Thermal stability has long been recognized as a major limitation for the application of ligand modification in high-temperature reactions. Herein, we demonstrate polymeric phosphate as an efficient and stable ligand t...Thermal stability has long been recognized as a major limitation for the application of ligand modification in high-temperature reactions. Herein, we demonstrate polymeric phosphate as an efficient and stable ligand to tune the selectivity of propane oxidative dehydrogenation. Beneficial from the weakened affinity of propene, NiO modified with polymeric phosphate shows a selectivity 2–3 times higher than NiO towards the production of propene. The success of this regulation verifies the feasibility of ligand modification in high-temperature gas-phase reactions and shines a light on its applications in other important industrial reactions.展开更多
Oxidative dehydrogenation of propane is an attractive route for the synthesis of propylene due to its favorable thermodynamic and kinetic characteristics, however, it is challenging to realize high selectivity towards...Oxidative dehydrogenation of propane is an attractive route for the synthesis of propylene due to its favorable thermodynamic and kinetic characteristics, however, it is challenging to realize high selectivity towards propylene. Recently, it has been discovered that boron nitride (BN) is a promising catalyst that affords superior selectivity towards propylene in oxidative dehydrogenation of propane. Summarizing the progress and unravelling the reaction mechanism of BN in oxidative dehydrogenation of propane are of great significance for the rational design of efficient catalysts in the future. Herein, in this review, the underlying reaction mechanisms of oxidative dehydrogenation of propane over BN are extracted;the developed BN catalysts are classified into pristine BN, functionalized BN, supported BN and others, and the applications of each category of BN catalysts in oxidative dehydrogenation of propane are summarized;the challenges and opportunities on oxidative dehydrogenation of propane over BN are pointed out, aiming to inspire more studies and advance this research field.展开更多
In this work, a series of Ni-Mo-Mg-O catalysts with mesoporous structure prepared by sol-gel method were investigated for the oxidative dehydrogenation of propane （ODHP）. The techniques of temperature-programmed red...In this work, a series of Ni-Mo-Mg-O catalysts with mesoporous structure prepared by sol-gel method were investigated for the oxidative dehydrogenation of propane （ODHP）. The techniques of temperature-programmed reduction with H2 （H2-TPR）, N2 adsorption-desolption, Fourier transform infrared spectroscopy （FT-IR）, X-ray diffraction （XRD） and X-ray photoelectron spectra （XPS） were employed for catalyst characterization. It is found that the activity of the catalysts for ODHP increases first and then decreases with the increase of Mo content. The catalyst with a Mo/Ni atomic ratio of 1/1 exhibits the best catalytic activity, which gives the propene selectivity of 81.4% at a propane conversion of 11.3% under 600 ~C and maintains the good catalytic performance for 22 h on stream. This is related not only to its high reducibility and dispersion as revealed by TPR and XRD, but also to the formation of more selective oxygen species on the MoOz-NiO interface as identified by XPS.展开更多
An industrial scale propylene production via oxidative dehydrogenation of propane （ODHP） in multi-tubular re- actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of small diame...An industrial scale propylene production via oxidative dehydrogenation of propane （ODHP） in multi-tubular re- actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of small diameter tubes immersed in a shell through a proper coolant flows. Herein, a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence olefln over V2O5/γ-Al203 catalyst was presented. Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions, gas process and coolant temperatures, as well as other pa- rameters affecting the reactor performance such as pressure. Furthermore, the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%. The optimized length of the reactor needed to reach 100% conversion of the oxygen was theoretically determined. For the single-bed reactor the optimized length of 11.96 m including 0.5 m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72 m for the first and 7.32 m for the second reactor were calculated. Ultimately, the use of a distributed oxygen feed with limited number of injection points indicated a significant improvement on the reactor performance in terms of propane conversion and propylene selectivity. Besides, this concept could overcome the reactor run- away temperature problem and enabled operations at the wider range of conditions to obtain enhanced propyl- ene production in an industrial scale reactor.展开更多
Oxidative dehydrogenation of propane over V-Mg-O and MCl_n(M=Cu^+,Li^+, Ag^+,Cd^(2+))promoted V-Mg-O catalysts was studied.XRD result showed that the V-Mg-O catalysts were composed of MgO and Mg_3(VO_4)_2.The yield of...Oxidative dehydrogenation of propane over V-Mg-O and MCl_n(M=Cu^+,Li^+, Ag^+,Cd^(2+))promoted V-Mg-O catalysts was studied.XRD result showed that the V-Mg-O catalysts were composed of MgO and Mg_3(VO_4)_2.The yield of propene was much higher over CuCl and LiCl promoted VMgO catalysts than that over VMgO catalysts at the same reaction temperature.The highest yield of propene reached 23.1% at 500℃ and 6000h^(-1) space velocity.展开更多
