A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst.The best catalyst Cu0.010/Nb1Ce3 presented over 90%NO conversion in a wide temperature range of 200-400℃...A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst.The best catalyst Cu0.010/Nb1Ce3 presented over 90%NO conversion in a wide temperature range of 200-400℃and exhibited an excellent H_(2)O or/and SO_(2) resistance at 275℃.To understand the promotional mechanism of Cu modification,the correlation among the"activity-structure-property"were tried to establish systematically.Cu species highly dispersed on NbCe catalyst to serve as the active component.The strong interaction among Cu,Nb and Ce promoted the emergence of NbO4 and induced more Bronsted acid sites.And Cu modification obviously enhanced the redox behavior of the NbCe catalyst.Besides,EPR probed the Cu species exited in the form of monomeric and dimeric Cu^(2+),the isolated Cu^(2+)acted as catalytic active sites to promote the reaction:Cu^(2+)-NO_(3)^(-)+NO(g)→Cu^(2+)-NO_(2)^(-)+NO_(2)(g).Then the generated NO_(2) would accelerate the fast-SCR reaction process and thus facilitated the lowtemperature deNO_(x) efficiency.Moreover,surface nitrates became unstable and easy to decompose after Cu modification,thus providing additional adsorption and activation sites for NH3,and ensuring the improvement of catalytic activity at high temperature.Since the NH3-SCR reaction followed by E-R reaction pathway efficaciously over Cu_(0.010)/Nb_(1)Ce_(3) catalyst,the excellent H_(2)O and SO_(2) resistance was as expected.展开更多
A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste...A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization(Ca–SD-FGD and Zn–SD-FGD) technologies, respectively. It was found that Zn SO3·2.5H2 O first lost crystal H2 O at 100 °C and then decomposed into SO2 and solid Zn O at 260 °C in the air, while Ca SO3 is oxidized at 450 °C before it decomposed in the air. The experimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2absorption, and the intermediate product Na HSO3 reacts with Zn O powders, producing Zn SO3·2.5H2 O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of Zn SO3·2.5H2 O, Zn O is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of Zn O only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.展开更多
Based on the TiO2 photocatalysis mechanism, a new method of simultaneous desulfurization and denitrification from flue gas was proposed. Preparation of TiO2 photocatalyst, design of photocatalysis reactor and influenc...Based on the TiO2 photocatalysis mechanism, a new method of simultaneous desulfurization and denitrification from flue gas was proposed. Preparation of TiO2 photocatalyst, design of photocatalysis reactor and influencing factors for simul- taneous removal of SO2 and NO, and removal mechanism of SO2 and NO were studied. After the optimal values of concentration of O2 in flue gas, the relative humidity of flue gas and the irradiation time in the photocatalysis reactor were used, the efficiencies of removal for SO2 and NO can be achieved above 98% and about 67%, respectively. According to the results of removal products analysis, the re- moval mechanism of SO2 and NO based on TiO2 photocatlysis can be put forward, namely, SO2 was oxidized to SO3 partly, the bulk of NO was oxidized to NO2, and both were removed by resorbing finally.展开更多
With the vigorous development of China's iron and steel industry and the introduction of ultra-low emission policies,the emission of pollutants such as SO_(2)and NO x has received unprecedented attention.Consideri...With the vigorous development of China's iron and steel industry and the introduction of ultra-low emission policies,the emission of pollutants such as SO_(2)and NO x has received unprecedented attention.Considering the increase of the proportion of semi-dry desulfurization technology in the desulfurization process,several semi-dry desulphurization technologies such as flue gas circulating fluidized bed(CFB),dense flow absorber(DFA)and spray drying absorption(SDA)are briefly summarized.Moreover,a method for simultaneous treatment of SO_(2)and NOx in sintering/pelletizing flue gas by O_(3)oxidation combined with semidry method is introduced.Meantime,the effects of key parameters such as O_(3)/NO molar ratio,Ca SO_(3),SO_(2),reaction temperature,Ca/(S+2 N)molar ratio,droplet size and approach to adiabatic saturation temperature(AAST)on denitrification and desulfurization are analyzed.Furthermore,the reaction mechanism of denitrification and desulfurization is further elucidated.Finally,the advantages and development prospects of the new technology are proposed.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
