Accurate measurement of trace heavy metal mercury(Hg) in flue gas of coal-fired units is great significance for ecological and environmental protection.Mixed gas was used to simulate the actual flue gas of a power pla...Accurate measurement of trace heavy metal mercury(Hg) in flue gas of coal-fired units is great significance for ecological and environmental protection.Mixed gas was used to simulate the actual flue gas of a power plant in this study.A laser-induced breakdown spectroscopy(LIBS)system for Hg measurement in mixed gas was built to study the effect of mixed gas pressure,Hg concentration in mixed gas and delay time on Hg measurement.The experimental results show that the appropriate low mixed gas pressure can obtain high Hg signal intensity and signal to noise ratio.The Hg signal intensity and signal to noise ratio increased with the increase of Hg concentration in mixed gas.The Hg signal intensity and signal to noise ratio decreased with the increase in delay time.According to the above results,the optimized measurement conditions can be determined.Different Hg concentrations in mixed gas were quantitatively analyzed by the internal standard method and traditional calibration method respectively.The relative error of prediction of the test sample obtained by the internal standard method was within 11.11%.The relative error of prediction of the traditional calibration method was less than 14.54%.This proved that the internal standard method can improve the accuracy of quantitative analysis of Hg concentration in flue gas using LIBS.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
Hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites were selected for elemental mercury(Hg^0) removal from non-ferrous metal smelting flue gas in this study. Results showed that the hierarchical Ag-SiO_2@Fe_3O_4 magneti...Hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites were selected for elemental mercury(Hg^0) removal from non-ferrous metal smelting flue gas in this study. Results showed that the hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites had favorable Hg^0 removal ability at low temperature. Moreover, the adsorption capacity of hierarchical magnetic composite is much larger than that of pure Fe_3O_4 and SiO_2@Fe_3O_4. The Hg^0 removal efficiency reached the highest value as approximately 92% under the reaction temperature of 150°C, while the removal efficiency sharply reduced in the absence of O_2. The characterization results indicated that Ag nanoparticles grew on the surface of SiO_2@Fe_3O_4 support. The large surface area of SiO_2 supplied efficient reaction room for Hg and Ag atoms. Ag–Hg amalgam is generated on the surface of the composites. In addition, this magnetic material could be easily separated from fly ashes when adopted for treating real flue gas, and the spent materials could be regenerated using a simple thermal-desorption method.展开更多
Air pollutant emissions represent a critical challenge in the green development of the non-ferrous metallurgy industry.This work studied the emission characteristics,formation mechanisms,phase transformation and separ...Air pollutant emissions represent a critical challenge in the green development of the non-ferrous metallurgy industry.This work studied the emission characteristics,formation mechanisms,phase transformation and separation of typical air pollutants,such as heavy metal particles,mercury,sulfur oxides and fluoride,during non-ferrous smelting.A series of purification technologies,including optimization of the furnace throat and hightemperature discharge,were developed to collaboratively control and recover fine particles from the flue gas of heavy metal smelting processes,including copper,lead and zinc.Significant improvements have been realized in wet scrubbing technology for removing mercury,fluoride and SO_(2)from flue gas.Gas-liquid sulfidation technology by applying H_(2)S was invented to recycle the acid scrubbing wastewater more efficiently and in an eco-friendly manner.Based on digital technology,a source reduction method was designed for sulfur and fluoride control during the whole aluminum electrolysis process.New desulfurization technologies were developed for catalytic reduction of the sulfur content in petroleum coke at low temperature and catalytic reduction of SO_(2)to elemental sulfur.This work has established the technology for coupling multi-pollutant control and resource recovery from the flue gas from non-ferrous metallurgy,which provides the scientific theoretical basis and application technology for the treatment of air pollutants in the non-ferrous metallurgy industry.展开更多
