Synthesis Of Formic Acid Research Articles

Silica Immobilized Ruthenium Catalyst for Formic Acid Synthesis from Supercritical Carbon Dioxide Hydrogenation II: Effect of Reaction Conditions on the Catalyst Performance

AbstractThe synthesis of formic acid from carbon dioxide and hydrogen using a silica immobilized ruthenium catalyst as precursor has been studied in different reaction conditions. The results revealed that the TOF (turn over frequency) of HCOOH achieved 1481.5 h‐1 on immobilized ruthenium catalyst near the critical pressure point of CO2 with H2 pressure of 4.0 MPa, reaction temperature of 80 °C and PPh3/Ru molar ratio of 6:1. The reaction activity of immobilized catalyst was higher than that of homogeneous catalyst, and the immobilized catalyst also offered the practical advantages such as easy separation and reuse.

The Preparation and Catalytic Performance of Novel Amine-Modified Silica Supported Ruthenium Complexes for Supercritical Carbon Dioxide Hydrogenation to Formic Acid

The three kinds of amine-modified silica supported ruthenium complexes developed for the first time are effective catalysts for the synthesis of formic acid from supercritical carbon dioxide and hydrogen, the activity is comparable to that of homogeneous catalysts, TOF up to 1190 h−1 can be obtained at 100% selectivity of formic acid over “Si”—NH2—RuCl3 with bis(1,2-diphenylphosphino)ethane used as ligand. These catalysts also offer the practical advantages such as easy separation and reuse.

Visible Light-induced Formic Acid Synthesis from HCO<sub>3</sub><sup>−</sup> with Formate Dehydrogenase and Water-soluble Zinc Porphyrin

Photochemical and enzymatic synthesis of formic acid was investigated from HCO 3 - with formate dehydrogenase (FDH) from Saccharomyces cerevisiae and reduced methylviologen (MV 2+ ) produced by the visible light photosensitization of zinc tetrakis(4-methylpyridyl) porphyrin (ZnTMPyP) in the presence of triethanolamine (TEOA) as an electron donating reagent. Irradiation of a solution containing TEOA, ZnTMPyP, MV 2+ , NaHCO 3 and FDH in potassium phosphate buffer, with visible light resulted in formic acid production and HCO 3 - consumption. The optimum FDH activity was 20 units and the amount of formic acid and the yield of HCO 3 - to formic acid after 4 h irradiation were estimated to be 50 μmol.dm -3 and 5.0%, respectively.

Photochemical synthesis of formic acid from CO 2 with formate dehydrogenase and water-soluble zinc porphyrin

Photochemical synthesis of formic acid was investigated from hydrogen carbonate ion with formate dehydrogenase (FDH) from Saccharomyces cerevisiae and methylviologen (MV 2+) photoreduction by the visible light photosensitisation of zinc tetrakis(4-methylpyridyl) porphyrin (ZnTMPyP) in the presence of triethanolamine (TEOA) as an electron donating reagent. Irradiation of a solution containing TEOA, ZnTMPyP, MV 2+, sodium hydrogen carbonate and FDH with visible light resulted in formic acid synthesis. The concentration of formic acid was 62 μM after 3 h irradiation under the condition of 30 μM MV 2+, 20 units FDH and pH 8.

Low-temperature methanol synthesis from carbon dioxide and hydrogen via formic ester

A new route of methanol synthesis, at 443 K and under pressurized conditions, from carbon dioxide and hydrogen through formic ester was investigated, by using Cu-based catalysts. This one-pot reaction consisted of three steps: 1. formic acid synthesis from CO 2 and H 2, 2. esterification of formic acid by ethanol to ethyl formate, and 3. hydrogenolysis of ethyl formate to methanol and ethanol.

Methanol Synthesis from Carbon Dioxide and Hydrogen via Formic Ester.

A new route of methanol synthesis, at 473K and 30bar, from carbon dioxide and hydrogen through formic ester was reported, by using active carbon supported palladium catalyst and coexisting weak base. This one-pot reaction consisted of 3 steps: (1) formic acid synthesis from CO2 and H2, (2) esterification of formic acid by ethanol to ethyl formate, (3) hydrogenolysis of ethyl formate to methanol and ethanol, the rate-determining step. Longer reaction time favored methanol synthesis and high CO2 conversion.

Homogeneous catalytic synthesis of formic acid (salts) by hydrogenation of CO 2 with H 2 in the presence of ruthenium species

The purpose of this investigation is to synthesize formic acid by hydrogenation of CO 2. The catalysts or catalyst precursors employed in these studies under 6 MPa( CO 2 H 2 ) and at 60°C, were ruthenium chloride or ruthenium complexes. The turnover number obtained for formic acid production was ca. 200 by using ethanol/water (5:1) for a 5 h reaction period. In the reaction mechanism the CO 2 is activated by the ruthenium complex with formation of metal-formate intermediate HCO 2RuH(CO)(PPh 3) 3, which releases formic acid by reductive elimination of the hydrido-formate ligands.

