To reveal the geochemical characters of water coproduced with coalbed gas and shallow groundwater,water samples were collected from 12 wells of coalbed methane and 7 wells of shallow groundwater.The pH,CODMn,fCO2,tota...To reveal the geochemical characters of water coproduced with coalbed gas and shallow groundwater,water samples were collected from 12 wells of coalbed methane and 7 wells of shallow groundwater.The pH,CODMn,fCO2,total dissolved solids (TDS),total hardness,and concentrations of metasilicic acid,sodium and kalium,calcium ion,magnesium ion,ammonium iron,bicarbonate ion,carbonate,chloride,sulfate ion,nitrate ion,fluoride,lithium,zinc,nickel,manganese,iron,boron,barium,etc.of the samples were measured.Research results showed the following:(1) Concentrations of TDS,chloride,fluoride,sodium and kalium,ammonium,iron,and barium in the water coproduced with coalbed gas exceeded the national standards of China; however,physical,chemical,and biological properties of shallow groundwater could meet the national standard.(2) The water produced from coalbed contained mainly Na-Cl·HCO3,with average TDS of 4588.5 ppm,whereas shallow groundwater contained a mixture of chemicals including Na.Mg.Ca-HCO3·SO4 and Na.Mg-HCO3·SO4,with average TDS of 663.8 ppm.(3) In general,it was observed that bicarbonate and sodium accumulated in a reducing environment and deeper system,while depletion of hydrogen ions and dissolution of sulfate,calcium,and magnesium occurred in a redox environment and shallow system.(4) Sodium and kalium,ammonium,chloride,and bicarbonate ions were the main ions found in the study area.展开更多
The primary aliphatic amine Primene JM-T was investigated as a potential absorbent for H2S removal.The solubility of H2S in JM-T was measured at 298,313,333,353,and 368 K with H2S partial pressures from 20 to760 kPa a...The primary aliphatic amine Primene JM-T was investigated as a potential absorbent for H2S removal.The solubility of H2S in JM-T was measured at 298,313,333,353,and 368 K with H2S partial pressures from 20 to760 kPa and H2S loading from 0.02 to 0.8 mol H2S per mol JM-T.Relevant physical properties,such as density,viscosity and dielectric constant,of the material were measured.The thermodynamic model with two-suffix Margules equation was used to correlate the experimental vapor-liquid equilibrium data.Furthermore,the absorption mechanism in non-aqueous system is suggested and the difference between non-aqueous and aqueous absorption system is pointed out.展开更多
In this study,the thermal stability of a Fe2 O3 catalyst for mercury oxidation was significantly improved by doping with Al2 O3.After 1 hr,the catalyst doped with 10 wt.%Al2 O3 still exhibited a mercury conversion eff...In this study,the thermal stability of a Fe2 O3 catalyst for mercury oxidation was significantly improved by doping with Al2 O3.After 1 hr,the catalyst doped with 10 wt.%Al2 O3 still exhibited a mercury conversion efficiency of 70.9%,while the undoped sample even lost its catalytic activity.Doping with Al2 O3 retarded the collapse of the catalyst mesoporous structure during high-temperature calcination,and the doped samples maintained a higher specific surface area,smaller pore size,and narrower pore size distribution.Transmission electron microscope images revealed that after calcination at 350℃,the average size of the catalyst grains in Fe2 O3 was 23.4 nm;however,the corresponding values for 1%Al2 O3/Fe2 O3,3%Al2 O3/Fe2 O3,and 10%Al2 O3/Fe2 O3 were only 13.3,7.1,and 4.7 nm,respectively.Results obtained from X-ray diffraction and thermogravimetry coupled with differential scanning calorimetry confirmed that doping with Al2 O3 also retards the crystallization of the catalysts at high temperature,constraining catalyst grains to a smaller size.展开更多
Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst,V2O5-WO3/TiO2,to investigate mercury oxidation in the presence of NO and O2.Mercury oxidation was improved by NO,and the efficienc...Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst,V2O5-WO3/TiO2,to investigate mercury oxidation in the presence of NO and O2.Mercury oxidation was improved by NO,and the efficiency was increased by simultaneously adding NO and O2.With NO and O2 pretreatment at 350°C,the catalyst exhibited higher catalytic activity for Hg^0 oxidation,whereas NO pretreatment did not exert a noticeable effect.Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O2.Although NO promoted Hg^0 oxidation at the very beginning,excessive NO counteracted this effect.The results show that NO plays different roles in Hg^0oxidation; NO in the gaseous phase may directly react with the adsorbed Hg^0,but excessive NO hinders Hg^0 adsorption.The adsorbed NO was converted into active nitrogen species(e.g.,NO2) with oxygen,which facilitated the adsorption and oxidation of Hg^0.Hg^0 was oxidized by NO mainly by the Eley-Rideal mechanism.The Hg^0 temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O2.展开更多
Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluoresc...Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.展开更多
Experiments were conducted in a fixed-bed reactor containing a commercial V2O5/WO3/TiO2 catalyst to investigate mercury oxidation in the presence of HCl and O2. Mercury oxidation was improved significantly in the pres...Experiments were conducted in a fixed-bed reactor containing a commercial V2O5/WO3/TiO2 catalyst to investigate mercury oxidation in the presence of HCl and O2. Mercury oxidation was improved significantly in the presence of HCl and O2, and the Hg^0 oxidation efficiencies decreased slowly as the temperature increased from 200 to 400℃. Upon pretreatment with HCl and O2 at 350℃, the catalyst demonstrated higher catalytic activity for Hg^0 oxidation. Notably,the effect of pretreatment with HCl alone was not obvious. For the catalyst treated with HCl and O2, better performance was observed with lower reaction temperatures. The results showed that both HCl and Hg^0 were first adsorbed onto the catalyst and then reacted with O2 following its adsorption, which indicates that the oxidation of Hg^0 over the commercial catalyst followed the Langmuir–Hinshelwood mechanism. Several characterization techniques, including Hg^0temperature-programmed desorption(Hg-TPD) and X-ray photoelectron spectroscopy(XPS), were employed in this work. Hg-TPD profiles showed that weakly adsorbed mercury species were converted to strongly bound species in the presence of HCl and O2. XPS patterns indicated that new chemisorbed oxygen species were formed by the adsorption of HCl, which consequently facilitated the oxidation of mercury.展开更多
In this study,the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La_(2)O_(3).The catalysts doped with La_(2)O_(3)maintained a higher surface are...In this study,the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La_(2)O_(3).The catalysts doped with La_(2)O_(3)maintained a higher surface area when subjected to high-temperature calcination,with lower average pore size and a narrower pore size distribution.X-ray diffraction(XRD)results revealed that La_(2)O_(3)doping hinders the growth of catalyst particles and crystallization of the material at high temperatures.Both NO and SO_(2)inhibited Hg^(0)oxidation over the La_(2)O_(3)/Fe_(2)O_(3)catalyst.Fourier transform infrared(FTIR)spectra revealed that SO_(2)reacts with O_(2)over the catalysts to form several species that are inert for mercury oxidation,such as S042^(-),HS04^(-),or other related species;these inert species cover the catalyst surface and consequently decrease Hg^(0)oxidation capacity.In addition,NO or SO_(2)competed with Hg^(0)for active sites on the La_(2)O_(3)/Fe_(2)O_(3)catalyst and hindered the adsorption of mercury,thereby inhibiting subsequent Hg^(0)oxidation.Hg^(0)oxidation on the La_(2)O_(3)/Fe_(2)O_(3)catalyst mainly followed the Eley-Rideal mechanism.Moreover,the inhibition effects of NO and SO_(2)were at least partially reversible,and the catalytic activity was temporarily restored after eliminating NO or S0_(2).展开更多
