Production of Mixed Alcohols

Simpler, mostly power law rate equations for the production of mixed alcohols from synthesis gas are cited by Forzatti, Tronconi, and... 

Ohno T. Yoshimoto M. Asselinau L. Courty P. Travers P. in "Production of mixed alcohols from synthesis gas AICHE Meeting ref.3 paper nr. 25e. 

Quarderer G.J., in "production of mixed alcohols from synthesis gas . AICHE Meeting ref. 3 paper nr. 25a. 

Bargagna, H, Production of mixed alcohols", 2nd European Oxygenated Fuels Conference, Paris (14 June 1984J... 

Gottschalk G (1986) Bacterial metabolism, 2nd edn. Springer, New York, pp 97-98 Grethlein AJ, Worden RM, Jain MK, Datta R (1990) Continuous production of mixed alcohols and acids from carbon monoxide. Appl Biochem Biotechnol... 

The products of oxidation (alcohol, ketone, acid) lower the concentration of active complexes and, in addition, form complexes with a mixed ligand sphere with lower catalytic activity (kdi >kd2). The values of equilibrium constants Ain (Lmol-1) measured spectrophotometri-cally in a decane solution for cupric stearate + product are given below [70],... 

Another important application of butyraldehyde is in the production of oxo-alcohols for use as plasticizers used to improve mixing of solid compounds that must be molded or extruded into specific shapes. The hydrogenation catalyst is Ni/Al203. 

One possible starting material for the production of Cio alcohols is the above-mentioned Raffinate-2, a C4 feedstock derived from mixed C4 streams of steam crackers. After butadiene has been removed from the mixed stream, Raffinate-1 is obtained. The isobutene content of Raffinate-1 is removed by conversion to MTBE (methyl t-butyl ether), leaving behind a stream rich in mixed butenes which do not react in the MTBE process this is designated Raffinate-2. Accordingly, in the USA and western Europe MTBE plants are the main consumers for Raffinate-2. 

Methyl alcohol occurs naturally in plants and animals, including humans, as the product of metabolic reactions that occur in all organisms. It also occurs in the atmosphere as the result of the decomposition of dead organisms in the soil. None of these sources is utilized for the commercial production of methyl alcohol. Instead, the primary method for the preparation of methyl alcohol is to react carbon monoxide with water at a temperature of about 25o°C (48o°F) and pressures of 50 to 100 atmospheres over a mixed catalyst of copper, zinc oxide, and aluminum oxide. Efforts are being made to develop other methods of synthesizing methyl alcohol. In one process, for... 

The products from the oxidation of such mixtures of hydrocarbons as are contained in kerosene or gas oil are very complex—so much so as to defy accurate analysis. They contain aldehydes, alcohols, ketones, acids, ethers, and esters.- In the oxidation of kerosene the oxidized oil may be as high as 40 per cent of the total and consist of 30-40 per cent of mixed aldehydes, 40-46 per cent of mixed alcohols, 5 per cent of free acids, 10 per cent of esters, and some ethers. About 85 per cent recovery is claimed with kero-... 

American companies became interested in the process during the war and initiated a substantial research program. Since production of specific alcohols was desired, more attention was focused on the use of narrow cuts of individual olefins in contrast to the mixed feeds employed by the Germans. The first commercial plant in the United States was constructed by the Standard Oil Company at Baton Rouge, La., in 1949. The main product from this plant is isooctyl alcohol produced from a heptene feed. As shown in Table 11-9, additional plants have been constructed by other large petrochemical companies, and the combined annual capacity at the end of 1956 exceeded 100 million lb of alcohols. In addition to isooctyl alcohol, the American plants produce normal and isobutyl aldehydes and alcohols, decyl and tridecyl alcohol. ... 

Table 3 presents the liquid phase results in the CO hydrogenation over ZnO and 5%Au/ZnO. Small quantities of liquid products were collected for both cases. For ZnO, the products include mixed alcohols, C5 to C23 hydrocarbons and wax. The 5%Au/ZnO produces the mixed alcohol products only. The calculation of alcohol and hydrocarbon phases was carried out separately for the purpose of a direct comparison. The observed results suggest that the presence of Au suppresses the activity of the catalyst for the production of hydrocarbons, and also it shifts the selectivity towards higher alcohols. 

There is activity to develop a variety of plant, animal, gas, and even coal. For years to come, we completely expect that surfactants will be derived from a combination of green- and petroleum-based sources. Moreover, as natural and bioderived sources become cheaper, and as such attract more investment, natural sourced feedstocks will compete head to head with synthetics and perhaps, someday, dominate the mix as a supply soiffce for the siu factant industry. New process technology may also begin to play a role to change how we apply even natural oils to production of surfactant alcohols. New research in the fuels industry by Neste Oil has now demonstrated an ability to convert fats and oils into paraffins, making potential feedstock for synthetic surfactants... 

