Pd/Cu liquid-phase composite was utilized as the catalyst in this study to remove PH_(3) at low temperatures.The anti-heterotoxicity of catalysts in the PH_(3) catalytic oxidation purification process was carefully ex...Pd/Cu liquid-phase composite was utilized as the catalyst in this study to remove PH_(3) at low temperatures.The anti-heterotoxicity of catalysts in the PH_(3) catalytic oxidation purification process was carefully explored and pioneered.The catalytic performance,thermodynamics,kinetics,and catalytic oxidation mechanism of Pd/Cu liquid-phase catalyst catalytic oxidation of PH_(3) were thoroughly investigated.The results showed that Pd/Cu has a superior catalytic effect on the removal of PH_(3) in the gas mixture under low temperature.With CO as the carrier gas,the removal efficiency of PH_(3) could be maintained at 100%for nearly 450 min,indicating that the Pd/Cu liquid phase catalyst has good resistance to heterotoxicity.According to the thermodynamic,kinetic,and related characterization results of the PH_(3) purification process,the kinetic region of the gas–liquid reaction of PH_(3) absorption by Pd/Cu solution was an interfacial reaction.Pd was the primary catalyst and Cu was the secondary catalyst,and the adsorption of PH_(3)was a primary reaction.PH_(3) was spontaneously oxidized to H_(3)PO_(4) in the Pd/Cu catalytic system during the removal process.Pd was regenerated by O_(2) and Cu,increasing the activity and stability of the Pd/Cu catalyst in the sustain and efficient purification of PH_(3) in tail gas.展开更多
The alkylation mechanism catalyzed by an ionic liquid （as a Lewis acid） may be different from the traditional alkylation mechanism catalyzed by Br nsted acid,especially as their initiation steps are still not clear....The alkylation mechanism catalyzed by an ionic liquid （as a Lewis acid） may be different from the traditional alkylation mechanism catalyzed by Br nsted acid,especially as their initiation steps are still not clear.In this paper,an isotope exchange method is used to investigate the catalytic mechanism of AlCl 3 /butyl-methyl-imidazolium chloride ionic liquid in the alkylation of benzene with 1-dodecene.The proposed catalytic mechanism was confirmed by analysis of ionic liquid before and after reaction and of the alkylation products of deuterated benzene （C 6 D 6） with 1-dodecene.The proposed mechanism consists of the equilibrium reaction between [Al 2 Cl 7 ] ＋H ＋ and [AlHCl 3 ] ＋ ＋[AlCl 4 ],in which the Br nsted acid [AlHCl 3 ] ＋ is supplied by the reaction of 2-H on the imidazolium ring and [Al 2 Cl 7 ].The alkylation reaction is initiated by the Br nsted acid [AlHCl 3 ] ＋ which reacts with 1-dodecene to form a carbonium ion,then the carbonium ion reacts with benzene to form an unstable σ complex,leading to the formation of 2-phenyldodecane.展开更多
The liquid phase catalytic exchange(LPCE) reaction is an effective process for heavy water detritiation and production of deuterium-depleted potable water. In the current study, hydrophobic carbon-supported platinum c...The liquid phase catalytic exchange(LPCE) reaction is an effective process for heavy water detritiation and production of deuterium-depleted potable water. In the current study, hydrophobic carbon-supported platinum catalysts(Pt/C/PTFE) with high efficiency as reported previously for LPCE were prepared and comprehensive performance evaluation method is applied to evaluate the separation behaviors of LPCE systematically. Experimental results indicate that the optimum reaction temperature of 60–80℃ and the molar feed ratio G/L of 1.5–2.5 would lead to higher separation efficiencies. As to the packing method, a random packing mode with a packing ratio of hydrophobic catalysts 0.25 is recommended. In addition, thermodynamic analysis corresponds well with experimental results under lower temperature and G/L, while the suppression of kinetic factors should not be neglected when T > 80℃ and G/L > 1.5.展开更多
Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange...Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange resin catalyst CT-145H. A packed CDC of 1.2 m height and 50 mm diameter with indigenously developed reactive sec-tion packing was used to generate experimental data. Effect of different key variables on product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions for 0.2 kg·s-1 of ethanol feed were found：reboiler duty of 375 W, molar feed ratio of 1︰1.3 of reactants, and reflux ratio of 7. Concentration profiles for each component along each column section at optimum conditions were also drawn. Neither output nor input multiplicity was observed at experimental conditions.展开更多
Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the me...Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the metal salt solution during ion exchange influenced the ion exchange capacity of Fe, and resulted in different activities of the Fe-Beta catalyst. Fe-Beta catalysts with the Fe contents of （2.6, 6.3 and 9） wt% were synthesized using different amounts of 0.02 mol/L Fe salt solution. These catalysts were studied by various characterization techniques and their NH3-SCR activities were evaluated. The Fe-Beta catalyst with the Fe content of 6.3 wt% exhibited the highest activity, with a temperature range of 202-616℃ where the NOx conversion was 〉 80%. The Fe content in Beta zeolite did not influence the structure of Beta zeolite and valence state of Fe. Compared with the Fe-Beta catalysts with low Fe content （2.6 wt%）, Fe-Beta catalysts with 6.3 wt% Fe content possessed more isolated Fe3. active sites which led to its higher NH3-SCR activity. A high capacity for NH3 and NO adsorption, and a high activity for NO oxidation also contributed to the high NH3-SCR activity of the Fe-Beta catalyst with 6.3 wt%. However, when the Fe content was further increased to 9.0 wt%, the amount of FexOy nanoparticles increased while the amount of isolated Fe3＋ active sites was unchanged, which promoted NH3 oxidation and decreased the NH3-SCR activity at high temperature.展开更多
利用Aspen Plus对某炼油厂4.20 Mt/a催化裂化(FCC)装置进行建模预测。基于所建模型提取装置冷热物流数据,利用夹点技术对整个装置进行换热网络分析,发现原FCC装置吸收稳定系统存在能耗高、热公用工程消耗大,原料油混合温差大,轻柴油、...利用Aspen Plus对某炼油厂4.20 Mt/a催化裂化(FCC)装置进行建模预测。基于所建模型提取装置冷热物流数据,利用夹点技术对整个装置进行换热网络分析,发现原FCC装置吸收稳定系统存在能耗高、热公用工程消耗大,原料油混合温差大,轻柴油、重柴油及产品油浆高质低用,除盐水终温较低,除氧器蒸汽消耗量大等问题。通过优化稳定塔回流比、补充吸收剂流量等方法降低吸收稳定系统负荷,优化分馏塔中段取热比例多产高品位蒸汽,并利用夹点技术优化装置换热网络。结果表明:优化后,可节省蒸汽量27.3 t h,相当于节能16603 tOE a(1 tOE=41.8 GJ)或23757 tCE a(1 tCE=29.27 GJ),减少二氧化碳排放量76457 t a,节能效果优异;同时,改造还减少FCC装置外送热媒水量300 t h,装置内利用热媒水10.27 MW的余热,减少了热量损失。展开更多
Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module （CH HCSB TBM） for the International Thermonuclear Experimental Reactor （ITER...Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module （CH HCSB TBM） for the International Thermonuclear Experimental Reactor （ITER）. In this paper, LiaSiO4 ceramic pebbles deposited with catalytic metals, including Pt, Pd, Ru and Ir, were prepared by wet impregnation method. The metal particles on Li4SiO4 pebble exhibit a good promotion of hydrogen isotope exchange reactions in H2-D20 gas system, with conversion equilibrium temperature reduction of 200-300 ~C. The out-of-pile tritium release experiments were performed using 1.0 wt% Pt/Li4SiO4 and Li4SiO4 pebbles irradiated in a thermal neutron reactor. The thermal desorption spectroscopy shows that Pt was effective to increase the tritium release rate at lower temperatures, and the ratio of tritium molecule （HT） to tritiated water （HTO） of 1.0 wt% Pt/LiaSiO4 was much more than that of Li4SiO4, which released mainly as HTO. Thus, catalytic metals deposited on LiaSiO4 pebble may help to accelerate the recovery of bred tritium particularly in low temperature region, and increase the tritium molecule form released from the tritium breedin~ materials.展开更多
基金supported by the National Key Research and Development Plan (2018YFC1900203)The National Science Fund for Distinguished Young Scholars (52000094)The National Natural Science Foundation of China (51968033)。
