The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application i...The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application in high-pressure solid rocket motors.In this work,the combustion characteristics of AP/HTPB/Al composite propellants containing ferrocene-based catalysts were investigated,including the burning rate,thermal behavior,the local heat transfer,and temperature profile in the range of 7-28 MPa.The results showed that the exponent breaks were still observed in the propellants after the addition of positive catalysts(Ce-Fc-MOF),the burning rate inhibitor((Ferrocenylmethyl)trimethylammonium bromide,Fc Br)and the mixture of Fc Br/catocene(GFP).However,the characteristic pressure has increased,and the exponent decreased from 1.14 to 0.66,0.55,and 0.48 when the addition of Ce-FcMOF,Fc Br and Fc Br/GFP in the propellants.In addition,the temperature in the first decomposition stage was increased by 7.50℃ and 11.40℃ for the AP/Fc Br mixture and the AP/Fc Br/GFP mixture,respectively,compared to the pure AP.On the other hand,the temperature in the second decomposition stage decreased by 48.30℃ and 81.70℃ for AP/Fc Br and AP/Fc Br/GFP mixtures,respectively.It was also found that Fc Br might generate ammonia to cover the AP surface.In this case,a reaction between the methyl in Fc Br and perchloric acid caused more ammonia to appear at the AP surface,resulting in the suppression of ammonia desorption.In addition,the coarse AP particles on the quenched surface were of a concave shape relative to the binder matrix under low and high pressures when the catalysts were added.In the process,the decline at the AP/HTPB interface was only exhibited in the propellant with the addition of Ce-Fc-MOF.The ratio of the gas-phase temperature gradient of the propellants containing catalysts was reduced significantly below and above the characteristic pressure,rather than 3.6 times of the difference in the blank propellant.Overall,the obtained results demonstrated that the pressure exponent could be effectively regulated and controlled by adjusting the propellant local heat and mass transfer under high and low pressures.展开更多
The optimizing utilization of ca rbon resources has drawn wide attention all over the world,while exploiting the high-efficiency catalytic routes remains a challenge.Here,a direct methanol synthesis route is realized ...The optimizing utilization of ca rbon resources has drawn wide attention all over the world,while exploiting the high-efficiency catalytic routes remains a challenge.Here,a direct methanol synthesis route is realized from pure CO and H_(2)O over 10%Cu/t-ZrO_(2) catalyst,where the time yield of methanol is144.43 mmol mol_(Cu)^(-1)h^(-1)and the methanol selectivity in hydrocarbons is 100%,The Cu species highly dispersed in the t-ZrO_(2) support lead parts of them in the cationic state.The Cu^(+)sites contribute to the dissociation of H_(2)O,providing the H*source for methanol synthesis,while the formed Cu^(0) sites promote the absorption and transfer of H*during the reaction.Moreover,the H_(2)O is even a better H resource than H_(2) due to its better dissociation effectivity in this catalytic system.The present work offers a new approach for methanol synthesis from CO and new insight into the process of supplying H donor.展开更多
A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energ...A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.展开更多
Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O ...Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O electrocatalysis.In this method,NO_(x)is provided by the gliding arc discharge and then electrolyzed by Cu/Cu_(2)O after alkaline absorption.The electrical characteristics,the optical characteristics and the NO_(x)production are investigated in discharges at different input voltage and the gas flow.The dependence of ammonia production through Cu/Cu_(2)O electrocatalysis on pH value and reduction potential are determined by colorimetric method.In our study,two discharge modes are observed.At high input voltage and low gas flow,the discharge is operated with a stable plasma channel which is called the steady arc gliding discharge mode(A-G mode).As lowering input voltage and raising gas flow,the plasma channel is destroyed and high frequency breakdown occurs instead,which is known as the breakdown gliding discharge mode(B-G mode).The optimal NO_(x)production of 7.34 mmol h^(-1)is obtained in the transition stage of the two discharge modes.The ammonia yield reaches0.402 mmol h^(-1)cm^(-2)at pH value of 12.7 and reduction potential of-1.0 V versus reversible hydrogen electrode(RHE).展开更多
Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on s...Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on source treatment is limited.This paper proposes a new coal combustion strategy that significantly reduces NO_(x) emissions during coal combustion.This strategy has two important advantages in reducing NO_(x) emissions.First,by introducing iron-based catalyst at the source,which will catalyze the conversion of coke nitrogen to volatile nitrogen during the pyrolysis process,thereby greatly reducing the coke nitrogen content.The second is de-NO_(x) process by a redox reaction between NO_(x) and reducing agents(coke,HCN,NH_(3),etc.)that occurred during coke combustion.Compared to direct combustion of coal,coke prepared by adding iron-based catalyst has 46.1% reduction in NO_(x) emissions.To determine the effect of iron-based additives on de-NO_(x) performance,demineralized coal(de-coal)was prepared to eliminate the effect of iron-based minerals in coal ash.The effects of iron compounds,additive dosages,and combustion temperatures on de-NO_(x) efficiency are systematically studied.The results revealed that the NO_(x) emission of the coke generated by pyrolysis of de-coal loaded with 3%(mass)Fe_(2)O_(3) decreases to 27.3% at combustion temperature of 900℃.Two main reasons for lower NO_(x) emissions were deduced:(1)During the catalytic coal pyrolysis stage,the nitrogen content in the coke decreases with the release of volatile nitrogen.(2)Part of the NO_(x) emitted during the coke combustion was converted into N_(2) for the catalytic effect of the Fe-based catalysts.It is of great practical value and scientific significance to the comprehensive treatment and the clean utilization process of coal.展开更多