Solid sorbents with enhanced capacity and selectivity towards CO2 are crucial in the design of an efficient capture process.Among the possible alternatives,K2CO3-doped activated carbons have shown high CO2 capture cap...Solid sorbents with enhanced capacity and selectivity towards CO2 are crucial in the design of an efficient capture process.Among the possible alternatives,K2CO3-doped activated carbons have shown high CO2 capture capacity and rapid carbonation reaction rate.In this work,a sustainable and low-cost approach is developed with a biomass-based activated carbon or biocarbon as support.The CO2 capture performance in cyclic sorption–desorption operation and the sorption kinetics have been investigated under different scenarios in a purpose-built fixed-bed set-up.Independent of the H2O concentration in the flue gas,a constant relative humidity(~20%)in the K2CO3-doped biocarbon bed promoted the carbonation reaction and boosted the CO2 sorption capacity(1.92 mmol/g at 50℃ and 14 kPa partial pressure of CO2).Carbonation is slower than physical adsorption of CO2 but wise process design could tune the operation conditions and balance capture capacity and sorption kinetics.展开更多
Cycloaddition of CO_(2) and epoxide into cyclic carbonate is one of the most efficient ways for CO_(2) conversion with 100% atom-utilization. Metal–organic frameworks are a kind of potential heterogeneous catalysts, ...Cycloaddition of CO_(2) and epoxide into cyclic carbonate is one of the most efficient ways for CO_(2) conversion with 100% atom-utilization. Metal–organic frameworks are a kind of potential heterogeneous catalysts, however, high temperature, high pressure, and high-purity CO_(2) are still required for the reaction.Here, we report two new Zn(Ⅱ) imidazolate frameworks incoporating MoO_(4)^(2–)or WO_(4)^(2–)units, which can catalyse cycloaddition of CO_(2) and epichlorohydrin at room temperature and atomospheric pressure, giving 95% yield after 24 h in pure CO_(2) and 98% yield after 48 h in simulated flue gas(15% CO_(2)+ 85% N_(2)),respectively. For comparison, the analogic Zn(Ⅱ) imidazolate framework MAF-6 without non-3d metal oxide units showed 71% and 33% yields under the same conditions, respectively. The insightful modulation mechanisms of the MoO_(4)^(2–)unit in optimizing the electronic structure of Zn(Ⅱ) centre, facilitating the rate-determined ring opening process, and minimizing the reaction activation energy, were revealed by X-ray photoelectron spectroscopy, temperature programmed desorption and computational calculations.展开更多
A series of Al2O3 and CeO2 modified MgO sorbents was prepared and studied for CO2 sorption at moderate temperatures. The CO2 sorption capacity of MgO was enhanced with the addition of either Al2O3 or CeO2. Over Al2O3-...A series of Al2O3 and CeO2 modified MgO sorbents was prepared and studied for CO2 sorption at moderate temperatures. The CO2 sorption capacity of MgO was enhanced with the addition of either Al2O3 or CeO2. Over Al2O3-MgO sorbents, the best capacity of 24.6 mg- CO2/g-sorbent was attained at 100 ℃, which was 61% higher than that of MgO （15.3 mg-CO2/g-sorbent）. The highest capacity of 35.3 mg-CO2/g-sorbent was obtained over the CeO2-MgO sorbents at the optimal temperature of 200 ℃. Combining with the characterization results, we conclude that the promotion effect on CO2 sorption with the addition of Al2O3 and CeO2 can be attributed to the increased surface area with reduced MgO crystallite size. Moreover, the addition of CeO2 increased the basicity of MgO phase, resulting in more increase in the CO2 capacity than Al2O3 promoter. Both the Al2O3-MgO and CeO2- MgO sorbents exhibited better cyclic stability than MgO over the course of fifteen CO2 sorption-desorption cycles. Compared to Al2O3, CeO2 is more effective for promoting the CO2 capacity of MgO. To enhance the CO2 capacity of MgO sorbent, increasing the basicity is more effective than the increase in the surface area.展开更多