ChemInform Abstract: Carbon Dioxide as a Raw Material: The Synthesis of Formic Acid and Its Derivatives from CO2

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Homogeneous Catalysis in Supercritical Fluids: Hydrogenation of Supercritical Carbon Dioxide to Formic Acid, Alkyl Formates, and Formamides

Rapid, selective, and high-yield hydrogenation of CO2 can be achieved if the CO2 is in the supercritical state (scCO2). Dissolving H2, a tertiary amine, a catalyst precursor such as RuH2[P(CH3)3]4 or RuCl2[P(CH3)3]4, and a promoting additive such as water, CH3OH, or DMSO in scCO2 at 50 °C leads to the generation of formic acid with turnover frequencies up to or exceeding 4000 h-1. In general, experiments in which a second phase was formed by one or more reagents or additives had lower rates of reaction. The high rate of reaction is attributed to rapid diffusion, weak catalyst solvation, and the high miscibility of H2 in scCO2. The formic acid synthesis can be coupled with subsequent reactions of formic acid, for example, with alcohols or primary or secondary amines, to give highly efficient routes to formate esters or formamides. With NH(CH3)2, for example 420 000 mol of dimethylformamide/mol of Ru catalyst was obtained at 100 °C. The demonstrated solubility and catalytic activity of complexes of tertiary...

Carbon Dioxide as a Raw Material: The Synthesis of Formic Acid and Its Derivatives from CO2

AbstractThe use of carbon dioxide as a raw material for chemical syntheses is an ecologically and economically valuable extension to the carbon sources used at the present time. In order to convert the thermodynamically stable and comparatively unreactive CO2 molecule into the desired product in an efficient manner, suitable reaction conditions and activation mechanisms must be found. The catalytic reduction of CO2 to formic acid and its derivatives has been intensively studied in recent years. A number of new approaches to the synthesis of formic acid from CO2 have reached such a state of knowledge that continuing development may well lead to industrial‐scale operation in the near future. This can to a large extent be attributed to the fruitful interaction between investigative work into reaction mechanisms and the development of new catalytic systems.

ChemInform Abstract: Photoinduced Direct Synthesis of Formic Acid and Methyl Formate from Methanol in the Presence of Hydrogen Peroxide.

Formic acid and methyl formate were directly synthesized by UV irradiation of the oxygen-saturated methanol containing hydrogen peroxide. The formations of formic acid and methyl formate were affected by H2O2 feeding rate. The combined selectivity of formic acid and methyl formate formations was 99%.

Photoinduced Organic Transformation. Selective Synthesis of Ethylene Glycol or Formic Acid and Methyl Formate from Methanol in the Presence of Hydrogen Peroxide

Abstract The photoinduced transformation of methanol (MeOH) has been investigated in the presence of H2O2. Ethylene glycol (EG) was selectively produced by UV light irradiation of the N2-saturated MeOH and the selectivity was 85–94% below 3 ml h−1 of H2O2 feeding rate (f). The quantity of EG reached the maximum at f=5 ml h−1 and the quantum yield was 0.73. EG was produced through the dimerization of hydroxymethyl radicals formed by the abstraction of hydrogen atom from MeOH by hydroxyl radical which was formed by the photolysis of H2O2. On the other hand, formic acid (FA) and methyl formate (MF) were selectively produced by UV light irradiation of the O2-bubbled MeOH and the combined selectivity was about 99% in the f range of 1–8 ml h−1. The quantities of FA and MF reached the maximum at f=5 ml h−1 and their quantum yields were 1.36 and 0.69, respectively. FA was mainly produced through the decomposition of hydroperoxyhydroxymethane formed by the abstraction of hydrogen atom from MeOH by hydroxymethyldioxy radical which was formed by the reaction of hydroxymethyl radical with oxygen, and MF through the reaction of MeOH with FA formed.

Photoinduced Direct Synthesis of Formic Acid and Methyl Formate from Methanol in the Presence of Hydrogen Peroxide

Abstract Formic acid and methyl formate were directly synthesized by UV irradiation of the oxygen-saturated methanol containing hydrogen peroxide. The formations of formic acid and methyl formate were affected by H2O2 feeding rate. The combined selectivity of formic acid and methyl formate formations was 99%.

