High-performance and cost-effective catalysts for water splitting are key components of hydrogen-based energy technologies. Metal-organic framework(MOF)-derived metal phosphide composites have immense potential as hig...High-performance and cost-effective catalysts for water splitting are key components of hydrogen-based energy technologies. Metal-organic framework(MOF)-derived metal phosphide composites have immense potential as highly active and stable electrocatalysts but suffer from the poor efficacy of available electrode assembly methods. In this study, an MOF-derived nitrogen-doped porous carbon/Co/Co P/carbon paper(NC/Co/Co P/CP) composite electrode was assembled by electrophoretic deposition and post-processing reactions. The binder-free electrode showed good catalytic activity, significantly higher than that of traditional electrodes. The electrode required overpotentials of 208 and 350 m V to achieve a current density of 10 m A/cm^2 for the hydrogen and oxygen evolution reactions, respectively. This facile synthetic method provides a promising route for designing metal-doped and multi-metal phase MOF-derived composite electrodes for energy storage and conversion devices.展开更多
The effects of the substituents on the cyclopentadienyl ring and the reducing agents on the catalytic activity and the stability of titanocene/NaH or n BuLi systems for the hydrogenation of olefins were investiga...The effects of the substituents on the cyclopentadienyl ring and the reducing agents on the catalytic activity and the stability of titanocene/NaH or n BuLi systems for the hydrogenation of olefins were investigated. For the catalyst systems composed of titanocene/NaH or n BuLi, the nature and the number of the substituents on the cyclopentadienyl ring control the catalytic behavior of those two systems. The effect of the reducing agent on the catalytic activity is relatively small. In addition, the characters of the hydrogenation of various olefins catalyzed respectively by Cp 2TiCl 2/NaH or n BuLi systems were compared.展开更多
Pd/oxide/cordierite monolithic catalysts(oxide = Al_2O_3, SiO_2 and SiO_2\\Al_2O_3) were prepared by the impregnation method. The results of ICP, XRD, SEM–EDX, XPS and N_2 adsorption–desorption measurements revealed...Pd/oxide/cordierite monolithic catalysts(oxide = Al_2O_3, SiO_2 and SiO_2\\Al_2O_3) were prepared by the impregnation method. The results of ICP, XRD, SEM–EDX, XPS and N_2 adsorption–desorption measurements revealed that the Pd penetration depth increased with increasing the thickness of oxide layer, and the catalysts with Al_2O_3 layers had the larger pore size than those with SiO_2 and SiO_2\\Al_2O_3 layers. Catalytic hydrogenation of 2-ethylanthraquinone(eA Q), a key step of the H_2O_2 production by the anthraquinone process, over the various monolithic catalysts(60 °C, atmosphere pressure) showed that the monolithic catalyst with the moderate thickness of Al_2O_3 layer(about 6 μm) exhibited the highest conversion of e AQ(99.1%) and hydrogenation efficiency(10.0 g·L^(-1)). This could be ascribed to the suitable Pd penetration depth and the larger pore size, which provides a balance between the distribution of Pd and accessibility of active sites by the reactants.展开更多
The effect of ammonia on the catalytic performance for 1-methylnaphthalene(1-MN) selective hydrogenation saturation was studied with Co-Mo/γ-Al_2O_3, Ni-W/γ-Al_2O_3, Ni-Mo/γ-Al_2O_3, and Ni-Mo-W/γ-Al_2O_3 catalyst...The effect of ammonia on the catalytic performance for 1-methylnaphthalene(1-MN) selective hydrogenation saturation was studied with Co-Mo/γ-Al_2O_3, Ni-W/γ-Al_2O_3, Ni-Mo/γ-Al_2O_3, and Ni-Mo-W/γ-Al_2O_3 catalysts. The results indicated that Ni-Mo-W/γ-Al_2O_3 catalyst exhibited the best performance for saturation of 1-MN. The introduction of NH3 remarkably inhibited the hydrogenation of 1-MN in the dynamic control area, but it had no effect in the thermodynamic control area. Besides, the mono-aromatics selectivity on the Ni-Mo-W and Ni-Mo catalysts was enhanced. However, it had little effect on the Ni-W and Co-Mo catalysts.展开更多