Activated carbon （AC） was considered to be an effective sorbent to control mercury in combustion systems. However, its capture capacity was low and it required a high carbon-to-mercury mass ratio. AC loaded with cat...Activated carbon （AC） was considered to be an effective sorbent to control mercury in combustion systems. However, its capture capacity was low and it required a high carbon-to-mercury mass ratio. AC loaded with catalyst showed a high elemental mercury （Hg 0 ） capture capacity due to large surface area of AC and high oxidization ability of catalyst. In this study, several metal chlorides and metal oxides were used to promote the sorption capacity of AC. As a result, metal chlorides were better than metal oxides loaded on AC to remove gaseous mercury. X-ray diffractometer （XRD）, thermogravimetric analyzer （TGA） and specific surface area by Brunauer- Emmett-Teller method （BET） analysis showed the main mechanisms： first, AC had an enormous surface area for loading enough MClx; second, Cl and MxOy were generated during pyrogenation of MClx; finally, there were lots of active elements such as Cl and MxOy which could react with elemental mercury and convert it to mercury oxide and mercury chloride. The HgO and HgCl 2 might be released from AC’s porous structure by thermo regeneration. A catalytic chemisorption mechanism predominates the sorption process of elemental mercury. As Co and Mn were valence variable metal elements, their catalytic effect on Hg 0 oxidization may accelerate both oxidation and halogenation of Hg 0 . The sorbents loaded with metal chlorides possessed a synergistic function of catalytic effect of valence variable metal and chlorine oxidation.展开更多
Oxidation of sulfite and competitive absorption existed in Na_(2)SO_(3) solution for simultaneous removal of NO_(x) and SO_(2),inhibited the long-term high-efficiency when used for practical applications.A matching st...Oxidation of sulfite and competitive absorption existed in Na_(2)SO_(3) solution for simultaneous removal of NO_(x) and SO_(2),inhibited the long-term high-efficiency when used for practical applications.A matching strategy was developed to solve these problems.Antioxidants combination was used to retard the oxidation of antioxidant and enhance inhibition of S(IV)(tetravalent sulfur)oxidation.Hydroquinone(HQ)and sodium thiosulfate(ST)showed a positive synergistic effect on inhibition of S(IV)oxidation.When SO_(2) concentration was 500 and 2000 ppmV,the addition of 0.1 wt.%HQ and 1 wt.%ST decreased the percentage of S(IV)oxidized by oxygen by over 30%and 40%,respectively.Alkali(Na_(2)CO_(3))alleviated the competitive absorption between NO_(x) and SO_(2).Moreover,Na_(2)CO_(3) exhibited an enhancement effect on the absorption of NO_(x) and SO_(2) when coupled with anti-oxidants.While the increase of oxygen pressure accelerated the oxidation of S(IV),the anti-oxidants can retard the oxidation.The measurement of pH suggested the removal efficiency of NO_(x) highly depended on SO_(3)^(2-) concentration rather than pH.The further investigation of the mechanism suggested the match effect was related to the interaction between ST and the intermediate product of HQ.The match strategy holds a potential for application of SO_(3)^(2-) to denitration.展开更多
Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of ...Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of Hg^0 absorption by HgCl2 and the factors that control the removal were studied in this paper. It was found that when the mole ratio of Cl^- to HgCl2 is 10：1, the Hg^0 removal efficiency is the highest. Among the main mercury chloride species, HgCl3^- is the most efficient ion for Hg^0 removal in the HgCl2 absorption system when moderate concentrations of chloride ions exist. The Hg^0 absorption reactions in the aqueous phase were investigated computationaIIy using Moller-Plesset perturbation theory. The calculated Gibbs free energies and energy barriers are in excellent agreement with the results obtained from experiments. In the presence of SO3^2- and SO2, Hg^2＋ reduction occurred and Hg^0 removal efficiency decreased. The reduced Hg^0 removal can be controlled through increased chloride concentration to some degree. Low pH value in HgCla solution enhanced the Hg^0 removal efficiency, and the effect was more significant in dilute HgCl2 solutions. The presence of SO4^2- and NO3^- did not affect Hg^0 removal by HgCl2.展开更多
In this work, a catalytic membrane using Mn/ Mo/Ru/A12O3 as the catalyst was employed to remove elemental mercury （Hg^0） from flue gas at low temperature. Compared with traditional catalytic oxidation （TCO） mode, ...In this work, a catalytic membrane using Mn/ Mo/Ru/A12O3 as the catalyst was employed to remove elemental mercury （Hg^0） from flue gas at low temperature. Compared with traditional catalytic oxidation （TCO） mode, Mn/A12O3 membrane catalytic system had much higher removal efficiency of Hg^0. After the incorporation of Mo and Ru, the production of C12 from the Deacon reaction and the retainability for oxidants over Mn/A12O3 membrane were greatly enhanced. As a result, the oxidization of Hg^0 over Mn/A12O3 membrane was obviously promoted due to incorporation of Mo and Ru. In the presence of 8 ppmv HC1, the removal efficiency of Hg^0 by Mn/Mo/Ru/A12O3 membrane reached 95% at 423 K. The influence of NO and SO2 on Hg^0 removal were insignificant even if 200 ppmv NO and 1000 ppmv SO2 were used. Moreover, compared with the TCO mode, the Mn/Mo/Ru/A12O3 membrane catalytic system could remarkably reduce the demanded amount of oxidants for Hg^0 removal. Therefore, the Mn/Mo/Ru/A12O3 membrane catalytic system may be a promising technology for the control of Hg~ emission.展开更多
