Nowadays,combined steam and dry reforming of methane(CSDRM)is viewed as a new alternative for the production of high-quality syngas(termed as"metgas",H2:CO of 2.0)suitable for subsequent synthesis of methano...Nowadays,combined steam and dry reforming of methane(CSDRM)is viewed as a new alternative for the production of high-quality syngas(termed as"metgas",H2:CO of 2.0)suitable for subsequent synthesis of methanol,considered as a promising renewable energy vector to substitute fossil fuel resources.Adequate operation conditions(molar feed composition,temperature and pressure)are required for the sole production of"metgas"while achieving high CH4,CO2 and H2O conversion levels.In this work,thermodynamic equilibrium analysis of CSDRM has been performed using Gibbs free energy minimization where;(i)the effect of temperature(range:200-1000℃),(ii)feed composition(stoichiometric ratio as compared to a feed under excess steam or excess carbon dioxide),(iii)pressure(range:1-20 bar)and,(iv)the presence of a gaseous diluent on coke yields,reactivity levels and selectivity towards"metgas"were investigated.Running CSDRM at a temperature of at least 800℃,a pressure of 1 bar and under a feed composition where CO2-H2O/CH4 is around 1.0,are optimum conditions for the theoretical production of"metgas"while minimizing C(S)formation for longer experimental catalytic runs.A second part of this work presents a review of the recent progresses in the design of(principally)Ni-based catalysts along with some mechanistic and kinetic modeling aspects for the targeted CSDRM reaction.As compared to noble metals,their high availability,low cost and good intrinsic activity levels are main reasons for increasing research dedications in understanding deactivation potentials and providing amelioration strategies for further development.Deactivation causes and main orientations towards designing deactivationresistant supported Ni nanoparticles are clearly addressed and analyzed.Reported procedures based on salient catalytic features(i.e.,acidity/basicity character,redox properties,oxygen mobility,metal-support interaction)and recently employed innovative tactics(such as confinement within mesoporous systems,stabilization through core shell structures or on carbide surfaces)are highlighted and their impact on Ni0reactivity and stability are discussed.The final aspect of this review encloses the major directions and trends for improving synthesis/preparation designs of Ni-based catalysts for the sake of upgrading their usage into industrially oriented combined reforming operations.展开更多
Cu-based catalysts with excellent activity at low temperatures are widely used for methanol steam reforming(MSR)but suffer from deactivation problems.The present work aims to elucidate the deactivation and regeneratio...Cu-based catalysts with excellent activity at low temperatures are widely used for methanol steam reforming(MSR)but suffer from deactivation problems.The present work aims to elucidate the deactivation and regeneration mechanisms of the commercial Cu/ZnO/Al_(2)O_(3) catalyst in low temperature MSR.By employing a series of(quasi)in situ characterization methods,it is found that the deactivation of the catalyst at a high weight hourly space velocity(WHSV)and a low reaction temperature is mainly due to the poisoning of Cu species associated with surface-oxygenated species with less Cu sintering,rather than carbon deposition,and strong metal-support interaction(SMSI).An in situ regeneration method was developed for the deactivated commercial Cu/ZnO/Al_(2)O_(3) catalyst via the simultaneous supply of O_(2).It is shown that the addition of O_(2)(≥1 vol%)can reverse the deactivation caused by surface-oxygenated poisoning due to the weak interaction between formed surface copper oxide and surface-oxygenated species,facilitating their desorption,but not deactivation caused by sintering,thereby partially restoring the catalytic activity.展开更多
The deactivation of nickel catalysts used in Arak and Razi petrochemical complexes followed by catalyst regeneration was evalu-ated. The characterization of the different structures was made by powder X-ray diffractio...The deactivation of nickel catalysts used in Arak and Razi petrochemical complexes followed by catalyst regeneration was evalu-ated. The characterization of the different structures was made by powder X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),transmission electron microscopy(TEM),and carbon & sulfur analyzer. The Ni particle size was estimated from XRD patterns and TEM graphs. The agglomeration of nickel particle and the poison by sulfur components were recognized as the main reasons in deactivation of Arak and Razi catalysts,respectively. The activity of the used catalysts before and after regeneration was measured on methane steam reforming at a CH4:H2O ratio of 1:3 at 850 oC. The regeneration processes for Arak and Razi samples were performed with CO2 as an oxidative atmosphere and steam as a regenerating agent,respectively. The results show that,(1) no residual sulfur components were on the regenerated Razi catalyst surface without changing the structure of the catalyst and the regenerated catalyst has gained 80% of its catalytic activity,and that(2) the nickel particle size of regenerated Arak specimen decreased remarkably as measured by Debye-Scherrer equation from XRD patterns. TEM images were in agreement with the XRD results and indicated a decrease in nickel particle size of regenerated catalyst. Additionally,in both regenerated catalysts all the coke on the surface of the support was eliminated after regeneration.展开更多