基金Financial support from the National Natural Science Foundation of China,China(Nos.21972062,21976081,21976111)。
文摘A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst.The best catalyst Cu0.010/Nb1Ce3 presented over 90%NO conversion in a wide temperature range of 200-400℃and exhibited an excellent H_(2)O or/and SO_(2) resistance at 275℃.To understand the promotional mechanism of Cu modification,the correlation among the"activity-structure-property"were tried to establish systematically.Cu species highly dispersed on NbCe catalyst to serve as the active component.The strong interaction among Cu,Nb and Ce promoted the emergence of NbO4 and induced more Bronsted acid sites.And Cu modification obviously enhanced the redox behavior of the NbCe catalyst.Besides,EPR probed the Cu species exited in the form of monomeric and dimeric Cu^(2+),the isolated Cu^(2+)acted as catalytic active sites to promote the reaction:Cu^(2+)-NO_(3)^(-)+NO(g)→Cu^(2+)-NO_(2)^(-)+NO_(2)(g).Then the generated NO_(2) would accelerate the fast-SCR reaction process and thus facilitated the lowtemperature deNO_(x) efficiency.Moreover,surface nitrates became unstable and easy to decompose after Cu modification,thus providing additional adsorption and activation sites for NH3,and ensuring the improvement of catalytic activity at high temperature.Since the NH3-SCR reaction followed by E-R reaction pathway efficaciously over Cu_(0.010)/Nb_(1)Ce_(3) catalyst,the excellent H_(2)O and SO_(2) resistance was as expected.
基金Supported by the National High Technology Research and Development Program of China(2009AA05Z302)
文摘A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization(Ca–SD-FGD and Zn–SD-FGD) technologies, respectively. It was found that Zn SO3·2.5H2 O first lost crystal H2 O at 100 °C and then decomposed into SO2 and solid Zn O at 260 °C in the air, while Ca SO3 is oxidized at 450 °C before it decomposed in the air. The experimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2absorption, and the intermediate product Na HSO3 reacts with Zn O powders, producing Zn SO3·2.5H2 O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of Zn SO3·2.5H2 O, Zn O is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of Zn O only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.
文摘Based on the TiO2 photocatalysis mechanism, a new method of simultaneous desulfurization and denitrification from flue gas was proposed. Preparation of TiO2 photocatalyst, design of photocatalysis reactor and influencing factors for simul- taneous removal of SO2 and NO, and removal mechanism of SO2 and NO were studied. After the optimal values of concentration of O2 in flue gas, the relative humidity of flue gas and the irradiation time in the photocatalysis reactor were used, the efficiencies of removal for SO2 and NO can be achieved above 98% and about 67%, respectively. According to the results of removal products analysis, the re- moval mechanism of SO2 and NO based on TiO2 photocatlysis can be put forward, namely, SO2 was oxidized to SO3 partly, the bulk of NO was oxidized to NO2, and both were removed by resorbing finally.
基金supported by the National Key Research and Development Program of China(No.2017YFC0210600)the National Natural Science Foundation of China(No.51978644)。
文摘With the vigorous development of China's iron and steel industry and the introduction of ultra-low emission policies,the emission of pollutants such as SO_(2)and NO x has received unprecedented attention.Considering the increase of the proportion of semi-dry desulfurization technology in the desulfurization process,several semi-dry desulphurization technologies such as flue gas circulating fluidized bed(CFB),dense flow absorber(DFA)and spray drying absorption(SDA)are briefly summarized.Moreover,a method for simultaneous treatment of SO_(2)and NOx in sintering/pelletizing flue gas by O_(3)oxidation combined with semidry method is introduced.Meantime,the effects of key parameters such as O_(3)/NO molar ratio,Ca SO_(3),SO_(2),reaction temperature,Ca/(S+2 N)molar ratio,droplet size and approach to adiabatic saturation temperature(AAST)on denitrification and desulfurization are analyzed.Furthermore,the reaction mechanism of denitrification and desulfurization is further elucidated.Finally,the advantages and development prospects of the new technology are proposed.
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.
