Catalytic co-cracking of Fischer–Tropsch(FT) light distillate and methanol combines highly endothermic olefin cracking reaction with exothermic methanol conversion over ZSM-5 catalyst to produce light olefins through...Catalytic co-cracking of Fischer–Tropsch(FT) light distillate and methanol combines highly endothermic olefin cracking reaction with exothermic methanol conversion over ZSM-5 catalyst to produce light olefins through a nearly thermoneutral process. The kinetic behavior of co-cracking reactions was investigated by different feed conditions: methanol feed only, olefin feed only and co-feed of methanol with olefins or F–T distillate. The results showed that methanol converted to C2–C6 olefins in first-order parallel reaction at low space time, methylation and oligomerization–cracking prevailed for the co-feed of methanol and C2–C5 olefins, while for C6–C8 olefins,monomolecular cracking was the dominant reaction whether fed alone or co-fed with methanol. For FT distillate and methanol co-feed, alkanes were almost un-reactive, C3–C5 olefins were obtained as main products, accounting for 71 wt% for all products. A comprehensive co-cracking reaction scheme was proposed and the model parameters were estimated by the nonlinear least square method. It was verified by experimental data that the kinetic model was reliable to predict major product distribution for co-cracking of FT distillate with methanol and could be used for further reactor development and process design.展开更多
Synergy between the intrinsic photon and thermal effects from full-spectrum sunlight for H_(2) production is considered to be central to further improve solar-driven H_(2) production.To that end,the photo-thermocataly...Synergy between the intrinsic photon and thermal effects from full-spectrum sunlight for H_(2) production is considered to be central to further improve solar-driven H_(2) production.To that end,the photo-thermocatalyst that demonstrates both photoelectronic and photothermal conversion capabilities have drawn much attention recently.Here,we propose a novel synergistic full-spectrum photo-thermo-catalysis technique for high-efficient H_(2) production by solar-driven methanol steam reforming(MSR),along with the Pt-Cu Oxphoto-thermo-catalyst featuring Pt-Cu/Cu_(2)O/CuO heterojunctions by Pt-mediated in-situ photoreduction of Cu O.The results show that the H_(2) production performance rises superlinearly with increasing light intensity.The optimal H_(2) production rate of 1.6 mol g^(-1) h^(-1) with the corresponding solar-to-hydrogen conversion efficiency of 7%and the CO selectivity of 5%is achieved under 15×sun full-spectrum irradiance(1×sun=1 k W m^(-2))at 180°C,which is much more efficient than the previously-reported Cu-based thermo-catalysts for MSR normally operating at 250~350°C.These attractive performances result from the optimized reaction kinetics in terms of intensified intermediate adsorption and accelerated carrier transfer by long-wave photothermal effect,and reduced activation barrier by short-wave photoelectronic effect,due to the broadened full-spectrum absorbability of catalyst.This work has brought us into the innovative technology of full-spectrum synergistic photothermo-catalysis,which is envisioned to expand the application fields of high-efficient solar fuel production.展开更多
Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode...Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant ki = exp(ai(e ? ei)). The analysis to the established model discloses the following: there are different kinetics be- haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidation, which is the in- duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in- volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab- lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.展开更多
文摘Catalytic co-cracking of Fischer–Tropsch(FT) light distillate and methanol combines highly endothermic olefin cracking reaction with exothermic methanol conversion over ZSM-5 catalyst to produce light olefins through a nearly thermoneutral process. The kinetic behavior of co-cracking reactions was investigated by different feed conditions: methanol feed only, olefin feed only and co-feed of methanol with olefins or F–T distillate. The results showed that methanol converted to C2–C6 olefins in first-order parallel reaction at low space time, methylation and oligomerization–cracking prevailed for the co-feed of methanol and C2–C5 olefins, while for C6–C8 olefins,monomolecular cracking was the dominant reaction whether fed alone or co-fed with methanol. For FT distillate and methanol co-feed, alkanes were almost un-reactive, C3–C5 olefins were obtained as main products, accounting for 71 wt% for all products. A comprehensive co-cracking reaction scheme was proposed and the model parameters were estimated by the nonlinear least square method. It was verified by experimental data that the kinetic model was reliable to predict major product distribution for co-cracking of FT distillate with methanol and could be used for further reactor development and process design.
基金financially supported by the National Natural Science Foundation of China(52176202)the Foshan Xianhu-Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(41200101)。
文摘Synergy between the intrinsic photon and thermal effects from full-spectrum sunlight for H_(2) production is considered to be central to further improve solar-driven H_(2) production.To that end,the photo-thermocatalyst that demonstrates both photoelectronic and photothermal conversion capabilities have drawn much attention recently.Here,we propose a novel synergistic full-spectrum photo-thermo-catalysis technique for high-efficient H_(2) production by solar-driven methanol steam reforming(MSR),along with the Pt-Cu Oxphoto-thermo-catalyst featuring Pt-Cu/Cu_(2)O/CuO heterojunctions by Pt-mediated in-situ photoreduction of Cu O.The results show that the H_(2) production performance rises superlinearly with increasing light intensity.The optimal H_(2) production rate of 1.6 mol g^(-1) h^(-1) with the corresponding solar-to-hydrogen conversion efficiency of 7%and the CO selectivity of 5%is achieved under 15×sun full-spectrum irradiance(1×sun=1 k W m^(-2))at 180°C,which is much more efficient than the previously-reported Cu-based thermo-catalysts for MSR normally operating at 250~350°C.These attractive performances result from the optimized reaction kinetics in terms of intensified intermediate adsorption and accelerated carrier transfer by long-wave photothermal effect,and reduced activation barrier by short-wave photoelectronic effect,due to the broadened full-spectrum absorbability of catalyst.This work has brought us into the innovative technology of full-spectrum synergistic photothermo-catalysis,which is envisioned to expand the application fields of high-efficient solar fuel production.
基金Supported by the National Natural Science Foundation of China (Grant No. 20676156)the Chinese Ministry of Education (Grant No. 307021)+1 种基金China National 863 Program (Grant Nos. 2006AA11A141 and 2007AA05Z124)Chongqing Sci&Tech Key Project (Grant No. CSTC2007AB6012)
文摘Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant ki = exp(ai(e ? ei)). The analysis to the established model discloses the following: there are different kinetics be- haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidation, which is the in- duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in- volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab- lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.
