We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst comp...We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic reforming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al2O3 catalysts, the Ni2O/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 ℃, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni2O/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.展开更多
The continual growth in transportation fuels and more strict environmental legislations have led to immense interest in developing green biomass energy. In this work, a proposed catalytic transformation of oxygenated ...The continual growth in transportation fuels and more strict environmental legislations have led to immense interest in developing green biomass energy. In this work, a proposed catalytic transformation of oxygenated organic compounds （related to bio-oil） into pure hydrogen was desighed, involving the catalytic reforming of oxygenated organic compounds to hydrogen- rich mixture gas followed by the conversion of CO to CO2 via the water gas reaction and the removal of CO2. The optimization of the different reforming catalyst, the reaction conditions as well as various sources of oxygenated organic compounds were investigated in detail. The production of pure hydrogen, with the H2 content up to 99.96% and the conversion of 97.1%, was achieved by the integrated catalytic transformation. The reaction pathways were addressed based on the investigation of decomposition, catalytic reforming, and the water gas reaction.展开更多
Methanol is regarded as an important liquid fuel for hydrogen storage, transportation, and in-situ generation due to its convenient conveyance, high energy density, and low conversion temperature. In this work, an ove...Methanol is regarded as an important liquid fuel for hydrogen storage, transportation, and in-situ generation due to its convenient conveyance, high energy density, and low conversion temperature. In this work, an overview of state-of-the-art investigations on methanol reforming is critically summarized, including the detailed introduction of methanol conversion pathways from the perspective of fuel cell applications, various advanced materials design for catalytic methanol conversion, as well as the development of steam methanol reformers. For the section of utilization pathways, reactions such as steam reforming of methanol, partial oxidation of methanol, oxidative steam reforming of methanol, and sorption-enhanced steam methanol reforming were elaborated;For the catalyst section, the strategies to enhance the catalytic activity and other comprehensive performances were summarized;For the reactor section, the newly designed steam methanol reformers were thoroughly described. This review will benefit researchers from both fundamental research and fuel cell applications in the field of catalyzing methanol to hydrogen.展开更多
The effects of ball milling time and Ni content on the dehydrogenation performance of MgH2/Ni composite weresystematically investigated.The structural evolution of ball milled MgH2+x%Ni(x=0,2,4,8,20,30,mass fraction)s...The effects of ball milling time and Ni content on the dehydrogenation performance of MgH2/Ni composite weresystematically investigated.The structural evolution of ball milled MgH2+x%Ni(x=0,2,4,8,20,30,mass fraction)samples duringmechanical milling process and dehydrogenation properties were investigated by a series of experimental techniques.The resultsshow that the desorption kinetics is independent of particle size,grain size and defects as the temperature is above380oC.Thedesorption kinetics is improved by prolonged milling time due to refined and uniformly distributed Ni.The formation of Mg2Ni afterdehydrogenation is proposed to explain the degradation of hydrogen storage properties of MgH2during de-/hydrogenation cyclingprocess.The desorption activation energy of MgH2decreases with the increase of Ni content due to the catalytic effect of Ni.It isfound Ni favors the nucleation of magnesium phase and accelerates the recombination of hydrogen atoms.展开更多
After analysing the disadvantages of the traditional residue hydrotreating-catalytic cracking combination process, RIPP has proposed a bi-directional combination technology integrating residue hydrotreating with catal...After analysing the disadvantages of the traditional residue hydrotreating-catalytic cracking combination process, RIPP has proposed a bi-directional combination technology integrating residue hydrotreating with catalytic cracking called RICP which does not further recycles the FCC heavy cycle oil (HCO) inside the FCC unit and delivers HCO to the residue hydrotreating unit as a diluting oil for the residue that is concurrently subjected to hydrotreating prior to being used as the FCC feed oil. The RICP technology can stimulate residue hydrotreating reactions through utilization of HCO along with an in- creased yield of FCC light distillate, resulting in enhanced petroleum utilization and economic benefits of the refinery.展开更多