An approach to the simultaneous reclamation of carbon and sulfur resources from CO2 and H2S has been proposed and effectively implemented with the aid of catalysts. A brief thermodynamic study reveals the potential of...An approach to the simultaneous reclamation of carbon and sulfur resources from CO2 and H2S has been proposed and effectively implemented with the aid of catalysts. A brief thermodynamic study reveals the potential of direct reduction of CO2 with H2S(15:15 mol% balanced with N2) for selective production of CO and elemental sulfur. The experiments carried out in a fixed-bed flow reactor over the temperature range of 400–800 °C give evidence of the importance of the employment of catalysts. Both the conversions of the reactants and the selectivities of the target products can be substantially promoted over most catalysts studied. Nevertheless, little difference appears among their catalytic performance. The results also prove that the presence of CO2 can remarkably enhance H2S conversion and the sulfur yield in comparison with H2S direct decomposition. A longtime reaction test on Mg O catalyst manifests its superior durability at high temperature(700 °C) and huge gas hourly space velocity(100,000 h-1). Free radicals initiated by catalysts are supposed to dominate the reactions between CO2 and H2S.展开更多
Ni supported on bentonite was prepared by the impregnation method with different nickel contents, applied to the hydrogenation of nitrobenzene to aniline in a fixed-bed reactor, and it was characterized by X-ray diffr...Ni supported on bentonite was prepared by the impregnation method with different nickel contents, applied to the hydrogenation of nitrobenzene to aniline in a fixed-bed reactor, and it was characterized by X-ray diffraction(XRD), H2-temperature programmed reduction(H2-TPR), and X-ray photoelectron spectrometry(XPS). The results showed that Ni/bentonite catalyst with 20 wt% nickel content provided a higher conversion of nitrobenzene and selectivity of aniline compared to other catalysts. NiO was the precursor of the active component of the catalyst, and the small crystallite size as well as the highly dispersed NiO on the Ni/bentonite-20 catalyst, contributed to the catalytic performance. The hydrogenation of nitrobenzene was carried out at 300℃ with a H_2 gaseous hourly space velocity of 4800 ml·(g cat)^-1·h^-1and a nitrobenzene liquid hourly space velocity of4.8 ml·(g cat)^-1·h^-1 over Ni/bentonite-20. A 95.7% nitrobenzene conversion and 98.8% aniline selectivity were obtained. While the nitrobenzene liquid hourly space velocity was 4.8 ml·(g cat)^-1·h^-1, the yield of aniline was more than 95.0% during a 10-hour reaction.展开更多
A decorated ruthenium catalyst was prepared by the coprecipitation method and used for the selective hydrogenation of maleic anhydride(MA) to γ-butyrolactone(GBL). The as-prepared catalyst was characterized by XRD, T...A decorated ruthenium catalyst was prepared by the coprecipitation method and used for the selective hydrogenation of maleic anhydride(MA) to γ-butyrolactone(GBL). The as-prepared catalyst was characterized by XRD, TGDTG and N2 adsorption techniques. The characterization tests revealed that the catalyst carrier was composed of monoclinic zirconia(m-ZrO2) and hydroxyl cobalt oxide(CoO(OH)). The hydrogenation results showed that the content of CoO(OH), the reaction temperature, the hydrogen pressure and the reaction time significantly affected the catalytic selectivity to GBL. The promotional effect of CoO(OH) was remarkable, which led to an obvious increase in GBL selectivity. An 100% MA conversion and 92.0% selectivity to GBL were achieved over the Ru/ZrO2-CoO(OH)(35%) catalyst in water solvent under the conditions involving a reaction temperature of 180 ℃, a hydrogen pressure of 3.0 MPa, and a reaction time of 6 h.展开更多
Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively....Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5^+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.展开更多
The Co3O4 and Zr-,Ce-,and La-Co3O4 catalysts were prepared,characterized,and applied to produce CH4 from CO2 catalytic hydrogenation in low temperature as 140–220℃.The results indicated that the addition of Zr,Ce,or...The Co3O4 and Zr-,Ce-,and La-Co3O4 catalysts were prepared,characterized,and applied to produce CH4 from CO2 catalytic hydrogenation in low temperature as 140–220℃.The results indicated that the addition of Zr,Ce,or La to the Co3O4 decreased the crystallite sizes of Co and the outer-shell electron density of Co^3+,and increased the specific surface area,which would provide more active sites for the CO2 methanation.Especially,the addition of Zr also changed the reducing state of Co3O4 via an obvious change in the interaction between Co3O4 and ZrO2.Furthermore,Zr doped into the Co3O4 increased the basic intensity of the weak and medium basic sites,as well as the amount of Lewis acid sites,and Bronsted acid sites were also found on the Zr-Co3O4 surface.The introduction of Zr,Ce,or La favored the production of CH4,and the Zr-Co3O4catalyst exhibited the highest CO2 conversion(58.2%)and CH4 selectivity(100%)at 200℃,and 0.5 MPa with a gaseous hourly space velocity of 18,000 ml·g^-1(cat)·h^-1,and the catalytic activity of CO2methanation for the Zr-,Ce-,and La-Co3O4 exhibited more stable than Co3O4 in a 20-h reaction.展开更多
The SHP-A1 type catalyst for hydrogenation of α-methylstyrene(AMS)developed by the SINOPEC Shanghai Petrochemical Research Institute(SPRI)has been successfully applied in the No.1 phenol unit at the Third Chemical Pl...The SHP-A1 type catalyst for hydrogenation of α-methylstyrene(AMS)developed by the SINOPEC Shanghai Petrochemical Research Institute(SPRI)has been successfully applied in the No.1 phenol unit at the Third Chemical Plant of Yanshan Petrochemical Company at the first attempt of commissioning.The said catalyst is the first AMS hydrogenation catalyst developed展开更多
A new C-2-symmetric diamine/diphosphine Ruthenium (II) complex, RuCl2P2N2H4, was used as an excellent catalyst to carry out the catalytic hydrogen transfer reduction of acetophenone. The conversion of acetophenone to ...A new C-2-symmetric diamine/diphosphine Ruthenium (II) complex, RuCl2P2N2H4, was used as an excellent catalyst to carry out the catalytic hydrogen transfer reduction of acetophenone. The conversion of acetophenone to 2-phenylethanol was up to 99% under the following reaction conditions: substrate:Ru:(CH3)(2)CHOK = 200:1:12; reaction temperature of 65 degrees C; reaction time of 2 h; normal pressure. A hydride transfer mechanism was also discussed.展开更多
The bimetallic catalysts prepared from SiO_2-supported Ru-Co,Ru- Fe and Ru-Mo carbonyl clusters exhibited high yields and selectivities towards oxygenates such as C_1-C_5 from CO+H_2,in contrast to the catalysts prepa...The bimetallic catalysts prepared from SiO_2-supported Ru-Co,Ru- Fe and Ru-Mo carbonyl clusters exhibited high yields and selectivities towards oxygenates such as C_1-C_5 from CO+H_2,in contrast to the catalysts prepared from homometallic and bimetallic Ru,Ru-Ni,Ru-Rh,Ru-Mn,and Ru- Cr carbonyl clusters.The FTIR investigation revealed that the 1584 cm^(-1) species plays an important role in the formation of oxygenates in CO hydrogenation,which is possibly assigned to surface formyl species.展开更多
Many catalysts were pcrpared by carbonization of ion exchange resin-PdCl_2 complexes at high temperature in nitrogen, hydrogen atmosphere. The rates for the hydrogenation of methyl acrylate and the amounts of Pd eluti...Many catalysts were pcrpared by carbonization of ion exchange resin-PdCl_2 complexes at high temperature in nitrogen, hydrogen atmosphere. The rates for the hydrogenation of methyl acrylate and the amounts of Pd elution of the carbonaceous products were measured and compared with those of commercial Pd/C catalyst. It indicates that the carbonaceous products are less active than Pd/C. However, the leaching of Pd from carbonaceous products is very small and much less than that from Pd/C.展开更多