基金financial support through the SOL-CARE(Energy-065,2016–2019)project(JC-ENERGY-2014 first call)。
文摘Nowadays,combined steam and dry reforming of methane(CSDRM)is viewed as a new alternative for the production of high-quality syngas(termed as"metgas",H2:CO of 2.0)suitable for subsequent synthesis of methanol,considered as a promising renewable energy vector to substitute fossil fuel resources.Adequate operation conditions(molar feed composition,temperature and pressure)are required for the sole production of"metgas"while achieving high CH4,CO2 and H2O conversion levels.In this work,thermodynamic equilibrium analysis of CSDRM has been performed using Gibbs free energy minimization where;(i)the effect of temperature(range:200-1000℃),(ii)feed composition(stoichiometric ratio as compared to a feed under excess steam or excess carbon dioxide),(iii)pressure(range:1-20 bar)and,(iv)the presence of a gaseous diluent on coke yields,reactivity levels and selectivity towards"metgas"were investigated.Running CSDRM at a temperature of at least 800℃,a pressure of 1 bar and under a feed composition where CO2-H2O/CH4 is around 1.0,are optimum conditions for the theoretical production of"metgas"while minimizing C(S)formation for longer experimental catalytic runs.A second part of this work presents a review of the recent progresses in the design of(principally)Ni-based catalysts along with some mechanistic and kinetic modeling aspects for the targeted CSDRM reaction.As compared to noble metals,their high availability,low cost and good intrinsic activity levels are main reasons for increasing research dedications in understanding deactivation potentials and providing amelioration strategies for further development.Deactivation causes and main orientations towards designing deactivationresistant supported Ni nanoparticles are clearly addressed and analyzed.Reported procedures based on salient catalytic features(i.e.,acidity/basicity character,redox properties,oxygen mobility,metal-support interaction)and recently employed innovative tactics(such as confinement within mesoporous systems,stabilization through core shell structures or on carbide surfaces)are highlighted and their impact on Ni0reactivity and stability are discussed.The final aspect of this review encloses the major directions and trends for improving synthesis/preparation designs of Ni-based catalysts for the sake of upgrading their usage into industrially oriented combined reforming operations.
基金sponsored by the National Natural Science Foundation of China (22078089)the Program for Professor of Special Appointment (Eastern Scholar)at Shanghai Institutions of Higher LearningShanghai Sailing Program (19YF1410600)。
文摘Cu-based catalysts with excellent activity at low temperatures are widely used for methanol steam reforming(MSR)but suffer from deactivation problems.The present work aims to elucidate the deactivation and regeneration mechanisms of the commercial Cu/ZnO/Al_(2)O_(3) catalyst in low temperature MSR.By employing a series of(quasi)in situ characterization methods,it is found that the deactivation of the catalyst at a high weight hourly space velocity(WHSV)and a low reaction temperature is mainly due to the poisoning of Cu species associated with surface-oxygenated species with less Cu sintering,rather than carbon deposition,and strong metal-support interaction(SMSI).An in situ regeneration method was developed for the deactivated commercial Cu/ZnO/Al_(2)O_(3) catalyst via the simultaneous supply of O_(2).It is shown that the addition of O_(2)(≥1 vol%)can reverse the deactivation caused by surface-oxygenated poisoning due to the weak interaction between formed surface copper oxide and surface-oxygenated species,facilitating their desorption,but not deactivation caused by sintering,thereby partially restoring the catalytic activity.
文摘The deactivation of nickel catalysts used in Arak and Razi petrochemical complexes followed by catalyst regeneration was evalu-ated. The characterization of the different structures was made by powder X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),transmission electron microscopy(TEM),and carbon & sulfur analyzer. The Ni particle size was estimated from XRD patterns and TEM graphs. The agglomeration of nickel particle and the poison by sulfur components were recognized as the main reasons in deactivation of Arak and Razi catalysts,respectively. The activity of the used catalysts before and after regeneration was measured on methane steam reforming at a CH4:H2O ratio of 1:3 at 850 oC. The regeneration processes for Arak and Razi samples were performed with CO2 as an oxidative atmosphere and steam as a regenerating agent,respectively. The results show that,(1) no residual sulfur components were on the regenerated Razi catalyst surface without changing the structure of the catalyst and the regenerated catalyst has gained 80% of its catalytic activity,and that(2) the nickel particle size of regenerated Arak specimen decreased remarkably as measured by Debye-Scherrer equation from XRD patterns. TEM images were in agreement with the XRD results and indicated a decrease in nickel particle size of regenerated catalyst. Additionally,in both regenerated catalysts all the coke on the surface of the support was eliminated after regeneration.
