hydrogenation

摘要： The efficient hydrogenation of CO_(2)-derived ethylene carbonate(EC)to yield methanol(MeOH)and ethylene glycol(EG)is a key process for indirect conversion of CO_(2)to MeOH.However,a high H_(2)/EC molar ratio during the hydrogenation process(usually as 180-300)is generally required to achieve good catalytic performance,resulting in high cost and energy consumption for H_(2)circulation in the promising industrial application.Here,we prepared a series of Ni-modified Cu/SiO_(2)catalysts and explored the effects of synthesis methods and Ni contents on catalytic performance under different H_(2)/EC molar ratios.The Cu/SiO_(2)catalyst with 0.2%(mass)Ni loading prepared by co-ammonia evaporation method exhibited above 99%conversion of EC,91%and 98%selectivity to MeOH and EG respectively at H_(2)/EC ratio of 60.And no significant deactivation was observed within 140 h at a lower H_(2)/EC of 40.It is demonstrated that a few of Ni addition could not only promote Cu dispersion and increase surface Cu^(+) species due to the strong interaction between Cu and Ni species,but also form uniformly-dispersed CuNi alloy species and thus enhance the adsorption and dissociation of H_(2).But the excess Ni species would aggregate and segregate to cover partial surface of Cu nanoparticles,leading to a significantly drop of catalytic performance in EC hydrogenation.These insights may provide guidance for further design of catalysts for the ester hydrogenation reactions.

摘要： This paper developed a new clean continuous process for the hydrogenation of 3,5-dimethylpyridine(DPY)to 3,5-dimethylpiperidine(DPI)without solvent.A series of Ru/C catalysts were prepared by impregnation method,which were characterized by the BET,ICP,CO chemisorptions,XRD,SEM,EDS,TEM and TG.The effect of active species,loading,catalyst support,reaction temperature and pressure on the catalytic performance was investigated.The influence of internal and external diffusion in the trickle-bed reactor(TBR)was basically eliminated by adjusting the particle size and dosage of the Ru/C catalyst.The reaction performance of the hydrogenation of DPY to DPI in the TBR and kettle reactor(KR)was compared,and the superiority of the TBR process was analyzed.The results show that this new continuous process developed in this study is an efficient way to realize the hydrogenation of DPY to DPI,and has a good industrial application prospect.

摘要： Copper-based catalysts were widely used in the heterogeneous selective hydrogenation of ethylene carbonate(EC),a key step in the indirect conversion of CO_(2) to methanol.However,a high H_(2)/EC molar ratio in feed is required to achieve favorable activity and the methanol selectivity still needs to be improved.Herein,we fabricated a series of Pt-modulated Cu/SiO_(2) catalysts and investigated their catalytic performance for hydrogenation of EC in a fixed bed reactor.By modulating the Pt amount,the optimal 0.2Pt-Cu/SiO_(2) catalyst exhibited the highest catalytic performance with
99%EC conversion,over 98%selectivity to ethylene glycol and 95.8%selectivity to methanol at the H_(2)/EC ratio as low as 60 in feed.In addition,0.2Pt-Cu/SiO_(2) catalyst showed excellent stability for 150 h on stream over different H_(2)/EC ratios of 180-40.It is demonstrated a proper amount of Pt could significantly lower the H_(2)/EC molar ratio,promote the reducibility and dispersion of copper,and also enhance surface density of Cu+species.This could be due to the strong interaction of Cu and Pt induced by formation of alloyed Pt single atoms on the Cu lattice.Meanwhile,a relatively higher amount of Pt would deteriorate the catalytic activity,which could be due to the surface coverage and aggregation of active species.These findings may enlighten some fundamental insights for further design of Cu-based catalysts for the hydrogenation of carbon–oxygen bonds.

摘要： In this study,the effect of channel baffles and louver baffles on the flow pattern in the large-scale industrial fluidized beds was studied by computational fluid dynamics(CFD)methods.Then,the effect of flow pattern on the chemical reaction performance was studied for the first time.Simulation results showed that the gas velocity distributed more uniformly,solid particles dispersed more homogeneously and aggregation scarcely occurred in the fluidized bed with louver baffles than that with channel baffles.The residence time distribution indicated that louver baffles remarkably suppressed gas back-mixing in comparison with channel baffles.The reasonable agreements of pressure distribution and reaction results between the simulation in the bed with channel baffles and the data on a large-scale industrial apparatus demonstrated the accuracy of the CFD model.The predicted conversion of SiCl_(4) in the bed with louver baffles(27.44%)was higher than that with channel baffles(22.69%),indicating that louver baffles markedly improved the performance of the fluidized bed.This study could provide useful information for future structural improvements of baffles in large-scale fluidized beds.

摘要： The hydrogenation of petroleum resin(PR)is an effective process to prepare high value-added hydrogenated PR(HPR).However,the preparation of non-noble metal-based catalysts with high catalytic activity for PR hydrogenation still remains a challenge.Herein,a La promoted Ni-based catalyst is reported through the thermal reduction of quaternary Ni La Mg Al-layered double hydroxides(Ni La Mg Al-LDHs).The incorporation of La is beneficial to the reduction and stability of Ni particles with reduced particle size,and the increased alkalinity effectively mitigates the breakage of molecular chains of PR.As a result,the La promoted Ni-based catalyst exhibits high catalytic activity and excellent stability for PR hydrogenation.A hydrogenation degree of 95.4%and 96.1%can be achieved for HC_(5)PR and HC_(9) PR with less reduced softening point,respectively.Notably,the hydrogenation degree still maintains at 92.7%even after 100 hours’reaction,much better than that without La incorporation or prepared using conventional impregnation method.

