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97-95-0Relevant articles and documents
Improving the Catalytic Stability of Ni/TiO2 for Ethanol Guerbet Condensation: Influence of Second Metal Component
An, Hualiang,Han, Xiaoxu,Li, Shuaiqi,Wang, Yanji,Zhao, Xinqiang
, p. 632 - 640 (2021/09/28)
Abstract: Ethanol Guerbet condensation (EGC) is a green process for preparing n-butanol and the development of highly effective solid catalysts is still the bottleneck of this reaction. In this work, a series of multifunctional catalysts Ni–X/TiO2 (X = Ru, Pt, Ir, Au, Cu, Mn, Co, Fe) were prepared by a co-impregnation method in order to improve the catalytic performance, especially the stability. It was found that the addition of the second metal component changed the acidity and alkalinity of Ni/TiO2 catalyst. What is more, acid site number affected ethanol conversion while alkali site number affected n-butanol selectivity. Among the Ni–X/TiO2 catalysts, Ni–Cu/TiO2 showed the best catalytic performance. The effects of preparation conditions on the catalytic performance of Ni–Cu/TiO2 were investigated and the results showed that the suitable preparation conditions were as follows: a Ni/Cu mass ratio of 59 : 1, a Ni–Cu loading of 12.5 wt %, a calcination temperature of 450°C, a calcination time of 2 h, a reduction temperature of 400°C, and a reduction time of 4?h. At a 10 wt % of catalyst loading, a reaction temperature of 210°C and a reaction time of 10 h, the ethanol conversion and the selectivity of n-butanol were 47.9 and 44.4%, respectively. Moreover, the stability of Ni–Cu/TiO2 catalyst was greatly improved due to the interaction between Ni and Cu as compared with the Ni/TiO2 catalyst: the catalytic activity of Ni–Cu/TiO2 did not decline significantly for reuse in three cycles.
Upgrading of Ethanol to n-Butanol via a Ruthenium Catalyst in Aqueous Solution
Dibenedetto, Tarah A.,Jones, William D.
supporting information, p. 1884 - 1888 (2021/06/30)
The upgrading of ethanol to n-butanol via the Guerbet reaction in aqueous media has been developed. This system allows for the upgrading of ethanol to n-butanol in up to a 28% yield and 57% selectivity, at only 80 °C. This system is also able to tolerate the same feedstock ratio found in fermentation broth (water to ethanol ratio of 90:10), albeit a decrease in yield and selectivity (20% yield of n-butanol, 48% selectivity). Smaller amounts of longer-chain alcohols are also formed.
PROCESSES FOR PRODUCING ALCOHOLS FROM BIOMASS AND FURTHER PRODUCTS DERIVED THEREFROM
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Paragraph 0539-0540, (2021/11/26)
Processes for producing alcohols from biomass are provided. The processes utilize supercritical methanol to depolymerize biomass with subsequent conversion to a mixture of alcohols. In particular the disclosure relates to continuous processes which produce high yields of alcohols through recycling gases and further employ dual reactor configurations which improve overall alcohol yields. Processes for producing higher ethers and olefins from the so-formed alcohols, through alcohol coupling and subsequent dehydration are also provided. The resulting distillate range ethers and olefins are useful as components in liquid fuels, such as diesel and jet fuel.
Iridium-Catalyzed Domino Hydroformylation/Hydrogenation of Olefins to Alcohols: Synergy of Two Ligands
Beller, Matthias,Huang, Weiheng,Jackstell, Ralf,Jiao, Haijun,Tian, Xinxin
supporting information, (2022/01/13)
A novel one-pot iridium-catalyzed domino hydroxymethylation of olefins, which relies on using two different ligands at the same time, is reported. DFT computation reveals different activities for the individual hydroformylation and hydrogenation steps in the presence of mono- and bidentate ligands. Whereas bidentate ligands have higher hydrogenation activity, monodentate ligands show higher hydroformylation activity. Accordingly, a catalyst system is introduced that uses dual ligands in the whole domino process. Control experiments show that the overall selectivity is kinetically controlled. Both computation and experiment explain the function of the two optimized ligands during the domino process.