Raman peaks at 1951 and 2165 cm^(-1) can be confirmed further by H_2/D_2 isotope exchange as H-adspecies on the doubly promoted iron catalyst for ammonia synthesis and are probably ascribed to two terminally adsorbed ...Raman peaks at 1951 and 2165 cm^(-1) can be confirmed further by H_2/D_2 isotope exchange as H-adspecies on the doubly promoted iron catalyst for ammonia synthesis and are probably ascribed to two terminally adsorbed H-species.展开更多
Several Pd--SnO2/ D3520 and Pd--PbO / D3520 catalysts with Pd/ D3J20, SnO2 / D3520 and PbO / D3520 catalysts as rference were studied by means of IR and XPS. Interaction between Pd and the second metal or between meta...Several Pd--SnO2/ D3520 and Pd--PbO / D3520 catalysts with Pd/ D3J20, SnO2 / D3520 and PbO / D3520 catalysts as rference were studied by means of IR and XPS. Interaction between Pd and the second metal or between metal and support was observed. Results show that there is a strong interaction between Pd and the second metal, but there is not an obvious interaction between metal and support. The active constituent is Pd ̄0. Hydrogenation activity of the catalysts is altered because of the interaction between Pd and the second,metal.The activity of the catalysts for hydrogenation has relation to outer layer valence electron density of Pd.展开更多
In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron don...In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron donors can decrease or even cease the monoene hydrogenation and thereby keep the high monoene selectivity after reaching its maximum.展开更多
This article mainly summarizes various aspects of hydrogen peroxide(H2O2)production through the anthraquinone route,including hydrogenation catalysts,working solution,regeneration technique,hydrogenation reactors,and ...This article mainly summarizes various aspects of hydrogen peroxide(H2O2)production through the anthraquinone route,including hydrogenation catalysts,working solution,regeneration technique,hydrogenation reactors,and environmental protection.The advances and breakthrough of SINOPEC in the production of H2O2 through the anthraquinone route is presented in this review,highlighting recent innovative technology on these aspects developed independently.The technical prospect and scientific challenges associated with the direct synthesis method from hydrogen and oxygen are also briefly discussed.展开更多
The influence of the carrier pseudo-boehmite (PB), which was impregnated with a Ni-Mo-P solution under over- saturation conditions and treated at different temperatures, on its property for adsorption of active meta...The influence of the carrier pseudo-boehmite (PB), which was impregnated with a Ni-Mo-P solution under over- saturation conditions and treated at different temperatures, on its property for adsorption of active metals (Ni, Mo) was studied. The results showed that the amount for adsorption of active metal was decreased with an increasing treatment tem- perature of the carrier. After phase transition of the carrier PB to γ-Al2O3, its capacity for adsorption of active metals was significantly reduced. The difference in properties for adsorption of active metals (Ni, Mo) by PB dried at 120℃ and γ-Al2O3 calcined at 600℃ was studied in detail. The results suggested that the ability of the PB carrier to adsorb metals was higher than that of theγ-Al2O3 carrier. Especially, the ratio of chemically adsorbed metals on the PB support was much higher than 3'-alumina. The chemical adsorption sites on the PB carrier were proved to be much more than those on the γ-Al2O3 carrier. Ni and Mo chemical adsorption sites differed a lot on the carrier possibly because of the difference in chemical adsorption sites.展开更多
