Ethanol from petroleum oils

To 16.3 g Na in 210 ml ethanol add 93 g ethyl-acetoacetate (ethyl-3-oxo-butanoate), heat to boil and add dropwise 92 g (II) over 20 minutes. Stir and reflux five hours and cool to precipitate. Filter, wash with ethanol and dissolve precipitate in 800 ml water. Cool to 0° C and slowly add 80 ml ice cold concentrated HC1 to precipitate. Filter, wash with water and ligroin to get about 108 g 6-carbethoxy-4,5-dihydro-olivetol (ID) (reciystallize from petroleum ether). To 104 g (III) in 260 ml glacial acetic acid at room temperature with good stirring, add dropwise over one hour 69 ml Bromine. Heat-four to five hours at 60° C, cool and add 300 ml water and let stand twelve hours. Oil separates which will precipitate on agitation and... 

Add with stirring 22.5 g S0C12 in 100 ml ether in 20 ml portions to a solution of 15 g 3,5-dimethoxybenzyl alcohol, 1 ml pyridine and 200 ml ether. Let stand and wash with 2X100 ml cold water separate and dry, evaporate in vacuum the ether to get 16 g 3,5-dimethoxybenzyl chloride (I). Recrystallize from petroleum ether. 16 g (I), 300 ml ethanol, 30 g NaCN, 75 ml water reflux three hours and pour onto 400 g ice. After ice melts, filter and recrystallize precipitate from petroleum ether to get about 14 g 3,5-dimethoxybenzyl CN (II). 5 g 50% NaH in mineral oil wash three times with pentane or hexane fill flask with N2 or argon and add dimethoxyethane or dimethylformamide (freshly distilled from K if possible). Stir and add 9 ml methyl iodide. Carefully add 8 g (II) and stir twelve hours. Add ice water and neutralize with NaHC03 to pH 7-8. Extract with ether and dry, evaporate in vacuum the ether (can distill 170/0.1) to get about 9 g alpha, alpha-dimethyl-3,5-... 

Ethanol from fermentation is relatively expensive because of the great financial and environmental costs of growing food biomass, a process that requires vast amounts of water and fertilizer. Ethanol derived from petroleum is actually less expensive. (But only because crude oil prices are kept artificially low. If taxpayer subsidies, exemptions from paying for the environmental damage from mining and drilling, and the cost of military protection are factored in, the price of crude oil quadruples.)... 

Some yeasts and bacteria are able to produce different alcohols like ethanol and butanol as well as polyols like glycerin and 2,3-butandiol. These compounds- are used in drinks such as beer and wines, and also may be used in or as solvents, drugs, chemicals, oils, waxes, lacquers, antifreezing and antifoaming agents, precipitants, dyestuff, pomades, raw materials for chemical syntheses, motor fuels, and carbon sources for SCP production. These products are mainly synthesized from petroleum — derived materials like ethylene and acetaldehyde. However, because of the insufficient availability and high prices of the raw materials, the microbial production of alcohols has become an interesting area for many researchers. 

A mixture of 10 g. (0.069 mole) of a-phenylbutyronitrile (p. 252), 15 g. (0.26 mole) of potassium hydroxide, and 60 g. of ethanol is heated under reflux for 8 hours. Most of the ethanol is distilled off, and water is added to the residue. The mixture is filtered, and the filtrate is acidified with hydrochloric acid. The precipitated oil solidifies slowly and is separated and recrystallized from petroleum ether. The product melts at 42°, and approximately 10 g. (88%) is obtained. 

Chrysler provided E85 FFV capability, at no cost to the customer, in all of its 3.3 liter, V-6 minivans between 1998 and 2002. More than a million of these vehicles were sold. Our competitors adopted similar strategies, and today there are nearly four million FFYs in service in the United States, all capable of running on E85. If a fuel infrastructure and appropriate incentives were in place to encourage these vehicles to run on E85, the United States could reduce its petroleum usage by over 1.5 billion gallons annually (or 100,000 barrels of oil per day) and avoid 7.5 million tons of C02 emissions per year. As more efficient processes for producing ethanol from other biomass resources are perfected, these benefits would increase significantly. 

Ethylene for the manufacture of polyethylene is derived from cracking various components of petroleum oil such as the gasoline fraction, gas oil, or from hydrocarbons such as ethane. While petroleum remains the predominant source of the monomer at the present time, it can also be produced using biomass. In fact ethylene has been commercially derived from molasses, a by-product of sugar cane industry, via the dehydration of ethanol. 

Chemical exploitation of renewable raw materials has a long tradition. Before the utilization of the fossil carbon resources coal and petroleum, they were the exclusive source of organic raw materials. Even today, a wide range of chemicals is produced on this basis, e.g. natural rubber, cellulose, fatty acids, ethanol and essential oils, citric acid, enzymes and antibiotics. In terms of quantity, around 8% of organic chemicals are recovered from renewable raw materials. Of the 20 Mt of renewable raw materials used annually, oils and fats have the largest share, amounting to some 40% (Figure 3.55). 

The world s 140 million metric tons of annual ethylene capacity almost exclusively employs steam cracking of hydrocarbon feedstocks [5]. The majority of the feedstocks come from petroleum refining, such as by cracking of naphtha, but some producers use liquefied natural gas as a feedstock. In Brazil, where sugar cane is plentiful, Braskem has built a 200,000 metric ton per year ethylene plant based upon the dehydration of sugar-derived ethanol [6]. In the United States, natural gas liquids, a mixture of ethane, propane, butane, and other hydrocarbons, are available from shale deposits. The ethane is separated and cracked to make ethylene. Depending on the cost of oil and natural gas, this can be an economic advantage. In 2012, about 70% of United States ethylene production was from ethane [7]. 

---