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Showing papers on "Methanol published in 1973"



Journal ArticleDOI
TL;DR: In this article, it was shown that in the presence of catalyst poisons such as acetonitrile or mercury, the currents for formic acid oxidation, measured in the potential range +0.4 to + 0.8V E(H) at Pt can be substantially increased.
Abstract: : In the presence of catalyst poisons such as acetonitrile or mercury, it is shown that the currents for formic acid oxidation, measured in the potential range +0.4 to +0.8V E(H) at Pt can be substantially increased. The effect is shown to originate from blocking of the surface at less positive potentials mainly in the H adsorption/desorption region where an inhibitor for the main formic acid oxidation reaction is normally formed in the absence of additive. Under the latter conditions, steady-state oxidation currents are normally small and decrease with time due to build-up of an inhibiting species from the HCOOH or intermediates involved in its oxidation. The competitive effects of Hg and CH3CN are different insofar as a given extent of surface blocking causes different effects on the formic acid oxidation current. Comparative experiments on the effect of CH3CN on methanol oxidation are described. (Modified author abstract)

136 citations


Journal ArticleDOI
TL;DR: An NAD-dependent alcohol dehydrogenase has been isolated from the yeast Candida boidinii grown on methanol and a study of the properties of the enzyme has shown that it is very similar to the alcohol: NAD oxidoreductase from baker's yeast.
Abstract: 1 An NAD-dependent alcohol dehydrogenase has been isolated from the yeast Candida boidinii grown on methanol. A study of the properties of the enzyme has shown that it is very similar to the alcohol: NAD oxidoreductase from baker's yeast. The alcohol dehydrogenase from Candida boidinii does not catalyze the oxidation of methanol and is constitutively formed. 2 A mutant, 48, has been isolated which is unable to grow on methanol as sole carbon and energy source. This strain lacks the methanol-oxidizing enzyme but not NAD-dependent alcohol dehydrogenase. 3 Cells grown on glucose or ethanol do not contain the methanol-oxidizing enzyme. During adaptation from glucose to methanol, enzyme activity appears before growth on methanol begins. 4 The methanol-oxidizing enzyme has been partially purified. It catalyzes the oxidation of methanol to formaldehyde and hydrogen peroxide, and is independent of the addition of a hydrogen acceptor. The prosthetic group of this enzyme is FAD. The molecular weight was calculated to be 600000, one subunit has a molecular weight of 74000. The optima of pH and temperature for enzyme activity are 7.5–9.5 and 30°C, respectively. It is unstable in acidic pH. The enzyme is not specific for methanol. It also oxidizes lower primary alcohols. The Km value for methanol is 2.0 mM and that for ethanol 4.5 mM.

132 citations


Journal ArticleDOI
TL;DR: Palladium(O) carbonyl complexes, Pd(CO)(PPh 3 ) 3 Pd 3 (CO) 3 (Pph 3 ) 2 PdCl 2 with carbon monoxide at room temperature in methanol/amine systems involving primary and secondary amines such as diethylamine and cyclohexylamine, are interconvertible under suitable conditions as mentioned in this paper.

94 citations


Patent
Charles P. Marion1
26 Mar 1973
TL;DR: In this article, a continuous process for producing methanol including the steps of producing synthesis gas i.e. H2 + CO by the partial oxidation of a hydrocarbonaceous feed in a free-flow non-catalytic synthesis gas generator, adjusting the mole ratio (H2/CO) of the process gas stream to a value in the range of about greater than 2 to 12.
Abstract: A continuous process for producing methanol including the steps of producing synthesis gas i.e. H2 + CO by the partial oxidation of a hydrocarbonaceous feed in a free-flow non-catalytic synthesis gas generator, adjusting the mole ratio (H2/CO) of the process gas stream to a value in the range of about greater than 2 to 12 by noncatalytic thermal direct water-gas shift, cooling the process gas stream by indirect heat exchange with water to produce steam for use in the process, purifying the gas stream preferably with a portion of the methanol product, catalytically reacting the purified synthesis gas stream under methanol producing conditions, and separating methanol from liquid impurities. All steps are preferably carried out at a pressure which is substantially that in the synthesis gas generator less ordinary line drop. Optionally, a portion of the liquid impurities e.g. dimethylether, water, and mixed alcohols, are introduced into the synthesis gas generator to reduce the specific consumption of free-oxygen gas and to increase the yield of synthesis gas.