Preparation method of remdesivir intermediate 2-ethyl-1-butanol
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Paragraph 0049-0050, (2020/08/09)
The invention relates to a preparation method of a remdesivir intermediate 2-ethyl-1-butanol. The preparation method comprises a step of substitution reaction, namely a step of carrying out a substitution reaction on alkyl acetoacetate and halogenated ethane under an alkaline condition to obtain alkyl 2-ethyl-3-oxo-butyrate; a step of addition reduction, namely a step of carrying out an addition reduction reaction on the alkyl 2-ethyl-3-oxo-butyate to obtain alkyl 2-ethylbutyrate; a step of reduction, namely a step of subjecting the alkyl 2-ethylbutyrate to a reduction reaction to prepare 2-ethyl-1-butanol (I). According to the preparation method of the remdesivir intermediate 2-ethyl-1-butanol, the alkyl acetoacetate and halogenated ethane serve as main raw materials, the raw materials are simple and easy to obtain, the 2-ethyl-1-butanol (I) is prepared through substitution reaction, addition reduction and reduction reaction, the process is simple, economical and environmentally friendly, the product is convenient to obtain, and industrial production of remdesivir bulk drugs is facilitated.
SATURATED HOMOETHER MANUFACTURING METHOD FROM UNSATURATED CARBONYL COMPOUND
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Paragraph 0037-0038; 0040; 0044; 0047-0048, (2020/05/14)
PROBLEM TO BE SOLVED: To provide a method for manufacturing saturated homoether from an unsaturated carboxyl compound at good efficiency. SOLUTION: There is provided a manufacturing method of saturated homoether using an unsaturated carboxyl compound and hydrogen as raw materials, and a catalyst in which a metal is carried on an acidic catalyst carrier. The metal of the catalyst is for example palladium, and the carrier of the catalyst is alumina, silica, silica-alumina, or the like. The unsaturated carbonyl compound as the raw material is 2-butenal, 2-ethyl-2-hexenal, 2-ethyl-2-butenal, 2-hexenal, and manufactured saturated homoether is dibuthylether, bis(2-ethylhexyl)ether, bis(2-ethylbuty)ether, dihexylether, or the like. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPO&INPIT
Successive vapour phase Guerbet condensation of ethanol and 1-butanol over Mg-Al oxide catalysts in a flow reactor
Larina, Olga V.,Valihura, Karina V.,Kyriienko, Pavlo I.,Vlasenko, Nina V.,Balakin, Dmytro Yu.,Khalakhan, Ivan,?endak, Toma?,Soloviev, Sergiy O.,Orlyk, Svitlana M.
, (2019/10/09)
The successive vapour phase condensation of ethanol and 1-butanol (via Guerbet reaction) in a flow reactor under atmospheric pressure was studied over catalytic Mg-Al oxide compositions. Wherein the vapour phase condensation of 1-butanol to 2-ethyl-1-hexanol in flow has been investigated for the first time. The acid/base capacity ratio, which is determined by the Mg/Al ratio, is an important characteristic for the activity and selectivity of Mg-Al oxide catalysts in the abovementioned processes. The carbon chain length of the reacting alcohols, an arrangement of surface active sites and other steric factors also have an impact on Guerbet condensation in the vapour phase. High productivity of Mg-Al oxide system to the Guerbet alcohols: 1-butanol – 25 g/(Lcat·h), 2-ethyl-1-hexanol – 19 g/(Lcat·h), has been achieved. The results have shown a prospect of successive conversion realization: 1) ethanol → 1-butanol; 2) 1-butanol → 2-ethyl-1-hexanol for the production of 2-ethyl-1-hexanol from ethanol.
