Butanol from ethanol

CHa CHlCH CHO. Colourless lachrymatory liquid with a pungent odour. B.p. 104 "C. Manufactured by the thermal dehydration of aldol. May be oxidized to crotonic acid and reduced to crolonyl alcohol and 1-butanol oxidized by oxygen in the presence of VjOj to maleic anhydride. It is an intermediate in the production of l-butanol from ethanol. 

Tian and co-workers reported the hydrothermal synthesis of n-butanol from ethanol [186]. This process used commercially available cobalt powder as a catalyst combined with NaHCOa (0.01 mol) as a base under hydrothermal conditions using 0.15 mol of ethanol and water (11.24 mL) at 200 °C for 3 days to give n-butanol with 69 % selectivity. 

In a process which is now largely of historical interest, 1-butanol has been produced from ethanol [64-17-5] via successive dehydrogenation (to acetaldehyde [75-07-0]) condensation (to crotonaldehyde [4170-30-3]) and hydrogenation. 

Ethanol s use as a chemical iatemiediate (Table 8) suffered considerably from its replacement ia the production of acetaldehyde, butyraldehyde, acetic acid, and ethyUiexanol. The switch from the ethanol route to those products has depressed demand for ethanol by more than 300 x 10 L (80 x 10 gal) siace 1970. This decrease reflects newer technologies for the manufacture of acetaldehyde and acetic acid, which is the largest use for acetaldehyde, by direct routes usiag ethylene, butane (173), and methanol. Oxo processes (qv) such as Union Carbide s Low Pressure Oxo process for the production of butanol and ethyUiexanol have totaUy replaced the processes based on acetaldehyde. For example, U.S. consumption of ethanol for acetaldehyde manufacture declined steadily from 50% ia 1962 to 37% ia 1964 and none ia 1990. Butadiene was made from ethanol on a large scale duriag World War II, but this route is no longer competitive with butadiene derived from petroleum operations. 

Acetaldehyde. Until the early 1970s, the maia use of iadustrial ethanol was for the production of acetaldehyde [75-07-0]. By 1977, the ethanol route to acetaldehyde had largely been phased out ia the United States as ethylene and ethane became the preferred feedstocks for acetaldehyde production (286—304). Acetaldehyde usage itself has also changed two primary derivatives of acetaldehyde, acetic acid, and butanol, are now produced from feedstocks other than acetaldehyde. Acetaldehyde is stiU produced from ethanol ia India. 

The phenol (Imol) in 5% aqueous NaOH is treated (while cooling) with benzoyl chloride (Imol) and the mixture is stirred in an ice bath until separation of the solid benzoyl derivative is complete. The derivative is filtered off, washed with alkali, then water, and dried (in a vacuum desiccator over NaOH). It is recrystalUsed from ethanol or dilute aqueous ethanol. The benzoylation can also be carried out in dry pyridine at low temperature ca 0°) instead of in NaOH solution, finally pouring the mixture into water and collecting the solid as above. The ester is hydrolysed by refluxing in an alcohol (for example, ethanol, n-butanol) containing two or three equivalents of the alkoxide of the corresponding alcohol (for example sodium ethoxide or sodium n-butoxide) and a few ca 5-10) millilitres of water, for half an hour to three hours. When hydrolysis is complete, an aliquot will remain clear on dilution with four to five times its volume of water. Most of the solvent is distilled off. The residue is diluted with cold water and acidified, and the phenol is steam distilled. The latter is collected from the distillate, dried and either fractionally distilled or recrystalUsed. 

Solid esters are easily crystallisable materials. It is important to note that esters of alcohols must be recrystallised either from non-hydroxylic solvents (e.g. toluene) or from the alcohol from which the ester is derived. Thus methyl esters should be crystallised from methanol or methanol/toluene, but not from ethanol, n-butanol or other alcohols, in order to avoid alcohol exchange and contamination of the ester with a second ester. Useful solvents for crystallisation are the corresponding alcohols or aqueous alcohols, toluene, toluene/petroleum ether, and chloroform (ethanol-free)/toluene. Esters of carboxylic acid derived from phenols... 

The oleoresin is obtained from turmeric powder by solvent extraction. Solvents approved for use by European Commission are ethylacetate, acetone, carbon dioxide, dichloromethane, n-butanol, methanol, ethanol, and hexane. The U.S. Food and Drug Administration (FDA) also authorized the use of mixtures of solvents that include those mentioned earlier plus isopropanol and trichloroethylene. After filtration the solvents must be completely removed from the oleoresin. 