58 citations


Journal ArticleDOI
TL;DR: The degree of catalase-mediated peroxidation should not be controlled or estimated from the residual catalatic activity when using catalases inhibitors, as this effect is completely prevented in the presence of alcohol.

56 citations


Journal ArticleDOI
TL;DR: Methanol concentrations of 100 times the Km for formaldehyde so that inhibition by formaldehyde formed as an intermediate in methanol oxidation would be very unlikely and a methane limited chemostat culture of this organism would be expected.
Abstract: . Methanol- and methane-utilizing organisms were grown in chemostat culture and the response of respiration rate to different concentrations of substrate was measured. Cells of Pseudomonas extorquens NCIB 9399 grown on methanol demonstrated a high affinity for methanol (Km=20·4 μM). The affinities for formaldehyde and formate were 104 μM and 228 μM, respectively. The maximum respiration rate was similar for all 3 substrates. Methanol concentrations of 100 times the Km for formaldehyde so that inhibition by formaldehyde formed as an intermediate in methanol oxidation would be very unlikely. The Km for methane of a culture of a pseudomonad grown on methane was very low, 26 μM; that of the same organism for methanol was 50 μM. The maximum respiration on methanol was c. twice that on methane so that no methanol accumulation would be expected in a methane limited chemostat culture of this organism.

56 citations


Journal ArticleDOI
TL;DR: In this article, it was shown that ΔS°t(M++ X−) is relatively independent of M+ and of X− if M+ is Na+, K+, Rb+ and Cs+ and if X− is Cl−, Br−, I−, and ClO−4.
Abstract: Heats of solution of 1:1 electrolytes in acetonitrile have been determined, and enthalpies of transfer of the electrolytes from water to acetonitrile thus calculated. Free energies of transfer of a number of electrolytes from water to nonaqueous solvents have also been determined. Together with previous data, these measurements yield entropies of transfer of electrolytes from water to N-methylformamide (NMF), methanol, ethanol, dimethyl sulphoxide (DMSO), acetonitrile, NN-dimethylformamide (DMF) and acetone; single-ion entropies of transfer from water to these solvents are tabulated for up to 11 cations and 5 anions. It is shown that ΔS°t(M++ X–) is relatively independent of M+ and of X– if M+ is Na+, K+, Rb+, and Cs+ and if X– is Cl–, Br–, I–, and ClO–4. For transfers to or from water and methanol, this constancy of ΔS°t(M++ X–) is not maintained if M+ is R4N+, Ph4As+, and Ph4P+ and if X– is Ph4B–.“Absolute” single-ion entropies of transfer have been obtained, and a treatment is given that enables these single-ion values to be reproduced accurately, and further single-ion values to be predicted, for transfers from water to NMF, methanol, ethanol, DMSO, acetonitrile, DMF, acetone, formamide and liquid ammonia. For these solvents (other than water and methanol) only one adjustable parameter per solvent is required. It is also shown that the so-called “iceberg effect” for solution of organic ions is very large in water, small in methanol, and non-existent in NMF, ethanol, acetonitrile, DMF, acetone and (possibly) DMSO.

55 citations


Journal ArticleDOI
TL;DR: Pituitary glands contain both the methanol-forming enzyme of Axelrod and Daly and S-adenosylmethionine dependent protein carboxyl-methylase, and it is proposed that the in vitro formation of meethanol is the result of chemical cleavage of enzymatically formed protein methyl esters.

53 citations


Journal ArticleDOI
01 Feb 1973-Polymer
TL;DR: In this article, the transesterification of DMT with EG was investigated in the presence of various catalysts at 197°C, and the reaction was followed by the measurement of the quantity of methanol which distilled from the reaction vessel.

50 citations


Journal ArticleDOI
TL;DR: It is suggested that after each addition of methanol a burst of growth occurred, followed by a period of starvation, which caused cycling in the values of a number of parameters, including pH, dissolved oxygen tension, CO2 production and amino acid pool concentration.
Abstract: Summary: As the interval between methanol additions to methanol-limited cultures of Pseudomonas methylotropha was increased beyond 20 s the yield of bacterial dry wt/g of methanol fell significantly. Discontinuous methanol additions also caused cycling in the values of a number of parameters, including pH, dissolved oxygen tension, CO2 production and amino acid pool concentration. It is suggested that after each addition of methanol a burst of growth occurred, followed by a period of starvation. These observations are discussed in the light of continuous culture practice and theory.