In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can r...In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.展开更多
Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub&...Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> was determined by nano-particle size analyzer, and the effects of nano-α-Al<sub>2</sub>O<sub>3</sub> content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al<sub>2</sub>O<sub>3</sub> dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al<sub>2</sub>O<sub>3</sub> increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al<sub>2</sub>O<sub>3</sub>.展开更多
Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried ...Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.展开更多
Trace amounts of noble metal-doped Ni/Mg（AI）O catalysts were pre- pared starting from Mg-Al hydrotalcites （HTs） and tested in daily start-up and shut-down （DSS） operation of steam reforming （SR） of methane or ...Trace amounts of noble metal-doped Ni/Mg（AI）O catalysts were pre- pared starting from Mg-Al hydrotalcites （HTs） and tested in daily start-up and shut-down （DSS） operation of steam reforming （SR） of methane or partial oxidation （PO） of propane. Although Ni/Mg（Al）O catalysts prepared from Mg（Ni）-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg（Al）O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a ＂memory effect＂ of HTs. Moreover, the noble metal-doped Ni/Mg（Al）O catalysts exhibited ＂intelligent＂ catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2＋ in Mg（Ni,Al）O periclase to Ni^0 assisted by hydrogen spillover from Pt （or Pt-Ni alloy）. The self-regenerative activity was accomplished by self-redispersion of active Ni^0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg（Al）O periclase crystal; surface Ni^0 was oxidized to Ni2＋ by steam and incorporated into Mg（Ni2＋,Al）O periclase, whereas the Ni2＋ in the periclase was reduced to Ni^0 by the hydrogen spillover and appeared as the fine Ni^0 particles on the catalyst surface. Further a ＂green＂ preparation of the Pt/Ni/[Mg3.sAl]O catalysts was accomplished starting from commercial Mg3.5-AI HT by calcination, followed by sequential impregnation of Ni and Pt.展开更多
Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TP...Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TPR and TPO techniques. The results revealed that the deactivation of Cr-Al2O3 catalyst was mainly caused by carbon deposition on its surface. The Cr3＋ ion could not be reduced by hydrogen but could be reduced to Cr2＋ by hydrocarbons and monoxide carbon. The active center for isobutane dehydrogenation could be Cr2＋/Cr3＋ produced from Cr6＋ by the on line reduction of hydrocarbon and carbon monoxide. The binding energy of Al3＋ was strongly affected by the state of chromium cations in the catalysts.展开更多
Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It...Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.展开更多
In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for met...In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.展开更多
基金the support of the National Natural Science Foundation of China grant number 51776175。
文摘The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application in high-pressure solid rocket motors.In this work,the combustion characteristics of AP/HTPB/Al composite propellants containing ferrocene-based catalysts were investigated,including the burning rate,thermal behavior,the local heat transfer,and temperature profile in the range of 7-28 MPa.The results showed that the exponent breaks were still observed in the propellants after the addition of positive catalysts(Ce-Fc-MOF),the burning rate inhibitor((Ferrocenylmethyl)trimethylammonium bromide,Fc Br)and the mixture of Fc Br/catocene(GFP).However,the characteristic pressure has increased,and the exponent decreased from 1.14 to 0.66,0.55,and 0.48 when the addition of Ce-FcMOF,Fc Br and Fc Br/GFP in the propellants.In addition,the temperature in the first decomposition stage was increased by 7.50℃ and 11.40℃ for the AP/Fc Br mixture and the AP/Fc Br/GFP mixture,respectively,compared to the pure AP.On the other hand,the temperature in the second decomposition stage decreased by 48.30℃ and 81.70℃ for AP/Fc Br and AP/Fc Br/GFP mixtures,respectively.It was also found that Fc Br might generate ammonia to cover the AP surface.In this case,a reaction between the methyl in Fc Br and perchloric acid caused more ammonia to appear at the AP surface,resulting in the suppression of ammonia desorption.In addition,the coarse AP particles on the quenched surface were of a concave shape relative to the binder matrix under low and high pressures when the catalysts were added.In the process,the decline at the AP/HTPB interface was only exhibited in the propellant with the addition of Ce-Fc-MOF.The ratio of the gas-phase temperature gradient of the propellants containing catalysts was reduced significantly below and above the characteristic pressure,rather than 3.6 times of the difference in the blank propellant.Overall,the obtained results demonstrated that the pressure exponent could be effectively regulated and controlled by adjusting the propellant local heat and mass transfer under high and low pressures.
