Transformation of lignin to valuable chemicals via sustainable pathways is recognized as one of the most efficient ways to explore its value and replace the nonrenewable petroleum resource. In this work, an environmen...Transformation of lignin to valuable chemicals via sustainable pathways is recognized as one of the most efficient ways to explore its value and replace the nonrenewable petroleum resource. In this work, an environmental-friendly transfer hydrogenation process has been developed to convert lignin derived2,6-dimethoxybenzoquinone to 1,4-cyclohexanediol. Compared with previous work under hydrogen pressure(30 bar), this process uses isopropanol as both solvent and hydrogen donor, which significantly simply the operation process. The core of this study is the design and preparation of Mn modified Raney Ni catalysts by ball milling process. A series of Raney Ni Mn catalysts with different ball milling time and Mn content were prepared and investigated. Characterizations by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscope(SEM) and transmission electron microscope(TEM) etc. showed that Ni Mn Al alloy was formed during the ball milling process and then transformed to Ni Mn alloy after treatment by aqueous Na OH. After optimization, a yield as high as 86.1% could be achieved for 1,4-cyclohexanediol at 200℃ in only 1 h.展开更多
How to remove trace amount of sulfur in benzene is of significance,and deep desulfurization by Ni-containing absorbents is an efficient and promising method.In this paper,The Raney Ni/Al2 O3 adsorbent was prepared and...How to remove trace amount of sulfur in benzene is of significance,and deep desulfurization by Ni-containing absorbents is an efficient and promising method.In this paper,The Raney Ni/Al2 O3 adsorbent was prepared and its kinetic and thermodynamic characteristics on adsorptive desulfurization of benzene were studied.The results showed that Raney Ni/Al2 O3 adsorbent exhibited good adsorption performance.The equilibrium isotherms indicated that the adsorption of thiophene over the Raney Ni/Al2 O3 adsorbent complied with the Freundlich model.The results of adsorption kinetics studies showed that the pseudo-second-order kinetics equation was more advantageous than the pseudo-first-order kinetics equation in describing the adsorption kinetics of thiophene on Raney Ni/Al2 O3.The rate constant value(kp)was positively correlated with the temperature whereas the adsorption mass transfer process was mainly determined by the intraparticle and film diffusion.The adsorption thermodynamic analysis proved that△G^0<0,△H^0>0,and△S^0>0,implying that the adsorption was a spontaneous,entropy-increasing and endothermic process.展开更多
[Objective]The research aimed to study rapid dechlodnation kinetics of 1,4-dichlorobenzene （1,4-DCB） by microwave-assisted Raney Ni -AI alloy catalyst. [ Method] Microwave-assisted Raney Ni -AI alloy catalyst was us...[Objective]The research aimed to study rapid dechlodnation kinetics of 1,4-dichlorobenzene （1,4-DCB） by microwave-assisted Raney Ni -AI alloy catalyst. [ Method] Microwave-assisted Raney Ni -AI alloy catalyst was used for dechlorination of chlorobenzene （CB） and 1,4-DCB to analyze dechlorination kinetics of 1,4-DCB. [ Result] Reductive dechlorination reaction of 1,4-DCB by microwave-assisted Raney Ni- AI alloy catalyst was in accordance of the two-order reaction kinetics. Reaction rate constants of 1,4-DCB dechlorination at 35 and 50 ℃ were 0.037 6 and 0.151 mol/（ L . min）, and the activation energy was 76.66 kJ/mol. By microwave-assisted Raney Ni - AI alloy catalyst, dechlorination rate of 1,4- DCB reached 90% at 10 rain and 35 ℃. Moreover, two chlorine atoms were removed simultaneously, reaching the target of efficient dechlorination. [ Condusion] Oechlodnation of polychlodnated organic compounds by microwave-assisted Raney Ni- AI alloy catalyst obtained good effect .展开更多
