A new technology was developed to recover multiple valuable elements from the spent Al2O3-based catalyst by X-ray phase analysis and exploratory experiments. The experimental results show that in the condition of roas...A new technology was developed to recover multiple valuable elements from the spent Al2O3-based catalyst by X-ray phase analysis and exploratory experiments. The experimental results show that in the condition of roasting temperature of 750℃ and roasting time of 30 min, molar ratio of Na2O to Al2O3 of 1.2, the leaching rates of alumina, vanadium and molybdenum in the spent catalyst are 97.2%, 95.8% and 98.9%, respectively. Vanadium and molybdenum in sodium aluminate solution can be recovered by precipitators A and B, and the precipitation rates of vanadium and molybdenum are 94.8% and 92.6%. Al（OH）3 was prepared from sodium aluminate solution in the carbonation decomposition process, and the purity of Al2O3 is 99.9% after calcination, the recovery of alumina reaches 90.6% in the whole process; the Ni-Co concentrate was leached by sulfuric acid, a nickel recovery of 98.2% and cobalt recovery over 98.5% can be obtained under the experimental condition of 30% H2SO4, 80℃, reaction time 4 h, mass ratio of liquid to solid 8, stirring rate 800r/min.展开更多
V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for N...V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for NOx conversion using NH3 as the reductant. Hydrothermal ageing decreased the NOx conversion of V2O5/WO3‐TiO2 catalyst severely over the entire measured tem‐perature range. Interestingly, the NH3‐SCR activity of the silica‐modified catalyst at 220–480℃ is enhanced after ageing. The catalysts were characterized by X‐ray diffraction, nitrogen adsorption, X‐ray fluorescence, Raman spectroscopy, H2 temperature‐programmed reduction, and NH3 temper‐ature‐programmed desorption. The addition of silica inhibited the phase transition from anatase to rutile titania, growth of TiO2 crystallite size and shrinkage of catalyst surface area. Consequently, the vanadia species remained highly dispersed and the hydrothermal stability of the V2O5/WO3‐TiO2 catalyst was significantly improved.展开更多
A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. ...A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m^2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction（SCR） performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was 80% from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.展开更多
In this work, the effectiveness of V2O5-WO3/TiO2 catalysts modified with different CeO2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied compara...In this work, the effectiveness of V2O5-WO3/TiO2 catalysts modified with different CeO2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V2O5-WO3/CeO2-TiO2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%（All Ce contents are in mass fractions）, but the NO conversion of V2O5-WO3/CeO2/TiO2 catalysts modified by impregnation methods was lower than V2O5-WO3/CeO2-TiO2 catalysts especially beyond 2.5% Ce doping contents. The V2O5-WO3/CeO2-TiO2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce^（3＋）species and more Br？nsted acid sites than that by impregnation. The vacancies caused by more Ce^（3＋）species were favorable for more NO oxidation to NO2, and the interaction between Ce species and WOxspecies generated more Br？nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V2O5-WO3/CeO2-TiO2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V2O5-WO3/TiO2 catalysts.展开更多
A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐W...A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐WO3/TiO2 catalyst.The physicochemical properties were investigated by using XRD,BET,NH3‐TPD,H2‐TPR,and XPS,and the catalytic performance and K‐poisoning resistance were evaluated via a NH3‐SCR model reaction.Ce^4+and Zr^4+co‐doping were found to enhance the conversion of NOx,and exhibit the best K‐poisoning resistance owing to the largest BET‐specific surface area,pore volume,and total acid site concentration,as well as the minimal effects on the surface acidity and redox ability from K poisoning.The V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst also presents outstanding H2O+SO2 tolerance.Finally,the in situ DRIFTS reveals that the NH3‐SCR reaction over the V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst follows an L‐H mechanism,and that K poisoning does not change the reaction mechanism.展开更多