Enzymatic synthesis of formic acid from H2 and CO2 and production of hydrogen from formic acid

Whole cells of Alcaligenes eutrophus (as well as isolated P. oxalaticus formate dehydrogenase and A. eutrophus hydrogenase coupled via NAD(+) or methyl viologen) have been shown to produce H(2) from formic acid. Immobilization of the cells in kappa-carrageenan gel greatly enhances their stability at room temperature. The rate of hydrogen production catalyzed by immobilized A. eutrophus has been studied as a function of the concentrations of the cells and formate and also pH. An inhibition by high concentrations of formate has been found. Immobilized cells were also capable of synthesizing formate from H(2) and bicarbonate. Yields of formate up to 30% have been obtained. The catalytic efficiency of immobilized A. eutrophus cells was compared with that of palladium adsorbed on activated carbon.

The production of volatile acids from glucose by soy yeast (Saccharomyces rouxii) NRRLY—1096

SummaryThe glucose metabolism of Saccharomyces rouxii NRRLY—1096, the soy yeast, under aerobic and anaerobic conditions, was investigated. The study was carried out at pH 4.5 and 7.0 with cells previously grown at either pH. The pH at which the cells had been grown as well as the pH at which glucose was fermented were found to affect the pattern of fermentation. A typical yeast type fermentation was obtained with cells grown at pH 4.5 and fermenting glucose at the same acid pH. An ability to fix CO2 for formic acid synthesis was demonstrated by cells grown at neutral pH. Acetic acid was produced by cells fermenting glucose at neutral pH irrespective of the pH at which they had been grown. Various schemes of glucose fermentation were therefore proposed. From results of the present study, optimal conditions for the formation of the desired fermentation products, resulting in the flavour and bouquet of good quality soy sauce, are suggested.

Biosynthesis and Accumulation of Formic Acid in the Poison Gland of the Carpenter Ant Camponotus pennsylvanicus

Formic acid synthesis in the poison gland of Camponotus pennsylvanicus is closely related to the C-1 metabolism of the glandular cells. Serine, glycine, and histidine are potential C-l donors to formic acid by several tetrahydrofolate intermediates. Formic acid is accumulated by its transfer to an insulated reservoir, so that the ant avoids the acid's cytotoxicity. This combination of biochemical and morphological features provides an autodefensive mechanism. Possible factors that regulate the biosynthesis of formic acid in the poison gland apparatus are discussed.

Synthesis and purification of fatty acids by the pyrolysis of esters

simple olefins, particularly those that were not sensitive to acid catalyzed rearrangements. It was recently reported however that if carbonization were avoided, this reaction could also be used for the synthesis of strained olefins (1). Thus 1,2-dimethylene-4-cyclohexene, an isomer of o-xylene, was prepared in a 92% yield by the pyrolysis of a diacetate (3) while the decomposition of the corresponding quaternary ammonium hydroxide gave only o-xylene (8). Since the pyrolysis of esters is such an excellent method for the synthesis of unsaturated compounds, it appeared likely that pyrolysis should also be useful for the synthesis of acids. For this reason a research program was initiated to determine in which cases the pyrolysis of esters was superior in some respects to the conventional hydrolysis for the preparation of acids or their derivatives. Although titration of the liberated acid has often been used to determine the extent of pyrolysis, very little has been published about the use of this reaction for the preparation of acids. Ratchford, Rchberg, and Fisher prepared acrylic and methacrylic acids in high yields by the pyrolysis of the corresponding esters (10, 11). Halbig developed a synthesis of formic acid which involved the pyrolysis of tert-amyl formate (6).

II. Note on the synthesis of marsh-gas and formic acid, and on the electric decomposition of carbonic oxide

In connexion with the investigation on the electric decomposition of carbonic-acid gas referred to in a previous communication to the Society, I was led to submit a mixture of hydrogen and carbonic-oxide gas to the action of electricity in the induction-tube, the mixed gases being circulated through the tube by means of an apparatus which I will not now describe. A contraction was soon observed to have taken place, which at the end of an hour amounted to 10 cub. centims. The rate of contraction steadily diminished, and during the fifth hour of the duration of the experiment amounted to only 2 cub. centims.

On the Synthesis of Marsh-Gas and Formic Acid, and on the Electric Decomposition of Carbonic Oxide *

IN connection with the investigation on the electric decomposition of carbonic-acid gas referred to in a previous communication to the Society, I was led to submit a mixture of hydrogen and carbonic-oxide gas to the action of electricity in the induction-tube, the mixed gases being circulated through the tube by means of an apparatus which I will not now describe. A contraction was soon observed to have taken place, which at the end of an hour amounted to 10 cub. centims. The rate of contraction steadily diminished, and during the fifth hour of the duration of the experiment amounted to only 2 cub. centims. The experiment was stopped, and the gas analyzed with the following results in two several analyses:—

IX.—On a new synthesis of formic acid

IX.—On a new synthesis of formic acid