A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for ...A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(Ⅵ) removal.The morphology and structure of rBDATN-HCl were analyzed and identified by SEM,FTIR,XRD and solid-state13C NMR.It is found that the active functional groups,such as hydroxyl and amide,were introduced into BDATN after radiation reduction and acidification.The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(Ⅵ) above 99%after 60min of illumination with a solid-liquid ratio of 0.5 mg/mL,showing outstanding performance,which is attributed to the increase of dispersibility and adsorption sites of r BDATN-HCl.In comparison to the cBDATN-HCl synthesized with chemical reduction,rBDATN-HCl exhibits a better photoreduction performance for Cr(Ⅵ),demonstrating the advantages of radiation preparation of rBDATN-HCl.It is expected that more functionalized sp^(2) carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.展开更多
The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The ef...The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.展开更多
This study explores the unique role of CO_(2)as an oxidant in stainless steel smelting,focusing on its effectiveness in decarbonization and chromium retention.The research begins by theoretically demonstrating that al...This study explores the unique role of CO_(2)as an oxidant in stainless steel smelting,focusing on its effectiveness in decarbonization and chromium retention.The research begins by theoretically demonstrating that although the introduction of CO_(2)increases the CO partial pressure in the reaction system,the decarburization and chromium(Cr)retention capabilities of CO_(2)can still be stably maintained through the rational adjustment of the molten steel composition,temperature,and inert gas proportions.Further experimental findings indicate that chromium does not exhibit significant oxidation losses when the carbon(C)content exceeds 1.0%(mass).Finally,a novel CO_(2)recovery and utilization approach is proposed,integrating CO_(2)capture from smelting flue gas and recycling it for smelting,reducing O_(2)consumption and energy costs.This innovative process,compatible with existing smelting plants,presents a promising pathway towards carbon neutrality in the iron and steel industry,bridging theoretical insights with practical applications.展开更多
A process for purifying aqueous solutions containing heavy and toxic metals such as chromium(Cr) has been investigated.One of the extremely harmful pollutants in rivers and seawater is the heavy metal ions due to thei...A process for purifying aqueous solutions containing heavy and toxic metals such as chromium(Cr) has been investigated.One of the extremely harmful pollutants in rivers and seawater is the heavy metal ions due to their direct impacts on human,animals and plants are hexavalent Cr(Ⅵ).Consequently,highly sensitive sensor to detect Cr is essential.Surface plasmon resonance(SPR) technique has attracted huge research interest in detecting heavy metals specifically.In this study,three types of prism-based SPR sensor,gold(Au)/silver(Ag),Au/polyaniline(PANI) and Au/titanium dioxide(TiO_(2)) nanostructured films,are investigated as potential sensing material to detect the presence of Cr(Ⅵ) ions in water.The base Au layer with thickness of 48.3 nm is deposited on a glass slide for all sensors.For Au/Ag,Au/PANI nanofibers and Au/TiO_(2) sensor films,the Cr(Ⅵ) concentration is varied from 1 ppm to 15 ppm with sensitivity of 0.270 °ppm^(-1),0.082 °ppm^(-1) and 0.039 °ppm^(-1),respectively.Based on these results,the Au/PANI nanofibers are the most sensitive to Cr(Ⅵ) among the tested sensing materials.展开更多
Chemical leaching techniques have been proven effective in removing heavymetal contaminants fromsoil using various leaching agents.Previous research has shown that both singleagent and composite leaching systems have ...Chemical leaching techniques have been proven effective in removing heavymetal contaminants fromsoil using various leaching agents.Previous research has shown that both singleagent and composite leaching systems have been applied for the remediation of chromiumcontaminated soils,with varying degrees of success depending on soil type and contaminant form.However,the removal rate of total chromium(Cr)and hexavalent chromium(Cr(Ⅵ))often fluctuates based on the chemical composition of the leaching agents,as well as the soil’s physicochemical properties,such as pH and Cr speciation stability.Therefore,this study investigates the effectiveness of 20 composite leaching systems,including deionized water,lime water,calcium