To investigate the feasibility of detoxifying chromium slag by sewage sludge,synthetic chromium slag containing 3%of Cr(Ⅵ)was mixed with sewage sludge followed by thermal treatment in nitrogen gas for stabilizing chr...To investigate the feasibility of detoxifying chromium slag by sewage sludge,synthetic chromium slag containing 3%of Cr(Ⅵ)was mixed with sewage sludge followed by thermal treatment in nitrogen gas for stabilizing chromium.The effects of slag to sludge ratio(0.5,1 and 2)and temperature(200,300,500,700 and 900℃)on treatment efficiency were investigated.During the mixing process before thermal treatment,59.8%-99.7%of Cr(Ⅵ)was reduced,but Cr could be easily leached from the reduction product.Increasing heating temperature and decreasing slag to sludge ratio strengthened the reduction and stabilization of Cr(Ⅵ).When the slag to sludge ratio was 0.5 and thermal treatment temperature was 300℃,the total leached Cr and Cr(Ⅵ)declined to 0.55 mg/L and 0.17 mg/L respectively,and 45.5%of Cr in the thermally treated residue existed as residual fraction.A two-stage mechanism was proposed for the reduction and stabilization of Cr.展开更多
M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr （ Ⅳ ） of Na2 CrO4 borne in the chromium slag to Cr （ Ⅲ ） in the solid phase re...M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr （ Ⅳ ） of Na2 CrO4 borne in the chromium slag to Cr （ Ⅲ ） in the solid phase reaction, and its thermodynamics and kinetics were studied. The reduction process of Na2CrO4 by carbon produced CO, whiCh＇was endothermic. Under the experimental condition, the apparent activation energy was 4. 41 kJ·mol^-1 , the＇apparent order of reaction for Na2 CrO4 was equal to one, and the partial pressure of CO was only 0.22 Pa at 1 330℃.展开更多
Chromium slag（CS）has become one of the most hazardous solid waste containing chromium and iron.Based on its characteristics,the technology of reduction roasting and magnetic separation was employed to treat CS.The m...Chromium slag（CS）has become one of the most hazardous solid waste containing chromium and iron.Based on its characteristics,the technology of reduction roasting and magnetic separation was employed to treat CS.The major impurity element of CS is magnesium and it exists in magnesium ferrite phase,which is hard to recover iron in the absence of additives.During reduction roasting,additives（Al2O3and CaF2）could destroy the structure of magnesium ferrite and improve the iron grade and recovery.The final product,i.e.chromium-iron powder,contains 72.54% Fe and 13.56% Cr,with the iron recovery of 80.34% and chromium recovery of 80.70%.展开更多
Calcification roasting–acid leaching of high-chromium vanadium slag(HCVS)was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium.The effects of the purity of Ca O,molar ratio between C...Calcification roasting–acid leaching of high-chromium vanadium slag(HCVS)was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium.The effects of the purity of Ca O,molar ratio between Ca O and V_2O_5(n(Ca O)/n(V_2O_5)),roasting temperature,holding time,and the heating rate used in the oxidation–calcification processes were investigated.The roasting process and mechanism were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),and thermogravimetry–differential scanning calorimetry(TG–DSC).The results show that most of vanadium reacted with Ca O to generate calcium vanadates and transferred into the leaching liquid,whereas almost all of the chromium remained in the leaching residue in the form of(Fe_(0.6)Cr_(0.4))_2O_3.Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with Ca O.Moreover,Ca O was more likely to combine with vanadium,as further confirmed by thermodynamic analysis.When the HCVS with Ca O added in an n(Ca O)/n(V_2O_5)ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min,the leaching ratios of vanadium and chromium reached91.14%and 0.49%,respectively;thus,efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium.Furthermore,the oxidation and calcification reactions of the spinel phases occurred at 592and 630°C for n(Ca O)/n(V_2O_5)ratios of 0.5 and 5,respectively.展开更多
Chromium salt is an important industrial material, but vast waste slag containing chrome(Ⅵ) is brought out in the process of its production. The slag is seriously harmful to environments and human health. The technol...Chromium salt is an important industrial material, but vast waste slag containing chrome(Ⅵ) is brought out in the process of its production. The slag is seriously harmful to environments and human health. The technologies on detoxification and comprehensive utilization of chromium containing slag were summarized abroad and at home. And various methods were also described for the detoxification mechanism, technology process, and practical application effects in detail. A new concept for detoxification of chromium containing slag, furthermore, was put forward by using microorganism.展开更多