文摘Pd/Cu liquid-phase composite was utilized as the catalyst in this study to remove PH_(3) at low temperatures.The anti-heterotoxicity of catalysts in the PH_(3) catalytic oxidation purification process was carefully explored and pioneered.The catalytic performance,thermodynamics,kinetics,and catalytic oxidation mechanism of Pd/Cu liquid-phase catalyst catalytic oxidation of PH_(3) were thoroughly investigated.The results showed that Pd/Cu has a superior catalytic effect on the removal of PH_(3) in the gas mixture under low temperature.With CO as the carrier gas,the removal efficiency of PH_(3) could be maintained at 100%for nearly 450 min,indicating that the Pd/Cu liquid phase catalyst has good resistance to heterotoxicity.According to the thermodynamic,kinetic,and related characterization results of the PH_(3) purification process,the kinetic region of the gas–liquid reaction of PH_(3) absorption by Pd/Cu solution was an interfacial reaction.Pd was the primary catalyst and Cu was the secondary catalyst,and the adsorption of PH_(3)was a primary reaction.PH_(3) was spontaneously oxidized to H_(3)PO_(4) in the Pd/Cu catalytic system during the removal process.Pd was regenerated by O_(2) and Cu,increasing the activity and stability of the Pd/Cu catalyst in the sustain and efficient purification of PH_(3) in tail gas.
基金financial support from the National Natural Science Foundation of China (NSFC,2052010)
文摘The alkylation mechanism catalyzed by an ionic liquid （as a Lewis acid） may be different from the traditional alkylation mechanism catalyzed by Br nsted acid,especially as their initiation steps are still not clear.In this paper,an isotope exchange method is used to investigate the catalytic mechanism of AlCl 3 /butyl-methyl-imidazolium chloride ionic liquid in the alkylation of benzene with 1-dodecene.The proposed catalytic mechanism was confirmed by analysis of ionic liquid before and after reaction and of the alkylation products of deuterated benzene （C 6 D 6） with 1-dodecene.The proposed mechanism consists of the equilibrium reaction between [Al 2 Cl 7 ] ＋H ＋ and [AlHCl 3 ] ＋ ＋[AlCl 4 ],in which the Br nsted acid [AlHCl 3 ] ＋ is supplied by the reaction of 2-H on the imidazolium ring and [Al 2 Cl 7 ].The alkylation reaction is initiated by the Br nsted acid [AlHCl 3 ] ＋ which reacts with 1-dodecene to form a carbonium ion,then the carbonium ion reacts with benzene to form an unstable σ complex,leading to the formation of 2-phenyldodecane.
基金Supported by the National Key Research and Development Program of China(2017YFE0300302)the National Natural Science Foundation of China(21503199,21406212)Key Project of Applied&Basic Research of Sichuan Province(18YYJC1594)
文摘The liquid phase catalytic exchange(LPCE) reaction is an effective process for heavy water detritiation and production of deuterium-depleted potable water. In the current study, hydrophobic carbon-supported platinum catalysts(Pt/C/PTFE) with high efficiency as reported previously for LPCE were prepared and comprehensive performance evaluation method is applied to evaluate the separation behaviors of LPCE systematically. Experimental results indicate that the optimum reaction temperature of 60–80℃ and the molar feed ratio G/L of 1.5–2.5 would lead to higher separation efficiencies. As to the packing method, a random packing mode with a packing ratio of hydrophobic catalysts 0.25 is recommended. In addition, thermodynamic analysis corresponds well with experimental results under lower temperature and G/L, while the suppression of kinetic factors should not be neglected when T > 80℃ and G/L > 1.5.
基金Part of this paper was included in the proceedings of World Congress on Engineering and Computer Science,San Francisco,USA,22-24 October,2008,pp.79-84(ISBN 978-988-98671-0-2)The first author is grateful to Higher Education Commission of Pakistan for funding this research under indigenous scheme
文摘Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange resin catalyst CT-145H. A packed CDC of 1.2 m height and 50 mm diameter with indigenously developed reactive sec-tion packing was used to generate experimental data. Effect of different key variables on product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions for 0.2 kg·s-1 of ethanol feed were found：reboiler duty of 375 W, molar feed ratio of 1︰1.3 of reactants, and reflux ratio of 7. Concentration profiles for each component along each column section at optimum conditions were also drawn. Neither output nor input multiplicity was observed at experimental conditions.