The use of coal fly ash（CFA）, municipal solid waste incinerator bottom ash（MSWIBA） and flue gas desulfurization residue（FGDR） in road construction has become very common owing to its economical advantages. Howev...The use of coal fly ash（CFA）, municipal solid waste incinerator bottom ash（MSWIBA） and flue gas desulfurization residue（FGDR） in road construction has become very common owing to its economical advantages. However, these residues may contain toxic constituents that pose an environmental risk if they leach out and flow through the soil, surface water and groundwater.Therefore, it is necessary to assess the ecotoxicity and groundwater impact of these residues before decisions can be made regarding their utilization for road construction. In this study,the physico-chemical characteristics, leaching and phytotoxicity of these residues were investigated. Specifically, multivariate analyses were used to evaluate the contributions of the leaching constituents of the CFA, MSWIBA and FGDR leachates to the germination index of wheat seeds. B, Ba, Cr, Cu, Fe and Pb were found to be more toxic to the wheat seeds than the other heavy metals. Furthermore, the leached concentrations of the constituents from the CFA, MSWIBA and FGDR were below the regulatory threshold limits of the Chinese identification standard for hazardous wastes. Analyses conducted using a numerical groundwater model（Wisc LEACH） indicated that the predicted field concentrations of metals from the CFA, MSWIBA and FGDR increased with time up to about 30 years at the point of compliance, then decreased with time and distance. Overall, this study demonstrated that the risks resulting from MSWIBA, CFA and FGDR leaching could be assessed before its utilization for road construction, providing crucial information for the adoption of these alternative materials.展开更多
基金supported by National Natural Science Foundation of China (No. 51506171)。
文摘Accurate measurement of trace heavy metal mercury(Hg) in flue gas of coal-fired units is great significance for ecological and environmental protection.Mixed gas was used to simulate the actual flue gas of a power plant in this study.A laser-induced breakdown spectroscopy(LIBS)system for Hg measurement in mixed gas was built to study the effect of mixed gas pressure,Hg concentration in mixed gas and delay time on Hg measurement.The experimental results show that the appropriate low mixed gas pressure can obtain high Hg signal intensity and signal to noise ratio.The Hg signal intensity and signal to noise ratio increased with the increase of Hg concentration in mixed gas.The Hg signal intensity and signal to noise ratio decreased with the increase in delay time.According to the above results,the optimized measurement conditions can be determined.Different Hg concentrations in mixed gas were quantitatively analyzed by the internal standard method and traditional calibration method respectively.The relative error of prediction of the test sample obtained by the internal standard method was within 11.11%.The relative error of prediction of the traditional calibration method was less than 14.54%.This proved that the internal standard method can improve the accuracy of quantitative analysis of Hg concentration in flue gas using LIBS.
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supported by the National Key R&D Program of China (No. 2017YFC0210500)the National Natural Science Foundation of China (No. 51508525)the Key Research and Development Program of Ningxia Hui Autonomous Region (No. 2016KJHM31)
文摘Hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites were selected for elemental mercury(Hg^0) removal from non-ferrous metal smelting flue gas in this study. Results showed that the hierarchical Ag-SiO_2@Fe_3O_4 magnetic composites had favorable Hg^0 removal ability at low temperature. Moreover, the adsorption capacity of hierarchical magnetic composite is much larger than that of pure Fe_3O_4 and SiO_2@Fe_3O_4. The Hg^0 removal efficiency reached the highest value as approximately 92% under the reaction temperature of 150°C, while the removal efficiency sharply reduced in the absence of O_2. The characterization results indicated that Ag nanoparticles grew on the surface of SiO_2@Fe_3O_4 support. The large surface area of SiO_2 supplied efficient reaction room for Hg and Ag atoms. Ag–Hg amalgam is generated on the surface of the composites. In addition, this magnetic material could be easily separated from fly ashes when adopted for treating real flue gas, and the spent materials could be regenerated using a simple thermal-desorption method.