Spinel phase is considered to be the optimal phase for stabilization of chromium in stainless steel slag.In order to restrain chromium leaching from slag for the effective environmental protection,Al2O3 was utilized f...Spinel phase is considered to be the optimal phase for stabilization of chromium in stainless steel slag.In order to restrain chromium leaching from slag for the effective environmental protection,Al2O3 was utilized for the modification treatment,and the effects on the enrichment and stabilization of chromium were investigated. The mineral phases and the existence state of chromium in slag with various Al2O3 contents at different basicities（ w（CaO）/w（SiO2） were analyzed by scanning electron microscopy-energy dispersive spectroscopy（ SEM-EDS） and X-ray diffraction（ XRD）. The results showed that chromium mainly existed in the glass and spinel phases at basicity of 1. 0 and 1. 5. As the slag basicity increased to 2. 0,chromium was also found in periclase phase. Al2O3 in the stainless steel slag reacted with MgO and Cr2O3,which could generate the Al-rich Mg（CrxAl（1- x））2O4 solid solution. Moreover,the addition of Al2O3 was favorable to reduce the solubility of chromium oxide in liquid phase and suppress the precipitation of periclase phase. The experimental results demonstrated that Al2O3 modification has a positive influence on the enrichment and the stabilization of chromium in the stainless steel slag.展开更多
To evaluate the metal chromium (Cr) contamination of soil at a chromium-containing slag site by ferrochromium production, the contaminated sites, under slag heap, in the vicinity of slag heap and arable soils near the...To evaluate the metal chromium (Cr) contamination of soil at a chromium-containing slag site by ferrochromium production, the contaminated sites, under slag heap, in the vicinity of slag heap and arable soils near the outlet of sewer channel, and unpolluted site 5 km away from one ferroalloy plant in Hunan Province, China, were selected. The concentrations of total Cr and water soluble Cr in bulk soil samples and profile depth samples were determined. The results show that the soils in the vicinity of slag heap have the highest total Cr content followed by the soils under the slag heap and near the outlet of sewer channel of the factory. The mean concentrations of total Cr in the top soils at above three contaminated locations exceed the critical level of Secondary Environmental Quality Standard for Soil in China by 3.5, 5.4 and 1.8 times. In most Cr polluted soils, total Cr has a relative accumulation in soil depth of 40-60 cm, but this trend is not found in unpolluted soils. The average concentrations of water soluble Cr (Ⅵ) in top soils under slag heap and in the vicinity of slag heap are 176.9 times and 52.7 times higher than that in the uncontaminated soils, respectively. However, water soluble Cr (Ⅵ) contents in soils near sewer channel are all low and the values are close to that in the uncontaminated soils. Although water soluble Cr (Ⅵ) content in soil profiles decreases with soil depths, it in soils under slag heap maintains a high level even at a depth of 100-150 cm. The results imply that the transportation of Cr (Ⅵ) can result in a potential risk of groundwater system in this area.展开更多
Basic oxygen furnace slag（BOFS） has the potential to remove hexavalent chromium（Cr（VI））from wastewater by a redox process due to the presence of minerals containing Fe2＋. The effects of the solution p H, initia...Basic oxygen furnace slag（BOFS） has the potential to remove hexavalent chromium（Cr（VI））from wastewater by a redox process due to the presence of minerals containing Fe2＋. The effects of the solution p H, initial Cr（VI） concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr（VI） was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope（SEM） equipped with an energy dispersive spectrometer（EDS）system and X-ray diffractometer（XRD）. The results show that Cr（VI） in wastewater can be efficiently removed by Fe2＋released from BOFS under appropriate acidic conditions. The removal of Cr（VI） by BOFS significantly depended on the parameters mentioned above. The reaction of Cr（VI） with BOFS followed the pseudo-second-order kinetic model. Fe2＋responsible for Cr（VI） removal was primarily derived from the dissolution of Fe O and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum（Ca SO4·2H2O）could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe2＋and the removal of Cr（VI）. Finally, the main mechanism of Cr（VI） removal by BOFS was described using several consecutive reaction steps.展开更多