基金supported by the National Natural Science Foundation of China under grant numbers 22172032,U22A20431 and U19B2003。
文摘The optimizing utilization of ca rbon resources has drawn wide attention all over the world,while exploiting the high-efficiency catalytic routes remains a challenge.Here,a direct methanol synthesis route is realized from pure CO and H_(2)O over 10%Cu/t-ZrO_(2) catalyst,where the time yield of methanol is144.43 mmol mol_(Cu)^(-1)h^(-1)and the methanol selectivity in hydrocarbons is 100%,The Cu species highly dispersed in the t-ZrO_(2) support lead parts of them in the cationic state.The Cu^(+)sites contribute to the dissociation of H_(2)O,providing the H*source for methanol synthesis,while the formed Cu^(0) sites promote the absorption and transfer of H*during the reaction.Moreover,the H_(2)O is even a better H resource than H_(2) due to its better dissociation effectivity in this catalytic system.The present work offers a new approach for methanol synthesis from CO and new insight into the process of supplying H donor.
基金supported by the National Natural Science Foundation of China,China(Grant Nos.U20B2018,U21B2086,11972087)。
文摘A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.
文摘Highly efficient and green ammonia production is an important demand for modern agriculture.In this study,a two-step ammonia production method is developed using a gliding arc discharge in combination with Cu/Cu_(2)O electrocatalysis.In this method,NO_(x)is provided by the gliding arc discharge and then electrolyzed by Cu/Cu_(2)O after alkaline absorption.The electrical characteristics,the optical characteristics and the NO_(x)production are investigated in discharges at different input voltage and the gas flow.The dependence of ammonia production through Cu/Cu_(2)O electrocatalysis on pH value and reduction potential are determined by colorimetric method.In our study,two discharge modes are observed.At high input voltage and low gas flow,the discharge is operated with a stable plasma channel which is called the steady arc gliding discharge mode(A-G mode).As lowering input voltage and raising gas flow,the plasma channel is destroyed and high frequency breakdown occurs instead,which is known as the breakdown gliding discharge mode(B-G mode).The optimal NO_(x)production of 7.34 mmol h^(-1)is obtained in the transition stage of the two discharge modes.The ammonia yield reaches0.402 mmol h^(-1)cm^(-2)at pH value of 12.7 and reduction potential of-1.0 V versus reversible hydrogen electrode(RHE).
基金supported by National Natural Science Foundation of China(21878210)Shanxi Provincial Science and Technology Achievement Transformation Guidance Special Program of China(202104021301052)Shanxi Province Patent Transformation Special Program Project(202202054).