基金supported by the National Key Basic Research Program of China (973 Program, 2013CB933201)the National Natural Science Foun-dation of China (21577034, 21333003, 91545103)+1 种基金Science and Technology Commission of Shanghai Municipality (16ZR1407900)Fundamental Research Funds for the Central Universities (WJ1514020)~~
文摘Fe doped Beta zeolite with different Fe contents were prepared by ion exchange by changing the volume or the concentration of a Fe salt solution. For a particular mass of Fe salt precursor, the concentration of the metal salt solution during ion exchange influenced the ion exchange capacity of Fe, and resulted in different activities of the Fe-Beta catalyst. Fe-Beta catalysts with the Fe contents of （2.6, 6.3 and 9） wt% were synthesized using different amounts of 0.02 mol/L Fe salt solution. These catalysts were studied by various characterization techniques and their NH3-SCR activities were evaluated. The Fe-Beta catalyst with the Fe content of 6.3 wt% exhibited the highest activity, with a temperature range of 202-616℃ where the NOx conversion was 〉 80%. The Fe content in Beta zeolite did not influence the structure of Beta zeolite and valence state of Fe. Compared with the Fe-Beta catalysts with low Fe content （2.6 wt%）, Fe-Beta catalysts with 6.3 wt% Fe content possessed more isolated Fe3. active sites which led to its higher NH3-SCR activity. A high capacity for NH3 and NO adsorption, and a high activity for NO oxidation also contributed to the high NH3-SCR activity of the Fe-Beta catalyst with 6.3 wt%. However, when the Fe content was further increased to 9.0 wt%, the amount of FexOy nanoparticles increased while the amount of isolated Fe3＋ active sites was unchanged, which promoted NH3 oxidation and decreased the NH3-SCR activity at high temperature.
文摘利用Aspen Plus对某炼油厂4.20 Mt/a催化裂化(FCC)装置进行建模预测。基于所建模型提取装置冷热物流数据,利用夹点技术对整个装置进行换热网络分析,发现原FCC装置吸收稳定系统存在能耗高、热公用工程消耗大,原料油混合温差大,轻柴油、重柴油及产品油浆高质低用,除盐水终温较低,除氧器蒸汽消耗量大等问题。通过优化稳定塔回流比、补充吸收剂流量等方法降低吸收稳定系统负荷,优化分馏塔中段取热比例多产高品位蒸汽,并利用夹点技术优化装置换热网络。结果表明:优化后,可节省蒸汽量27.3 t h,相当于节能16603 tOE a(1 tOE=41.8 GJ)或23757 tCE a(1 tCE=29.27 GJ),减少二氧化碳排放量76457 t a,节能效果优异;同时,改造还减少FCC装置外送热媒水量300 t h,装置内利用热媒水10.27 MW的余热,减少了热量损失。
基金supported by the Development Fund of China Academy of Engineering Physics (No.2010B0301035)the National Magnetic Confinement Fusion Science Program (No. 2010GB112004)
文摘Li4SiO4 ceramic pebble is considered as a candidate tritium breeding material of Chinese Helium Cooled Solid Breeder Test Blanket Module （CH HCSB TBM） for the International Thermonuclear Experimental Reactor （ITER）. In this paper, LiaSiO4 ceramic pebbles deposited with catalytic metals, including Pt, Pd, Ru and Ir, were prepared by wet impregnation method. The metal particles on Li4SiO4 pebble exhibit a good promotion of hydrogen isotope exchange reactions in H2-D20 gas system, with conversion equilibrium temperature reduction of 200-300 ~C. The out-of-pile tritium release experiments were performed using 1.0 wt% Pt/Li4SiO4 and Li4SiO4 pebbles irradiated in a thermal neutron reactor. The thermal desorption spectroscopy shows that Pt was effective to increase the tritium release rate at lower temperatures, and the ratio of tritium molecule （HT） to tritiated water （HTO） of 1.0 wt% Pt/LiaSiO4 was much more than that of Li4SiO4, which released mainly as HTO. Thus, catalytic metals deposited on LiaSiO4 pebble may help to accelerate the recovery of bred tritium particularly in low temperature region, and increase the tritium molecule form released from the tritium breedin~ materials.