chloride,sodium carbonate,and sodium phosphate,through soil column leaching tests.The aim was to evaluate their impact on soil pH,total Cr,and Cr(Ⅵ)removal,and to examine the transformation of various Cr species during the leaching process.Results reveal that lime water and sodium phosphate were particularly effective in stabilizing Cr(Ⅵ)and neutralizing soil pH,while total Cr removal amount ranged from 197.4 mg/kg to 1671.6 mg/kg and Cr(Ⅵ)removal amount ranged from 113.2mg/kg to 316.8mg/kg.We also find that using 0.2 mol/L citric acid,0.1 mol/L hydrochloric acid,and 1.2 mL/g lime solution adjusted soil pH to 7.37,with average removal efficiencies of 34.6%.for total Cr and 72.7%for Cr(Ⅵ).Overall,our results suggest that the combined use of lime water and sodium phosphate is an effective strategy for remediating chromium-contaminated soil,particularly for stabilizing unleached Cr and adjusting soil pH.展开更多
Hexavalent chromium Cr(Ⅵ),as a well-established carcinogen,contributes to tumorigenesis for many human cancers,especially respiratory and digestive tumors.However,the potential function and relevant mechanism of Cr(...Hexavalent chromium Cr(Ⅵ),as a well-established carcinogen,contributes to tumorigenesis for many human cancers,especially respiratory and digestive tumors.However,the potential function and relevant mechanism of Cr(Ⅵ)on the initiation of esophageal carcinogenesis are largely unknown.Here,immortalized human esophageal epithelial cells(HEECs)were induced to be malignantly transformed cells,termed HEEC-Cr(Ⅵ)cells,via chronic exposure to Cr(Ⅵ),which simulates the progress of esophageal tumorigenesis.In vitro and in vivo experiments demonstrated that HEEC-Cr(Ⅵ)cells obtain the ability of anchorage-independent growth,greater proliferative capacity,cancer stem cell properties,and the capacity to form subcutaneous xenografts in BALB/c nude mice when compared to their parental cells,HEECs.Additionally,HEEC-Cr(Ⅵ)cells exhibited weakened cell motility and enhanced cell adhesion.Interestingly,HEECs with acute exposure to Cr(Ⅵ)failed to display those malignant phenotypes of HEEC-Cr(Ⅵ)cells,suggesting that Cr(Ⅵ)-induced malignant transformation,but not Cr(Ⅵ)itself,is the cause for the tumor characteristics of HEEC-Cr(Ⅵ)cells.Mechanistically,chronic exposure to Cr(Ⅵ)induced abnormal activation of Notch signaling,which is crucial to maintaining the capacity for malignant proliferation and stemness of HEEC-Cr(Ⅵ)cells.As expected,N-[N-(3,5-difluorophenacetyl)-L-alanyl]-S-phenylglycine t-butyl ester(DAPT),an inhibitor for the Notch pathway,drastically attenuated cancerous phenotypes of HEEC-Cr(Ⅵ)cells.In conclusion,our study clarified the molecular mechanism underlying Cr(Ⅵ)-induced esophageal tumorigenesis,which provides novel insights for further basic research and clinical therapeutic strategies about Cr(Ⅵ)-associated esophageal cancer.展开更多
The electro-reduction of chromium oxide（Cr2O3） was investigated in an equimolar mixture of CaCl2-NaCl molten salt at 800℃ for developing a more efficient process for chromium preparation. Cyclic voltammetry and pot...The electro-reduction of chromium oxide（Cr2O3） was investigated in an equimolar mixture of CaCl2-NaCl molten salt at 800℃ for developing a more efficient process for chromium preparation. Cyclic voltammetry and potentiostatic electrolysis were used to study the electro-reduction of the Cr2O3-loaded metallic cavity electrode. In addition, a number of parameters affecting the rate and extent of Cr2O3 electrolysis were considered to better understand the electrolysis process. The results demonstrate that CaCl2-NaCl molten salt is applicable for preparing Cr directly from Cr2O3 and the electrolysis parameters exert great influence on the cathode product. Under optimal experimental conditions, nodular Cr with an oxygen content of 0.5%（mass fraction） was obtained without any chromium carbides detected by XRD. Furthermore, the relatively high solubility of CaO and quite rapid crystal growth result in the formation of large platelet CaCr2O4, and the addition of NaCl to CaCl2 results in several variations on the electrolysis process and the product morphology from pure CaCl2 molten salt.展开更多