基金supported by the National Natural Science Foundation of China(No.52234011)the National Key R&D Program of China(No.2017YFC0210400)。
文摘Air pollutant emissions represent a critical challenge in the green development of the non-ferrous metallurgy industry.This work studied the emission characteristics,formation mechanisms,phase transformation and separation of typical air pollutants,such as heavy metal particles,mercury,sulfur oxides and fluoride,during non-ferrous smelting.A series of purification technologies,including optimization of the furnace throat and hightemperature discharge,were developed to collaboratively control and recover fine particles from the flue gas of heavy metal smelting processes,including copper,lead and zinc.Significant improvements have been realized in wet scrubbing technology for removing mercury,fluoride and SO_(2)from flue gas.Gas-liquid sulfidation technology by applying H_(2)S was invented to recycle the acid scrubbing wastewater more efficiently and in an eco-friendly manner.Based on digital technology,a source reduction method was designed for sulfur and fluoride control during the whole aluminum electrolysis process.New desulfurization technologies were developed for catalytic reduction of the sulfur content in petroleum coke at low temperature and catalytic reduction of SO_(2)to elemental sulfur.This work has established the technology for coupling multi-pollutant control and resource recovery from the flue gas from non-ferrous metallurgy,which provides the scientific theoretical basis and application technology for the treatment of air pollutants in the non-ferrous metallurgy industry.
基金supported by the National Natural Science Foundation of China(No.90510009)
文摘Activated carbon （AC） was considered to be an effective sorbent to control mercury in combustion systems. However, its capture capacity was low and it required a high carbon-to-mercury mass ratio. AC loaded with catalyst showed a high elemental mercury （Hg 0 ） capture capacity due to large surface area of AC and high oxidization ability of catalyst. In this study, several metal chlorides and metal oxides were used to promote the sorption capacity of AC. As a result, metal chlorides were better than metal oxides loaded on AC to remove gaseous mercury. X-ray diffractometer （XRD）, thermogravimetric analyzer （TGA） and specific surface area by Brunauer- Emmett-Teller method （BET） analysis showed the main mechanisms： first, AC had an enormous surface area for loading enough MClx; second, Cl and MxOy were generated during pyrogenation of MClx; finally, there were lots of active elements such as Cl and MxOy which could react with elemental mercury and convert it to mercury oxide and mercury chloride. The HgO and HgCl 2 might be released from AC’s porous structure by thermo regeneration. A catalytic chemisorption mechanism predominates the sorption process of elemental mercury. As Co and Mn were valence variable metal elements, their catalytic effect on Hg 0 oxidization may accelerate both oxidation and halogenation of Hg 0 . The sorbents loaded with metal chlorides possessed a synergistic function of catalytic effect of valence variable metal and chlorine oxidation.
基金financially supported by the National Key R and D Program of China(No.2018YFC0213400)the National Natural Science Foundation of China(No.21976118)supported by the Startup Fund for Youngman Research at SJTU(No.19X100040083)。
文摘Oxidation of sulfite and competitive absorption existed in Na_(2)SO_(3) solution for simultaneous removal of NO_(x) and SO_(2),inhibited the long-term high-efficiency when used for practical applications.A matching strategy was developed to solve these problems.Antioxidants combination was used to retard the oxidation of antioxidant and enhance inhibition of S(IV)(tetravalent sulfur)oxidation.Hydroquinone(HQ)and sodium thiosulfate(ST)showed a positive synergistic effect on inhibition of S(IV)oxidation.When SO_(2) concentration was 500 and 2000 ppmV,the addition of 0.1 wt.%HQ and 1 wt.%ST decreased the percentage of S(IV)oxidized by oxygen by over 30%and 40%,respectively.Alkali(Na_(2)CO_(3))alleviated the competitive absorption between NO_(x) and SO_(2).Moreover,Na_(2)CO_(3) exhibited an enhancement effect on the absorption of NO_(x) and SO_(2) when coupled with anti-oxidants.While the increase of oxygen pressure accelerated the oxidation of S(IV),the anti-oxidants can retard the oxidation.The measurement of pH suggested the removal efficiency of NO_(x) highly depended on SO_(3)^(2-) concentration rather than pH.The further investigation of the mechanism suggested the match effect was related to the interaction between ST and the intermediate product of HQ.The match strategy holds a potential for application of SO_(3)^(2-) to denitration.