Patent
21 Jun 1973
TL;DR: In this article, a process for producing formaldehyde by oxidizing dehydrogenation of methanol in the presence of a silver catalyst is described, where a vaporous mixture of water and oxygen is introduced into the starting mixture containing water, methanols and oxygen before entry into the catalyst bed.
Abstract: A process for producing formaldehyde by oxidizing dehydrogenation of methanol in the presence of a silver catalyst, wherein a vaporous mixture of water and oxygen is introduced into the vaporous starting mixture containing water, methanol and oxygen before entry into the catalyst bed. Formaldehyde produced by the process is a disinfectant, tanning agent, reducing agent and raw material for the production of synthetic resins, adhesives and plastics.

Journal ArticleDOI
TL;DR: In this article, the alpha-lactose hydrate was converted to the stable anhydrous alpha lactose in methanol and showed that alpha-hydrate is stable in low moisture.

Journal ArticleDOI
TL;DR: Methyl oleate is converted in high yield to methyl 9(10)-methoxystearate by reaction with methanol in the presence of mercuric acetate followed by demercuration with sodium borohydride as discussed by the authors.

Journal ArticleDOI
TL;DR: In this paper, the cobalt carbonyl-catalyzed hydromethoxy carbonylation of butadiene is studied and the reaction proceeds in the presence of a pyridine base to give methyl 3-pentenoate.
Abstract: The cobalt carbonyl-catalyzed hydromethoxycarbonylation of butadiene is studied The reaction proceeds in the presence of a pyridine base to give methyl 3-pentenoate Isoquinoline is found to be a better solvent for the production of methyl 3-pentenoate than pyridine, not only because the yield of the ester is somewhat higher in the presence of isoquinoline than in the presence of pyridine, but also because it is far less volatile than pyridine, so that the product can be easily separated from the solvent and the catalyst by distillation Also, the hydromethoxycarbonylation of methyl 3-pentenoate under somewhat different conditions is found to give a good yield of dimethyl adipate The hydroformylation of methyl 3-pentenoate is studied as well The effect of such a solvent as THF, benzene, and acetonitrile in increasing the selectivity to methyl 5-formylpentanoate is found to increase in this order: acetonitrile

Journal ArticleDOI
TL;DR: Growth of Methylococcus capsulatus on methane was inhibited by methanol, ethanol, n-propanol and n-butanol, but was unaffected by galactose, glucose, fructose, maltose, sucrose, or lactose, and 14C-Labelled ethanol and acetate showed restricted incorporation into lipid, leucine, glutamate, proline and arginine, indicating that M. Capsulatus can produce acetyl coenzyme A from
Abstract: SUMMARY: Growth of Methylococcus capsulatus on methane was inhibited by methanol (0.1%, v/v, and above), ethanol, n-propanol and n-butanol (0.01%, v/v, and above), but was unaffected by galactose, glucose, fructose, maltose, sucrose (at 0.1 M) or lactose (0.05 M). About one organism in 7 million grew well on solid medium using methanol vapour as a sole source of carbon and energy, but [14C]methanol was readily metabolized and assimilated by cultures growing on methane. Labelling patterns from [14C]methane and [14C]methanol were similar, indicating their assimilation by a common pathway. Dissimilarities between the labelling patterns obtained with 14CH4 and 14C-labelled formaldehyde, formate and carbonate indicated that the ribose phosphate cycle of formaldehyde assimilation may not account for all the carbon assimilated by M. capsulatus: significant incorporation of formate, carbon dioxide and possibly of intermediates of methane oxidation more reduced than formaldehyde may occur. 14C-Labelled ethanol and acetate showed restricted incorporation into lipid, leucine, glutamate, proline and arginine, indicating that M. capsulatus can produce acetyl coenzyme A from both compounds and introduce it into an incomplete biosynthetic tricarboxylic acid cycle. Methylococcus capsulatus was unable to assimilate more than trace amounts of [14C]glucose or sucrose.

Journal ArticleDOI
TL;DR: In this article, the vapor phase catalytic air oxidation of methanol to formaldehyde over vanadium pentoxide-molybdenum trioxide was investigated between 250 and 530 °C at atmospheric pressure.

Patent
Stiles Alvin Barber1
08 Nov 1973
TL;DR: In this article, a copper oxide-zinc oxide catalyst, low in sodium and sulfur, is obtained by combining ammonium carbonate or ammonium bicarbonate with copper and zinc nitrates.
Abstract: A catalyst particularly useful in the production of methanol can be made by preparing a solution of copper and zinc nitrates, the ratio of copper to zinc being from 1:1 to 8:1 and then precipitating the copper and zinc by the addition of ammonium carbonate or ammonium bicarbonate. After the precipitated material has been agglomerated and calcined, a copper oxide-zinc oxide catalyst, low in sodium and sulfur is obtained.

