Carbon monoxide from ethanol

The removal of low concentrations of carbon monoxide from the pre-cleaned reformate of hydrocarbon and ethanol reformers is commonly performed by oxidation with air. Owing to the lower carbon monoxide concentration achieved by the low temperatures of methanol reforming, in this case the reformate goes directly to the preferential CO oxidation (PrOx) ... 

Recently, Sen has reported two catalytic systems, one heterogeneous and the other homogeneous, which simultaneously activate dioxygen and alkane C-H bonds, resulting in direct oxidations of alkanes. In the first system, metallic palladium was found to catalyze the oxidation of methane and ethane by dioxygen in aqueous medium at 70-110 °C in the presence of carbon monoxide [40]. In aqueous medium, formic acid was the observed oxidation product from methane while acetic acid, together with some formic acid, was formed from ethane [40 a]. No alkane oxidation was observed in the absence of added carbon monoxide. The essential role of carbon monoxide in achieving difficult alkane oxidation was shown by a competition experiment between ethane and ethanol, both in the presence and absence of carbon monoxide. In the absence of added carbon monoxide, only ethanol was oxidized. When carbon monoxide was added, almost half of the products were derived from ethane. Thus, the more inert ethane was oxidized only in the presence of added carbon monoxide. 

Ethyl Acrylate. 2-Propenoic acid ethyl ester acryl -ic acid ethyl ester, CsH(02 mol wt 100.11. C 59.98%, H 8.05%, O 31.96%. CH.=CHCOOCH2CH,. Prepd from ethylene chlorohydrin or acrylonitrile, ethanol, and sulfuric acid also by an oxo reaction from acetylene, carbon monoxide, and ethanol in the presence of suitable catalysts. See the refs under Methyl Acrylate,... 

Fig. 5.19 (a) Variation of normalized photosensitivity of CdS films with concentration for hydrogen, carbon monoxide, and ethanol at 200 °C and 200 Hz. (Reprinted with permission from Miremadi et al. (1997). Copyright 1997 AIR (b) Selectivity of the carbon tetrachloride ZnS-based gas sensor. Conditions wavelength, 460 nm =335 °C gas concentration, 4.5 p,g/mL and air flow rate, 210 mL/min (Reprinted with permission from Luo et al. (2009). Copyright 2009 Elsevier)... 

Also, ethyl acrylate may be prepared in one step from acetylene, carbon monoxide and ethanol. The solution technique described in Section 6.2.1 does not appear to be used in this way but a process involving nickel carbonyl and hydrochloric acid is operated commercially. The stoichiometric equation for the reaction is ... 

In the presence of Ni or Co catalysts, only saturated monocarboxylic acids could be obtained starting from cyclooctadiene [491] as well as from cyclododecatriene [492]. Dienes with conjugated double bonds may be converted with palladium catalysts [448, 511]. Butadiene reacts with carbon monoxide and ethanol at 70 °C in the presence of PdClg or di-benzonitrile palladium dichloride to give the ethyl ester of penten-3-oic-acid-l ... 

Gasohol boosts octane rating and reduces emissions of carbon monoxide. From a resource viewpoint, because of its photosynthetic origin, alcohol may be considered a renewable resource rather than a depletable fossil fuel. Ethanol is most commonly produced biochemically by fermentation of carbohydrates. Brazil, a country that produces copious amounts of fermentable sugar from sugarcane, has been a leader in the manufacture of ethanol for fuel uses, with an annual production rate of about 24 billion liters. However, due to sugarcane crop shortfalls in 2009-2010, Brazil actually had to import some ethanol from the United States in early 2011 to make up for a deficiency in this fuel. 

General.—catalyst system for the production of linear acids or esters by carbonylation of terminal olefins has been described excellent yields and a high degree of linearity enhance the utility of this system. A related process concerning the carbonylation-dimerization of butadiene is noted a palladium acetonylacetonate-triphenylphosphine complex is catalytically active for the preparation of ethyl nona-3,8-dienoate from butadiene, carbon monoxide, and ethanol. The preparation of but-3-enylsuccinic acid by the catalysed carbonylation of allyl chlorides with double-bond insertion is reported the intermediacy of but-3-enoic acid is suggested. ... 

The changeover from ROO radicals to HOO radicals and the switch from organic peroxides to HOOH has been shown as temperature is increased in propane VPO (87,141). Tracer experiments have been used to explore product sequences in propane VPO (142—145). Propylene oxide comes exclusively from propylene. Ethylene, acetaldehyde, formaldehyde, methanol, carbon monoxide, and carbon dioxide come from both propane and propylene. Ethanol comes exclusively from propane. 