The V/O5-WO3-MoOy＇TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction （XRD）, scanning electron micrograph （SEM...The V/O5-WO3-MoOy＇TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction （XRD）, scanning electron micrograph （SEM） and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass per- centage of V ： W ： Mo ： TiO2 ： fiber glass = 1 ： 4.5 ： 4.5 ： 72 ： 18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to ruffle by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3. The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615 1640 mg.m-3. Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.展开更多
The purpose of this work is to explore the effects of the introduction methods of Ce^4+and Zr^4+on the physicochemical properties,activity,and K tolerance of V2 O5-WO3/TiO2 catalyst for the selective catalytic reducti...The purpose of this work is to explore the effects of the introduction methods of Ce^4+and Zr^4+on the physicochemical properties,activity,and K tolerance of V2 O5-WO3/TiO2 catalyst for the selective catalytic reduction of NOx by NH3.Four different methods,namely pre-impregnation,post-impregnation,coimpregnation,and co-precipitation,were used to synthesize a series of V2 O5-WO3-TiO2-CeO2-ZrO2 catalysts.The catalysts were characterized by XRD,BET,NH3-TPD,XPS,and H2-TPR techniques.Moreover,the activity and anti-K poisoning performance were tested by an NH3-SCR model reaction.The results show that the introduction of Ce^4+and Zr^4+can improve the catalytic performance of V2O5-WO3/TiO2 catalyst,but the impregnation method cannot enhance the anti-K poisoning performance.Ce^4+and Zr^4+introduced by co-precipitation method can effectively improve the tolerance of K,which is mainly due to the incorporation of Ce^4+and Zr^4+into TiO2 lattice to form a uniform TiO2-CeO2-ZrO2 solid solution,resulting in the optimal surface acidity and redox performance,and reducing the decreases caused by Kpoisoning.Furthermore,based on the best introduction method,we further optimized the molar ratio of Ce^4+/Zr^4+,It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce^4+/Zr^4+is 2:1.展开更多
基金Project(2003 UDBEA00C020) supported by the Collaborative Project of School and Province of Yunnan Province
文摘A new technology was developed to recover multiple valuable elements from the spent Al2O3-based catalyst by X-ray phase analysis and exploratory experiments. The experimental results show that in the condition of roasting temperature of 750℃ and roasting time of 30 min, molar ratio of Na2O to Al2O3 of 1.2, the leaching rates of alumina, vanadium and molybdenum in the spent catalyst are 97.2%, 95.8% and 98.9%, respectively. Vanadium and molybdenum in sodium aluminate solution can be recovered by precipitators A and B, and the precipitation rates of vanadium and molybdenum are 94.8% and 92.6%. Al（OH）3 was prepared from sodium aluminate solution in the carbonation decomposition process, and the purity of Al2O3 is 99.9% after calcination, the recovery of alumina reaches 90.6% in the whole process; the Ni-Co concentrate was leached by sulfuric acid, a nickel recovery of 98.2% and cobalt recovery over 98.5% can be obtained under the experimental condition of 30% H2SO4, 80℃, reaction time 4 h, mass ratio of liquid to solid 8, stirring rate 800r/min.
基金supported by the National Natural Science Foundation of China (51372137)the National High Technology Research and Development Program of China (863 Program,2015AA034603)~~
文摘V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for NOx conversion using NH3 as the reductant. Hydrothermal ageing decreased the NOx conversion of V2O5/WO3‐TiO2 catalyst severely over the entire measured tem‐perature range. Interestingly, the NH3‐SCR activity of the silica‐modified catalyst at 220–480℃ is enhanced after ageing. The catalysts were characterized by X‐ray diffraction, nitrogen adsorption, X‐ray fluorescence, Raman spectroscopy, H2 temperature‐programmed reduction, and NH3 temper‐ature‐programmed desorption. The addition of silica inhibited the phase transition from anatase to rutile titania, growth of TiO2 crystallite size and shrinkage of catalyst surface area. Consequently, the vanadia species remained highly dispersed and the hydrothermal stability of the V2O5/WO3‐TiO2 catalyst was significantly improved.
基金supported by the National Natural Science Foundation of China(21325731,21221004)the National High Technology Research and Development Program of China(863 Program)the State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex
文摘A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m^2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction（SCR） performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was 80% from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.
