Xn:Harmful;
71-36-3Relevant articles and documents
Merrow, R. T.,Cristol, S. J.,Dolah, R. W. van
, p. 4259 - 4265 (1953)
Step mechanism of 1-butanol formation in the course of liquid-phase catalytic hydrogenation of 2-butyne-1,4-diol
El'chaninov,Pyatnitsyna,El'chaninov
, p. 585 - 589 (2015)
Exhaustive hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol on suspended palladium and Raney nickel catalysts under atmospheric pressure at 40 C was studied with the aim to determine the mechanism of 1-butanol formation. The previously unknown pathway of 1-butanol synthesis is realized under these conditions. The content of 1-butanol precursors in hydrogenation catalyzates was estimated by gas-liquid chromatography. The graphic dependence of the content of the intermediates and 1-butanol on time was found. The possibility of increasing the hydrogenation selectivity on Raney Ni catalysts with respect to the target product was revealed.
Hydrogen transfer reactions relevant to Guerbet coupling of alcohols over hydroxyapatite and magnesium oxide catalysts
Young, Zachary D.,Davis, Robert J.
, p. 1722 - 1729 (2018)
Hydrogenation and dehydrogenation reactions were performed over hydroxyapatite (Ca10(PO4)6(OH)2, HAP) and magnesia (MgO) to explore their role in the reaction network for the Guerbet coupling of ethanol to butanol. In particular, the dehydrogenation of benzyl alcohol at 633 K and the hydrogenation of ethene and acetone at 473 K using both H2 and ethanol as a hydrogen source were studied. The H2-D2 exchange reaction at room temperature and the Guerbet coupling of ethanol at 613-673 K in the presence of D2 were also performed. Although there was no consequence of adding D2 to the Guerbet coupling of ethanol in terms of rate or selectivity, incorporation of deuterium into product butanol was only observed over MgO. This was attributed to the rapid exchange of H2-D2 that can occur over MgO but not over HAP. Hydrogenation of acetone occurred with ethanol as a sacrificial hydrogen donor via an MPV-like reaction whereas hydrogenation with H2 was not observed. Hydrogenation of ethene with H2 or ethanol was not observed above background. Comparing the rate of benzyl alcohol dehydrogenation to the rate of ethanol coupling over HAP and MgO suggests that the MPV-like hydrogen transfer reaction over HAP is mostly responsible for generating intermediate acetaldehyde during the Guerbet reaction instead of direct dehydrogenation.
A green process for the production of butanol from butyraldehyde using alcohol dehydrogenase: Process details
Jadhav, Swati B.,Harde, Shirish,Bankar, Sandip B.,Granstroem, Tom,Ojamo, Heikki,Singhal, Rekha S.,Survase, Shrikant A.
, p. 14597 - 14602 (2014)
Depletion of energy sources has drawn attention towards production of bio-butanol by fermentation. However, the process is constrained by product inhibition which results in low product yield. Hence, a new strategy wherein butanol was produced from butyraldehyde using alcohol dehydrogenase and NADH as a cofactor was developed. Butyraldehyde can be synthesized chemically or through fermentation. The problem of cofactor regeneration during the reaction for butanol production was solved using substrate coupled and enzyme coupled reactions. The conventional reaction produced 35% of butanol without regeneration of cofactor using 300 μM NADH. The process of substrate coupled reaction was optimized to get maximum conversion. NADH (30 μM) and 100 μg per ml of alcohol dehydrogenase (320 U mg-1) could convert 17.39 mM of butyraldehyde to butanol using ethanol (ratio of butyraldehye to ethanol 1:4) giving a maximum conversion of 75%. The enzyme coupled reaction under the same conditions showed only 24% conversion of butyraldehyde to butanol using the glutamate dehydrogenase-l-glutamate enzyme system for the regeneration of cofactor. Hence, substrate coupled reaction is suggested as a better method over the enzyme coupled reaction for the cost effective production of butanol. This journal is the Partner Organisations 2014.
Kinetics of complexation between cyclodextrin and alcohol by ultrasonic relaxation method: β-cyclodextrin solutions with 1-butanol and 2-methyl-2-propanol
Nishikawa, Sadakatsu
, p. 1003 - 1007 (1997)
The ultrasonic absorption coefficients over frequency range from 1.0 to 220 MHz were measured in aqueous β-cyclodextrin solutions with 1-butanol and 2-methyl-2-propanol at 25 °C. A clear single relaxational absorption with a relaxation frequency from 5 to 20 MHz was observed in a solution with 1-butanol, while the relaxational absorption was found in a lower frequency range in a solution with 2-methyl-2-propanol. The cause of the relaxation was attributed to a perturbation of a chemical equilibrium associated with complexation between β-cyclodextrin (host) and alcohol (guest). The rate and equilibrium constants for the complexation were determined from the concentration dependence of the relaxation frequency for the solution with 1-butanol. The standard volume change of the reaction was also obtained from the maximum absorption per wavelength. These results were compared with those for complexation between β-cyclodextrin and 1-propanol, and were considered in relation to the alcohol molecular structure. It was found that the rate of complex formation is almost independent of the guest molecule, and, therefore, the equilibrium constant for the complexation is controlled by the rate of departure of the guest molecule from the host. From this fact, the rate parameters for a solution with 2-methyl-2-propanol were estimated, and the calculated ultrasonic relaxation parameter was compared with the experimental data.