基金funded by the National Science and Technology Major Project (2011ZX05060-005 2009ZX05039-003)
文摘To reveal the geochemical characters of water coproduced with coalbed gas and shallow groundwater,water samples were collected from 12 wells of coalbed methane and 7 wells of shallow groundwater.The pH,CODMn,fCO2,total dissolved solids (TDS),total hardness,and concentrations of metasilicic acid,sodium and kalium,calcium ion,magnesium ion,ammonium iron,bicarbonate ion,carbonate,chloride,sulfate ion,nitrate ion,fluoride,lithium,zinc,nickel,manganese,iron,boron,barium,etc.of the samples were measured.Research results showed the following:(1) Concentrations of TDS,chloride,fluoride,sodium and kalium,ammonium,iron,and barium in the water coproduced with coalbed gas exceeded the national standards of China; however,physical,chemical,and biological properties of shallow groundwater could meet the national standard.(2) The water produced from coalbed contained mainly Na-Cl·HCO3,with average TDS of 4588.5 ppm,whereas shallow groundwater contained a mixture of chemicals including Na.Mg.Ca-HCO3·SO4 and Na.Mg-HCO3·SO4,with average TDS of 663.8 ppm.(3) In general,it was observed that bicarbonate and sodium accumulated in a reducing environment and deeper system,while depletion of hydrogen ions and dissolution of sulfate,calcium,and magnesium occurred in a redox environment and shallow system.(4) Sodium and kalium,ammonium,chloride,and bicarbonate ions were the main ions found in the study area.
基金Supported by the National Natural Science Foundation of China(51178446,21206168)
文摘The primary aliphatic amine Primene JM-T was investigated as a potential absorbent for H2S removal.The solubility of H2S in JM-T was measured at 298,313,333,353,and 368 K with H2S partial pressures from 20 to760 kPa and H2S loading from 0.02 to 0.8 mol H2S per mol JM-T.Relevant physical properties,such as density,viscosity and dielectric constant,of the material were measured.The thermodynamic model with two-suffix Margules equation was used to correlate the experimental vapor-liquid equilibrium data.Furthermore,the absorption mechanism in non-aqueous system is suggested and the difference between non-aqueous and aqueous absorption system is pointed out.
基金supported by the National Key Research and Development Program of China(No.2017YFC0210501)National Natural Science Foundation of China(No.21607009)National Engineering Laboratory for Flue Gas Pollutants Control Technology and Equipment(No.NEL-KF-201902)
文摘In this study,the thermal stability of a Fe2 O3 catalyst for mercury oxidation was significantly improved by doping with Al2 O3.After 1 hr,the catalyst doped with 10 wt.%Al2 O3 still exhibited a mercury conversion efficiency of 70.9%,while the undoped sample even lost its catalytic activity.Doping with Al2 O3 retarded the collapse of the catalyst mesoporous structure during high-temperature calcination,and the doped samples maintained a higher specific surface area,smaller pore size,and narrower pore size distribution.Transmission electron microscope images revealed that after calcination at 350℃,the average size of the catalyst grains in Fe2 O3 was 23.4 nm;however,the corresponding values for 1%Al2 O3/Fe2 O3,3%Al2 O3/Fe2 O3,and 10%Al2 O3/Fe2 O3 were only 13.3,7.1,and 4.7 nm,respectively.Results obtained from X-ray diffraction and thermogravimetry coupled with differential scanning calorimetry confirmed that doping with Al2 O3 also retards the crystallization of the catalysts at high temperature,constraining catalyst grains to a smaller size.