基金Project supported by the Guangxi Natural Science Foundation(2014GXNSFAA118057)Guangxi Science and Technology Planning Project(AB16380276)
文摘In this work, the effectiveness of V2O5-WO3/TiO2 catalysts modified with different CeO2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V2O5-WO3/CeO2-TiO2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%（All Ce contents are in mass fractions）, but the NO conversion of V2O5-WO3/CeO2/TiO2 catalysts modified by impregnation methods was lower than V2O5-WO3/CeO2-TiO2 catalysts especially beyond 2.5% Ce doping contents. The V2O5-WO3/CeO2-TiO2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce^（3＋）species and more Br？nsted acid sites than that by impregnation. The vacancies caused by more Ce^（3＋）species were favorable for more NO oxidation to NO2, and the interaction between Ce species and WOxspecies generated more Br？nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V2O5-WO3/CeO2-TiO2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V2O5-WO3/TiO2 catalysts.
基金supported by the National Natural Science Foundation of China(21876168,21507130)the Key Projects for Common Key Technology Innovation in Key Industries in Chongqing(cstc2016zdcy-ztzx0020-01)+2 种基金the Chongqing Science&Technology Commission(cstc2016jcyjA0070,cstckjcxljrc13)the Open Project Program of Chongqing Key Laboratory of Catalysis and Functional Organic Molecules from Chongqing Technology and Business University(1456029)the Graduate Innovation Project of Chongqing Technology and Business University(yjscxx201803-028-22)~~
文摘A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐WO3/TiO2 catalyst.The physicochemical properties were investigated by using XRD,BET,NH3‐TPD,H2‐TPR,and XPS,and the catalytic performance and K‐poisoning resistance were evaluated via a NH3‐SCR model reaction.Ce^4+and Zr^4+co‐doping were found to enhance the conversion of NOx,and exhibit the best K‐poisoning resistance owing to the largest BET‐specific surface area,pore volume,and total acid site concentration,as well as the minimal effects on the surface acidity and redox ability from K poisoning.The V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst also presents outstanding H2O+SO2 tolerance.Finally,the in situ DRIFTS reveals that the NH3‐SCR reaction over the V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst follows an L‐H mechanism,and that K poisoning does not change the reaction mechanism.
基金Supported by the Science and Technology Development Planning of Shandong Province(2011GSF11716)China Scholarship Council for Researching in University of Birmingham
文摘The V/O5-WO3-MoOy＇TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction （XRD）, scanning electron micrograph （SEM） and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass per- centage of V ： W ： Mo ： TiO2 ： fiber glass = 1 ： 4.5 ： 4.5 ： 72 ： 18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to ruffle by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3. The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615 1640 mg.m-3. Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.
基金Project supported by the National Natural Science Foundation of China(21876168)the Key Projects for Common Key Technology Innovation in Key Industries in Chongqing(cstc2016zdcy-ztzx0020-01)+1 种基金Youth Innovation Promotion Association CAS(2019376)the Graduate Innovation Project of Chongqing Technology and Business University(yjscxx201803-028-22)。
文摘The purpose of this work is to explore the effects of the introduction methods of Ce^4+and Zr^4+on the physicochemical properties,activity,and K tolerance of V2 O5-WO3/TiO2 catalyst for the selective catalytic reduction of NOx by NH3.Four different methods,namely pre-impregnation,post-impregnation,coimpregnation,and co-precipitation,were used to synthesize a series of V2 O5-WO3-TiO2-CeO2-ZrO2 catalysts.The catalysts were characterized by XRD,BET,NH3-TPD,XPS,and H2-TPR techniques.Moreover,the activity and anti-K poisoning performance were tested by an NH3-SCR model reaction.The results show that the introduction of Ce^4+and Zr^4+can improve the catalytic performance of V2O5-WO3/TiO2 catalyst,but the impregnation method cannot enhance the anti-K poisoning performance.Ce^4+and Zr^4+introduced by co-precipitation method can effectively improve the tolerance of K,which is mainly due to the incorporation of Ce^4+and Zr^4+into TiO2 lattice to form a uniform TiO2-CeO2-ZrO2 solid solution,resulting in the optimal surface acidity and redox performance,and reducing the decreases caused by Kpoisoning.Furthermore,based on the best introduction method,we further optimized the molar ratio of Ce^4+/Zr^4+,It is found that the catalyst exhibits the best anti-K poisoning performance when the molar ratio of Ce^4+/Zr^4+is 2:1.