Unexpected transformation of butyl vinyl ether treated with HF
Shainyan,Grigor'eva
, p. 1177 - 1178 (2001)
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Takahashi,Ikui
, (1948)
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Multiproduct steady-state isotopic transient kinetic analysis of the ethanol coupling reaction over hydroxyapatite and magnesia
Hanspal, Sabra,Young, Zachary D.,Shou, Heng,Davis, Robert J.
, p. 1737 - 1746 (2015)
The Guerbet coupling of ethanol into butanol was investigated using multiproduct steady-state isotopic transient kinetic analysis (SSITKA) in a comparative study between stoichiometric hydroxyapatite (HAP) and magnesia (MgO) catalysts at 613 and 653 K, respectively. The steady-state catalytic reactions were conducted in a gas-phase, fixed-bed, differential reactor at 1.3 atm total system pressure. Multiproduct SSITKA results showed that the mean surface residence time of reactive intermediates leading to acetaldehyde was significantly shorter than that of intermediates leading to butanol on both HAP and MgO. This finding may suggest that the dehydrogenation of ethanol to acetaldehyde is fast on these surfaces compared with C-C bond formation. If adsorbed acetaldehyde is a key reaction intermediate in the Guerbet coupling of ethanol into butanol, then SSITKA revealed that the majority of adsorbed acetaldehyde produced on the surface of MgO desorbs into the gas-phase, whereas the majority of adsorbed acetaldehyde on HAP likely undergoes sequential aldol-type reactions required for butanol formation. Adsorption microcalorimetry of triethylamine and CO2 showed a significantly higher number of acid and base sites on the surface of HAP compared with those on MgO. Diffuse reflectance infrared Fourier transform spectroscopy of adsorbed ethanol followed by stepwise temperature-programmed desorption revealed that ethoxide is more weakly bound to the HAP surface compared with MgO. A high surface density of acid-base site pairs along with a weak binding affinity for ethanol on HAP may provide a possible explanation for the increased activity and high butanol selectivity observed with HAP compared with MgO catalysts in the ethanol coupling reaction.
SINGLE-STAGE VAPOR-PHASE HYDROGENATION OF CROTONALDEHYDE TO n-BUTYL ALCOHOL.
Morozova,Zhorov,Panchenkov
, p. 259 - 261 (1974)
The commercial hydrogenation of crotonaldehyde to n-butyl alcohol is conducted in two stages. First the feedstock is 90-95% hydrogenated, then the product is rehydrogenated. Supported copper and nickel oxide catalysts are used. In order to carry out the single-stage vapor-phase hydrogenation of crotonaldehyde, work was performed on the preparation of a new, active catalyst with good mechanical strength; this was obtained by coprecipitation of copper compounds with other added metals from solutions of their salts, together with silica gel. The resulting catalyst mass was subjected to further treatment, including stages of syneresis, washing, drying, pelletizing, and activation. In the reported investigation, crotonaldehyde was hydrogenated on several catalyst specimens differing in chemical composition. The hydrogenations were performed at temperatures of 160, 180, and 200 C, liquid feedstock space velocities of 1. 2-2. 4 h** minus **1, and hydrogen space velocities of 1000 and 2000 h** minus **1. The composition of the liquid reaction products was determined by gas chromatography. Results obtained with the modified copper catalyst prepared under laboratory conditions are tabulated and compared with those obtained with commercial catalysts. It is shown that the modified catalyst has been more active than the commercial catalyst. This catalyst as prepared by the authors proved to have approximately twice the mechanical strength of the commercial catalyst.