Hydrogen production by catalytic steam reforming of the bio-oil, naphtha, and CH4 was investigated over a novel metal-doped catalyst of （Ca24Al28O64）^4＋·4O^-/Mg （C12A7-Mg）. The catalytic steam reforming was ...Hydrogen production by catalytic steam reforming of the bio-oil, naphtha, and CH4 was investigated over a novel metal-doped catalyst of （Ca24Al28O64）^4＋·4O^-/Mg （C12A7-Mg）. The catalytic steam reforming was investigated from 250 to 850℃ in the fixed-bed continuous flow reactor. For the reforming of bio-oil, the yield of hydrogen of 80% was obtained at 750℃, and the maximum carbon conversion is nearly close to 95% under the optimum steam reforming condition. For the reforming of naphtha and CH4, the hydrogen yield and carbon conversion are lower than that of bio-oil at the same temperature. The characteristics of catalyst were also investigated by XPS. The catalyst deactivation was mainly caused by the deposition of carbon in the catalytic steam reforming process.展开更多
To explore the effect of removing different impurities to hydrogen networks, an MINLP model is proposed with all matching possibilities and the trade-off between operation cost and capital cost is considered. Furtherm...To explore the effect of removing different impurities to hydrogen networks, an MINLP model is proposed with all matching possibilities and the trade-off between operation cost and capital cost is considered. Furthermore,the impurity remover, hydrogen distribution, compressor and pipe setting are included in the model. Based on this model, the impurity and source(s) that are in higher priority for impurity removal, the optimal targeted concentration, and the hydrogen network with the minimum annual cost can be identified. The efficiency of the proposed model is verified by a case study.展开更多
Evaluation of hydrocracking catalyst CHC-1 showed superior qualities ofcatalyst CMC-1. When it was used for hydrocracking reaction, the yield of middle distillates (jetfuel and diesel fuel) can reach more than 71 m%. ...Evaluation of hydrocracking catalyst CHC-1 showed superior qualities ofcatalyst CMC-1. When it was used for hydrocracking reaction, the yield of middle distillates (jetfuel and diesel fuel) can reach more than 71 m%. When it was used for medium-pressurehydro-upgrading of Daqing FCC diesel fuel, diesel density was decreased by 0.0284―0.0365 g/cm^3(20℃). Cetane number increased by 7.8―10.5 and the contents of sulphur and nitrogen wereremarkably reduced. The storage stability of the upgraded diesel was improved.展开更多
Highly effective production of hydrogen from bio-oil was achieved by using a low-temperature electrochemical catalytic reforming approach over the conventional Ni-based reforming catalyst （NiO-Al2O3）, where an AC el...Highly effective production of hydrogen from bio-oil was achieved by using a low-temperature electrochemical catalytic reforming approach over the conventional Ni-based reforming catalyst （NiO-Al2O3）, where an AC electronic current passed through the catalyst bed. The promoting effects of current on the bio-oil reforming were studied. It was found that the performance of the bio-oil reforming was remarkably enhanced by the current which passed through the catalyst. The effects of currents on the microcosmic properties of the catalyst, including the Brunauer-Emmett-Teller （BET） surface area, pore diameter, pore volume, the size of the crystallites and the reduction level of NiO into Ni, were carefully characterized by BET, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscope. The desorption of the thermal electrons from the electrified catalyst was directly observed by the TOF （time of flight） measurements. The mechanism of the electrochemical catalytic reforming of bio-oil is discussed based on the above investigation.展开更多
Autothermal steam reforming （ATR） of bio-oil, which couples the endothermic steam reform- ing reaction with the exothermic partial oxidation, offers many advantages from a technical and economic point of view. Effec...Autothermal steam reforming （ATR） of bio-oil, which couples the endothermic steam reform- ing reaction with the exothermic partial oxidation, offers many advantages from a technical and economic point of view. Effective production of hydrogen through ATR of bio-oil was performed at lower temperature with NiCuZnAl catalyst. The highest hydrogen yield from bio-oil reached 64.3% with a nearly complete bio-oil conversion at 600℃, the ratio of steam to carbon fed （S/C） of 3 and the oxygen to carbon ratio （O/C） of 0.34. The reaction conditions in ATR including temperature, O/C, S/C and weight hourly space velocity can be used to control both hydrogen yield and products distribution. The comparison between the ATR and common steam reforming of bio-oil was studied. The mechanism of the ATR of bio-oil was also discussed.展开更多
