The main cause to the deactivation of ZSM-5 catalyst, used for oxidation of benzene to phenol (BTOP) by nitrous oxide, is that the carbon deposition on the catalyst surface blocks the mouth of pores of the catalyst.In...The main cause to the deactivation of ZSM-5 catalyst, used for oxidation of benzene to phenol (BTOP) by nitrous oxide, is that the carbon deposition on the catalyst surface blocks the mouth of pores of the catalyst.In the experiments, ZSM-5 catalyst was modified by chemical surface deposition of silicon, and then the effect of modification condition on the catalyst activation was studied. The catalyst samples were characterized by XRF,EPS, XRD, TEM, N2 adsorption at low temperature, pyridine adsorption-infrared technique and etc. All the above results show that the uniform SiO2 membrane can be formed on ZSM-5 crystal surface. The SiO2 membrane covers the acid centers on ZSM-5 surface to inhibit surface coking, to avoid or decrease the possibility of ZSM-5 pore blockage so that the catalyst activity and stability can be improved efficiently. The optimum siliconiting conditions determined by the experiments are as follows: 4% load of silanizing agent, volume (ml)/mass (g) ratio of hexane/ZSM-5=15/1, and 16 h of modification time. Compared with the samples without siliconiting treatment,the samples treated under the above optimum condition can increase the productivity of phenol by 14% for 3 h reaction time and by 41% for 6 h reaction time respectively.展开更多
Direct nitrous oxide(N2O) emissions(DNEs) from croplands are required in national inventories of greenhouse gases. The Intergovernmental Panel on Climate Change(IPCC) guidelines provide an approach using direct emissi...Direct nitrous oxide(N2O) emissions(DNEs) from croplands are required in national inventories of greenhouse gases. The Intergovernmental Panel on Climate Change(IPCC) guidelines provide an approach using direct emission factors(EFds) to estimate DNEs, which are constants for large regions. The goal of this paper is to establish empirical models to account for the temporal and spatial variations of EFds, which, apart from the nitrogen addition rate, also vary with a range of environmental factors, so as to enhance the accuracy of regional/national DNE estimates. Therefore, the seasonal/annual DNEs(n = 71) from upland croplands, which are the differences in N2 O emissions between fields with and without fertilizer-nitrogen addition, were used to statistically relate DNEs to regulating factors including the fertilizer-nitrogen addition rate(FN), and environmental(climate and soil) factors. The multivariate stepwise linear regression results showed positive combined effects of FN and clay fraction on DNEs(R2 = 0.61, p < 0.001). Furthermore, the nonlinear regression of FN, precipitation, and clay fraction was also adopted for prediction(R2 = 0.50, p < 0.001). Validation with an independent dataset(n = 31) suggested that both models were better predictors of DNEs than the IPCC model, which only depends on FN. These empirical models may provide simple but reliable approaches for compiling regional/national, and even global inventories of DNEs from croplands. However, both models were restricted to a limited sample size. Understandably, more field observations are still required to further validate the global applicability of these simple approaches.展开更多
Solid oxide fuel cell(SOFC)is a promising energy conversion device because of its high efficiency and fuel/oxidant flexibility,enabling the direct conversion of chemical energy to electrical power.By using N_(2)O as a...Solid oxide fuel cell(SOFC)is a promising energy conversion device because of its high efficiency and fuel/oxidant flexibility,enabling the direct conversion of chemical energy to electrical power.By using N_(2)O as an oxidant instead of air,we develop a dual-phase catalyst La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)-Gd_(0.1)Ce_(0.9)O_(2-δ)(LSCF-GDC),which exhibits efficient bifunctionality as a cathode for SOFC,synergistic ally promoting simultaneous N_(2)O decomposition and oxygen reduction kinetics.展开更多
以Ni/Al_2O_3为催化剂,H_2O_2为氧化剂,研究了直接氧化苯合成苯酚的工艺。采用正交试验设计方法,对影响苯酚收率的因素进行了优化设计试验。对试验中的6个因素各作了5个水平的考察,得出了该合成工艺的最优方案:反应时间3.0 h,反应温度70...以Ni/Al_2O_3为催化剂,H_2O_2为氧化剂,研究了直接氧化苯合成苯酚的工艺。采用正交试验设计方法,对影响苯酚收率的因素进行了优化设计试验。对试验中的6个因素各作了5个水平的考察,得出了该合成工艺的最优方案:反应时间3.0 h,反应温度70℃,催化剂用量0.1 g,H_2O_2用量3 m L,乙酸用量20 m L,苯用量7 m L。在此条件下,苯酚收率为30.03%。展开更多
在常压和N2气氛下,实验考察了高温焙烧处理对离子交换法制备的Fe改性ZSM-5分子筛性能的影响.利用XRD、NH3-TPD2、7Al MAS NMR、FTIR、XPS、UV-vis和H2-TPR等检测方法表征了Fe-ZSM-5分子筛高温焙烧前后的性能变化,并以N2O气相一步氧化苯...在常压和N2气氛下,实验考察了高温焙烧处理对离子交换法制备的Fe改性ZSM-5分子筛性能的影响.利用XRD、NH3-TPD2、7Al MAS NMR、FTIR、XPS、UV-vis和H2-TPR等检测方法表征了Fe-ZSM-5分子筛高温焙烧前后的性能变化,并以N2O气相一步氧化苯制苯酚为模型反应,考察了高温焙烧对Fe-ZSM-5分子筛催化性能的影响.结果表明:1)Fe离子以非骨架铁的形式负载于Fe-ZSM-5分子筛的表面或孔道中,其存在态为Fe2O3;2)高温焙烧处理导致分子筛发生骨架脱铝,并在表面形成新的五配位铝;3)高温焙烧使Fe-ZSM-5表面的Fe2O3含量降低,所诱发的Fe离子表面迁移形成了更多有利于苯酚生成的活性位,因而能显著提高苯酚的选择性.展开更多
文摘The main cause to the deactivation of ZSM-5 catalyst, used for oxidation of benzene to phenol (BTOP) by nitrous oxide, is that the carbon deposition on the catalyst surface blocks the mouth of pores of the catalyst.In the experiments, ZSM-5 catalyst was modified by chemical surface deposition of silicon, and then the effect of modification condition on the catalyst activation was studied. The catalyst samples were characterized by XRF,EPS, XRD, TEM, N2 adsorption at low temperature, pyridine adsorption-infrared technique and etc. All the above results show that the uniform SiO2 membrane can be formed on ZSM-5 crystal surface. The SiO2 membrane covers the acid centers on ZSM-5 surface to inhibit surface coking, to avoid or decrease the possibility of ZSM-5 pore blockage so that the catalyst activity and stability can be improved efficiently. The optimum siliconiting conditions determined by the experiments are as follows: 4% load of silanizing agent, volume (ml)/mass (g) ratio of hexane/ZSM-5=15/1, and 16 h of modification time. Compared with the samples without siliconiting treatment,the samples treated under the above optimum condition can increase the productivity of phenol by 14% for 3 h reaction time and by 41% for 6 h reaction time respectively.