Study was carried out to analyze the distribution and migration patterns,soil-to-plant transfer and potential health risks of chromium in soil-vegetable system in areas near a ferro-alloy manufactory in Hunan province...Study was carried out to analyze the distribution and migration patterns,soil-to-plant transfer and potential health risks of chromium in soil-vegetable system in areas near a ferro-alloy manufactory in Hunan province.The results show that soils near sewer outlet,sewer channel and in control area are averaged 2 239.5,995.33 and 104.9 mg/kg,respectively.The total Cr has a relative accumulation in soil depth of 200-400 mm near the sewer outlet,mainly enriches in the surface layer（0-200 mm） near the sewer channel and decreases gradually in unpolluted soils.The differential concentration level of enrichment between layers is little.The results also indicate that the three vegetables of celery,lettuce and Chinese cabbage are able to convert the potentially toxic Cr（Ⅵ） species into the non-toxic Cr（Ⅲ） species,and the chromium contents in the edible parts of the vegetables are averaged 11.95 mg/kg.The transfer factors of the three vegetables follow the order：Chinese cabbage lettuce celery.The estimated total daily intake of chromium substantially exceeds the dietary allowable value,which may pose health risks to local population.展开更多
[Objective] The aim was to develop a rapid, simple method for determination of chromium and zinc in soil samples by flame atomic absorption spectrometry.[Method] The method for determination of Cr and Zn in soil by co...[Objective] The aim was to develop a rapid, simple method for determination of chromium and zinc in soil samples by flame atomic absorption spectrometry.[Method] The method for determination of Cr and Zn in soil by combined flame atomic absorption spectrometry and microwave digestion was used. [Result] The concentration curve was linear within the range of 0-0.8 mg/L for Cr and 0-0.8 mg/L for Zn, the detection limits of Cr and Zn was 0.0025 mg/L and 0.002 3 mg/L, respectively. Recoveries of 102.4%-103.2% for Cr and 97.7%-98.3% for Zn were obtained for there soil samples. [Conclusion] The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for determination of Cr and Zn in soil samples.展开更多
[Objective] To optimize the techniques for culturing Cr-enriched Dendrobi-um candidum protocorm. [Method] By adopting Plackett-Burman test, the effects of time, temperature, Cr-content in medium, NAA content, KT conte...[Objective] To optimize the techniques for culturing Cr-enriched Dendrobi-um candidum protocorm. [Method] By adopting Plackett-Burman test, the effects of time, temperature, Cr-content in medium, NAA content, KT content and light intensi-ty on Cr-enriched protocorm were researched. Three factors of time, Cr-content in medium and light intensity had statistical y significant effects; then steepest ascent procedures were applied to define optimal response region of these three factors; fi-nal y the optimal factors were determined by RSM analysis. [Result] The results showed that the optimal conditions for Cr-enrichment were chromium concentration at 0.37 mg/L, culture time of 59 d and il umination intensity of 1 822.22 lx. The predicted value of Cr-content in protocorm was 5.08 mg/kg. [Conclusion] RSM can optimize the techniques for culturing Cr-enriched protocorm of Dendrobium can-didum, provide the optimum process parameters and lay the foundation for further research.展开更多
The extraction experiments of chromium（W） from aqueous waste solution by predispersed solvent extraction （PDSE） process with extractant （HEHPEHE） and its mixture, including acidic extractant （D2EHPA）, alkaline...The extraction experiments of chromium（W） from aqueous waste solution by predispersed solvent extraction （PDSE） process with extractant （HEHPEHE） and its mixture, including acidic extractant （D2EHPA）, alkaline extractant （TOA） and neutral extractant （TBP） were carried out respectively. It is found that the extractant HEHPEHE exhibited high extraction selectivity to chromium（III） from aqueous waste solution. The colloidal liquid aphrons （CLAs） were successfully generated using kerosene as a solvent, HEHPEHE as an extractant, sodium dodecyl benzene sulphate （SDBS） as a surfactant in aqueous phase and polyoxyethylene sorbitol anhydride monolaurate （Tween-20） in oil phase. To study the extraction efficiency and advantages of the PDSE process in the removal of chromium（III）, the effects of major factors, such as initial chromium（III） concentration, volume of colloidal gas aphrons （CGAs）, HEHPEHE volume fraction, phase ratio （solvent phase to water phase）, mass fraction of dodecyl trimethylammonium bromide （HTAB）, mass fraction of SDBS, mass fraction of Tween-20 and initial pH of aqueous waste solution were also investigated and the appropriate process conditions were obtained. Under the appropriate conditions, the extraction efficiency of chromium（III） above 99.9 % can be achieved and the treated aqueous waste solution can be discharged directly without polluting the environment.展开更多
