Catalytic ethane dehydrogenation(EDH) to ethylene over Pt-based catalysts has received increasing interests in recent years as it is a potential alternative route to conventional steam cracking. However, the catalysts...Catalytic ethane dehydrogenation(EDH) to ethylene over Pt-based catalysts has received increasing interests in recent years as it is a potential alternative route to conventional steam cracking. However, the catalysts used in this reaction often suffer from rapid deactivation due to serious coke deposition and metal sintering. Herein, we reported the effects of Zn modification on the stability of Pt/Al2 O3 for EDH.The Zn-modified sample(PtZn2/Al2 O3) exhibits stable ethane conversion(20%) with over 95% ethylene selectivity. More importantly, it exhibits a significantly low deactivation rate of only 0.003 h-1 at 600 °C for70 h, which surpasses most of previously reported catalysts. Detailed characterizations including in situ FT-IR, ethylene adsorption microcalorimetry, and HAADF-STEM etc. reveal that Zn modifier reduces the number of Lewis acid sites on the catalyst surface. Moreover, it could modify Pt sites and preferentially cover the step sites, which decrease surface energy and retard the sintering of Pt particle, then prohibiting the further dehydrogenation of ethylene to ethylidyne. Consequently, the good stability is realized due to anti-sintering and the decrease of coke formation on the Pt Zn2/Al2 O3 catalyst.展开更多
V/SiO2 catalysts compared to Cr/SiO2 catalysts were studied for dehydrogenation of n-butane to butenes. Several methods for characterization of catalysts such as FT-IR, UV-vis and Raman spectroscopies were used. Some ...V/SiO2 catalysts compared to Cr/SiO2 catalysts were studied for dehydrogenation of n-butane to butenes. Several methods for characterization of catalysts such as FT-IR, UV-vis and Raman spectroscopies were used. Some differences between two catalysts were showed, including the performances of catalysts, distribution of products and mechanism of reactions. The results showed that prepared catalysts with 12m% of active component loading all demonstrated best conversion of n-butane to butene at a reaction temperature of around 590 ℃. Two different reaction mechanisms were mentioned to well explain why iso-butene was produced on V/SiO2 catalysts but not on Cr/SiO2 catalysts.展开更多
A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal...A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production.For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used.Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogenation method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and signi ficant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.展开更多
VOx/SiO2 catalysts prepared by impregnation method were used for catalytic dehydrogenation of n-butane to butenes and characterized by X-ray diffraction, FT-IR, UV-vis, Raman, and BET measurements. The effects of VOx ...VOx/SiO2 catalysts prepared by impregnation method were used for catalytic dehydrogenation of n-butane to butenes and characterized by X-ray diffraction, FT-IR, UV-vis, Raman, and BET measurements. The effects of VOx loading and the reaction temperature on the VOx/SiO2 catalysts and their catalytic performances for the dehydrogenation of n-butane were studied. When the VOx loading was 12% g/gcat and reaction temperature was between 590 ℃ and 600℃, n-butane conversion and butenes yields reached the highest value under H2 flux of 10 ml/min and n-butane flux of 10 ml/min. Product distribution, such as the ratio of 2-butene to 1-butene and the ratio of cis-2-butene to trans-2-butene, was mainly influenced by the reaction temperature.展开更多
Long-chain alkanes are abundant feedstocks supplied by natural resources and chemical industry. Specially, normal long-chain alkanes are primary products from Fischer-Tropsch synthesis(FTS) process, which is an import...Long-chain alkanes are abundant feedstocks supplied by natural resources and chemical industry. Specially, normal long-chain alkanes are primary products from Fischer-Tropsch synthesis(FTS) process, which is an important route for the utilization of coal in China. Facing a shift of energy nexus towards sustainable society, the conversion of long-chain alkanes derived from coal into value-added products(such as alkenes and oxygenates) is of great importance for securing China’s energy supply and the role transition of the commercial FTS plants from fuel makers to chemical suppliers. Among the potential transformation routes,the direct dehydrogenation of long-chain alkanes into alkenes is an attractive and practical route, due to the broad applications of long-chain alkenes(especially the linear α-olefins). In this review, we will summary the key insights obtained from the literature on the dehydrogenation of light alkanes based on supported metal catalysts and the dehydrogenation of alkanes with homogeneous molecular catalysts and then discuss how to translate these lessons into the development of efficient catalysts and processes for the dehydrogenation of long-chain alkanes into long-chain alkenes.展开更多
基金supported by the National Natural Science Foundation of China (NNSFC 21573232, 21576251, 21676269, 21878283)the Strategic Priority Research Program of Chinese Academy of Sciences Grant No. XDB17000000+2 种基金National Key Projects for Fundamental Research and Development of China (2016YFA0202801)The Youth Innovation Promotion Association CAS (2017223)Department of Science and Technology of Liaoning province under contract of 2015020086-101。
文摘Catalytic ethane dehydrogenation(EDH) to ethylene over Pt-based catalysts has received increasing interests in recent years as it is a potential alternative route to conventional steam cracking. However, the catalysts used in this reaction often suffer from rapid deactivation due to serious coke deposition and metal sintering. Herein, we reported the effects of Zn modification on the stability of Pt/Al2 O3 for EDH.The Zn-modified sample(PtZn2/Al2 O3) exhibits stable ethane conversion(20%) with over 95% ethylene selectivity. More importantly, it exhibits a significantly low deactivation rate of only 0.003 h-1 at 600 °C for70 h, which surpasses most of previously reported catalysts. Detailed characterizations including in situ FT-IR, ethylene adsorption microcalorimetry, and HAADF-STEM etc. reveal that Zn modifier reduces the number of Lewis acid sites on the catalyst surface. Moreover, it could modify Pt sites and preferentially cover the step sites, which decrease surface energy and retard the sintering of Pt particle, then prohibiting the further dehydrogenation of ethylene to ethylidyne. Consequently, the good stability is realized due to anti-sintering and the decrease of coke formation on the Pt Zn2/Al2 O3 catalyst.