Synthesis Ga.s, Since petroleum prices rose abmpdy in 1974, the production of ethanol from synthesis gas, a mixture of carbon monoxide and hydrogen, has received considerable attention. The use of synthesis gas as a base raw material has the same drawback as fermentation technology low yields limited by stoichiometry. 

A Belgian patent (178) claims improved ethanol selectivity of over 62%, starting with methanol and synthesis gas and using a cobalt catalyst with a hahde promoter and a tertiary phosphine. At 195°C, and initial carbon monoxide pressure of 7.1 MPa (70 atm) and hydrogen pressure of 7.1 MPa, methanol conversions of 30% were indicated, but the selectivity for acetic acid and methyl acetate, usehil by-products from this reaction, was only 7%. Ruthenium and osmium catalysts (179,180) have also been employed for this reaction. The addition of a bicycHc trialkyl phosphine is claimed to increase methanol conversion from 24% to 89% (181). 

These processes have supplanted the condensation reaction of ethanol, carbon monoxide, and acetylene as the principal method of generating ethyl acrylate [140-88-5] (333). Acidic catalysts, particularly sulfuric acid (334—338), are generally effective in increasing the rates of the esterification reactions. Care is taken to avoid excessive polymerisation losses of both acryflc acid and the esters, which are accentuated by the presence of strong acid catalysts. A synthesis for acryflc esters from vinyl chloride (339) has also been examined. 

Ethanol, CH3CH2OH, is produced from the biological fermentation of the starches in grains, mainly corn. It currently makes up about 10% by volume of gasoline in the United States, thereby reducing pollution as well as the use of petroleum. The oxygen atom in the ethanol molecule reduces emissions of carbon monoxide and hydrocarbons by helping to ensure complete combustion. One bushel of... 

Acetic acid, CH,COOH(l), could be produced from (a) the reaction of methanol with carbon monoxide (b) the oxidation of ethanol (c) the reaction of carbon dioxide with... 

Palladium (II) chloride and ferric (III) chloride were purchased from Sigma Chemicals Co. Cerium(III) nitrate from Pfaltz Bauer, Inc. y-Al203 (100 m2/g) from Alfa Chemicals ethanol (HPLC grade) and nitrobenzene (Certified ACS) from Fisher Scientific. Bis(triphenylphosphine)palladium(II) dichloride was generously donated by Dr. Ivan J.B. Lin (National Dong Hwa University, Taiwan). All compounds were used without further treatment. Carbon monoxide (99.0%) was obtained from Praxair. 

The other large-scale ethanol user is the USA, where ethanol has been used to increase the octane rating of gasoline, to decrease carbon monoxide emissions, and, more recently, to replace MTBE (methyl tert-butyl ether) in reformulated gasoline. Ethanol production in the USA grew from about 0.6 billion liters in 1980 to... 

Photolytic. Major products reported from the photooxidation of butane with nitrogen oxides under atmospheric conditions were acetaldehyde, formaldehyde, and 2-butanone. Minor products included peroxyacyl nitrates and methyl, ethyl and propyl nitrates, carbon monoxide, and carbon dioxide. Biacetyl, tert-butyl nitrate, ethanol, and acetone were reported as trace products (Altshuller, 1983 Bufalini et al, 1971). The amount of sec-butyl nitrate formed was about twice that of n-butyl nitrate. 2-Butanone was the major photooxidation product with a yield of 37% (Evmorfopoulos and Glavas, 1998). Irradiation of butane in the presence of chlorine yielded carbon monoxide, carbon dioxide, hydroperoxides, peroxyacid, and other carbonyl compounds (Hanst and Gay, 1983). Nitrous acid vapor and butane in a smog chamber were irradiated with UV light. Major oxidation products identified included 2-butanone, acetaldehyde, and butanal. Minor products included peroxyacetyl nitrate, methyl nitrate, and unidentified compounds (Cox et al., 1981). 

Photolytic. Products identified from the photoirradiation of 1-butene with nitrogen dioxide in air are epoxybutane, 2-butanone, propanal, ethanol, ethyl nitrate, carbon monoxide, carbon dioxide, methanol, and nitric acid (Takeuchi et ah, 1983). 

Fig. 35. A rliodium(III)-caxbon bonded product formed from RhCls and vp in ethanol under carbon monoxide...

Compressed synthesis gas is passed through a CuZn catalyst to yield crude methanol, water, and low quantities of ethanol, acetone, and other impurities. Noncondensable gases from the process such as hydrogen, carbon monoxide, and carbon dioxide are recycled, recompressed, and again passed across the CuZn catalyst. 

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