The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of t...The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.展开更多
This paper aims to investigate if the dental restoration of nickel-chromium based alloy(Ni-Cr) leads to the enhanced excretions of Ni and Cr in urine.Seven hundred and ninety-five patients in a dental hospital had sin...This paper aims to investigate if the dental restoration of nickel-chromium based alloy(Ni-Cr) leads to the enhanced excretions of Ni and Cr in urine.Seven hundred and ninety-five patients in a dental hospital had single or multiple Ni-Cr alloy restoration recently and 198 controls were recruited to collect information on dental restoration by questionnaire and clinical examination.Urinary concentrations of Ni and Cr from each subject were measure by graphite furnace atomic absorption spectrometry.Compared to the control group,the urinary level of Ni was significantly higher in the patient group of < 1 month of the restoration duration,among which higher Ni excretions were found in those with either a higher number of teeth replaced by dental alloys or a higher index of metal crown not covered with the porcelain.Urinary levels of Cr were significantly higher in the three patient groups of <1,1 to <3 and 3 to <6 months,especially in those with a higher metal crown exposure index.Linear curve estimations showed better relationships between urinary Ni and Cr in patients within 6-month groups.Our data suggested significant increased excretions of urinary Ni and Cr after dental restoration.Potential short- and long-term effects of Ni-Cr alloy restoration need to be investigated.展开更多
Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the co...Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the conditions of COFCC with n(O)-n(C) (molar ratio) as 1.00-0.84 and n(SiO2)-n(CaO) as 1.00-0.39, the samples were heated by 10 kW microwave power to reach the given temperatures and held for different times respectively. The results show that the low-C-Cr ferrochromium metal phase in the reduced materials forms before the high-C-Cr ferrochromium metal phase does. With increasing temperature the C content of ferrochromium metals is in a positive correlation with the content of Cr. The C content of ferrochromium metal in reduced materials is 0-10.07% with an average value of 4.68%. With the increase of holding time the Cr content in ferrochromium metals is in a negative correlation with the content of C, while the content of Fe changes in the contrary way. In the microwave field the kinetic conditions of carburization are closely related with the temperature of microwave heating, holding time and carbon fitting ratio.展开更多
A new method by liquid-liquid-liquid three phase system, consisting of acidified primary amine N1923 （abbreviated as A-N1923）, poly（ethylene glycol） （PEG） and （NH4）2S04 aqueous solution, was suggested for the ...A new method by liquid-liquid-liquid three phase system, consisting of acidified primary amine N1923 （abbreviated as A-N1923）, poly（ethylene glycol） （PEG） and （NH4）2S04 aqueous solution, was suggested for the separation and simultaneous extraction of Ⅴ（Ⅴ） and Cr（Ⅵ） from the acidic leach solutions of high- chromium vanadium-titanium magnetite. Experimental results indicated that Ⅴ（Ⅴ） and Cr（Ⅵ） could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while AI（Ⅲ） and other co-existing impurity ions, such as Si（Ⅳ）, Fe（Ⅲ）, Ti（Ⅳ）, Mg（Ⅱ） and Ca（Ⅱ） in acidic leach solutions, could be enriched in the （NH4）2SO4 bottom aqueous phase. During the process for extraction and separation of Ⅴ（Ⅴ） and Cr（Ⅵ）, almost all of impurity ions could be removed. The separation factors between Ⅴ （Ⅴ） and Cr（Ⅵ） could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered Ⅴ（Ⅴ） and Cr（Ⅵ） in the top phase and middle phase respectively were all above 90%. Various effects including aqueous pH, A-N1923 concentration, PEG added amount and （NH4）2SO4 concentration on three-phase partitioning of Ⅴ（Ⅴ） and Cr（Ⅵ） were discussed. It was found that the partition of Cr（Ⅵ） into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of Ⅴ（Ⅴ） by A-N1923 resulted of anion exchange between NO; and H2V10O4-28. Stripping of Ⅴ（Ⅴ） and Cr（Ⅵ） from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NANO3 aqueous solutions and NaOH-（NH4）2SO4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium-titanium magnetite.展开更多
CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were...CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were constructed for different tempera- tures. Chromium nitride formed at 700-1200℃ under relatively higher nitrogen and lower oxygen partial pressures. Phases in the products were then investigated using X-ray diffraction （XRD）, and the Cr2N content varied with reaction temperature and holding time. The results indicate that the Cr metal powder nitridation process can be explained by a diffusion model. Further, Cr2N formed as an intermediate product because of an incomplete reaction, which was observed by high-resolution transmission electron microscopy （HRTEM）. After nitriding at 1000℃ for 20 h, CrN powder with an average grain size of 63 nm was obtained, and the obtained sample was analyzed by using a scanning electron microscope （SEM）.展开更多
The removal of chromium（Vl） from an aqueous solution using persimmon gel was examined. The amount of chromium（VI） removed was strongly affected by the pH of the solution, with all ehromium（VI） being removed at p...The removal of chromium（Vl） from an aqueous solution using persimmon gel was examined. The amount of chromium（VI） removed was strongly affected by the pH of the solution, with all ehromium（VI） being removed at pH 2 or lower. However, in a solution containing, 15 mg dry weight of immobilized persimmon gel, the amount of removed chromium（VI） decreased as the pH increased. A part of chromium（VI） was reduced another oxidation stage, mainly chromium（III）, by immobilized persimmon gel. The amount of reduced chromium（III） in the solution was increased with decreasing the pH of the solution. As a result, the amount of total chromium removed was maximal at pH 2. The amount of chromium removed were affected by the chromium concentration and the amount of gel. The maximal amount of chromium removed by the column system was also discussed.展开更多
基金supported by the National Natural Science Foundation of China(No.U2067212)the National Science Fund for Distinguished Young Scholars(No.21925603).
文摘A sp^(2) carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(Ⅵ) removal.The morphology and structure of rBDATN-HCl were analyzed and identified by SEM,FTIR,XRD and solid-state13C NMR.It is found that the active functional groups,such as hydroxyl and amide,were introduced into BDATN after radiation reduction and acidification.The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(Ⅵ) above 99%after 60min of illumination with a solid-liquid ratio of 0.5 mg/mL,showing outstanding performance,which is attributed to the increase of dispersibility and adsorption sites of r BDATN-HCl.In comparison to the cBDATN-HCl synthesized with chemical reduction,rBDATN-HCl exhibits a better photoreduction performance for Cr(Ⅵ),demonstrating the advantages of radiation preparation of rBDATN-HCl.It is expected that more functionalized sp^(2) carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
基金Projects(2013CB632601,2013CB632604)supported by the National Basic Research Program of ChinaProject(51125018)supported by the National Science Foundation for Distinguished Young Scholars of China+1 种基金Project(KGZD-EW-201-2)supported by the Key Research Program of the Chinese Academy of SciencesProjects(51374191,21106167,51104139)supported by the National Natural Science Foundation of China
文摘The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.
基金supported by the Postdoctoral Fellowship Program of CPSF(GZC20230017)the Natural Science Research Project of Anhui Educational Committee(2024AH050153)+1 种基金the National Natural Science Foundation of China(52322407,52274313)the China Postdoctoral Science Foundation(2024M750013).
文摘This study explores the unique role of CO_(2)as an oxidant in stainless steel smelting,focusing on its effectiveness in decarbonization and chromium retention.The research begins by theoretically demonstrating that although the introduction of CO_(2)increases the CO partial pressure in the reaction system,the decarburization and chromium(Cr)retention capabilities of CO_(2)can still be stably maintained through the rational adjustment of the molten steel composition,temperature,and inert gas proportions.Further experimental findings indicate that chromium does not exhibit significant oxidation losses when the carbon(C)content exceeds 1.0%(mass).Finally,a novel CO_(2)recovery and utilization approach is proposed,integrating CO_(2)capture from smelting flue gas and recycling it for smelting,reducing O_(2)consumption and energy costs.This innovative process,compatible with existing smelting plants,presents a promising pathway towards carbon neutrality in the iron and steel industry,bridging theoretical insights with practical applications.