文摘Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on source treatment is limited.This paper proposes a new coal combustion strategy that significantly reduces NO_(x) emissions during coal combustion.This strategy has two important advantages in reducing NO_(x) emissions.First,by introducing iron-based catalyst at the source,which will catalyze the conversion of coke nitrogen to volatile nitrogen during the pyrolysis process,thereby greatly reducing the coke nitrogen content.The second is de-NO_(x) process by a redox reaction between NO_(x) and reducing agents(coke,HCN,NH_(3),etc.)that occurred during coke combustion.Compared to direct combustion of coal,coke prepared by adding iron-based catalyst has 46.1% reduction in NO_(x) emissions.To determine the effect of iron-based additives on de-NO_(x) performance,demineralized coal(de-coal)was prepared to eliminate the effect of iron-based minerals in coal ash.The effects of iron compounds,additive dosages,and combustion temperatures on de-NO_(x) efficiency are systematically studied.The results revealed that the NO_(x) emission of the coke generated by pyrolysis of de-coal loaded with 3%(mass)Fe_(2)O_(3) decreases to 27.3% at combustion temperature of 900℃.Two main reasons for lower NO_(x) emissions were deduced:(1)During the catalytic coal pyrolysis stage,the nitrogen content in the coke decreases with the release of volatile nitrogen.(2)Part of the NO_(x) emitted during the coke combustion was converted into N_(2) for the catalytic effect of the Fe-based catalysts.It is of great practical value and scientific significance to the comprehensive treatment and the clean utilization process of coal.
基金financial support from National Natural Science Foundation of China(Nos.52004102 and 22078125)Postdoctoral Science Foundation of China(No.2021M690068)+2 种基金Fundamental Research Funds for the Central Universities(Nos.JUSRP221018 and JUSRP622038)Key Laboratory of Green Cleaning Technology and Detergent of Zhejiang Province(No.Q202204)Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(No.GCP202112)。
文摘In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.
文摘Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> was determined by nano-particle size analyzer, and the effects of nano-α-Al<sub>2</sub>O<sub>3</sub> content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al<sub>2</sub>O<sub>3</sub> dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al<sub>2</sub>O<sub>3</sub> increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al<sub>2</sub>O<sub>3</sub>.
基金financially supported by Independent Research Subject from Ministry of Science and Technology of China(No.2008BWZ005)
文摘Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.
基金supported by the New Energy and Industrial Technology Development Organization (NEDO),Japan
文摘Trace amounts of noble metal-doped Ni/Mg（AI）O catalysts were pre- pared starting from Mg-Al hydrotalcites （HTs） and tested in daily start-up and shut-down （DSS） operation of steam reforming （SR） of methane or partial oxidation （PO） of propane. Although Ni/Mg（Al）O catalysts prepared from Mg（Ni）-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg（Al）O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a ＂memory effect＂ of HTs. Moreover, the noble metal-doped Ni/Mg（Al）O catalysts exhibited ＂intelligent＂ catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2＋ in Mg（Ni,Al）O periclase to Ni^0 assisted by hydrogen spillover from Pt （or Pt-Ni alloy）. The self-regenerative activity was accomplished by self-redispersion of active Ni^0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg（Al）O periclase crystal; surface Ni^0 was oxidized to Ni2＋ by steam and incorporated into Mg（Ni2＋,Al）O periclase, whereas the Ni2＋ in the periclase was reduced to Ni^0 by the hydrogen spillover and appeared as the fine Ni^0 particles on the catalyst surface. Further a ＂green＂ preparation of the Pt/Ni/[Mg3.sAl]O catalysts was accomplished starting from commercial Mg3.5-AI HT by calcination, followed by sequential impregnation of Ni and Pt.
基金supported by the Natural Science Foundation of Shandong Provence of China(ZR2013BM008)
文摘Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TPR and TPO techniques. The results revealed that the deactivation of Cr-Al2O3 catalyst was mainly caused by carbon deposition on its surface. The Cr3＋ ion could not be reduced by hydrogen but could be reduced to Cr2＋ by hydrocarbons and monoxide carbon. The active center for isobutane dehydrogenation could be Cr2＋/Cr3＋ produced from Cr6＋ by the on line reduction of hydrocarbon and carbon monoxide. The binding energy of Al3＋ was strongly affected by the state of chromium cations in the catalysts.
文摘Characteristics of carbon deposition of CH 4 and C 2H 4 decomposition over supported Ni and Ni Ce catalysts were studied by using a pulse reaction as well as BET, TPR, XPS and hydrogen chemisorption techniques. It is found that there is a metal semiconductor interaction (MScI) in the Ni Ce catalyst, and the effect of MScI on the carbon deposition of CH 4 decomposition is opposite to that of C 2H 4. A novel model of carbon deposition of CH 4 or C 2H 4 decomposition was proposed.
基金supported by the National Basic Research Program of China(973 Program,2013CB933104)the National Natural Science Foundation of China(Nos.11275258 and 11135008)
文摘In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.