Journal ArticleDOI
TL;DR: Cell suspensions of pseudomonad C, a bacterium capable of growth on meethanol as sole carbon source, were able to oxidize methanol, formaldehyde, and formate, although the rates of oxidation for the latter two compounds were much slower.
Abstract: Cell suspensions of pseudomonad C, a bacterium capable of growth on methanol as sole carbon source, were able to oxidize methanol, formaldehyde, and formate, although the rates of oxidation for the latter two compounds were much slower. The latter compounds also could not serve as sole carbon sources. Through the use of labeled compounds, it was shown that in the presence of methanol, formaldehyde, formate, and bicarbonate were incorporated into trichloroacetic acid-precipitable material. Hexose phosphate synthetase activity was found, indicating the assimilation of methanol via an allulose pathway. No hydroxypyruvate reductase activity was found, nor was any complex membrane structure observed. Such a combination of characteristics has been observed in an obligate methylotroph (Pseudomonas W1), but pseudomonad C can utilize a variety of non-methyl substrates.

Journal ArticleDOI
TL;DR: In this article, the enthalpies of mixing and total and partial vapour pressures of methanol + acetone, carbon disulphide+ acetone (CDE) and other mixing agents have been determined.

Patent
04 Oct 1973
TL;DR: A process for preparing hydrogen cyanide which comprises reacting methanol or formaldehyde or their mixture, ammonia and oxygen in the presence of a catalyst composition at a temperature of 250* to 550*C and a space velocity of 50 to 5,000 hr 1 under a pressure of 0.5 to 10 atm is described in this article, where the said catalyst composition comprising a catalyst system of the formula: MoaBibFecXdYeZfOg wherein X is one or more of Cr, Mn, Co, Ni, Zn, Cd
Abstract: A process for preparing hydrogen cyanide which comprises reacting methanol or formaldehyde or their mixture, ammonia and oxygen in the presence of a catalyst composition at a temperature of 250* to 550*C and a space velocity of 50 to 5,000 hr 1 under a pressure of 0.5 to 10 atm., the said catalyst composition comprising a catalyst system of the formula: MoaBibFecXdYeZfOg wherein X is one or more of Cr, Mn, Co, Ni, Zn, Cd, Sn, W and Pb, Y is one or more of Tl and elements belonging to Group IA or IIA in the periodic table, Z is one or more of P, As and Sb and a, b, c, d, e, f and g represent respectively the number of atoms and are respectively 12, 0.1 to 24, 0 to 24, 0 to 15, 0 to 15, 0 to 5 and the total number of the oxygen atoms in the oxides of the other atoms.

Journal ArticleDOI
TL;DR: In this paper, the hydroxyl proton resonance frequency for various binary solvent mixtures, including water with methanol, t-butyl alcohol, triethylamine and acetone, has been measured over the complete mole fraction range.
Abstract: The hydroxyl proton resonance frequency for various binary solvent mixtures, including water with methanol, t-butyl alcohol, triethylamine and acetone, has been measured over the complete mole fraction range. Results of similar experiments for alcohol + alcohol and alcohol + amine mixtures are used for comparative purposes. At low concentrations water behaves normally in these solvents, but in the water-rich region shifts to low-field were generally observed, especially for aqueous alcohols and amines. These are interpreted in terms of an acid-base effect, and an effect involving local changes in water structure, equivalent to a temperature reduction. Various methods for differentiating between these two factors are outlined. It is concluded that for aqueous methanol, the acid-base effect dominates, whilst for aqueous t-butyl alcohol the water-structure effect is of major significance. Other solvents fit between these extremes.

Patent
26 Dec 1973
TL;DR: In this paper, a non-alcohol-soluble nylon polymer and a formic acid solvent are used to form a microporus film, which is then regenerated by contacting it with a heterogeneous esterification catalyst in the presence of methanol to form methyl formate.
Abstract: Method of forming a microporus film by casting a solution of a film-forming polymer and quenching the film in a non-solvent system quench bath wherein the polymer is preferably a non-alcohol-soluble nylon polymer and the solvent is formic acid. The contaminated non-solvent system is then regenerated by contacting it with a heterogeneous esterification catalyst in the presence of methanol to form methyl formate and then removing the methyl formate by volatilization and recycling a portion of the treated non-solvent system to the quench bath.