The hierarchical structure of molybdenum disulfide(MoS2)nanosheet arrays stemmed from nickelcobalt layered double hydroxide(NiCo-LDH)/carbon cloth was prepared by growing the MoS_(2) nanosheet arrays onto the NiCo-LDH...The hierarchical structure of molybdenum disulfide(MoS2)nanosheet arrays stemmed from nickelcobalt layered double hydroxide(NiCo-LDH)/carbon cloth was prepared by growing the MoS_(2) nanosheet arrays onto the NiCo-LDH template which was pre-deposited onto the carbon cloth substrate.In this electrode configuration,carbon cloth is the three dimensional and conductive skeleton;NiCo-LDH nanosheets,as the template,ensure the oriented growth of MoS2 nanosheet arrays.Therefore,more MoS_(2) active sites are exposed and the catalyst exhibits good hydrogen evolution reaction activity.展开更多
Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. He...Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.展开更多
基金supported by the National Natural Science Foundation of China(21573033)Shandong Provincial Natural Science Foundation,China(ZR2018BB037)+1 种基金Project of Shandong Province Higher Educational Science and Technology Program(J17KA104)Project of Qingdao Applied Basic Research Programs of Science and Technology(18-2-2-10-jch and 18-2-2-35-jch)~~
文摘High-performance and cost-effective catalysts for water splitting are key components of hydrogen-based energy technologies. Metal-organic framework(MOF)-derived metal phosphide composites have immense potential as highly active and stable electrocatalysts but suffer from the poor efficacy of available electrode assembly methods. In this study, an MOF-derived nitrogen-doped porous carbon/Co/Co P/carbon paper(NC/Co/Co P/CP) composite electrode was assembled by electrophoretic deposition and post-processing reactions. The binder-free electrode showed good catalytic activity, significantly higher than that of traditional electrodes. The electrode required overpotentials of 208 and 350 m V to achieve a current density of 10 m A/cm^2 for the hydrogen and oxygen evolution reactions, respectively. This facile synthetic method provides a promising route for designing metal-doped and multi-metal phase MOF-derived composite electrodes for energy storage and conversion devices.
基金Supported by the Educational Com mittee of L iaoning Province
文摘The effects of the substituents on the cyclopentadienyl ring and the reducing agents on the catalytic activity and the stability of titanocene/NaH or n BuLi systems for the hydrogenation of olefins were investigated. For the catalyst systems composed of titanocene/NaH or n BuLi, the nature and the number of the substituents on the cyclopentadienyl ring control the catalytic behavior of those two systems. The effect of the reducing agent on the catalytic activity is relatively small. In addition, the characters of the hydrogenation of various olefins catalyzed respectively by Cp 2TiCl 2/NaH or n BuLi systems were compared.
基金Supported by the Sinopec Corp.Scientific Research Projects(414076)
文摘Pd/oxide/cordierite monolithic catalysts(oxide = Al_2O_3, SiO_2 and SiO_2\\Al_2O_3) were prepared by the impregnation method. The results of ICP, XRD, SEM–EDX, XPS and N_2 adsorption–desorption measurements revealed that the Pd penetration depth increased with increasing the thickness of oxide layer, and the catalysts with Al_2O_3 layers had the larger pore size than those with SiO_2 and SiO_2\\Al_2O_3 layers. Catalytic hydrogenation of 2-ethylanthraquinone(eA Q), a key step of the H_2O_2 production by the anthraquinone process, over the various monolithic catalysts(60 °C, atmosphere pressure) showed that the monolithic catalyst with the moderate thickness of Al_2O_3 layer(about 6 μm) exhibited the highest conversion of e AQ(99.1%) and hydrogenation efficiency(10.0 g·L^(-1)). This could be ascribed to the suitable Pd penetration depth and the larger pore size, which provides a balance between the distribution of Pd and accessibility of active sites by the reactants.
