The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMC...The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.展开更多
Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct ...Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct photolysis and by biological treatment is difficult and usually slow. In our two previous published papers, we have discussed the advanced oxidation of nitrobenzene and nitrophenols in aqueous solutions irradiated by direct photolysis using polychromatic light and by means of UV/H2O2 process. The experimental results suggested the UV/H2O2 process is an effective and efficient technology for complete mineralization of these organic compounds. Based on the results therein, comprehensive reaction mechanism for nitrobenzene photolysis was proposed with detailed discussions.展开更多
The batch photodegradation reactor was used to investigate the influence of the common coexisting substances in wastewater,such as H+,anions (HCO3-,Cl-and NO3-) and organic compounds (methanol and bisphenol A),on the ...The batch photodegradation reactor was used to investigate the influence of the common coexisting substances in wastewater,such as H+,anions (HCO3-,Cl-and NO3-) and organic compounds (methanol and bisphenol A),on the photodegradation behaviors of EE2 in the UV/H2O2 process.The results indicated that the addition of coexisting substances can influence the photodegradation behaviors of EE2 and it also follows the first-order kinetics.The acidic (pH 2-4) and alkaline (pH 10-12) medium benefit the photodegradation of EE2,but the photodegradation rate constant of EE2 keeps almost constant in the pH value of 4-10.The addition of anions,such as HCO3-,Cl-and NO3-,can inhibit the photodegradation of EE2,and the rate constant has a negative linear relationship with the concentration of the anions.However,the reduction degrees vary with the anions kinds,and the inhibition effect of the three anions is in the order of HCO3->NO3->Cl-.Addition of 5 mg/L methanol and bisphenol A can reduce the photodegradation rate constant of EE2by 84.31% and 72%,respectively.By comparison,the retardant effect of methanol is much more evident.In the studied concentrations range,the photodegradation rate constant of EE2 is the unary quadratic function of the organic compounds concentrations.展开更多
The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount...The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.展开更多
Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irrad...Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irradiated NB aqueous solutions. The distribution of nitrophenol isomers follows the order p-〉 m-〉 o-nitrophenol. Other intermediates detected include nitrohydroquinone, nitrocatechol, catechol, benzoquinone, phenol, nitrate/nitrite ions, formic acid, glyoxylic acid, maleic acid, oxalic acid and some aliphatic ketones and aldehydes. The degradation of nitrobenzene and nitrophenols at initial stages follows the first-order kinetics and the decay rate constants for nitrobenzene（NB） are around l0^-3-10^-2 s^-1 and for nitrophenols are around 10^-2 s^-1. The decomposition of H2 O2 in the presence of NB and each nitrophenol isomers follows zero-order kinetics. The quantum yields at initial stages for NB decay were estimated around 0.30 to 0.36, and for NPs decay is around 0.31-0.54.展开更多
A lab-incubation experiment was conducted to investigate the effects of different forms of nitrogen application （ammonium, NH4＋-N; nitrate, NO3--N; and amide-N, NH2-N） and different concentrations （40, 200 and 800...A lab-incubation experiment was conducted to investigate the effects of different forms of nitrogen application （ammonium, NH4＋-N; nitrate, NO3--N; and amide-N, NH2-N） and different concentrations （40, 200 and 800 mg L-1） on N2O emission from the fluvo-aquic soil subjected to a freezing-thawing cycling. N2O emission sharply decreased at the start of soil freezing, and then showed a smooth line with soil freezing. In subject to soil thawing, N2O emission increased and reached a peak at the initial thawing stage. The average N2O emissions with addition of NH4＋-N, NO3 -N and NH2-N are 119.01, 611.61 and 148. 22 ug m-2 h-1, respectively, at the concentration of 40 mg L-1; 205.28, 1 084.40 and 106.13 ug m2 h-1 at the concentration of 200 mg L-1; and 693.95, 1 820.02 and 49.74 ug m-2 h4 at the concentration of 800 mg L-1. The control is only 100.35 ug m-2 h-1. N2O emissions with addition of NH4＋-N and NO3--N increased with increasing concentration, by ranging from 17.49 to 425.67% for NH4＋-N, and from 563.38 to 1458.6% for NO3--N compared with control. There was a timelag for N2O emission to reach a steady state with an increase of concentration. In contrast, by adding NH2-N to soil, N2O emission decreased with increasing concentration. In sum, NH4＋-N or NO3--N fertilizer incorporated in soil enhanced the cumulative N2O emission from the fluvo-aquic soil relative to amide-N. This study suggested that ammonium and nitrate concentration in overwintering water should be less than 200 and 40 mg L-1 in order to reduce N2O emissions from soil, regardless of amide-N.展开更多
文摘The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.
文摘Nitroaromatic compounds such as nitrobenzene and nitrophenols are largely synthesised and particularly often occur in water bodies as toxic pollutants. The degradation of these compounds in the environment via direct photolysis and by biological treatment is difficult and usually slow. In our two previous published papers, we have discussed the advanced oxidation of nitrobenzene and nitrophenols in aqueous solutions irradiated by direct photolysis using polychromatic light and by means of UV/H2O2 process. The experimental results suggested the UV/H2O2 process is an effective and efficient technology for complete mineralization of these organic compounds. Based on the results therein, comprehensive reaction mechanism for nitrobenzene photolysis was proposed with detailed discussions.
