- Catalytic Transfer Hydrogenation of Furfural over CuNi@C Catalyst Prepared from Cu–Ni Metal-Organic Frameworks
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Abstract: Cu/Ni-based metal-organic frameworks (CuNi@BTC) were prepared with benzene-1,3,5-tricarboxylate (H3BTC) as the organic ligand via the solvothermal method, and were then calcinated under N2 atmosphere to form C-coated CuNi catalysts (CuNi@C). TEM showed that carbon material on the surface of CuNi@C was a graphene-like structure. Then transfer hydrogenation of furfural catalyzed by CuNi@C was tested with alcohols as the hydrogen donor to optimize the Cu : Ni ratio, metal : organic ligand ratio, solvothermal synthesis, and calcination conditions. It was found that strong synergistic effect between Cu and Ni in the CuNi@C significantly enhanced the furfural transfer hydrogenation activity and raised the furfural selectivity. The reaction conditions of furfural transfer hydrogenation such as catalyst dosage, hydrogen donor, reaction temperature, and reaction time were studied. The catalytic mechanism for CTH of FF over CuNi@C catalyst was discussed.
- Feng Li,Jiang, Shanshan,Wang, Yue,Huang, Jin,Li, Cuiqin
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- Doping Pd/SiO2 with Na+: Changing the reductive etherification of CO to furan ring hydrogenation of furfural in ethanol
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The production of biofuels and chemicals by hydrogenation of furfural has attracted much attention recently. Herein the effect of Na+ doping on the catalytic performance of Pd/SiO2 in hydrogenation and reductive-etherification of furfural in ethanol was systematically studied. Two Pd/SiO2 catalysts with and without the modification by Na+ were prepared by impregnation and calcination. Their catalytic properties were compared for the hydrogenation of furfural and furfural diethyl acetal under mild conditions. The silanol groups on Pd/SiO2 catalysed the acetalization of furfural and alcohol and the resulted acetal underwent hydrogenolysis on Pd nanoparticles (NPs) with an average particle size of 8 nm, leading to a moderate yield (～58%) of furfuryl ethyl ether. Doping Na+ on Pd/SiO2 led to the diminishing of silanol groups as well as strong interaction between Na+ and Pd NPs. No acetalization occurred on Na+ modified Pd/SiO2 due to the exchange of H+ of Si-OH with Na+, thus the reductive etherification of CO group in furfural was completely inhibited. Meanwhile the hydrogenation of furan-ring over Na+ coordinated Pd NPs could proceed with very high selectivity (>90%) forming tetrahydrofurfural in high yield. Kinetics study on the hydrogenation of furfural diethyl acetal over Pd/SiO2 and Na+ doped Pd/SiO2 suggested that the Na+ greatly impeded the hydrogenolysis of C-O-C bond of acetal, while the hydrogenation of the furan ring took place selectively.
- Long, Yinshuang,Wang, Yun,Wu, Haihong,Xue, Teng,Wu, Peng,Guan, Yejun
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p. 25345 - 25350
(2019/08/28)
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- Method for the synthesis and purification of ethers
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Methods of synthesizing and purifying ethers are described. The synthesis and purification are achieved using an etherification technique followed by one or two fractional distillations. The etherification utilizes an element having low work function properties. Examples of low work function elements include, but are not limited to, metals or their hydrides, such as sodium, lithium or potassium or some combination thereof. This technique yields ethers of greater than 90% purity.
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Page/Page column 3; 4; 5
(2018/02/23)
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- Facile synthesis of furfuryl ethyl ether in high yield: Via the reductive etherification of furfural in ethanol over Pd/C under mild conditions
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The one-pot synthesis of furfuryl ethyl ether (FEE) over Pd nanoparticles supported on TiO2, Al2O3, SiO2, and active carbon via the catalytic reductive etherification of furfural in ethanol was systematically studied. The Pd nanoparticles supported on SiO2, TiO2 and active carbon are all active for this novel process under mild reaction conditions, with Pd/C showing the highest selectivity to FEE. The effects of palladium loading, reaction temperature, and hydrogen pressure on the activity and selectivity of Pd/C have been investigated in detail. The results demonstrate that suitable Pd amount, low reaction temperature of about 60 °C, and low H2 pressure of about 0.3 MPa are favorable for the formation of the desired ether product. Under the optimized conditions, an unprecedented high yield of up to 81% of FEE was firstly obtained with the major by-products being furfuryl alcohol and 2-methyltetrahydrofuran. Compared with the conventional hydrogenation-etherification route via furfural alcohol as a reaction intermediate, the reductive etherification shows significant advantage in product yield because of its much lower reaction temperature that is required.