Direct hydrogenation of biomass-derived butyric acid to n-butanol over a ruthenium-tin bimetallic catalyst
Lee, Jong-Min,Upare, Pravin P.,Chang, Jong-San,Hwang, Young Kyu,Lee, Jeong Ho,Hwang, Dong Won,Hong, Do-Young,Lee, Seung Hwan,Jeong, Myung-Geun,Kim, Young Dok,Kwon, Young-Uk
, p. 2998 - 3001 (2014)
Catalytic hydrogenation of organic carboxylic acids and their esters, for example, cellulosic ethanol from fermentation of acetic acid and hydrogenation of ethyl acetate is a promising possibility for future biorefinery concepts. A hybrid conversion process based on selective hydrogenation of butyric acid combined with fermentation of glucose has been developed for producing biobutanol. ZnO-supported Ru-Sn bimetallic catalysts exhibits unprecedentedly superior performance in the vapor-phase hydrogenation of biomass-derived butyric acid to n-butanol (>98% yield) for 3500 h without deactivation.
Basson,du Plessis
, p. 775 (1967)
Direct electrochemical addressing of immobilized alcohol dehydrogenase for the heterogeneous bioelectrocatalytic reduction of butyraldehyde to butanol
Schlager,Neugebauer,Haberbauer,Hinterberger,Sariciftci
, p. 967 - 971 (2015)
Modified electrodes using immobilized alcohol dehydrogenase enzymes for the efficient electroreduction of butyraldehyde to butanol are presented as an important step for the utilization of CO2-reduction products. Alcohol dehydrogenase was immobilized, embedded in an alginate-silicate hybrid gel, on a carbon felt (CF) electrode. The application of this enzyme to the reduction of an aldehyde to an alcohol with the aid of the coenzyme nicotinamide adenine dinucleotide (NADH), in analogy to the final step in the natural reduction cascade of CO2 to alcohol, has been already reported. However, the use of such enzymatic reductions is limited because of the necessity of providing expensive NADH as a sacrificial electron and proton donor. Immobilization of such dehydrogenase enzymes on electrodes and direct pumping of electrons into the biocatalysts offers an easy and efficient way for the biochemical recycling of CO2 to valuable chemicals or alternative synthetic fuels. We report the direct electrochemical addressing of immobilized alcohol dehydrogenase for the reduction of butyraldehyde to butanol without consumption of NADH. The selective reduction of butyraldehyde to butanol occurs at room temperature, ambient pressure and neutral pH. Production of butanol was detected by using liquid-injection gas chromatography and was estimated to occur with Faradaic efficiencies of around 40%.
Boosting the guerbet reaction: A cooperative catalytic system for the efficient bio-ethanol refinery to second-generation biofuels
Calcagno, Francesco,Cavani, Fabrizio,Cesari, Cristiana,Gagliardi, Anna,Lucarelli, Carlo,Mazzoni, Rita,Messori, Alessandro,Monti, Nicola,Rivalta, Ivan,Tabanelli, Tommaso,Zacchini, Stefano,Zanotti, Valerio
, p. 47 - 59 (2021/12/16)
The catalytic activity of anionic ruthenium complexes toward the transformation of bio-ethanol to 1-butanol and higher alcohols is found to be dependent on the imidazolium counterion. After the identification of a parallel reaction involving the catalyst in hydrogen evolution, conversion and selectivity are impressively boosted by the addition of p-benzoquinones as co-catalysts. The catalytic system avoids the side reaction and led to highly competitive conversions up to 88% (0.2 % mol ruthenium catalyst loading, 1.5 % mol benzoquinone loading). Butanol and higher alcohols are produced in yields up to 85% (overall selectivity 97%) as a mixture of valuable alcohols for advanced biofuel and lubricants applications. The catalytic system can be recycled and the reaction shows comparable efficiency on a real matrix (alcohol from wine production chain wastes) even in the presence of significant amounts of water, thus closing a hypothetic economic circle. A reaction mechanism is proposed for the most promising ruthenium complex working in cooperation with the most efficient co-catalyst: p-benzoquinone.
COMPOSITION OF CATALYSTS FOR CONVERSION OF ETHANOL TO N-BUTANOL AND HIGHER ALCOHOLS
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Paragraph 0103-0121, (2021/05/21)
A method of producing a catalyst comprises forming a decomposed material comprising a decomposed hydrotalcite, a decomposed hydrocalumite, or a combination of both, combining the decomposed material with a mixture to form a catalyst mixture, and heating the catalyst mixture to convert the metal salt to a metal oxide. The mixture comprises a metal salt and a chelating agent, and the resulting metal oxide combined with the decomposed material forms the catalyst.
SELECTIVE PRODUCTION OF METHANOL AND ETHANOL FROM CO HYDROGENATION
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Paragraph 0036-0037, (2021/02/12)
A method for producing methanol and ethanol is disclosed. The method can include contacting a gaseous stream comprising carbon monoxide (CO) and hydrogen (H22) with a crystalline cobalt molybdenum catalyst under conditions suitable to produce a products stream comprising methanol and ethanol from the CO and H22.