Using the JQ-II high pressure hydrogenation micro-reactor unit, the reactivity of Athabasca bitumen derived heavy gas oil was studied over commercial and homemade hydrotreating catalysts. The effects of catalyst prepa...Using the JQ-II high pressure hydrogenation micro-reactor unit, the reactivity of Athabasca bitumen derived heavy gas oil was studied over commercial and homemade hydrotreating catalysts. The effects of catalyst preparation variables and the influences of operation conditions, such as pressure, temperature, hydrogen/oil ratio and space velocity were also examined. It was shown that the optimal concentrations of the active components were 5% of NiO, 20% of MoO3 and 3.5% of phosphorus (by mass), and the suitable operation conditions were determined experimentally.展开更多
Autothermal reforming (ATR) is one of the leading methods for hydrogen production from hydrocar- bons. Liquefied petroleum gas, with propane as the main component, is a promising fuel for on-board hydrogen producing s...Autothermal reforming (ATR) is one of the leading methods for hydrogen production from hydrocar- bons. Liquefied petroleum gas, with propane as the main component, is a promising fuel for on-board hydrogen producing systems in fuel cell vehicles and for domestic fuel cell power generation devices. In this article, propane ATR process is studied and operation conditions are optimized with PRO/Ⅱ? from SIMSCI for proton exchange membrane fuel cell application. In the ATR system including water gas shift and preferential oxidation, heat in the hot streams and cold streams is controlled to be in balance. Different operation conditions are studied and drawn in contour plots. The region for ATR reforming with the highest efficiency can thus be identified. One operation point was chosen with the following process parameters: feed temperature for the ATR reactor is 425℃, steam to carbon ratio S/C is 2.08, air stoichiometry is 0.256. Thermal efficiency for the integrated system is calculated to be as high as 84.0 % with 38.27 % H2 and 3.2μl·L-1 CO in the product gas.展开更多
The interplay between analytical technique and industrial practice has been central in the development of catalytic materials for processing petroleum. This article presents reviews of key aspects of two of the most i...The interplay between analytical technique and industrial practice has been central in the development of catalytic materials for processing petroleum. This article presents reviews of key aspects of two of the most important classes of catalytic materials: noble-metal Pt nanoparticles (NPs) on alumina, which are the basis of catalytic reforming;and layered sulfides of Mo and W, which catalyze hydrogenation and hetero-atom removal in hydroprocessing. The state of understanding of Pt cluster growth and resulting structures, as developed using X-ray absorption spectroscopy and STEM, is reviewed. Influences of both Pt reduction temperature in hydrogen gas, and oxidizing pretreatment conditions prior to Pt reduction, are considered. Recent work by the present authors on Pt NP structure evolution is presented in the context of the previous work. A review is subsequently presented of layered sulfide based NPs, summarizing contributions from a range of analytical techniques. Work on active site structures of sulfide NPs is reviewed, focusing particularly on the critical interactions of active edge sites with sulfur and hydrogen in chemisorption, physisorption, and spillover interactions. New temperature programmed reduction (TPR) results are presented for supported and unsupported sulfide NPs. Structural changes in TPR of alumina-supported MoS2 are investigated using extended X-ray absorption fine structure and density functional theory modeling, and are determined to arise from removal of identifiable edge-site sulfur species.展开更多
基金ACKNOWLEDGMENTS This work is supported by the National High Tech Research and Development Program （No.2009AA05Z435）, the National Basic Research Program of Ministry of Science and Technology of China （No.2007CB210206）, and the General Program of the National Natural Science Foundation of China （No.50772107）.