文摘The effect of ammonia on the catalytic performance for 1-methylnaphthalene(1-MN) selective hydrogenation saturation was studied with Co-Mo/γ-Al_2O_3, Ni-W/γ-Al_2O_3, Ni-Mo/γ-Al_2O_3, and Ni-Mo-W/γ-Al_2O_3 catalysts. The results indicated that Ni-Mo-W/γ-Al_2O_3 catalyst exhibited the best performance for saturation of 1-MN. The introduction of NH3 remarkably inhibited the hydrogenation of 1-MN in the dynamic control area, but it had no effect in the thermodynamic control area. Besides, the mono-aromatics selectivity on the Ni-Mo-W and Ni-Mo catalysts was enhanced. However, it had little effect on the Ni-W and Co-Mo catalysts.
基金financial supports from the Fushun Research Institute of Petroleum&Petrochemicals(no.KG12009)the Natural Science Foundation of China(no.21276077)the Fundamental Research Funds for Central Universities(no.WG1213011)
文摘An approach to the simultaneous reclamation of carbon and sulfur resources from CO2 and H2S has been proposed and effectively implemented with the aid of catalysts. A brief thermodynamic study reveals the potential of direct reduction of CO2 with H2S(15:15 mol% balanced with N2) for selective production of CO and elemental sulfur. The experiments carried out in a fixed-bed flow reactor over the temperature range of 400–800 °C give evidence of the importance of the employment of catalysts. Both the conversions of the reactants and the selectivities of the target products can be substantially promoted over most catalysts studied. Nevertheless, little difference appears among their catalytic performance. The results also prove that the presence of CO2 can remarkably enhance H2S conversion and the sulfur yield in comparison with H2S direct decomposition. A longtime reaction test on Mg O catalyst manifests its superior durability at high temperature(700 °C) and huge gas hourly space velocity(100,000 h-1). Free radicals initiated by catalysts are supposed to dominate the reactions between CO2 and H2S.
基金Supported by the National Natural Science Foundation of China(21566005,21425627)Natural Science Foundation of Guangxi province(2014GXNSFAA118049)+1 种基金the Open Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2013K011)the Patent Project of Colleges and Universities of Guangxi Zhuang Autonomous Region(KY2015ZL001)
文摘Ni supported on bentonite was prepared by the impregnation method with different nickel contents, applied to the hydrogenation of nitrobenzene to aniline in a fixed-bed reactor, and it was characterized by X-ray diffraction(XRD), H2-temperature programmed reduction(H2-TPR), and X-ray photoelectron spectrometry(XPS). The results showed that Ni/bentonite catalyst with 20 wt% nickel content provided a higher conversion of nitrobenzene and selectivity of aniline compared to other catalysts. NiO was the precursor of the active component of the catalyst, and the small crystallite size as well as the highly dispersed NiO on the Ni/bentonite-20 catalyst, contributed to the catalytic performance. The hydrogenation of nitrobenzene was carried out at 300℃ with a H_2 gaseous hourly space velocity of 4800 ml·(g cat)^-1·h^-1and a nitrobenzene liquid hourly space velocity of4.8 ml·(g cat)^-1·h^-1 over Ni/bentonite-20. A 95.7% nitrobenzene conversion and 98.8% aniline selectivity were obtained. While the nitrobenzene liquid hourly space velocity was 4.8 ml·(g cat)^-1·h^-1, the yield of aniline was more than 95.0% during a 10-hour reaction.