文摘A process for purifying aqueous solutions containing heavy and toxic metals such as chromium(Cr) has been investigated.One of the extremely harmful pollutants in rivers and seawater is the heavy metal ions due to their direct impacts on human,animals and plants are hexavalent Cr(Ⅵ).Consequently,highly sensitive sensor to detect Cr is essential.Surface plasmon resonance(SPR) technique has attracted huge research interest in detecting heavy metals specifically.In this study,three types of prism-based SPR sensor,gold(Au)/silver(Ag),Au/polyaniline(PANI) and Au/titanium dioxide(TiO_(2)) nanostructured films,are investigated as potential sensing material to detect the presence of Cr(Ⅵ) ions in water.The base Au layer with thickness of 48.3 nm is deposited on a glass slide for all sensors.For Au/Ag,Au/PANI nanofibers and Au/TiO_(2) sensor films,the Cr(Ⅵ) concentration is varied from 1 ppm to 15 ppm with sensitivity of 0.270 °ppm^(-1),0.082 °ppm^(-1) and 0.039 °ppm^(-1),respectively.Based on these results,the Au/PANI nanofibers are the most sensitive to Cr(Ⅵ) among the tested sensing materials.
基金supported by the National Key Research and Development Program of China(No.2023YFC3707902)China Postdoctoral Science Foundation(No.2024M752168)+1 种基金Jiangsu Funding Programfor Excellent Postdoctoral Talent(No.2024ZB393)the National Natural Science Foundation of China(No.42407126).
文摘Chemical leaching techniques have been proven effective in removing heavymetal contaminants fromsoil using various leaching agents.Previous research has shown that both singleagent and composite leaching systems have been applied for the remediation of chromiumcontaminated soils,with varying degrees of success depending on soil type and contaminant form.However,the removal rate of total chromium(Cr)and hexavalent chromium(Cr(Ⅵ))often fluctuates based on the chemical composition of the leaching agents,as well as the soil’s physicochemical properties,such as pH and Cr speciation stability.Therefore,this study investigates the effectiveness of 20 composite leaching systems,including deionized water,lime water,calcium chloride,sodium carbonate,and sodium phosphate,through soil column leaching tests.The aim was to evaluate their impact on soil pH,total Cr,and Cr(Ⅵ)removal,and to examine the transformation of various Cr species during the leaching process.Results reveal that lime water and sodium phosphate were particularly effective in stabilizing Cr(Ⅵ)and neutralizing soil pH,while total Cr removal amount ranged from 197.4 mg/kg to 1671.6 mg/kg and Cr(Ⅵ)removal amount ranged from 113.2mg/kg to 316.8mg/kg.We also find that using 0.2 mol/L citric acid,0.1 mol/L hydrochloric acid,and 1.2 mL/g lime solution adjusted soil pH to 7.37,with average removal efficiencies of 34.6%.for total Cr and 72.7%for Cr(Ⅵ).Overall,our results suggest that the combined use of lime water and sodium phosphate is an effective strategy for remediating chromium-contaminated soil,particularly for stabilizing unleached Cr and adjusting soil pH.
基金supported by the Special Construction Project Fund for Taishan Mountain Scholars of Shandong Provincethe Jinan Medicine Research Program+1 种基金the Nurturing and Development Fund from The Second Hospital of Shandong University(No.2022YP62)the Shandong Provincial Natural Science Foundation for Young Scholars(No.ZR2022QH285),China.
文摘Hexavalent chromium Cr(Ⅵ),as a well-established carcinogen,contributes to tumorigenesis for many human cancers,especially respiratory and digestive tumors.However,the potential function and relevant mechanism of Cr(Ⅵ)on the initiation of esophageal carcinogenesis are largely unknown.Here,immortalized human esophageal epithelial cells(HEECs)were induced to be malignantly transformed cells,termed HEEC-Cr(Ⅵ)cells,via chronic exposure to Cr(Ⅵ),which simulates the progress of esophageal tumorigenesis.In vitro and in vivo experiments demonstrated that HEEC-Cr(Ⅵ)cells obtain the ability of anchorage-independent growth,greater proliferative capacity,cancer stem cell properties,and the capacity to form subcutaneous xenografts in BALB/c nude mice when compared to their parental cells,HEECs.Additionally,HEEC-Cr(Ⅵ)cells exhibited weakened cell motility and enhanced cell adhesion.Interestingly,HEECs with acute exposure to Cr(Ⅵ)failed to display those malignant phenotypes of HEEC-Cr(Ⅵ)cells,suggesting that Cr(Ⅵ)-induced malignant transformation,but not Cr(Ⅵ)itself,is the cause for the tumor characteristics of HEEC-Cr(Ⅵ)cells.Mechanistically,chronic exposure to Cr(Ⅵ)induced abnormal activation of Notch signaling,which is crucial to maintaining the capacity for malignant proliferation and stemness of HEEC-Cr(Ⅵ)cells.As expected,N-[N-(3,5-difluorophenacetyl)-L-alanyl]-S-phenylglycine t-butyl ester(DAPT),an inhibitor for the Notch pathway,drastically attenuated cancerous phenotypes of HEEC-Cr(Ⅵ)cells.In conclusion,our study clarified the molecular mechanism underlying Cr(Ⅵ)-induced esophageal tumorigenesis,which provides novel insights for further basic research and clinical therapeutic strategies about Cr(Ⅵ)-associated esophageal cancer.