Journal ArticleDOI
TL;DR: In this article, the potential electroreduction of methanol solutions of p-methoxycarbonylbenzyl acetate and p-methyl p-toluate was investigated.
Abstract: Controlled potential electroreduction of methanol solutions of p-methoxycarbonylbenzyl acetate and p-methoxycarbonylbenzyl methyl ether results in cleavage to methyl p-toluate in high yield and with good current efficiency. Substituted benzotrifluorides may similarly be cleaved to the substituted toluene. For efficient reduction an electron-accepting substituent (CO2Me or CN) is required which must be para to the group undergoing cleavage. The effect of substituents and of added acetic acid on the product distribution, together with voltammetric data, indicate an e.c.e. mechanism. Attempts to effect partial defluorination of the CF3 group, including the use of a rapidly rotating lead disc electrode, failed.

Journal ArticleDOI
TL;DR: In this article, a highly selective catalytic, one-step synthesis of oleic acid into 9(10)-carboxystearic acid in high yields is described.
Abstract: A highly selective catalytic, one-step synthesis converts oleic acid into 9(10)-carboxystearic acid in high yields (85–99%). Hydrocarboxylation with water and carbon monoxide under pressure (3000–4000 psi) is catalyzed with a mixture of palladium chloride and triphenylphosphine at 120–150 C with or without acetone or acetic acid solvents. Palladium supported on carbon is also an effective hydrocarboxylation catalyst in the presence of triphenylphosphine and HCl. Methyl 9(10)-carbomethoxystearate was prepared by catalytic carbomethoxylation of methyl oleate with methanol and carbon monoxide but in lower yields. The carboxystearic acids and esters consisted of the 9 and 10 isomers (87–94%) in approximately equal proportions. This catalytic carboxylation procedure is a more efficient route to carboxystearic acid and ester than the two-step hydroformylation-oxidation process reported previously. Carboxylated acids, methyl esters and triglycerides of potential industrial importance have been prepared.

Patent
21 May 1973
TL;DR: In this paper, an acrylic acid ester is continuously synthesized by esterifying one part by mole of acrylic acid with 2.0 to 3.0 parts by methanol or 1.5 to 2.5 parts by ethanol in the presence of 0.1 to 1.0 part of a water-insoluble and unreactive organic solvent.
Abstract: Acrylic acid esters such as methyl acrylate or ethyl acrylate are continuously synthesized by esterifying one part by mole of acrylic acid with 2.0 to 3.0 parts by mole of methanol or 1.5 to 2.5 parts by mole of ethanol in the presence of 0.1 to 1.0 part by mole of a water-insoluble and unreactive organic solvent, such as a linear, cyclic or aromatic hydrocarbon compound having a boiling point of 100 DEG to 160 DEG C and sulfuric acid having a concentration of 5 to 50 % by weight in an esterification solution as a catalyst at boiling temperature, for example, 50 DEG to 100 DEG C approximately under atmospheric pressure, while azeotropically boiling water formed in the esterification together with the organic solvent and distilling acrylic acid esters simultaneously, thereby keeping the concentration of sulfuric acid constant in the esterification solution; separating the resulting effluent esterification solution into an organic solvent layer and an aqueous layer by decantation; recycling the aqueous layer containing sulfuric acid to the esterification; separating and recovering the resulting ester and organic solvent contained in the organic solvent layer by steam distillation from the resulting polymers and high boiling materials; and leading the ester and organic solvent to further purification together with the resulting distillate of the esterification.

Patent
26 Dec 1973
TL;DR: In this paper, a process for the simultaneous separation of carbon dioxide and carbon dioxide from the gaseous mixtures obtained in the direct oxidation of ethylene with oxygen is described.
Abstract: Process for the simultaneous separation of ethylene oxide and carbon dioxide from the gaseous mixtures obtained in the direct oxidation of ethylene with oxygen, comprising A. cooling the gaseous mixture containing ethylene oxide, unreacted ethylene, water vapour, carbon dioxide and inert gases after addition of methanol to a temperature such that the water vapour present separates in the form of an aqueous methanol solution; B. washing the obtained gaseous mixture in an absorption zone with methanol, the methanol being fed into the intermediate part of the absorption zone as a main methanol stream and into the upper part as a secondary methanol stream, maintaining the temperature of the secondary methanol stream at least about 30°C lower than that of the main methanol stream and removing from the upper part a gaseous mixture being practically free of ethylene oxide and containing carbon dioxide and ethylene and from the lower part of the absorption zone a solution of ethylene oxide in methanol; and C. recovering the ethylene oxide from the methanol solution.