Electrochemical measurements of the solid-oxide galvanic cell, Mo|Mo+MoO2|ZrO2 (MgO)| Fe+ (FexO)+Ag| Fe, have been made at temperatures of 1473K and 1573K in order to obtain the activities of FexO in BaO-BaF2-FexO sla...Electrochemical measurements of the solid-oxide galvanic cell, Mo|Mo+MoO2|ZrO2 (MgO)| Fe+ (FexO)+Ag| Fe, have been made at temperatures of 1473K and 1573K in order to obtain the activities of FexO in BaO-BaF2-FexO slags used for dephosphorization of chromium-containing hot metal. The FexO activities show a significant dependence upon the molar ratio of BaO/BaF2. Within the homogeneous liquid region, the substitution of BaF2 for BaO has an effect of raising the FexO activity. From these activity data, the phase diagrams of the system BaO -BaF2-FexO are drawn at 1473K and 1573K. The temperature dependence of the activity coefficient of FexO at a fixed BaO/ BaF2 molar ratio can be expressed by formula RTlnγ(FexO)=constant.展开更多
Synthetic slag samples of the CaO-SiO2-MgO-A1203-Cr203 system were obtained to clarify the effect of FeO on the formation of spinel phases and Cr distribution. X-ray diffraction （XRD） and scanning electron microsco...Synthetic slag samples of the CaO-SiO2-MgO-A1203-Cr203 system were obtained to clarify the effect of FeO on the formation of spinel phases and Cr distribution. X-ray diffraction （XRD） and scanning electron microscopy （SEM） equipped with energy-dispersive spectroscopy （EDS）, as well as the thermodynamic software FactSage 6.2, were used for sample characterization. The results show that the addition of FeO can decrease the viscosity of molten slag and the precipitation temperatures of melilite and merwinite. The solidus temperature significantly decreases from 1400 to 1250℃ with the increase of FeO content from 0wt% to 6wt%. The addition of FeO could enhance the content of Cr in spinel phases and reduce the content of Cr in soluble minerals, such as merwinite, melilite, and dicalcium silicate. Hence, the addition of FeO is conducive to decreasing Cr leaching.展开更多
To improve the efficiency of melting modification for stainless steel(SS) slag, a shear force was introduced in this work and its effects on the spinel and silicate melt were experimentally investigated. The results i...To improve the efficiency of melting modification for stainless steel(SS) slag, a shear force was introduced in this work and its effects on the spinel and silicate melt were experimentally investigated. The results indicated that the use of shear force changed the nucleation and growth behaviors of spinel and that the effects of shear force varied with its intensity. The aggregation behavior of spinel under different shear-force conditions was studied, revealing that large spinel clusters could be formed when the stirring speed was controlled. However, no notable change in the melt structure of the silicate was detected in this study. The optimal stirring speed for the melting modification treatment was 50 r·min^(-1), which substantially promoted spinel growth and aggregation, resulting in modified SS slag with excellent chromium sequestration capability.展开更多
基金supported by the National High-Tech Research and Development Program(863)of China(No.2007AA061300)the International Cooperation Project of Science and Technology Commission of Shanghai Municipality(No.08230707000)
文摘To investigate the feasibility of detoxifying chromium slag by sewage sludge,synthetic chromium slag containing 3%of Cr(Ⅵ)was mixed with sewage sludge followed by thermal treatment in nitrogen gas for stabilizing chromium.The effects of slag to sludge ratio(0.5,1 and 2)and temperature(200,300,500,700 and 900℃)on treatment efficiency were investigated.During the mixing process before thermal treatment,59.8%-99.7%of Cr(Ⅵ)was reduced,but Cr could be easily leached from the reduction product.Increasing heating temperature and decreasing slag to sludge ratio strengthened the reduction and stabilization of Cr(Ⅵ).When the slag to sludge ratio was 0.5 and thermal treatment temperature was 300℃,the total leached Cr and Cr(Ⅵ)declined to 0.55 mg/L and 0.17 mg/L respectively,and 45.5%of Cr in the thermally treated residue existed as residual fraction.A two-stage mechanism was proposed for the reduction and stabilization of Cr.
基金Item Sponsored by National Natural Science Foundation of China (50234040)
文摘M, a particular industrial waste, was selected to detoxify chromium slag at a high temperature. The carbon remaining in M reduced Cr （ Ⅳ ） of Na2 CrO4 borne in the chromium slag to Cr （ Ⅲ ） in the solid phase reaction, and its thermodynamics and kinetics were studied. The reduction process of Na2CrO4 by carbon produced CO, whiCh＇was endothermic. Under the experimental condition, the apparent activation energy was 4. 41 kJ·mol^-1 , the＇apparent order of reaction for Na2 CrO4 was equal to one, and the partial pressure of CO was only 0.22 Pa at 1 330℃.