摘要： Selective hydrogenation plays an important role in chemical industries,yet its selectivity is usually limited by the mass transfer.In this work,the enhanced hydrogenation selectivity was achieved in a rotating packed bed(RPB)reactor with excellent mass transfer efficiency.Aiming to be used under the centrifugal filed,a monolithic catalyst Pd/c-Al_(2)O_(3)/nickel foam suiting for the shape and size of the rotor of RPB reactor was prepared by the electrophoretic deposition method.The mechanical strength of the catalyst can meet the requirement of high centrifugal force in the RPB.The hydrogenation selectivity in the RPB reactor using the 3-methyl-1-pentyn-3-ol hydrogenation system was 3–8 times higher than that in a stirred tank reactor under similar conditions.This work proves the feasibility of intensifying the selectivity of hydrogenation process in the RPB reactor.

摘要： A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.

摘要： Zeolite-supported metal catalysts containing hydrogenation centers and acid sites are promising in the chemoselective hydrogenation of biomass platform molecules into value-added chemicals and fuels.The primary challenge of employing such bifunctional catalysts for biomass conversion lies in catalyst stability in the liquid phase under harsh conditions. Herein, we have prepared a Ni/La-Y nanocatalyst via an improved wet impregnation method. Compared with Ni nanoparticles on H-Y, La addition shows a significantly enhanced stability and performance in the continuous liquid-phase hydrogenation of γ-valerolactone(GVL) into ethyl pentanoate(EP) at 200 °C for 1000 h. Complementary characterization studies reveal that La addition in the metal/zeolite catalyst not only efficiently modulates the acid property of the zeolite to alleviate coke formation, but also suppresses zeolite dealumination and metal agglomeration and leaching upon catalysis over a 1000 h period. These findings provide an efficient approach for improving the stability of zeolite-supported bifunctional catalysts, leading to potential application in hydrogen-assisted biomass valorization under the liquid-phase conditions.

摘要： Silver catalyst has been extensively investigated for photocatalytic and electrochemical CO_(2)reduction.However,its high activity for selective hydrogenation of CO_(2)to methanol has not been confirmed.Here,the feasibility of the indium oxide supported silver catalyst was investigated for CO_(2)hydrogenation to methanol by the density functional theoretical(DFT)study and then by the experimental investigation.The DFT study shows there exists an intense Ag-In_(2)O_(3)interaction,which causes silver to be positively charged.The positively charged Ag species changes the electronic structure of the metal,facilitates the formation of the Ag-In_(2)O_(3)interfacial site for activation and dissociation of carbon dioxide.The promoted CO_(2)dissociation leads to the enhanced methanol synthesis via the CO hydrogenation route as CO_(2)^(*)→CO^(*)→HCO^(*)→H_(2)CO^(*)→H_(3)CO^(*)→H_(3)COH^(*).The Ag/In_(2)O_(3)catalyst was then prepared using the deposition-precipitation method.The experimental study confirms the theoretical prediction.The methanol selectivity of CO_(2)hydrogenation on Ag/In_(2)O_(3)reaches 100.0%at reaction temperature of 200°C.It remains more than 70.0%between 200 and 275°C.At 300°Cand 5 MPa,the methanol selectivity still keeps 58.2%with a CO_(2)conversion of 13.6%and a space-time yield(STY)of methanol of 0.453 g_(methanol)g_(cat)^(-1)h^(-1),which is the highest methanol STY ever reported for silver catalyst.The catalyst characterization confirms the intense Ag-In_(2)O_(3)interaction as well,which causes high Ag dispersion,increases and stabilizes the oxygen vacancies and creates the active Ag-In_(2)O_(3)interfacial site for the enhanced CO_(2)hydrogenation to methanol.

摘要： The present energy dilemma in conjunction with the adverse environmental impacts caused by fossil fuel combustion motivates researchers to seek for new renewable energy with minimal CO_(2)footprint.As a practice pathway,it is of significance to produce biofuel and platform chemicals from sustainable biomass resources.However,the research and development of high-efficiency catalysts remain one key scientific challenge.Among the catalysts developed,transition metal carbides,especially molybdenum carbide,show promising performances on biomass-based conversion.Significant efforts have been made in past few decades on tuning the structure and electronic property of molybdenum carbide via controlling particle size and morphology,metal and nonmetal doping and vacancies,etc.The review summarizes recent developments of molybdenum carbide as catalysts in converting biomass into fuel,mainly focused on the preparation methods,the structure-dependent effects and the electronic modulation.The controllable selective cleavage of C-C,C-O and C-H bonds over modified molybdenum carbides that has been demonstrated in the conversion of biomass feedstocks is then highlighted.In addition,the possible deactivation mechanisms of molybdenum carbide are also presented in the review.This review provides systematic and fundamental information for the further design and development of molybdenum carbide for the conversion of biomass resources.