Amylcinnamic aldehyde is an oxidation product of amylcinnamic alcohol, one component of the fragrance mix and can be found as a sensitizer in cases of contact dermatitis in bakers. 

Based on mechanistic and kinetic studies of the higher alcohol synthesis from synthesis gas, it has been shown that the ethanol in the mixed-oxygenate product is produced from intermediates derived from methanol, not CO [103,109]. Kinetic models of the synthesis have been developed that are able to explain the observed product distribution [110,111]. These models are based on a detailed understanding of the reaction mechanism in which two types of reactions dominate aldol condensation, which yields primarily 2-methyl branched alcohols, and Cl coupling reactions, which yield linear alcohols [106,111]. Estimates of the parameters of the kinetic models that quantitatively describe the oxygenate product distributions suggest that the rate of ethanol formation is about an order of magnitude lower than the rate of production of branched alcohols [111,112]. On the Cs/Cu/Zn catalysts, this results in a minimum in yield of ethanol compared with the yields of methanol, 1-propanol, and 2-methyl-1 propanol. Althou methanol conversion to ethanol has been confirmed as part of the hi er alcohol synthesis from synthesis gas, this synthesis does not offer a plausible route for the conversion of methanol to ethanol. Under the reaction conditions methanol rapidly decomposes, even at a pressme of 0.1 MPa [113], to yield an equilibrium mix of methanol, CO, and H2. Furthermore, as shown by the data in T able 7, the yield of ethanol remains low even with methanol in the feed. 

Shimao M, Taniguchi Y, Shikata S, Kato N, Sakazawa C (1982), Production of polyvinyl alcohol oxidase by a symbiotic mixed culture , Appl Environ Microbiol, 44, 28—32. 

Method 2. Mix 1 0 g. of 3 5-dinitrobenzoic acid with 1 5 g. of phosphorus pentachloride in a small, dry test-tube. Warm the mixture gently over a small smoky fiame to start the reaction when the reaction has subsided (but not before), boil for 1-2 minutes or until the solid matter has dissolved. Pour the mixture while still liquid on a dry watch glass (CAUTION the fumes are irritating to the eyes). When the product has solidified, remove the liquid by-product (phosphorus oxychloride) by transferring the pasty mixture to a pad of several thicknesses of filter paper or to a small piece of porous tile. Spread the material until the liquid has been absorbed and the residual solid is dry. Transfer the 3 5 dinitrobenzoyl chloride to a test-tube, add 0-5-1 ml. of the alcohol, and continue as in Method 1. 

The sodio derivative, which is prepared by mixing alcoholic solutions of the ester and of sodium ethoxide, condenses with alkyl halides to yield mono-alkyl C-substituted products, for example ... 

Add 40 ml. of ethyl alcohol to 21 -5 g. of 70 per cent, ethylenediamine solution (0 -25 mol) dissolve 36 -5 g. of adipic acid (0 -25 mol) in 50 ml. of a 6 1 mixture of ethyl alcohol and water. Mix the two solutions, stir and cool. Filter off the resulting salt and recrystalliae it from 60 ml. of a 6 1 ethyl alcohol - water mixture, and dry the salt in the air. Heat the salt in an atmosphere of oxygen-free nitrogen or of carbon dioxide in an oil bath until it melts (ca. 160°) the product will sohdify after a short time. Reduce the pressure to 15 mm. of mercury or less and raise the temperature of the oil bath until the product remelts (about 290°) and continue the heating for 4r-5 hours. Upon coohng, a nylon type polymer is obtained. 

Plasticizer Range Alcohols. Commercial products from the family of 6—11 carbon alcohols that make up the plasticizer range are available both as commercially pure single carbon chain materials and as complex isomeric mixtures. Commercial descriptions of plasticizer range alcohols are rather confusing, but in general a commercially pure material is called "-anol," and the mixtures are called "-yl alcohol" or "iso...yl alcohol." For example, 2-ethyIhexanol [104-76-7] and 4-methyl-2-pentanol [108-11-2] are single materials whereas isooctyl alcohol [68526-83-0] is a complex mixture of branched hexanols and heptanols. Another commercial product contains linear alcohols of mixed 6-, 8-, and 10-carbon chains. 

Methyl /-Butyl Ether. MTBE is produced by reaction of isobutene and methanol on acid ion-exchange resins. The supply of isobutene, obtained from hydrocarbon cracking units or by dehydration of tert-huty alcohol, is limited relative to that of methanol. The cost to produce MTBE from by-product isobutene has been estimated to be between 0.13 to 0.16/L ( 0.50—0.60/gal) (90). Direct production of isobutene by dehydrogenation of isobutane or isomerization of mixed butenes are expensive processes that have seen less commercial use in the United States. 

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