文摘We investigated high catalytic activity of Ni/HZSM-5 catalysts synthesized by the impregnation method, which was successfully applied for low-temperature steam reforming of bio-oil. The influences of the catalyst composition, reforming temperature and the molar ratio of steam to carbon fed on the stream reforming process of bio-oil over the Ni/HZSM-5 catalysts were investigated in the reforming reactor. The promoting effects of current passing through the catalyst on the bio-oil reforming were also studied using the electrochemical catalytic reforming approach. By comparing Ni/HZSM-5 with commonly used Ni/Al2O3 catalysts, the Ni2O/ZSM catalyst with Ni-loading content of about 20% on the HZSM-5 support showed the highest catalytic activity. Even at 450 ℃, the hydrogen yield of about 90% with a near complete conversion of bio-oil was obtained using the Ni2O/ZSM catalyst. It was found that the performance of the bio-oil reforming was remarkably enhanced by the HZSM-5 supporter and the current through the catalyst. The features of the Ni/HZSM-5 catalysts were also investigated via X-ray diffraction, inductively coupled plasma and atomic emission spectroscopy, hydrogen temperature-programmed reduction, and Brunauer-Emmett-Teller methods.
文摘The continual growth in transportation fuels and more strict environmental legislations have led to immense interest in developing green biomass energy. In this work, a proposed catalytic transformation of oxygenated organic compounds （related to bio-oil） into pure hydrogen was desighed, involving the catalytic reforming of oxygenated organic compounds to hydrogen- rich mixture gas followed by the conversion of CO to CO2 via the water gas reaction and the removal of CO2. The optimization of the different reforming catalyst, the reaction conditions as well as various sources of oxygenated organic compounds were investigated in detail. The production of pure hydrogen, with the H2 content up to 99.96% and the conversion of 97.1%, was achieved by the integrated catalytic transformation. The reaction pathways were addressed based on the investigation of decomposition, catalytic reforming, and the water gas reaction.
基金Project(51876224)supported by the National Natural Science Foundation of ChinaProject(2020CX008)supported by the Innovation-Driven Project of Central South University,China。
文摘Methanol is regarded as an important liquid fuel for hydrogen storage, transportation, and in-situ generation due to its convenient conveyance, high energy density, and low conversion temperature. In this work, an overview of state-of-the-art investigations on methanol reforming is critically summarized, including the detailed introduction of methanol conversion pathways from the perspective of fuel cell applications, various advanced materials design for catalytic methanol conversion, as well as the development of steam methanol reformers. For the section of utilization pathways, reactions such as steam reforming of methanol, partial oxidation of methanol, oxidative steam reforming of methanol, and sorption-enhanced steam methanol reforming were elaborated;For the catalyst section, the strategies to enhance the catalytic activity and other comprehensive performances were summarized;For the reactor section, the newly designed steam methanol reformers were thoroughly described. This review will benefit researchers from both fundamental research and fuel cell applications in the field of catalyzing methanol to hydrogen.
基金Project(95-QZ-2014) supported by the Research Fund of the State Key Laboratory of Solidification Processing(NWPU),ChinaProject supported by the Defense Industrial Technology Development Program,ChinaProject(B08040) supported by the 111 Program,China
文摘The effects of ball milling time and Ni content on the dehydrogenation performance of MgH2/Ni composite weresystematically investigated.The structural evolution of ball milled MgH2+x%Ni(x=0,2,4,8,20,30,mass fraction)samples duringmechanical milling process and dehydrogenation properties were investigated by a series of experimental techniques.The resultsshow that the desorption kinetics is independent of particle size,grain size and defects as the temperature is above380oC.Thedesorption kinetics is improved by prolonged milling time due to refined and uniformly distributed Ni.The formation of Mg2Ni afterdehydrogenation is proposed to explain the degradation of hydrogen storage properties of MgH2during de-/hydrogenation cyclingprocess.The desorption activation energy of MgH2decreases with the increase of Ni content due to the catalytic effect of Ni.It isfound Ni favors the nucleation of magnesium phase and accelerates the recombination of hydrogen atoms.