Exothermic hydrogenation reaction of acetone is an important part of an IAH-CHP, and the performance of IAH-CHP is affected directly by this reaction. This paper studies the influence of space velocity, temperature, h...Exothermic hydrogenation reaction of acetone is an important part of an IAH-CHP, and the performance of IAH-CHP is affected directly by this reaction. This paper studies the influence of space velocity, temperature, hydrogen flow rate and pressure on conversion and selectivity experimentally. The byproducts are analyzed and classified into three types: hydrogenation product, cracking products and condensation products. Both the conversion and selectivity of this reaction have the same trend with the change of space velocity, temperature and hydrogen flow rate, and has the opposite trend with the change of pressure. As the space velocity increases, the conversion curve is a gradual decline parabola but the selectivity curve is close to a straight line. Hydrogen flow rate has a more obvious influence on conversion than temperature, whereas on selectivity the situation is opposite. High pressure increases the conversion of acetone to all products, but the increment of byproducts is more than that of isopropanol, so the selectivity decreases as pressure increases.展开更多
A newly-developed polyamide supported Raney Ni catalyst, which is suitable for use in fix-bed reactions with high selectivity, was studied in this paper. Selective hydrogenation of acetone to isopropanol was chosen as...A newly-developed polyamide supported Raney Ni catalyst, which is suitable for use in fix-bed reactions with high selectivity, was studied in this paper. Selective hydrogenation of acetone to isopropanol was chosen as a probe reaction. It has been found that clean preparation of isopropanol could be achieved, that is to say, the two main byproducts(isopropyl ether and methyl-iso-butyl carbinol) could be eliminated with the newly-developed polyamide supported Raney Ni catalyst. The elimination of these side reactions was attributed to the adsorption effect of polyamide support and a model was proposed. The proposed model was further proved by hydroamination reaction of acetone. According to this model, catalyst support can play an important role in chemical reactions. Different products could be produced when different catalyst support is used, the main reaction and side reactions can even be reversed sometimes when the chemicals, active component of catalyst and reaction condition are the same. This model could help to improve catalytic selectivity of many Raney metal catalysts used routinely in chemical and oil refining industry, and is also useful for hydrogenation reactions in pharmaceutical and food industry.展开更多
基金supported by the Fundamental Research Funds for the Central Universities (BLX202132)the Foreign expert program (G2022109001L)+1 种基金the Beijing Forestry University Outstanding Young Talent Cultivation Project (2019JQ03005)the Young Tip-top Talent Project of Science and Technology Innovation by National Forestry and Grassland Administration of China(2019132609)。
文摘Transformation of lignin to valuable chemicals via sustainable pathways is recognized as one of the most efficient ways to explore its value and replace the nonrenewable petroleum resource. In this work, an environmental-friendly transfer hydrogenation process has been developed to convert lignin derived2,6-dimethoxybenzoquinone to 1,4-cyclohexanediol. Compared with previous work under hydrogen pressure(30 bar), this process uses isopropanol as both solvent and hydrogen donor, which significantly simply the operation process. The core of this study is the design and preparation of Mn modified Raney Ni catalysts by ball milling process. A series of Raney Ni Mn catalysts with different ball milling time and Mn content were prepared and investigated. Characterizations by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscope(SEM) and transmission electron microscope(TEM) etc. showed that Ni Mn Al alloy was formed during the ball milling process and then transformed to Ni Mn alloy after treatment by aqueous Na OH. After optimization, a yield as high as 86.1% could be achieved for 1,4-cyclohexanediol at 200℃ in only 1 h.