基金Sponsored by National Natural Science Foundation of China(50904001,U1260101)Program for Innovative Research Team in Anhui University of Technology(TD200909)
文摘Chromium slag（CS）has become one of the most hazardous solid waste containing chromium and iron.Based on its characteristics,the technology of reduction roasting and magnetic separation was employed to treat CS.The major impurity element of CS is magnesium and it exists in magnesium ferrite phase,which is hard to recover iron in the absence of additives.During reduction roasting,additives（Al2O3and CaF2）could destroy the structure of magnesium ferrite and improve the iron grade and recovery.The final product,i.e.chromium-iron powder,contains 72.54% Fe and 13.56% Cr,with the iron recovery of 80.34% and chromium recovery of 80.70%.
基金financially supported by the National Natural Science Foundation of China (Nos.51604065 and 51574082)the National Basic Research Program of China (No.2013CB632603)the Fundamental Funds for the Central Universities (Nos.150203003 and 150202001)
文摘Calcification roasting–acid leaching of high-chromium vanadium slag(HCVS)was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium.The effects of the purity of Ca O,molar ratio between Ca O and V_2O_5(n(Ca O)/n(V_2O_5)),roasting temperature,holding time,and the heating rate used in the oxidation–calcification processes were investigated.The roasting process and mechanism were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),and thermogravimetry–differential scanning calorimetry(TG–DSC).The results show that most of vanadium reacted with Ca O to generate calcium vanadates and transferred into the leaching liquid,whereas almost all of the chromium remained in the leaching residue in the form of(Fe_(0.6)Cr_(0.4))_2O_3.Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with Ca O.Moreover,Ca O was more likely to combine with vanadium,as further confirmed by thermodynamic analysis.When the HCVS with Ca O added in an n(Ca O)/n(V_2O_5)ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min,the leaching ratios of vanadium and chromium reached91.14%and 0.49%,respectively;thus,efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium.Furthermore,the oxidation and calcification reactions of the spinel phases occurred at 592and 630°C for n(Ca O)/n(V_2O_5)ratios of 0.5 and 5,respectively.
基金ProjectsupportedbytheExcellentYoungTeachersProgramofMinistryofEducation China
文摘Chromium salt is an important industrial material, but vast waste slag containing chrome(Ⅵ) is brought out in the process of its production. The slag is seriously harmful to environments and human health. The technologies on detoxification and comprehensive utilization of chromium containing slag were summarized abroad and at home. And various methods were also described for the detoxification mechanism, technology process, and practical application effects in detail. A new concept for detoxification of chromium containing slag, furthermore, was put forward by using microorganism.
基金financial support by the National Natural Science Foundation of China(Project No.51374059 and 51304042)
文摘Spinel phase is considered to be the optimal phase for stabilization of chromium in stainless steel slag.In order to restrain chromium leaching from slag for the effective environmental protection,Al2O3 was utilized for the modification treatment,and the effects on the enrichment and stabilization of chromium were investigated. The mineral phases and the existence state of chromium in slag with various Al2O3 contents at different basicities（ w（CaO）/w（SiO2） were analyzed by scanning electron microscopy-energy dispersive spectroscopy（ SEM-EDS） and X-ray diffraction（ XRD）. The results showed that chromium mainly existed in the glass and spinel phases at basicity of 1. 0 and 1. 5. As the slag basicity increased to 2. 0,chromium was also found in periclase phase. Al2O3 in the stainless steel slag reacted with MgO and Cr2O3,which could generate the Al-rich Mg（CrxAl（1- x））2O4 solid solution. Moreover,the addition of Al2O3 was favorable to reduce the solubility of chromium oxide in liquid phase and suppress the precipitation of periclase phase. The experimental results demonstrated that Al2O3 modification has a positive influence on the enrichment and the stabilization of chromium in the stainless steel slag.