基金supported by the National Basic Research Program (973) of China (No.2013CB430005)the Special Research Funding for Public Benefit Industries from National Ministry of Environmental Protection (No.201309018)the National Hi-Tech Research and Development Program (863) of China (No.2013AA065404)
文摘Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst,V2O5-WO3/TiO2,to investigate mercury oxidation in the presence of NO and O2.Mercury oxidation was improved by NO,and the efficiency was increased by simultaneously adding NO and O2.With NO and O2 pretreatment at 350°C,the catalyst exhibited higher catalytic activity for Hg^0 oxidation,whereas NO pretreatment did not exert a noticeable effect.Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O2.Although NO promoted Hg^0 oxidation at the very beginning,excessive NO counteracted this effect.The results show that NO plays different roles in Hg^0oxidation; NO in the gaseous phase may directly react with the adsorbed Hg^0,but excessive NO hinders Hg^0 adsorption.The adsorbed NO was converted into active nitrogen species(e.g.,NO2) with oxygen,which facilitated the adsorption and oxidation of Hg^0.Hg^0 was oxidized by NO mainly by the Eley-Rideal mechanism.The Hg^0 temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O2.
基金supported by the National Natural Science Foundation of China (No.21007073)the National Basic Research Program (973) of China (No.2013CB430005)the National Hi-Tech Research and Development Program (863) of China (No.2011AA060802)
文摘Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.
基金supported by the National Basic Research Program(973)of China(No.2013CB430005)the Special Research Funding for Public Benefit Industries from National Ministry of Environmental Protection(No.201309018)the National Hi-Tech Research and Development Program(863)of China(No.2013AA065404)
文摘Experiments were conducted in a fixed-bed reactor containing a commercial V2O5/WO3/TiO2 catalyst to investigate mercury oxidation in the presence of HCl and O2. Mercury oxidation was improved significantly in the presence of HCl and O2, and the Hg^0 oxidation efficiencies decreased slowly as the temperature increased from 200 to 400℃. Upon pretreatment with HCl and O2 at 350℃, the catalyst demonstrated higher catalytic activity for Hg^0 oxidation. Notably,the effect of pretreatment with HCl alone was not obvious. For the catalyst treated with HCl and O2, better performance was observed with lower reaction temperatures. The results showed that both HCl and Hg^0 were first adsorbed onto the catalyst and then reacted with O2 following its adsorption, which indicates that the oxidation of Hg^0 over the commercial catalyst followed the Langmuir–Hinshelwood mechanism. Several characterization techniques, including Hg^0temperature-programmed desorption(Hg-TPD) and X-ray photoelectron spectroscopy(XPS), were employed in this work. Hg-TPD profiles showed that weakly adsorbed mercury species were converted to strongly bound species in the presence of HCl and O2. XPS patterns indicated that new chemisorbed oxygen species were formed by the adsorption of HCl, which consequently facilitated the oxidation of mercury.
基金supported by the National Key Research and Development Program of China(No.2017YFC0210501)the Fundamental Research Funds for the Central Universities(No.N2123031)the National Engineering Laboratory for Flue Gas Pollutants Control Technology and Equipment(No.NEL-KF-201902).
文摘In this study,the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La_(2)O_(3).The catalysts doped with La_(2)O_(3)maintained a higher surface area when subjected to high-temperature calcination,with lower average pore size and a narrower pore size distribution.X-ray diffraction(XRD)results revealed that La_(2)O_(3)doping hinders the growth of catalyst particles and crystallization of the material at high temperatures.Both NO and SO_(2)inhibited Hg^(0)oxidation over the La_(2)O_(3)/Fe_(2)O_(3)catalyst.Fourier transform infrared(FTIR)spectra revealed that SO_(2)reacts with O_(2)over the catalysts to form several species that are inert for mercury oxidation,such as S042^(-),HS04^(-),or other related species;these inert species cover the catalyst surface and consequently decrease Hg^(0)oxidation capacity.In addition,NO or SO_(2)competed with Hg^(0)for active sites on the La_(2)O_(3)/Fe_(2)O_(3)catalyst and hindered the adsorption of mercury,thereby inhibiting subsequent Hg^(0)oxidation.Hg^(0)oxidation on the La_(2)O_(3)/Fe_(2)O_(3)catalyst mainly followed the Eley-Rideal mechanism.Moreover,the inhibition effects of NO and SO_(2)were at least partially reversible,and the catalytic activity was temporarily restored after eliminating NO or S0_(2).