基金supported by the Ministry of Science and Technology(Grant No. 2012CB417106)the National Natural Science Foundation of China(Grant No. 41321064)
文摘Direct nitrous oxide(N2O) emissions(DNEs) from croplands are required in national inventories of greenhouse gases. The Intergovernmental Panel on Climate Change(IPCC) guidelines provide an approach using direct emission factors(EFds) to estimate DNEs, which are constants for large regions. The goal of this paper is to establish empirical models to account for the temporal and spatial variations of EFds, which, apart from the nitrogen addition rate, also vary with a range of environmental factors, so as to enhance the accuracy of regional/national DNE estimates. Therefore, the seasonal/annual DNEs(n = 71) from upland croplands, which are the differences in N2 O emissions between fields with and without fertilizer-nitrogen addition, were used to statistically relate DNEs to regulating factors including the fertilizer-nitrogen addition rate(FN), and environmental(climate and soil) factors. The multivariate stepwise linear regression results showed positive combined effects of FN and clay fraction on DNEs(R2 = 0.61, p < 0.001). Furthermore, the nonlinear regression of FN, precipitation, and clay fraction was also adopted for prediction(R2 = 0.50, p < 0.001). Validation with an independent dataset(n = 31) suggested that both models were better predictors of DNEs than the IPCC model, which only depends on FN. These empirical models may provide simple but reliable approaches for compiling regional/national, and even global inventories of DNEs from croplands. However, both models were restricted to a limited sample size. Understandably, more field observations are still required to further validate the global applicability of these simple approaches.
基金financially supported by the National Natural Science Foundation of China(No.52336009)Guangdong Basic and Applied Basic Research Foundation(No.2023A1515010429)+4 种基金the Natural Science Basic Research Plan in Shaanxi Province of China(No.2024JC-YBQN-0475)Xidian University Specially Funded Project for Interdisciplinary Exploration(No.TZJH2024063)the Fundamental Research Funds for the Central Universities(No.QTZX23061)Qinchuangyuan Project(No.QCYRCXM-2022-236)the Innovation Center of Nuclear Power Technology(No.HDLCXZX-2022-ZH-013)
文摘Solid oxide fuel cell(SOFC)is a promising energy conversion device because of its high efficiency and fuel/oxidant flexibility,enabling the direct conversion of chemical energy to electrical power.By using N_(2)O as an oxidant instead of air,we develop a dual-phase catalyst La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)-Gd_(0.1)Ce_(0.9)O_(2-δ)(LSCF-GDC),which exhibits efficient bifunctionality as a cathode for SOFC,synergistic ally promoting simultaneous N_(2)O decomposition and oxygen reduction kinetics.
文摘以Ni/Al_2O_3为催化剂,H_2O_2为氧化剂,研究了直接氧化苯合成苯酚的工艺。采用正交试验设计方法,对影响苯酚收率的因素进行了优化设计试验。对试验中的6个因素各作了5个水平的考察,得出了该合成工艺的最优方案:反应时间3.0 h,反应温度70℃,催化剂用量0.1 g,H_2O_2用量3 m L,乙酸用量20 m L,苯用量7 m L。在此条件下,苯酚收率为30.03%。
文摘在常压和N2气氛下,实验考察了高温焙烧处理对离子交换法制备的Fe改性ZSM-5分子筛性能的影响.利用XRD、NH3-TPD2、7Al MAS NMR、FTIR、XPS、UV-vis和H2-TPR等检测方法表征了Fe-ZSM-5分子筛高温焙烧前后的性能变化,并以N2O气相一步氧化苯制苯酚为模型反应,考察了高温焙烧对Fe-ZSM-5分子筛催化性能的影响.结果表明:1)Fe离子以非骨架铁的形式负载于Fe-ZSM-5分子筛的表面或孔道中,其存在态为Fe2O3;2)高温焙烧处理导致分子筛发生骨架脱铝,并在表面形成新的五配位铝;3)高温焙烧使Fe-ZSM-5表面的Fe2O3含量降低,所诱发的Fe离子表面迁移形成了更多有利于苯酚生成的活性位,因而能显著提高苯酚的选择性.