Different routes for converting biomass into chemicals are possible. Fermentation of starches or sugars yields ethanol, which can be converted into ethylene. Other chemicals that can be produced from ethanol are acetaldehyde and butadiene. Other fermentation routes yield acetone/butanol (e.g., in South Africa). Submerged aerobic fermentation leads to citric acid, gluconic acid and special polysaccharides, giving access to new biopolymers such as polyester from poly-lactic acid, or polyester with a bio-based polyol and fossil acid, e.g., biopolymers . 

M. Tomsic, A. Jamnik, G. Fritz-Popovski, O. Glatter, and L. Vlcek. Structural properties of pure simple alcohols from ethanol, propanol, butanol, pentanol, to hexanol Comparing Monte Carlo simulations with experimental SAXS data. J. Phys. Chem. B, 111(7) 1738-1751, 2007. 

Separation of citric acid from fermentation broth Separation of lactic acid from fermentation broth Production of acetone, butanol, and ethanol (ABE) from potato wastes Separation of long-chain unsaturated fatty acids... 

Next, an experiment was run in which 2.5 g/L of sodium butyrate was added to P2 medium to investigate whether it could be converted to butanol. A control experiment was run containing P2 medium. A separate control experiment was run before each experiment. This is essential because biomass accumulation in the reactor changes with time, thus affecting performance of the reactor (5). The reactor produced 4.77 g/L of total ABE, of which acetone, butanol, and ethanol were 1.51,3.14, and 0.12 g/L, respectively (Table 1). It resulted in a total ABE productivity of 1.53 g/(L-h) and a glucose utilization of 29.4% of that available in the feed of 59.1 g/L. The acid concentration in the effluent was 1.56 g/L. Following this, P2 medium was supplemented with sodium butyrate and the experiment was conducted at the same dilution rate. The reactor produced 1.55 g/L of acetone, 4.04 g/L of butanol, and 0.11 g/L of ethanol, for a total ABE concentration of 5.70 g/L, compared with 4.77 g/L in the control experiment. The productivity was 1.82 g/(L-h), compared with 1.53 g/(L-h) for the control experiment. These experiments suggested that butyrate was used by the culture to produce additional butanol. Note that 0.9 g/L of butanol was produced from 1.65 g/L of butyrate (2.5 g/L in feed, 0.85 g/L in effluent). The yield calculations do not include the amount of butyrate that was utilized by the culture. 

After 606 h, the dilution rate in reactor L was decreased from 1.2 to 0.6 hr1. When the pH was adjusted to 3.5 at 623 h, the concentrations of acetone, butanol, and ethanol decreased dramatically and reduced to almost 0 g/L by 700 h (see Fig. 4A). In the meantime, the concentrations of glucose and butyric acid increased with time to reach almost their feed concentrations. Coupled with the low OD value, these findings make it apparent that the fermentation had almost ceased at this low pH value. 

As many as 70 products were at one time produced commercially from ethanol. Some of these downstream products are butanol, 2-ethyl hexanol, crotonaldehyde, butyraldehyde, acetaldehyde, acetic acid, butadiene, sorbic acid, 2-ethylbutanol, ethyl ether, many esters, ethanol-glycol ethers, acetic anhydride, vinyl acetate, ethyl vinyl ether, even ethylene gas. Many of these products are now more economically made from other feedstocks such as ethylene for acetaldehyde and methanol-carbon monoxide for acetic acid. Time will tell when a revival of biologically-oriented processes will offer lower-cost routes to at least the simpler products. 

The reactor is an enameled apparatus with an agitator and a water vapour jacket. The production of sodium dihydroxyphenylsilanolate is carried out in butanol and toluene or ethanol and toluene medium at 35-50 °C. The consumption of other components is calculated by the amount of the loaded condensation product. After loading the product of condensation, the reactor is filled with toluene and butanol (or ethanol and toluene) from batch boxes 10 and 11. The ratio of the solvents should be 1 1.4 to obtain 10% silanol solution. The calculation takes into account toluene contained in the product of hydrolytic condensation. The loaded mixture is agitated in the reactor for 30 minutes after that it receives 20% alkali solution from batch box 12 at agitation. The reaction forms sodium dihydroxydiphenylsi-lanolate and water. 

If during the water flushing the organic layer is difficult to separate from the aqueous layer, one should add butanol or ethanol. When SO4"2 ions are... 