文摘Solid sorbents with enhanced capacity and selectivity towards CO2 are crucial in the design of an efficient capture process.Among the possible alternatives,K2CO3-doped activated carbons have shown high CO2 capture capacity and rapid carbonation reaction rate.In this work,a sustainable and low-cost approach is developed with a biomass-based activated carbon or biocarbon as support.The CO2 capture performance in cyclic sorption–desorption operation and the sorption kinetics have been investigated under different scenarios in a purpose-built fixed-bed set-up.Independent of the H2O concentration in the flue gas,a constant relative humidity(~20%)in the K2CO3-doped biocarbon bed promoted the carbonation reaction and boosted the CO2 sorption capacity(1.92 mmol/g at 50℃ and 14 kPa partial pressure of CO2).Carbonation is slower than physical adsorption of CO2 but wise process design could tune the operation conditions and balance capture capacity and sorption kinetics.
基金supported by the National Natural Science Foundation of China (Nos. 22090061, 21731007, 21890380 and 22161021)the Guangdong Pearl River Talents Program (No. 2017BT01C161)the support of Jiangxi Province (No. jxsq2018106041)。
文摘Cycloaddition of CO_(2) and epoxide into cyclic carbonate is one of the most efficient ways for CO_(2) conversion with 100% atom-utilization. Metal–organic frameworks are a kind of potential heterogeneous catalysts, however, high temperature, high pressure, and high-purity CO_(2) are still required for the reaction.Here, we report two new Zn(Ⅱ) imidazolate frameworks incoporating MoO_(4)^(2–)or WO_(4)^(2–)units, which can catalyse cycloaddition of CO_(2) and epichlorohydrin at room temperature and atomospheric pressure, giving 95% yield after 24 h in pure CO_(2) and 98% yield after 48 h in simulated flue gas(15% CO_(2)+ 85% N_(2)),respectively. For comparison, the analogic Zn(Ⅱ) imidazolate framework MAF-6 without non-3d metal oxide units showed 71% and 33% yields under the same conditions, respectively. The insightful modulation mechanisms of the MoO_(4)^(2–)unit in optimizing the electronic structure of Zn(Ⅱ) centre, facilitating the rate-determined ring opening process, and minimizing the reaction activation energy, were revealed by X-ray photoelectron spectroscopy, temperature programmed desorption and computational calculations.
基金Acknowledgements The authors gratefully acknowledge the financial support from Pennsylvania State University through the Penn State Institutes of Energy and the Environment, and from the National Natural Science Foundation of China （Grant No. 21005083） and the Innovative Fund of Shanghai Institute of Ceramics, Chinese Academy of Sciences （Grant No. Y37ZC4140G）. Dr. Huimei Yu would like to thank the Chinese Academy of Sciences for the visiting scholarship and Dr. Song for the visiting scholar invitation to the EMS Energy Institute at Penn State.
文摘A series of Al2O3 and CeO2 modified MgO sorbents was prepared and studied for CO2 sorption at moderate temperatures. The CO2 sorption capacity of MgO was enhanced with the addition of either Al2O3 or CeO2. Over Al2O3-MgO sorbents, the best capacity of 24.6 mg- CO2/g-sorbent was attained at 100 ℃, which was 61% higher than that of MgO （15.3 mg-CO2/g-sorbent）. The highest capacity of 35.3 mg-CO2/g-sorbent was obtained over the CeO2-MgO sorbents at the optimal temperature of 200 ℃. Combining with the characterization results, we conclude that the promotion effect on CO2 sorption with the addition of Al2O3 and CeO2 can be attributed to the increased surface area with reduced MgO crystallite size. Moreover, the addition of CeO2 increased the basicity of MgO phase, resulting in more increase in the CO2 capacity than Al2O3 promoter. Both the Al2O3-MgO and CeO2- MgO sorbents exhibited better cyclic stability than MgO over the course of fifteen CO2 sorption-desorption cycles. Compared to Al2O3, CeO2 is more effective for promoting the CO2 capacity of MgO. To enhance the CO2 capacity of MgO sorbent, increasing the basicity is more effective than the increase in the surface area.
