Gas-liquid (G-L) and liquid-solid (L-S) mass transfer coefficients were characterized in a gas-liquid-solid (G-L-S) three-phase magnetically stabilized bed (MSB) using amorphous alloy SRNA-4 as the solid phase. Effect...Gas-liquid (G-L) and liquid-solid (L-S) mass transfer coefficients were characterized in a gas-liquid-solid (G-L-S) three-phase magnetically stabilized bed (MSB) using amorphous alloy SRNA-4 as the solid phase. Effects such as superficial liquid velocity, superficial gas velocity, magnetic strength, liquid viscosity, and particle size were investigated. Experimental results indicated that the G-L volumetric mass transfer coefficients (KLa) increased along with the magnetic strength, superficial gas and liquid velocities. Proper increase of liquid viscosity promoted KLa only in the range of lower liquid viscosity. The external magnetic field made L-S mass transfer coefficients (Ks) in the G-L-S MSB lower than those of conventional fluidized beds. Ks in the MSB almost kept constant as the su- perficial liquid velocity and superficial gas velocity increased and decreased with the liquid viscosity and surface tension, while increased with the particle size Ks showed uniform axial and radial distributions except of small de- creases close to the wall. Dimensionless correlations were established to estimate KLa and Ks of the MSB with SRNA-4 catalysts , which showed the average error of 5.4% and 2.5% respectively.展开更多
Liquid-solid （L-S） mass transfer coefficients （Ks） were characterized in a gas-liquid-solid （G-L-S） three-phase countercurrent magnetically stabilized bed （MSB） using amorphous alloy SRNA-4 as the solid phase....Liquid-solid （L-S） mass transfer coefficients （Ks） were characterized in a gas-liquid-solid （G-L-S） three-phase countercurrent magnetically stabilized bed （MSB） using amorphous alloy SRNA-4 as the solid phase. Effects of superficial liquid velocity, superficial gas velocity, magnetic field strength, liquid viscosity and surface tension were investigated. Experimental results indicated that the external magnetic field increased Ks in three-phase MSB, as compared to those in conventional G-L-S fluidized beds; that Ks increased with magnetic field strength, superficial gas and liquid velocities and decreased with liquid viscosity and surface tension; and that Ks showed uniform axial and radial distributions except for small increases close to the wall. Dimensionless correlations were established to estimate Ks of the G-L-S countercurrent MSB using SRNA-4 catalyst, with an average error of 3.6%.展开更多
氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过...氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。展开更多
The catalytic hydrogenation of 2-nitro-4-acetylamino anisole(NMA)is a less-polluting and efficient method to produce 2-amino-4-acetamino anisole(AMA).However,the kinetics of catalytic hydrogenation of NMA to AMA remai...The catalytic hydrogenation of 2-nitro-4-acetylamino anisole(NMA)is a less-polluting and efficient method to produce 2-amino-4-acetamino anisole(AMA).However,the kinetics of catalytic hydrogenation of NMA to AMA remains obscure.In this work,the kinetic models including power-law model and Langmuir-Hinshelwood-Hougen-Watson(LHHW)model of NMA hydrogenation to AMA catalyzed by Raney nickel catalyst were investigated.All experiments were carried out under the elimination of mass transfer resistance within the temperature range of 70–100°C and the hydrogen pressure of 0.8–1.5 MPa.The reaction was found to follow 0.52-order kinetics with respect to the NMA concentration and 1.10-order kinetics in terms of hydrogen pressure.Based on the LHHW model,the dual-site dissociation adsorption of hydrogen was analyzed to be the rate determining step.The research of intrinsic kinetics of NMA to AMA provides the guidance for the reactor design and inspires the catalyst modification.展开更多
Sodium borohydride(NaBH_(4)) is considered as the most potential hydrogen storage material for portable proton exchange membrane fuel cells(PEMFC)because of its high theoretical hydrogen capacity.However,the slow and ...Sodium borohydride(NaBH_(4)) is considered as the most potential hydrogen storage material for portable proton exchange membrane fuel cells(PEMFC)because of its high theoretical hydrogen capacity.However,the slow and poor kinetic stability of hydrogen generation from NaBH_(4) hydrolysis limits its application.There are two main factors influencing the kinetics stability of hydrogen generation from NaBH_(4).One factor is that the alkaline byproducts(NaBO_(2)) of the hydrolysis reaction can increase the pH of the solution,thus inhibiting the reaction process.It mainly happens in the NaBH_(4) solution hydrolysis system.Another factor is that the monotonous increase in reaction temperature leads to uncontrollable and unpredictable hydrolysis rates in the solid NaBH_(4) hydrolysis system.This is due to the excess heat generated from this exothermic reaction in the initial reaction of NaBH_(4) hydrolysis.In this perspective,we summarize the latest research progress in hydrogen generation from NaBH_(4) and emphasize the design principles of catalysts for hydrogen generation from NaBH_(4) solution and solid state NaBH_(4).The importance of carbon as catalyst support material for NaBH_(4) hydrolysis is also highlighted.展开更多
基金the National Natural Science Foundation of China (No.20206023, No.20676096)the Special Funds for MajorState Basic Research Program of China (973 Program, 2006CB202500)SINOPEC (X504029).