A series ofnanosized cobalt oxide catalysts modified with phosphorus have been synthesized by the solgel method and investigated in the oxidative dehydrogenation of propane to propene. With the addition of phosphorus,...A series ofnanosized cobalt oxide catalysts modified with phosphorus have been synthesized by the solgel method and investigated in the oxidative dehydrogenation of propane to propene. With the addition of phosphorus, the crystallite size of the catalyst was largely decreased, while the P species in the catalyst were highly dispersed. Compared to pure cobalt oxide, the P-modified samples showed higher propane conversion and enhanced propene selectivity. Over the PCoO catalyst with a P/Co atomic ratio of 0.05, the maximal propene yields of 15.7% with a propane conversion of 28.3% were obtained at 520 ℃.展开更多
ZnO could be a suitable catalyst for the oxidative conversion of CH4,C2H6 and C3H8.However,the main drawback is its thermal instability.Therefore,ZnO supported on ZrO 2,TiO2,γ-Al2O and SiO2 was investigated for the o...ZnO could be a suitable catalyst for the oxidative conversion of CH4,C2H6 and C3H8.However,the main drawback is its thermal instability.Therefore,ZnO supported on ZrO 2,TiO2,γ-Al2O and SiO2 was investigated for the oxidative dehydrogenation of propane and ethane,and the oxidative coupling of methane.The stability of the supported ZnO is partially improved,but ZnO reacts with the support material,forming new compounds （Zn-zirconates,-titanates,-aluminates and-silicates）,which already occurs below reaction temperature.This might also be the case for many other heterogeneous catalysts.展开更多
PtSnNa/γ-Al2O3 catalyst is widely used in the dehydrogenation of light alkane. This paper reports a new fabrication method of the catalyst. In the work, γ-Al2O3, SnCl4 and NaCl were ball milled to upload Sn and Na＋...PtSnNa/γ-Al2O3 catalyst is widely used in the dehydrogenation of light alkane. This paper reports a new fabrication method of the catalyst. In the work, γ-Al2O3, SnCl4 and NaCl were ball milled to upload Sn and Na＋ onto the support instead of the conventionally used immersion method. The subsequent baking procedures frimly fixed Sn onto the support, which could disperse Pt introduced by immersion. The effects of Sn and Na＋ additives on the catalytic performance of PtSnNa/y-Al2O3 catalyst were investigated. It was found that the appropriate molar ratio of Sn/Pt was 6：1 while the favorable weight percentage of Na＋ was 0.90%. Compared with the reaction catalyzed by the industrially employed PtSnNa/ γ-Al2O3 catalyst, the conversion of propane and the selectivity of propylene had been greatly improved, which were 26.97%; and 99.18% respectivelv after 12 h reaction.展开更多
基金was supported by the National Natural Science Foundation of China(91545113,21703050)the China Postdoctoral Science Foundation(2017M610363,2018T110584)+2 种基金Shell Global Solutions International B.V.(PT71423,PT74557)the Fok Ying Tong Education Foundation(131015)the Science&Technology Program of Ningbo(2017C50014)~~
文摘Thermal stability has long been recognized as a major limitation for the application of ligand modification in high-temperature reactions. Herein, we demonstrate polymeric phosphate as an efficient and stable ligand to tune the selectivity of propane oxidative dehydrogenation. Beneficial from the weakened affinity of propene, NiO modified with polymeric phosphate shows a selectivity 2–3 times higher than NiO towards the production of propene. The success of this regulation verifies the feasibility of ligand modification in high-temperature gas-phase reactions and shines a light on its applications in other important industrial reactions.
基金This work received financial support from the National Natural Science Foundation of China(21902116)Scientific Research Foundation of Technology Department of Liaoning province of China(2022-MS-379)Liaoning Revitalization Talents Program(XLYC1902070).
文摘Oxidative dehydrogenation of propane is an attractive route for the synthesis of propylene due to its favorable thermodynamic and kinetic characteristics, however, it is challenging to realize high selectivity towards propylene. Recently, it has been discovered that boron nitride (BN) is a promising catalyst that affords superior selectivity towards propylene in oxidative dehydrogenation of propane. Summarizing the progress and unravelling the reaction mechanism of BN in oxidative dehydrogenation of propane are of great significance for the rational design of efficient catalysts in the future. Herein, in this review, the underlying reaction mechanisms of oxidative dehydrogenation of propane over BN are extracted;the developed BN catalysts are classified into pristine BN, functionalized BN, supported BN and others, and the applications of each category of BN catalysts in oxidative dehydrogenation of propane are summarized;the challenges and opportunities on oxidative dehydrogenation of propane over BN are pointed out, aiming to inspire more studies and advance this research field.