基金financially supported by the Importation and Development of High-Caliber Talents Project of Beijing Municipal Institutions(CIT&TCD 20130325)the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under Beijing Municipality(IDHT20180508)。
文摘How to remove trace amount of sulfur in benzene is of significance,and deep desulfurization by Ni-containing absorbents is an efficient and promising method.In this paper,The Raney Ni/Al2 O3 adsorbent was prepared and its kinetic and thermodynamic characteristics on adsorptive desulfurization of benzene were studied.The results showed that Raney Ni/Al2 O3 adsorbent exhibited good adsorption performance.The equilibrium isotherms indicated that the adsorption of thiophene over the Raney Ni/Al2 O3 adsorbent complied with the Freundlich model.The results of adsorption kinetics studies showed that the pseudo-second-order kinetics equation was more advantageous than the pseudo-first-order kinetics equation in describing the adsorption kinetics of thiophene on Raney Ni/Al2 O3.The rate constant value(kp)was positively correlated with the temperature whereas the adsorption mass transfer process was mainly determined by the intraparticle and film diffusion.The adsorption thermodynamic analysis proved that△G^0<0,△H^0>0,and△S^0>0,implying that the adsorption was a spontaneous,entropy-increasing and endothermic process.
文摘[Objective]The research aimed to study rapid dechlodnation kinetics of 1,4-dichlorobenzene （1,4-DCB） by microwave-assisted Raney Ni -AI alloy catalyst. [ Method] Microwave-assisted Raney Ni -AI alloy catalyst was used for dechlorination of chlorobenzene （CB） and 1,4-DCB to analyze dechlorination kinetics of 1,4-DCB. [ Result] Reductive dechlorination reaction of 1,4-DCB by microwave-assisted Raney Ni- AI alloy catalyst was in accordance of the two-order reaction kinetics. Reaction rate constants of 1,4-DCB dechlorination at 35 and 50 ℃ were 0.037 6 and 0.151 mol/（ L . min）, and the activation energy was 76.66 kJ/mol. By microwave-assisted Raney Ni - AI alloy catalyst, dechlorination rate of 1,4- DCB reached 90% at 10 rain and 35 ℃. Moreover, two chlorine atoms were removed simultaneously, reaching the target of efficient dechlorination. [ Condusion] Oechlodnation of polychlodnated organic compounds by microwave-assisted Raney Ni- AI alloy catalyst obtained good effect .
基金supported by the National Natural Science Foundation of China under Grant No 51276181the National Basic Research Program of China under Grant No 2011CB710705
文摘Exothermic hydrogenation reaction of acetone is an important part of an IAH-CHP, and the performance of IAH-CHP is affected directly by this reaction. This paper studies the influence of space velocity, temperature, hydrogen flow rate and pressure on conversion and selectivity experimentally. The byproducts are analyzed and classified into three types: hydrogenation product, cracking products and condensation products. Both the conversion and selectivity of this reaction have the same trend with the change of space velocity, temperature and hydrogen flow rate, and has the opposite trend with the change of pressure. As the space velocity increases, the conversion curve is a gradual decline parabola but the selectivity curve is close to a straight line. Hydrogen flow rate has a more obvious influence on conversion than temperature, whereas on selectivity the situation is opposite. High pressure increases the conversion of acetone to all products, but the increment of byproducts is more than that of isopropanol, so the selectivity decreases as pressure increases.
文摘A newly-developed polyamide supported Raney Ni catalyst, which is suitable for use in fix-bed reactions with high selectivity, was studied in this paper. Selective hydrogenation of acetone to isopropanol was chosen as a probe reaction. It has been found that clean preparation of isopropanol could be achieved, that is to say, the two main byproducts(isopropyl ether and methyl-iso-butyl carbinol) could be eliminated with the newly-developed polyamide supported Raney Ni catalyst. The elimination of these side reactions was attributed to the adsorption effect of polyamide support and a model was proposed. The proposed model was further proved by hydroamination reaction of acetone. According to this model, catalyst support can play an important role in chemical reactions. Different products could be produced when different catalyst support is used, the main reaction and side reactions can even be reversed sometimes when the chemicals, active component of catalyst and reaction condition are the same. This model could help to improve catalytic selectivity of many Raney metal catalysts used routinely in chemical and oil refining industry, and is also useful for hydrogenation reactions in pharmaceutical and food industry.