Tris(pyrazolyl)borate Cobalt-Catalyzed Hydrogenation of C=O, C=C, and C=N Bonds: An Assistant Role of a Lewis Base
Lin, Yang,Zhu, De-Ping,Du, Yi-Ran,Zhang, Rui,Zhang, Suo-Jiang,Xu, Bao-Hua
supporting information, p. 2693 - 2698 (2019/04/25)
The combination of tris(pyrazolyl)borate cobalt complexes and Lewis base is developed as an efficient catalyst precursor in the homogeneous hydrogenation. A broad substrate scope including carbonyls, alkenes, enamines, and imines is reduced with 60 atm of H2 at 60 °C. Mechanistic studies support the hydrogenation operates through a frustrated Lewis pair (FLP)-like reduction process. These results highlight the development of novel non-noble metal catalytic processes, when combined with the diverse small molecule activation chemistry associated with FLPs.
Catalytic synthesis of distillate-range ethers and olefins from ethanol through Guerbet coupling and etherification
Eagan, Nathaniel M.,Moore, Benjamin M.,McCelland, Daniel J.,Wittrig, Ashley M.,Canales, Emmanuel,Lanci, Michael P.,Huber, George W.
, p. 3300 - 3318 (2019/06/24)
Synthesis of distillate-range fuels from biomass-derived alcohols has recently received considerable attention due to projected increases in the demands of these fuels and the extensive commercialization of alcohol production. Here we present a two-stage process by which an alcohol such as ethanol or 1-butanol can be converted with high yields into distillate-range ethers and olefins by combining Guerbet coupling and intermolecular dehydration. The ethers can be used as cetane-improvers in diesel fuel, while the olefins can be hydrogenated and blended with gasoline or oligomerized and hydrogenated to jet-range paraffins. The first stage was executed using calcium hydroxyapatite to produce higher linear and branched alcohols at above 80% selectivity at up to 40% conversion with high stability for over 400 h time-on-stream operation. Increasing conversion decreases selectivity, producing predominantly mono-ene and diene byproducts. Etherification was performed using the acidic resin Amberlyst 70 at around 65% conversion. Linear alcohols were converted at above 90% selectivity while branched alcohols were far more selective to olefins (65-75%). Etherification occurs via two mechanisms: a direct mechanism involving the reaction of two alcohols and an indirect mechanism between an alcohol and equilibrated pool of olefins. Cross-etherification was observed between linear and branched alcohols, improving the selectivity to ethers in conversion of the latter. A mixture of C4+ alcohols produced from ethanol condensation at 40% conversion was effectively utilized in etherification at selectivities comparable to the model mixtures. An overall process is presented for the conversion of ethanol to diesel-range ethers and olefins with yields of approximately 80%.
Importance of the Nature of the Active Acid/Base Pairs of Hydroxyapatite Involved in the Catalytic Transformation of Ethanol to n-Butanol Revealed by Operando DRIFTS
Osman, Manel Ben,Krafft, Jean-Marc,Thomas, Cyril,Yoshioka, Tetsuya,Kubo, Jun,Costentin, Guylène
, p. 1765 - 1778 (2019/02/26)
Operando DRIFTS is used to identify the nature and the role of the surface sites of hydroxyapatites (HAps) involved in the catalytic transformation of ethanol to n-butanol. The surface processes occurring upon a first reaction step followed by a step under He flow greatly influence the reactivity of HAps in a subsequent second reaction step. Ethanol is found to be mostly activated by the basic OH? groups of HAps, as indicated by the concomitant recovery of ethanol conversion and OH? groups under He flow. The drastic changes in selectivity observed during the second reaction step reveal the key role of acidic sites cooperatively acting with basic sites for basic reaction steps. Once the POH groups are poisoned by extensive formation of polymeric carbon species and the Ca2+ sites are available, the production of acetaldehyde is drastically promoted at the expense of that of n-butanol. It is concluded that i) acetaldehyde acts as an intermediate in the formation of n-butanol, and ii) various active sites are involved in the key basic reaction steps such as Ca2+?OH? and POH?OH? acid-base pairs in the dehydrogenation of ethanol to acetaldehyde and the aldol condensation for n-butanol formation, respectively.