文摘After analysing the disadvantages of the traditional residue hydrotreating-catalytic cracking combination process, RIPP has proposed a bi-directional combination technology integrating residue hydrotreating with catalytic cracking called RICP which does not further recycles the FCC heavy cycle oil (HCO) inside the FCC unit and delivers HCO to the residue hydrotreating unit as a diluting oil for the residue that is concurrently subjected to hydrotreating prior to being used as the FCC feed oil. The RICP technology can stimulate residue hydrotreating reactions through utilization of HCO along with an in- creased yield of FCC light distillate, resulting in enhanced petroleum utilization and economic benefits of the refinery.
文摘Hydrogen production by catalytic steam reforming of the bio-oil, naphtha, and CH4 was investigated over a novel metal-doped catalyst of （Ca24Al28O64）^4＋·4O^-/Mg （C12A7-Mg）. The catalytic steam reforming was investigated from 250 to 850℃ in the fixed-bed continuous flow reactor. For the reforming of bio-oil, the yield of hydrogen of 80% was obtained at 750℃, and the maximum carbon conversion is nearly close to 95% under the optimum steam reforming condition. For the reforming of naphtha and CH4, the hydrogen yield and carbon conversion are lower than that of bio-oil at the same temperature. The characteristics of catalyst were also investigated by XPS. The catalyst deactivation was mainly caused by the deposition of carbon in the catalytic steam reforming process.
基金Supported by the National Natural Science Foundation of China(21276205)
文摘To explore the effect of removing different impurities to hydrogen networks, an MINLP model is proposed with all matching possibilities and the trade-off between operation cost and capital cost is considered. Furthermore,the impurity remover, hydrogen distribution, compressor and pipe setting are included in the model. Based on this model, the impurity and source(s) that are in higher priority for impurity removal, the optimal targeted concentration, and the hydrogen network with the minimum annual cost can be identified. The efficiency of the proposed model is verified by a case study.
文摘Evaluation of hydrocracking catalyst CHC-1 showed superior qualities ofcatalyst CMC-1. When it was used for hydrocracking reaction, the yield of middle distillates (jetfuel and diesel fuel) can reach more than 71 m%. When it was used for medium-pressurehydro-upgrading of Daqing FCC diesel fuel, diesel density was decreased by 0.0284―0.0365 g/cm^3(20℃). Cetane number increased by 7.8―10.5 and the contents of sulphur and nitrogen wereremarkably reduced. The storage stability of the upgraded diesel was improved.
基金ACKNOWLEDGMENTS This work was supported by the National Basic Research Program of China （No.2007CB210206）, the National High Tech Research and Development Program （No.2006AA05Z118）, the General Program of the National Natural Science Foundation of China （No.50772107）, and the Green Agriculture Scientific Research Demonstration Program （No.2007-15）.
文摘Highly effective production of hydrogen from bio-oil was achieved by using a low-temperature electrochemical catalytic reforming approach over the conventional Ni-based reforming catalyst （NiO-Al2O3）, where an AC electronic current passed through the catalyst bed. The promoting effects of current on the bio-oil reforming were studied. It was found that the performance of the bio-oil reforming was remarkably enhanced by the current which passed through the catalyst. The effects of currents on the microcosmic properties of the catalyst, including the Brunauer-Emmett-Teller （BET） surface area, pore diameter, pore volume, the size of the crystallites and the reduction level of NiO into Ni, were carefully characterized by BET, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscope. The desorption of the thermal electrons from the electrified catalyst was directly observed by the TOF （time of flight） measurements. The mechanism of the electrochemical catalytic reforming of bio-oil is discussed based on the above investigation.