- Wang, Yun,Cui, Qianqian,Guan, Yejun,Wu, Peng
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p. 2110 - 2117
(2018/05/24)
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- Preparation method for tetrahydrofurfuryl ether compound
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The invention relates to the field of tetrahydrofurfuryl ether compound synthesis and discloses a preparation method for a tetrahydrofurfuryl ether compound, wherein the structure of the compound is shown as a formula (I). The method comprises the steps that in the existence of concentrated sulphuric acid, tetrahydrofurfuryl alcohol and the olefin of C2-C8 are subjected to a contact reaction. According to the preparation method, the tetrahydrofurfuryl ether compound is high in pureness and low in impurity content, and meanwhile the preparation technology is simple, high in safety, and good in universality. The formula (I) is shown in the description, wherein R is an alkyl group of C2-C8.
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Paragraph 0037-0039
(2017/08/31)
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- Method and device for producing tetrahydrofurfuryl alcohol diethyl ether through industrialized ultrasonic wave reaction
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The invention relates to a method for producing tetrahydrofurfuryl alcohol diethyl ether through industrialized ultrasonic wave reaction. The method comprises the steps that tetrahydrofurfuryl alcohol, bromoethane and a potassium hydroxide water solution are specifically mixed to perform sufficient reaction under the ultrasonic wave condition, most of moisture of a reaction product is removed, and reduced pressure distillation is performed to obtain the tetrahydrofurfuryl alcohol diethyl ether. The invention further relates to a device for industrially producing the tetrahydrofurfuryl alcohol diethyl ether. In the technical scheme, the potassium hydroxide water solution is adopted in the reaction raw materials, a strong base environment is provided for reaction, the reaction rate is improved, ultrasonic waves are utilized to perform the reaction, more thorough moisture removal is performed, dangerous factors of a production process are eliminated, pollutant discharge and product separation difficulty in the production process are reduced, the production cost is effectively reduced, the whole production process is simple, high in conversion rate and stable in operation, product nature is excellent, and the method and the device can be suitable for the production process of organic chemical ether compounds.
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Paragraph 0049; 0053; 0040; 0042; 0043
(2016/12/16)
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- Industrial continuous production method and apparatus for tetrahydrofurfuryl alcohol diethyl ether
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The present invention relates to an industrial continuous production method for tetrahydrofurfuryl alcohol diethyl ether. The method comprises the following steps: mixing tetrahydrofurfuryl alcohol and ethanol according to a specific ratio at first; then continuously transporting the mixture into a pipe reactor filled with a solid super acid catalyst; dehydrating and drying a crude product after reaction; and then rectifying the dehydrated crude product to obtain tetrahydrofurfuryl alcohol diethyl ether fractions. The present invention further relates to an industrial continuous production apparatus for the tetrahydrofurfuryl alcohol diethyl ether. The technical scheme provided by the present invention is suitable for industrial continuous production; the pipe reactor filled with the super acid solid catalyst is used, and the step of adding a super acid solution is omitted, danger factors of a production technique is eliminated, pollution emission in the production process is reduced, and production costs are effectively reduced; the whole production process is simple, the conversion rate is high, the operation is stable, and the product properties are excellent; and the method and apparatus are applicable to the production process of organic chemical ether compounds.
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Paragraph 0054; 0055; 0056; 0057; 0058; 0059
(2016/12/22)
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- Simultaneous hydrogenation and acid-catalyzed conversion of the biomass-derived furans in solvents with distinct polarities
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Furfural and 5-hydroxymethylfurfural (HMF), the two typical biomass-derived furans, can be converted into biofuels and value-added chemicals via hydrogenation or acid catalysis or both. The potential competition between the hydrogenation and the catalyzed-conversion of HMF and furfural has been investigated with Pd/C and Amberlyst 70 as the catalysts at 170°C in various solvents. In water, the hydrogenation of HMF or the derivatives of HMF could take place, but the acid-catalyzed conversion of HMF to the diketones (2,5-hexanedione) was the dominant reaction pathway. On the contrary, with ethanol as the solvent, the full hydrogenation of HMF to 2,5-tetrahydrofurandimethanol was the dominant route, and the acid-catalyzed routes became insignificant. The efficiency for hydrogenation of HMF was much higher in ethanol than in water. As for furfural, its hydrogenation proceeded more efficiently in the polar solvents (i.e. ethanol, diethyl ether) than in non-polar solvents (i.e. toluene): a polar solvent tended to favor the hydrogenation of the furan ring in furfural over that of the carbonyl group in the same furfural.
- Hu, Xun,Kadarwati, Sri,Song, Yao,Li, Chun-Zhu
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p. 4647 - 4656
(2016/01/29)
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- Solid acid-catalyzed conversion of furfuryl alcohol to alkyl tetrahydrofurfuryl ether
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The acidic zeolite HZSM-5 (Si/Al = 25) achieved 58.9% selectivity of methyl furfuryl ether (MFE) and 44.8% selectivity of ethyl furfuryl ether (EFE) from etherification of furfuryl alcohol with methanol and ethanol. MFE and EFE were quantitatively hydrogenated into methyl tetrahydrofurfuryl ether (MTE) and ethyl tetrahydrofurfuryl ether (ETE) using a Raney Ni catalyst.
- Cao, Quan,Guan, Jing,Peng, Gongming,Hou, Tonggang,Zhou, Jianwei,Mu, Xindong
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