基金the financial support from the Natural Science Foundation of China(No.21303139)the Key Fund Project of Educational Department of Sichuan Province(No.14ZA0126)the Open Project of Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province(No.CSPC2013-1)
文摘A decorated ruthenium catalyst was prepared by the coprecipitation method and used for the selective hydrogenation of maleic anhydride(MA) to γ-butyrolactone(GBL). The as-prepared catalyst was characterized by XRD, TGDTG and N2 adsorption techniques. The characterization tests revealed that the catalyst carrier was composed of monoclinic zirconia(m-ZrO2) and hydroxyl cobalt oxide(CoO(OH)). The hydrogenation results showed that the content of CoO(OH), the reaction temperature, the hydrogen pressure and the reaction time significantly affected the catalytic selectivity to GBL. The promotional effect of CoO(OH) was remarkable, which led to an obvious increase in GBL selectivity. An 100% MA conversion and 92.0% selectivity to GBL were achieved over the Ru/ZrO2-CoO(OH)(35%) catalyst in water solvent under the conditions involving a reaction temperature of 180 ℃, a hydrogen pressure of 3.0 MPa, and a reaction time of 6 h.
基金Supports by the National Natural Science Foundation of China(21666030,21366025)National First-rate Discipline Construction Project of Ningxia(NXYLXK2017A04)
文摘Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5^+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.
基金Supported by the National Natural Science Foundation of China(21366004)Guangxi Natural Science Foundation(2016GXNSFFA380015)the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2016Z003)
文摘The Co3O4 and Zr-,Ce-,and La-Co3O4 catalysts were prepared,characterized,and applied to produce CH4 from CO2 catalytic hydrogenation in low temperature as 140–220℃.The results indicated that the addition of Zr,Ce,or La to the Co3O4 decreased the crystallite sizes of Co and the outer-shell electron density of Co^3+,and increased the specific surface area,which would provide more active sites for the CO2 methanation.Especially,the addition of Zr also changed the reducing state of Co3O4 via an obvious change in the interaction between Co3O4 and ZrO2.Furthermore,Zr doped into the Co3O4 increased the basic intensity of the weak and medium basic sites,as well as the amount of Lewis acid sites,and Bronsted acid sites were also found on the Zr-Co3O4 surface.The introduction of Zr,Ce,or La favored the production of CH4,and the Zr-Co3O4catalyst exhibited the highest CO2 conversion(58.2%)and CH4 selectivity(100%)at 200℃,and 0.5 MPa with a gaseous hourly space velocity of 18,000 ml·g^-1(cat)·h^-1,and the catalytic activity of CO2methanation for the Zr-,Ce-,and La-Co3O4 exhibited more stable than Co3O4 in a 20-h reaction.
文摘The SHP-A1 type catalyst for hydrogenation of α-methylstyrene(AMS)developed by the SINOPEC Shanghai Petrochemical Research Institute(SPRI)has been successfully applied in the No.1 phenol unit at the Third Chemical Plant of Yanshan Petrochemical Company at the first attempt of commissioning.The said catalyst is the first AMS hydrogenation catalyst developed
文摘A new C-2-symmetric diamine/diphosphine Ruthenium (II) complex, RuCl2P2N2H4, was used as an excellent catalyst to carry out the catalytic hydrogen transfer reduction of acetophenone. The conversion of acetophenone to 2-phenylethanol was up to 99% under the following reaction conditions: substrate:Ru:(CH3)(2)CHOK = 200:1:12; reaction temperature of 65 degrees C; reaction time of 2 h; normal pressure. A hydride transfer mechanism was also discussed.
文摘The bimetallic catalysts prepared from SiO_2-supported Ru-Co,Ru- Fe and Ru-Mo carbonyl clusters exhibited high yields and selectivities towards oxygenates such as C_1-C_5 from CO+H_2,in contrast to the catalysts prepared from homometallic and bimetallic Ru,Ru-Ni,Ru-Rh,Ru-Mn,and Ru- Cr carbonyl clusters.The FTIR investigation revealed that the 1584 cm^(-1) species plays an important role in the formation of oxygenates in CO hydrogenation,which is possibly assigned to surface formyl species.
