternative to petroleum for Hquid fuels production. New Zealand, heavily dependent on foreign oil imports, utilizes the MTG process to convert vast offshore reserves of natural gas to gasoline (59). 

Alternative fuels fall into two general categories. The first class consists of fuels that are made from sources other than cmde oil but that have properties the same as or similar to conventional motor fuels. In this category are fuels made from coal and shale (see Fuels, synthetic). In the second category are fuels that are different from gasoline and diesel fuel and which require redesigned or modified engines. These include methanol (see Alcohol fuels), compressed natural gas (CNG), and Hquefted petroleum gas (LPG). 

A mixture of 50 g of betamethasone, 50 cc of dimethylformamide, 50 cc of methyl orthobenzoate and 1.5 g of p-toluenesulfonicacid Is heated for 24 hours on oil bath at 105°C while a slow stream of nitrogen is passed through the mixture and the methanol produced as a byproduct of the reaction is distilled off. After addition of 2 cc of pyridine to neutralize the acid catalyst the solvent and the excess of methyl orthobenzoate are almost completely eliminated under vacuum at moderate temperature. The residue Is chromatographed on a column of 1,500 g of neutral aluminum oxide. By elution with ether-petroleum ether 30 g of a crystalline mixture are obtained consisting of the epimeric mixture of 170 ,21 -methyl orthobenzoates. This mixture is dissolved without further purification, in 600 cc of methanol and 240 cc of methanol and 240 cc of aqueous 2 N oxalic acid are added to the solution. The reaction mixture is heated at 40°-50°C on water bath, then concentrated under vacuum. The residue, crystallized from acetone-ether, gives betamethasone 17-benzoate, MP 225°-231°C. 

When addition is complete the mixture is heated under reflux during 5 hours and then the acetone is removed by distillation. The residue is dissolved in water, acidified with hydrochloric acid and the mixture extracted with chloroform. The chloroform extract is stirred with sodium hydrogen carbonate solution and the aqueous layer is separated. The alkaline extract is acidified with hydrochloric acid and filtered. The solid product is drained free from oil on a filter pump, then washed with petroleum ether (BP 40° to 60°C), and dried at 50°C. The solid residue, MP 114° to 116°C, may be crystallized from methanol (with the addition of charcoal) to give p-chlorophenoxyisobutyric acid, MP 118° to 119°C. 

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