文摘We discovered a new approach modification Bamberger, Barton, Beckmann, Wallach, Gabriel, Hofmann, Hofmann A.W. Martius, Dimroth, Semmler-Wolff-Schroeter, Sus, Claisen, Newman-Kwart, Orlon, Pistschimuka, Robev, Smiles, Sawdey, Sommelet, Stevens, Tiemann, Fischer-Hepp, Chapman, Chattaway, Schonberg, Stieglitz Rearrangements with of phosphorous, arsine, stibine and bismuthine in organometallic chemistry. The authors have proposed a new mechanism for possible reactions.
文摘Autothermal steam reforming （ATR） of bio-oil, which couples the endothermic steam reform- ing reaction with the exothermic partial oxidation, offers many advantages from a technical and economic point of view. Effective production of hydrogen through ATR of bio-oil was performed at lower temperature with NiCuZnAl catalyst. The highest hydrogen yield from bio-oil reached 64.3% with a nearly complete bio-oil conversion at 600℃, the ratio of steam to carbon fed （S/C） of 3 and the oxygen to carbon ratio （O/C） of 0.34. The reaction conditions in ATR including temperature, O/C, S/C and weight hourly space velocity can be used to control both hydrogen yield and products distribution. The comparison between the ATR and common steam reforming of bio-oil was studied. The mechanism of the ATR of bio-oil was also discussed.
文摘Using the JQ-II high pressure hydrogenation micro-reactor unit, the reactivity of Athabasca bitumen derived heavy gas oil was studied over commercial and homemade hydrotreating catalysts. The effects of catalyst preparation variables and the influences of operation conditions, such as pressure, temperature, hydrogen/oil ratio and space velocity were also examined. It was shown that the optimal concentrations of the active components were 5% of NiO, 20% of MoO3 and 3.5% of phosphorus (by mass), and the suitable operation conditions were determined experimentally.
基金Supported by the National 973 Program of China on Hydrogen Energy (TG2000026410) and International Cooperation Projecton Hydrogen Energy (2001AA515080).
文摘Autothermal reforming (ATR) is one of the leading methods for hydrogen production from hydrocar- bons. Liquefied petroleum gas, with propane as the main component, is a promising fuel for on-board hydrogen producing systems in fuel cell vehicles and for domestic fuel cell power generation devices. In this article, propane ATR process is studied and operation conditions are optimized with PRO/Ⅱ? from SIMSCI for proton exchange membrane fuel cell application. In the ATR system including water gas shift and preferential oxidation, heat in the hot streams and cold streams is controlled to be in balance. Different operation conditions are studied and drawn in contour plots. The region for ATR reforming with the highest efficiency can thus be identified. One operation point was chosen with the following process parameters: feed temperature for the ATR reactor is 425℃, steam to carbon ratio S/C is 2.08, air stoichiometry is 0.256. Thermal efficiency for the integrated system is calculated to be as high as 84.0 % with 38.27 % H2 and 3.2μl·L-1 CO in the product gas.
基金the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357
文摘The interplay between analytical technique and industrial practice has been central in the development of catalytic materials for processing petroleum. This article presents reviews of key aspects of two of the most important classes of catalytic materials: noble-metal Pt nanoparticles (NPs) on alumina, which are the basis of catalytic reforming;and layered sulfides of Mo and W, which catalyze hydrogenation and hetero-atom removal in hydroprocessing. The state of understanding of Pt cluster growth and resulting structures, as developed using X-ray absorption spectroscopy and STEM, is reviewed. Influences of both Pt reduction temperature in hydrogen gas, and oxidizing pretreatment conditions prior to Pt reduction, are considered. Recent work by the present authors on Pt NP structure evolution is presented in the context of the previous work. A review is subsequently presented of layered sulfide based NPs, summarizing contributions from a range of analytical techniques. Work on active site structures of sulfide NPs is reviewed, focusing particularly on the critical interactions of active edge sites with sulfur and hydrogen in chemisorption, physisorption, and spillover interactions. New temperature programmed reduction (TPR) results are presented for supported and unsupported sulfide NPs. Structural changes in TPR of alumina-supported MoS2 are investigated using extended X-ray absorption fine structure and density functional theory modeling, and are determined to arise from removal of identifiable edge-site sulfur species.