基金supported by the Major State Basic Research Development Program (No. 2013CB430005)the National Natural Science Foundation of China (No. 51278294)the National High Technology Research and Development Program (No. 2012AA062504)
文摘Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of Hg^0 absorption by HgCl2 and the factors that control the removal were studied in this paper. It was found that when the mole ratio of Cl^- to HgCl2 is 10：1, the Hg^0 removal efficiency is the highest. Among the main mercury chloride species, HgCl3^- is the most efficient ion for Hg^0 removal in the HgCl2 absorption system when moderate concentrations of chloride ions exist. The Hg^0 absorption reactions in the aqueous phase were investigated computationaIIy using Moller-Plesset perturbation theory. The calculated Gibbs free energies and energy barriers are in excellent agreement with the results obtained from experiments. In the presence of SO3^2- and SO2, Hg^2＋ reduction occurred and Hg^0 removal efficiency decreased. The reduced Hg^0 removal can be controlled through increased chloride concentration to some degree. Low pH value in HgCla solution enhanced the Hg^0 removal efficiency, and the effect was more significant in dilute HgCl2 solutions. The presence of SO4^2- and NO3^- did not affect Hg^0 removal by HgCl2.
文摘In this work, a catalytic membrane using Mn/ Mo/Ru/A12O3 as the catalyst was employed to remove elemental mercury （Hg^0） from flue gas at low temperature. Compared with traditional catalytic oxidation （TCO） mode, Mn/A12O3 membrane catalytic system had much higher removal efficiency of Hg^0. After the incorporation of Mo and Ru, the production of C12 from the Deacon reaction and the retainability for oxidants over Mn/A12O3 membrane were greatly enhanced. As a result, the oxidization of Hg^0 over Mn/A12O3 membrane was obviously promoted due to incorporation of Mo and Ru. In the presence of 8 ppmv HC1, the removal efficiency of Hg^0 by Mn/Mo/Ru/A12O3 membrane reached 95% at 423 K. The influence of NO and SO2 on Hg^0 removal were insignificant even if 200 ppmv NO and 1000 ppmv SO2 were used. Moreover, compared with the TCO mode, the Mn/Mo/Ru/A12O3 membrane catalytic system could remarkably reduce the demanded amount of oxidants for Hg^0 removal. Therefore, the Mn/Mo/Ru/A12O3 membrane catalytic system may be a promising technology for the control of Hg~ emission.
基金supported by the National Basic Research Program (973) of China (No. 2011CB201500)the National Natural Science Foundation of China (No. 21277096)+1 种基金the Collaborative Innovation Center for Regional Environmental Qualitythe China Scholarship Council (CSC), Ministry of Education, China (No. 2011GXZT67)
文摘The use of coal fly ash（CFA）, municipal solid waste incinerator bottom ash（MSWIBA） and flue gas desulfurization residue（FGDR） in road construction has become very common owing to its economical advantages. However, these residues may contain toxic constituents that pose an environmental risk if they leach out and flow through the soil, surface water and groundwater.Therefore, it is necessary to assess the ecotoxicity and groundwater impact of these residues before decisions can be made regarding their utilization for road construction. In this study,the physico-chemical characteristics, leaching and phytotoxicity of these residues were investigated. Specifically, multivariate analyses were used to evaluate the contributions of the leaching constituents of the CFA, MSWIBA and FGDR leachates to the germination index of wheat seeds. B, Ba, Cr, Cu, Fe and Pb were found to be more toxic to the wheat seeds than the other heavy metals. Furthermore, the leached concentrations of the constituents from the CFA, MSWIBA and FGDR were below the regulatory threshold limits of the Chinese identification standard for hazardous wastes. Analyses conducted using a numerical groundwater model（Wisc LEACH） indicated that the predicted field concentrations of metals from the CFA, MSWIBA and FGDR increased with time up to about 30 years at the point of compliance, then decreased with time and distance. Overall, this study demonstrated that the risks resulting from MSWIBA, CFA and FGDR leaching could be assessed before its utilization for road construction, providing crucial information for the adoption of these alternative materials.