基金supported by the National Natural Science Foundation of China (20776089)the New Century Excellent Talent Project of China(NCET-05-0783)
文摘In this work, a series of Ni-Mo-Mg-O catalysts with mesoporous structure prepared by sol-gel method were investigated for the oxidative dehydrogenation of propane （ODHP）. The techniques of temperature-programmed reduction with H2 （H2-TPR）, N2 adsorption-desolption, Fourier transform infrared spectroscopy （FT-IR）, X-ray diffraction （XRD） and X-ray photoelectron spectra （XPS） were employed for catalyst characterization. It is found that the activity of the catalysts for ODHP increases first and then decreases with the increase of Mo content. The catalyst with a Mo/Ni atomic ratio of 1/1 exhibits the best catalytic activity, which gives the propene selectivity of 81.4% at a propane conversion of 11.3% under 600 ~C and maintains the good catalytic performance for 22 h on stream. This is related not only to its high reducibility and dispersion as revealed by TPR and XRD, but also to the formation of more selective oxygen species on the MoOz-NiO interface as identified by XPS.
文摘An industrial scale propylene production via oxidative dehydrogenation of propane （ODHP） in multi-tubular re- actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of small diameter tubes immersed in a shell through a proper coolant flows. Herein, a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence olefln over V2O5/γ-Al203 catalyst was presented. Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions, gas process and coolant temperatures, as well as other pa- rameters affecting the reactor performance such as pressure. Furthermore, the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%. The optimized length of the reactor needed to reach 100% conversion of the oxygen was theoretically determined. For the single-bed reactor the optimized length of 11.96 m including 0.5 m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72 m for the first and 7.32 m for the second reactor were calculated. Ultimately, the use of a distributed oxygen feed with limited number of injection points indicated a significant improvement on the reactor performance in terms of propane conversion and propylene selectivity. Besides, this concept could overcome the reactor run- away temperature problem and enabled operations at the wider range of conditions to obtain enhanced propyl- ene production in an industrial scale reactor.
文摘Oxidative dehydrogenation of propane over V-Mg-O and MCl_n(M=Cu^+,Li^+, Ag^+,Cd^(2+))promoted V-Mg-O catalysts was studied.XRD result showed that the V-Mg-O catalysts were composed of MgO and Mg_3(VO_4)_2.The yield of propene was much higher over CuCl and LiCl promoted VMgO catalysts than that over VMgO catalysts at the same reaction temperature.The highest yield of propene reached 23.1% at 500℃ and 6000h^(-1) space velocity.
基金supported by the National Basic Research Program of China(Nos.2010CB732303 and 2013CB933102)the National Natural Science Foundation of China(Nos.21073148 and 21033006)the Program for Innovative Research Team of the Ministry of Education of China(No.IRT1036)
文摘A series ofnanosized cobalt oxide catalysts modified with phosphorus have been synthesized by the solgel method and investigated in the oxidative dehydrogenation of propane to propene. With the addition of phosphorus, the crystallite size of the catalyst was largely decreased, while the P species in the catalyst were highly dispersed. Compared to pure cobalt oxide, the P-modified samples showed higher propane conversion and enhanced propene selectivity. Over the PCoO catalyst with a P/Co atomic ratio of 0.05, the maximal propene yields of 15.7% with a propane conversion of 28.3% were obtained at 520 ℃.
基金supported by the Deutsche Forschungsgemeinschaft (DFG) within the Framework of the German Initiative for Excellence
文摘ZnO could be a suitable catalyst for the oxidative conversion of CH4,C2H6 and C3H8.However,the main drawback is its thermal instability.Therefore,ZnO supported on ZrO 2,TiO2,γ-Al2O and SiO2 was investigated for the oxidative dehydrogenation of propane and ethane,and the oxidative coupling of methane.The stability of the supported ZnO is partially improved,but ZnO reacts with the support material,forming new compounds （Zn-zirconates,-titanates,-aluminates and-silicates）,which already occurs below reaction temperature.This might also be the case for many other heterogeneous catalysts.
基金the Doctoral Program of Higher Education(No. SRFDP-2012009111001)NNSFC(No. 21202141)+1 种基金Priority Academic Program Development(PAPD) of Jiangsu Higher Education Institutions, Key Science & Technology Specific Projects of Yangzhou(No. YZ20122029)Yangzhou Nature Science Foundation(No. YZ2014040) for financial support
文摘PtSnNa/γ-Al2O3 catalyst is widely used in the dehydrogenation of light alkane. This paper reports a new fabrication method of the catalyst. In the work, γ-Al2O3, SnCl4 and NaCl were ball milled to upload Sn and Na＋ onto the support instead of the conventionally used immersion method. The subsequent baking procedures frimly fixed Sn onto the support, which could disperse Pt introduced by immersion. The effects of Sn and Na＋ additives on the catalytic performance of PtSnNa/y-Al2O3 catalyst were investigated. It was found that the appropriate molar ratio of Sn/Pt was 6：1 while the favorable weight percentage of Na＋ was 0.90%. Compared with the reaction catalyzed by the industrially employed PtSnNa/ γ-Al2O3 catalyst, the conversion of propane and the selectivity of propylene had been greatly improved, which were 26.97%; and 99.18% respectivelv after 12 h reaction.