文摘Gas-liquid (G-L) and liquid-solid (L-S) mass transfer coefficients were characterized in a gas-liquid-solid (G-L-S) three-phase magnetically stabilized bed (MSB) using amorphous alloy SRNA-4 as the solid phase. Effects such as superficial liquid velocity, superficial gas velocity, magnetic strength, liquid viscosity, and particle size were investigated. Experimental results indicated that the G-L volumetric mass transfer coefficients (KLa) increased along with the magnetic strength, superficial gas and liquid velocities. Proper increase of liquid viscosity promoted KLa only in the range of lower liquid viscosity. The external magnetic field made L-S mass transfer coefficients (Ks) in the G-L-S MSB lower than those of conventional fluidized beds. Ks in the MSB almost kept constant as the su- perficial liquid velocity and superficial gas velocity increased and decreased with the liquid viscosity and surface tension, while increased with the particle size Ks showed uniform axial and radial distributions except of small de- creases close to the wall. Dimensionless correlations were established to estimate KLa and Ks of the MSB with SRNA-4 catalysts , which showed the average error of 5.4% and 2.5% respectively.
文摘Liquid-solid （L-S） mass transfer coefficients （Ks） were characterized in a gas-liquid-solid （G-L-S） three-phase countercurrent magnetically stabilized bed （MSB） using amorphous alloy SRNA-4 as the solid phase. Effects of superficial liquid velocity, superficial gas velocity, magnetic field strength, liquid viscosity and surface tension were investigated. Experimental results indicated that the external magnetic field increased Ks in three-phase MSB, as compared to those in conventional G-L-S fluidized beds; that Ks increased with magnetic field strength, superficial gas and liquid velocities and decreased with liquid viscosity and surface tension; and that Ks showed uniform axial and radial distributions except for small increases close to the wall. Dimensionless correlations were established to estimate Ks of the G-L-S countercurrent MSB using SRNA-4 catalyst, with an average error of 3.6%.
文摘氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。
基金the National Natural Science Foun-dation of China(22022802 and 22288102).
文摘The catalytic hydrogenation of 2-nitro-4-acetylamino anisole(NMA)is a less-polluting and efficient method to produce 2-amino-4-acetamino anisole(AMA).However,the kinetics of catalytic hydrogenation of NMA to AMA remains obscure.In this work,the kinetic models including power-law model and Langmuir-Hinshelwood-Hougen-Watson(LHHW)model of NMA hydrogenation to AMA catalyzed by Raney nickel catalyst were investigated.All experiments were carried out under the elimination of mass transfer resistance within the temperature range of 70–100°C and the hydrogen pressure of 0.8–1.5 MPa.The reaction was found to follow 0.52-order kinetics with respect to the NMA concentration and 1.10-order kinetics in terms of hydrogen pressure.Based on the LHHW model,the dual-site dissociation adsorption of hydrogen was analyzed to be the rate determining step.The research of intrinsic kinetics of NMA to AMA provides the guidance for the reactor design and inspires the catalyst modification.
基金supported by MOST of China(No.2021YFB4000603)NSFC(No.22179002 and 51971004).
文摘Sodium borohydride(NaBH_(4)) is considered as the most potential hydrogen storage material for portable proton exchange membrane fuel cells(PEMFC)because of its high theoretical hydrogen capacity.However,the slow and poor kinetic stability of hydrogen generation from NaBH_(4) hydrolysis limits its application.There are two main factors influencing the kinetics stability of hydrogen generation from NaBH_(4).One factor is that the alkaline byproducts(NaBO_(2)) of the hydrolysis reaction can increase the pH of the solution,thus inhibiting the reaction process.It mainly happens in the NaBH_(4) solution hydrolysis system.Another factor is that the monotonous increase in reaction temperature leads to uncontrollable and unpredictable hydrolysis rates in the solid NaBH_(4) hydrolysis system.This is due to the excess heat generated from this exothermic reaction in the initial reaction of NaBH_(4) hydrolysis.In this perspective,we summarize the latest research progress in hydrogen generation from NaBH_(4) and emphasize the design principles of catalysts for hydrogen generation from NaBH_(4) solution and solid state NaBH_(4).The importance of carbon as catalyst support material for NaBH_(4) hydrolysis is also highlighted.