基金Sponsored by the Key Project of National Science Foundation of China (Grant NO.50638020)the National High Technology Research and Development Program of China (Grant No.2007AA06A411)the State Key Laboratory of Urban Water Resource & Environment (Grant No.2009TS04)
文摘The batch photodegradation reactor was used to investigate the influence of the common coexisting substances in wastewater,such as H+,anions (HCO3-,Cl-and NO3-) and organic compounds (methanol and bisphenol A),on the photodegradation behaviors of EE2 in the UV/H2O2 process.The results indicated that the addition of coexisting substances can influence the photodegradation behaviors of EE2 and it also follows the first-order kinetics.The acidic (pH 2-4) and alkaline (pH 10-12) medium benefit the photodegradation of EE2,but the photodegradation rate constant of EE2 keeps almost constant in the pH value of 4-10.The addition of anions,such as HCO3-,Cl-and NO3-,can inhibit the photodegradation of EE2,and the rate constant has a negative linear relationship with the concentration of the anions.However,the reduction degrees vary with the anions kinds,and the inhibition effect of the three anions is in the order of HCO3->NO3->Cl-.Addition of 5 mg/L methanol and bisphenol A can reduce the photodegradation rate constant of EE2by 84.31% and 72%,respectively.By comparison,the retardant effect of methanol is much more evident.In the studied concentrations range,the photodegradation rate constant of EE2 is the unary quadratic function of the organic compounds concentrations.
基金Project supported by the Science Project of Harbin City(No. H2001-12)the Youth Foundation of School of Municipal and Environmental Engineering in Harbin Institute of Technology(No. 01306914).
文摘The degradation of formaldehyde gas was studied using UV/TiO2/O3 process under the condition of continuous flow mode. The effects of humidity, initial formaldehyde concentration, residence time and ozone adding amount on degradation of formaldehyde gas were investigated. The experimental results indicated that the combination of ozonation with photocatalytic oxidation on the degradation of formaldehyde showed a synergetic action, e.g,, it could considerably increase decomposing of formaldehyde. The degradation efficiency of formaldehyde was between 73.6% and 79.4% while the initial concentration in the range of 1.84--24 mg/m^3 by O3/TiO2flJV process. The optimal humidity was about 50% in UV/TiO2/O3 processs and degradation of formaldehyde increases from 39.0% to 94.1% when the ozone content increased from 0 to 141 mg/m^3. Furthermore, the kinetics of formaldehyde degradation reaction could be described by Langmuir-Hinshelwood model. The rate constant k of 46.72 mg/（m^3.min） and Langmuir adsorption coefficient K of 0.0268 m^3/mg were obtained.
文摘Photodegradation of nitrobenzene and nitrophenols in aqueous solutions by means of UV/H2 O2 process was studied in the Rayox batch reactors. Three nitrophenol isomers were identified as main photoproducts in the irradiated NB aqueous solutions. The distribution of nitrophenol isomers follows the order p-〉 m-〉 o-nitrophenol. Other intermediates detected include nitrohydroquinone, nitrocatechol, catechol, benzoquinone, phenol, nitrate/nitrite ions, formic acid, glyoxylic acid, maleic acid, oxalic acid and some aliphatic ketones and aldehydes. The degradation of nitrobenzene and nitrophenols at initial stages follows the first-order kinetics and the decay rate constants for nitrobenzene（NB） are around l0^-3-10^-2 s^-1 and for nitrophenols are around 10^-2 s^-1. The decomposition of H2 O2 in the presence of NB and each nitrophenol isomers follows zero-order kinetics. The quantum yields at initial stages for NB decay were estimated around 0.30 to 0.36, and for NPs decay is around 0.31-0.54.
基金supported by the Key Tech-nologies R&D Program of China during the 11th Five-Year Plan period (2006BAD17B02)Central Public Research Institutes Basic Funds for Research and Development (Institute of Agro-Environmental Protection,Ministry of Agriculture), China
文摘A lab-incubation experiment was conducted to investigate the effects of different forms of nitrogen application （ammonium, NH4＋-N; nitrate, NO3--N; and amide-N, NH2-N） and different concentrations （40, 200 and 800 mg L-1） on N2O emission from the fluvo-aquic soil subjected to a freezing-thawing cycling. N2O emission sharply decreased at the start of soil freezing, and then showed a smooth line with soil freezing. In subject to soil thawing, N2O emission increased and reached a peak at the initial thawing stage. The average N2O emissions with addition of NH4＋-N, NO3 -N and NH2-N are 119.01, 611.61 and 148. 22 ug m-2 h-1, respectively, at the concentration of 40 mg L-1; 205.28, 1 084.40 and 106.13 ug m2 h-1 at the concentration of 200 mg L-1; and 693.95, 1 820.02 and 49.74 ug m-2 h4 at the concentration of 800 mg L-1. The control is only 100.35 ug m-2 h-1. N2O emissions with addition of NH4＋-N and NO3--N increased with increasing concentration, by ranging from 17.49 to 425.67% for NH4＋-N, and from 563.38 to 1458.6% for NO3--N compared with control. There was a timelag for N2O emission to reach a steady state with an increase of concentration. In contrast, by adding NH2-N to soil, N2O emission decreased with increasing concentration. In sum, NH4＋-N or NO3--N fertilizer incorporated in soil enhanced the cumulative N2O emission from the fluvo-aquic soil relative to amide-N. This study suggested that ammonium and nitrate concentration in overwintering water should be less than 200 and 40 mg L-1 in order to reduce N2O emissions from soil, regardless of amide-N.