文摘Many catalysts were pcrpared by carbonization of ion exchange resin-PdCl_2 complexes at high temperature in nitrogen, hydrogen atmosphere. The rates for the hydrogenation of methyl acrylate and the amounts of Pd elution of the carbonaceous products were measured and compared with those of commercial Pd/C catalyst. It indicates that the carbonaceous products are less active than Pd/C. However, the leaching of Pd from carbonaceous products is very small and much less than that from Pd/C.
基金Supported from the State Key Laboratory for Physical Chemistry of the Solid Surface of Xiamen University.
文摘Raman peaks at 1951 and 2165 cm^(-1) can be confirmed further by H_2/D_2 isotope exchange as H-adspecies on the doubly promoted iron catalyst for ammonia synthesis and are probably ascribed to two terminally adsorbed H-species.
文摘Several Pd--SnO2/ D3520 and Pd--PbO / D3520 catalysts with Pd/ D3J20, SnO2 / D3520 and PbO / D3520 catalysts as rference were studied by means of IR and XPS. Interaction between Pd and the second metal or between metal and support was observed. Results show that there is a strong interaction between Pd and the second metal, but there is not an obvious interaction between metal and support. The active constituent is Pd ̄0. Hydrogenation activity of the catalysts is altered because of the interaction between Pd and the second,metal.The activity of the catalysts for hydrogenation has relation to outer layer valence electron density of Pd.
文摘In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron donors can decrease or even cease the monoene hydrogenation and thereby keep the high monoene selectivity after reaching its maximum.
文摘This article mainly summarizes various aspects of hydrogen peroxide(H2O2)production through the anthraquinone route,including hydrogenation catalysts,working solution,regeneration technique,hydrogenation reactors,and environmental protection.The advances and breakthrough of SINOPEC in the production of H2O2 through the anthraquinone route is presented in this review,highlighting recent innovative technology on these aspects developed independently.The technical prospect and scientific challenges associated with the direct synthesis method from hydrogen and oxygen are also briefly discussed.
文摘The influence of the carrier pseudo-boehmite (PB), which was impregnated with a Ni-Mo-P solution under over- saturation conditions and treated at different temperatures, on its property for adsorption of active metals (Ni, Mo) was studied. The results showed that the amount for adsorption of active metal was decreased with an increasing treatment tem- perature of the carrier. After phase transition of the carrier PB to γ-Al2O3, its capacity for adsorption of active metals was significantly reduced. The difference in properties for adsorption of active metals (Ni, Mo) by PB dried at 120℃ and γ-Al2O3 calcined at 600℃ was studied in detail. The results suggested that the ability of the PB carrier to adsorb metals was higher than that of theγ-Al2O3 carrier. Especially, the ratio of chemically adsorbed metals on the PB support was much higher than 3'-alumina. The chemical adsorption sites on the PB carrier were proved to be much more than those on the γ-Al2O3 carrier. Ni and Mo chemical adsorption sites differed a lot on the carrier possibly because of the difference in chemical adsorption sites.
基金financial support for this work from the Strategic Priority Research Program of CAS(XDB36030000)the National Natural Science Foundation of China(21422303,21573049,21872043,22002028)+3 种基金the National Basic Research Plan of China(2016YFA0201600)the Beijing Natural Science Foundation(2142036)the Youth Innovation Promotion Associationthe Special Program of “One Belt One Road”of CAS。
文摘The hierarchical structure of molybdenum disulfide(MoS2)nanosheet arrays stemmed from nickelcobalt layered double hydroxide(NiCo-LDH)/carbon cloth was prepared by growing the MoS_(2) nanosheet arrays onto the NiCo-LDH template which was pre-deposited onto the carbon cloth substrate.In this electrode configuration,carbon cloth is the three dimensional and conductive skeleton;NiCo-LDH nanosheets,as the template,ensure the oriented growth of MoS2 nanosheet arrays.Therefore,more MoS_(2) active sites are exposed and the catalyst exhibits good hydrogen evolution reaction activity.
基金supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal(Fe, Co, Ni, Mo and W) phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.