The solvent is distilled from polyalumophenylsiloxane in the same apparatus, 8. Before the distillation the product is clarified at 45-50 °C. The settled water is poured into collector 18 the clarified product (after switching inverse cooler 9 into the direct mode) is distilled to separate the toluene and butanol or ethanol mixture at a residual pressure of 800 65 GPa. The distillation temperature gradually rises to 90 °C. The distillation is considered finished when the resin concentration in the varnish is 40-65%. The vapours of the distilled solvent enter water cooler 9. There they condense and flow into receptacle 14. 

Ethanol is formed by the anaerobic metabolism of yeasts like Saccharomyces and many other species. In the presence of sulfite salts or in alkaline solutions, the alcohol formation can be changed to glycerin formation. Clostridium and Bacillus species participate in the production of butanol-acetone-butyric acid. Besides n-butanol, acetone and butyric acid, other organic compounds like propionic and lactic acids, 2-propanol, ethanol, and acetyl methylcarbinol (3-oxo-2-butanol) as well as C02 and H2 are produced as by-products. Some bacteria generate 2-propanol from acetone and others form acetone from ethanol. 

This can be purified by crystallization from n-butanol, dioxan, ethanol or ethyl acetate. 

Diphenyl carbonate from dimethyl carbonate and phenol Dibutyl phthalate from butanol and phthalic acid Ethyl acetate from ethanol and butyl acetate Recovery of acetic acid and methanol from methyl acetate by-product of vinyl acetate production Nylon 6,6 prepolymer from adipic acid and hexamethylenediamine MTBE from isobutene and methanol TAME from pentenes and methanol Separation of close boiling 3- and 4-picoline by complexation with organic acids Separation of close-boiling meta and para xylenes by formation of tert-butyl meta-xyxlene Cumene from propylene and benzene General process for the alkylation of aromatics with olefins Production of specific higher and lower alkenes from butenes... 

The one-step synthesis of a,co-hydroxylated dimers of 1,3-dienes or maleic acid uses alcohol (t-butanol, n-butanol, isopropanol, ethanol)/H202/FeS04 as a catalyst 72 73>. Organic hydroxylated radicals are generated from the alcohol by hydrogen abstraction ... 

ABE (acetone, butanol, and ethanol) fermentation has a long history of commercial use and perhaps the greatest potential for an industrial comeback. Acetone, butanol, and ethanol can all be isolated from this remarkable metabolic system carbon dioxide and hydrogen are additional products. The solvents were used as paint solvents in the expanding automobile industry. Ultimately these processes proved uncompetitive because of poor yields, low product... 

Processes for production of ethanol and acetone-butanol-ethanol mixture from fermentation products in membrane contactor devices were presented in Refs. [88,89]. Recovery of butanol from fermentation was reported in Ref. [90]. Use of composite membrane in a membrane reactor to separate and recover valuable biotechnology products was discussed in Refs. [91,92]. A case study on using membrane contactor modules to extract small molecular weight compounds of interest to pharmaceutical industry was shown in Ref. [93]. Extraction of protein and separation of racemic protein mixtures were discussed in Refs. [94,95]. Extractions of ethanol and lactic acid by membrane solvent extraction are reported in Refs. [96,97]. A membrane-based solvent extraction and stripping process was discussed in Ref. [98] for recovery of Phenylalanine. Extraction of aroma compounds from aqueous feed solutions into sunflower oil was investigated in Ref. [99]. 

Deacetylation was accomplished by treating 258 mg of the above product for 40 min with 5 ml of 6 N HCl at 121 C. The resulting was dried under reduced pressure and dissolved in water. After adjusting the pH to 7.0 with aqueous ammonia, the solution was evaporated to dryness again. The residue was dissolved in a little water and applied to a 0.9 X 30 cm column of resin XE-64 which had been previously equilibrated with 1 M ammonium formate pH 4.0 and washed with 250 ml of water. The column was washed with 850 ml of water after application of the sample followed by 70 ml of 0.72 M acetic acid to remove unhydrolyzed material. The e-pyridoxyl lysine was eluted with 0.81 M acetic acid, and fractions containing the product were evaporated to dryness. On recrystallization of pyridoxyl-lysine from ethanol the yield was 110 mg of pale yellow crystals, m.p. 214-214.5°C. On paper chromatography in butanol pyridine acetic acid-HjO (30 20 6 24 v/v) Rf = 0.28 (Ronchi et al. 1969). 

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