基金Project(k0802144-31) supported by the Program of Science and Technology of Changsha, ChinaProjects(2006AA062374, 2007AA021304) supported by the National Hi-tech Research and Development Program of China
文摘To evaluate the metal chromium (Cr) contamination of soil at a chromium-containing slag site by ferrochromium production, the contaminated sites, under slag heap, in the vicinity of slag heap and arable soils near the outlet of sewer channel, and unpolluted site 5 km away from one ferroalloy plant in Hunan Province, China, were selected. The concentrations of total Cr and water soluble Cr in bulk soil samples and profile depth samples were determined. The results show that the soils in the vicinity of slag heap have the highest total Cr content followed by the soils under the slag heap and near the outlet of sewer channel of the factory. The mean concentrations of total Cr in the top soils at above three contaminated locations exceed the critical level of Secondary Environmental Quality Standard for Soil in China by 3.5, 5.4 and 1.8 times. In most Cr polluted soils, total Cr has a relative accumulation in soil depth of 40-60 cm, but this trend is not found in unpolluted soils. The average concentrations of water soluble Cr (Ⅵ) in top soils under slag heap and in the vicinity of slag heap are 176.9 times and 52.7 times higher than that in the uncontaminated soils, respectively. However, water soluble Cr (Ⅵ) contents in soils near sewer channel are all low and the values are close to that in the uncontaminated soils. Although water soluble Cr (Ⅵ) content in soil profiles decreases with soil depths, it in soils under slag heap maintains a high level even at a depth of 100-150 cm. The results imply that the transportation of Cr (Ⅵ) can result in a potential risk of groundwater system in this area.
基金financially supported by the Fundamental Research Fund for the Central Universities(No.N130302004)the National Natural Science Foundation of China(No.21407020)
文摘Basic oxygen furnace slag（BOFS） has the potential to remove hexavalent chromium（Cr（VI））from wastewater by a redox process due to the presence of minerals containing Fe2＋. The effects of the solution p H, initial Cr（VI） concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr（VI） was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope（SEM） equipped with an energy dispersive spectrometer（EDS）system and X-ray diffractometer（XRD）. The results show that Cr（VI） in wastewater can be efficiently removed by Fe2＋released from BOFS under appropriate acidic conditions. The removal of Cr（VI） by BOFS significantly depended on the parameters mentioned above. The reaction of Cr（VI） with BOFS followed the pseudo-second-order kinetic model. Fe2＋responsible for Cr（VI） removal was primarily derived from the dissolution of Fe O and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum（Ca SO4·2H2O）could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe2＋and the removal of Cr（VI）. Finally, the main mechanism of Cr（VI） removal by BOFS was described using several consecutive reaction steps.
文摘Electrochemical measurements of the solid-oxide galvanic cell, Mo|Mo+MoO2|ZrO2 (MgO)| Fe+ (FexO)+Ag| Fe, have been made at temperatures of 1473K and 1573K in order to obtain the activities of FexO in BaO-BaF2-FexO slags used for dephosphorization of chromium-containing hot metal. The FexO activities show a significant dependence upon the molar ratio of BaO/BaF2. Within the homogeneous liquid region, the substitution of BaF2 for BaO has an effect of raising the FexO activity. From these activity data, the phase diagrams of the system BaO -BaF2-FexO are drawn at 1473K and 1573K. The temperature dependence of the activity coefficient of FexO at a fixed BaO/ BaF2 molar ratio can be expressed by formula RTlnγ(FexO)=constant.
基金the Chinese Scholarship Council for financial support
文摘Synthetic slag samples of the CaO-SiO2-MgO-A1203-Cr203 system were obtained to clarify the effect of FeO on the formation of spinel phases and Cr distribution. X-ray diffraction （XRD） and scanning electron microscopy （SEM） equipped with energy-dispersive spectroscopy （EDS）, as well as the thermodynamic software FactSage 6.2, were used for sample characterization. The results show that the addition of FeO can decrease the viscosity of molten slag and the precipitation temperatures of melilite and merwinite. The solidus temperature significantly decreases from 1400 to 1250℃ with the increase of FeO content from 0wt% to 6wt%. The addition of FeO could enhance the content of Cr in spinel phases and reduce the content of Cr in soluble minerals, such as merwinite, melilite, and dicalcium silicate. Hence, the addition of FeO is conducive to decreasing Cr leaching.
基金financially supported by the National Natural Science Foundation of China(No.51704068)the National Key Technologies R&D Program of China(No.2017YFC0805100)the Fundamental Research Funds for the Central Universities(No.N172504020)
文摘To improve the efficiency of melting modification for stainless steel(SS) slag, a shear force was introduced in this work and its effects on the spinel and silicate melt were experimentally investigated. The results indicated that the use of shear force changed the nucleation and growth behaviors of spinel and that the effects of shear force varied with its intensity. The aggregation behavior of spinel under different shear-force conditions was studied, revealing that large spinel clusters could be formed when the stirring speed was controlled. However, no notable change in the melt structure of the silicate was detected in this study. The optimal stirring speed for the melting modification treatment was 50 r·min^(-1), which substantially promoted spinel growth and aggregation, resulting in modified SS slag with excellent chromium sequestration capability.