基金The Program for New Century Excellent Talents in University (Grant No.NCET-04-0987)Doctor Fund of Science Research of Xinjiang University (Grant No. BS060101)
文摘V/SiO2 catalysts compared to Cr/SiO2 catalysts were studied for dehydrogenation of n-butane to butenes. Several methods for characterization of catalysts such as FT-IR, UV-vis and Raman spectroscopies were used. Some differences between two catalysts were showed, including the performances of catalysts, distribution of products and mechanism of reactions. The results showed that prepared catalysts with 12m% of active component loading all demonstrated best conversion of n-butane to butene at a reaction temperature of around 590 ℃. Two different reaction mechanisms were mentioned to well explain why iso-butene was produced on V/SiO2 catalysts but not on Cr/SiO2 catalysts.
文摘A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production.For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used.Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogenation method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and signi ficant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.
基金The project was supported by Program for New Century Excellent Talents in University (Grant No. NCET-04-0987)Doctor Fund of Science Research of Xinjiang University (Grant No. BS060101).
文摘VOx/SiO2 catalysts prepared by impregnation method were used for catalytic dehydrogenation of n-butane to butenes and characterized by X-ray diffraction, FT-IR, UV-vis, Raman, and BET measurements. The effects of VOx loading and the reaction temperature on the VOx/SiO2 catalysts and their catalytic performances for the dehydrogenation of n-butane were studied. When the VOx loading was 12% g/gcat and reaction temperature was between 590 ℃ and 600℃, n-butane conversion and butenes yields reached the highest value under H2 flux of 10 ml/min and n-butane flux of 10 ml/min. Product distribution, such as the ratio of 2-butene to 1-butene and the ratio of cis-2-butene to trans-2-butene, was mainly influenced by the reaction temperature.
基金supported by Tsinghua University(Initiative Scientific Research Program 20211080079)the National Natural Science Foundation of China(21972161,22172186)+7 种基金Chinese Academy of Sciences(CAS)Pioneer Talents Program(2018-095)Shanxi Talent Program(2019SBRJH01)Autonomous Research Project of State Key Laboratory of Coal Conversion(SKLCC)(2020BWZ006,2021BWZ007)Institute of Coal Chemistry(ICC)Innovation Fund(SCJJ-2020-02)Inner Mengolia Science&Technology Project Plan(2021GG0311)Major science and technology project of Ordos(2022EEDSKJZDZX001)Start-Up Grant of Institute of Coal Chemistry(2020SC001)Synfuels China Co.,Ltd.
文摘Long-chain alkanes are abundant feedstocks supplied by natural resources and chemical industry. Specially, normal long-chain alkanes are primary products from Fischer-Tropsch synthesis(FTS) process, which is an important route for the utilization of coal in China. Facing a shift of energy nexus towards sustainable society, the conversion of long-chain alkanes derived from coal into value-added products(such as alkenes and oxygenates) is of great importance for securing China’s energy supply and the role transition of the commercial FTS plants from fuel makers to chemical suppliers. Among the potential transformation routes,the direct dehydrogenation of long-chain alkanes into alkenes is an attractive and practical route, due to the broad applications of long-chain alkenes(especially the linear α-olefins). In this review, we will summary the key insights obtained from the literature on the dehydrogenation of light alkanes based on supported metal catalysts and the dehydrogenation of alkanes with homogeneous molecular catalysts and then discuss how to translate these lessons into the development of efficient catalysts and processes for the dehydrogenation of long-chain alkanes into long-chain alkenes.