基金Project(2013CB632600)supported by the National Basic Research Program of ChinaProjects(21376251,21406233)supported by the National Natural Science Foundation of ChinaProject supported by the Fund of Hubei Zhenhua Chemical Co.,Ltd.,China
文摘The electro-reduction of chromium oxide（Cr2O3） was investigated in an equimolar mixture of CaCl2-NaCl molten salt at 800℃ for developing a more efficient process for chromium preparation. Cyclic voltammetry and potentiostatic electrolysis were used to study the electro-reduction of the Cr2O3-loaded metallic cavity electrode. In addition, a number of parameters affecting the rate and extent of Cr2O3 electrolysis were considered to better understand the electrolysis process. The results demonstrate that CaCl2-NaCl molten salt is applicable for preparing Cr directly from Cr2O3 and the electrolysis parameters exert great influence on the cathode product. Under optimal experimental conditions, nodular Cr with an oxygen content of 0.5%（mass fraction） was obtained without any chromium carbides detected by XRD. Furthermore, the relatively high solubility of CaO and quite rapid crystal growth result in the formation of large platelet CaCr2O4, and the addition of NaCl to CaCl2 results in several variations on the electrolysis process and the product morphology from pure CaCl2 molten salt.
基金Project (2009ZX07212-001-01) supported by the Key Project of National Natural Science Foundation for Water Pollution Control and RemediationProject (50925417) supported by the National Funds for Distinguished Young Scientists+1 种基金Project (50830301) supported by the National Natural Science Foundation of ChinaProject (51074191) supported by the National Natural Science Foundation of China
文摘Study was carried out to analyze the distribution and migration patterns,soil-to-plant transfer and potential health risks of chromium in soil-vegetable system in areas near a ferro-alloy manufactory in Hunan province.The results show that soils near sewer outlet,sewer channel and in control area are averaged 2 239.5,995.33 and 104.9 mg/kg,respectively.The total Cr has a relative accumulation in soil depth of 200-400 mm near the sewer outlet,mainly enriches in the surface layer（0-200 mm） near the sewer channel and decreases gradually in unpolluted soils.The differential concentration level of enrichment between layers is little.The results also indicate that the three vegetables of celery,lettuce and Chinese cabbage are able to convert the potentially toxic Cr（Ⅵ） species into the non-toxic Cr（Ⅲ） species,and the chromium contents in the edible parts of the vegetables are averaged 11.95 mg/kg.The transfer factors of the three vegetables follow the order：Chinese cabbage lettuce celery.The estimated total daily intake of chromium substantially exceeds the dietary allowable value,which may pose health risks to local population.
基金Supported by Key Fund of Guangxi Academy of Agricultural Sciences(2014JZ01 and2013YZ07)~~
文摘[Objective] The aim was to develop a rapid, simple method for determination of chromium and zinc in soil samples by flame atomic absorption spectrometry.[Method] The method for determination of Cr and Zn in soil by combined flame atomic absorption spectrometry and microwave digestion was used. [Result] The concentration curve was linear within the range of 0-0.8 mg/L for Cr and 0-0.8 mg/L for Zn, the detection limits of Cr and Zn was 0.0025 mg/L and 0.002 3 mg/L, respectively. Recoveries of 102.4%-103.2% for Cr and 97.7%-98.3% for Zn were obtained for there soil samples. [Conclusion] The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for determination of Cr and Zn in soil samples.
文摘[Objective] To optimize the techniques for culturing Cr-enriched Dendrobi-um candidum protocorm. [Method] By adopting Plackett-Burman test, the effects of time, temperature, Cr-content in medium, NAA content, KT content and light intensi-ty on Cr-enriched protocorm were researched. Three factors of time, Cr-content in medium and light intensity had statistical y significant effects; then steepest ascent procedures were applied to define optimal response region of these three factors; fi-nal y the optimal factors were determined by RSM analysis. [Result] The results showed that the optimal conditions for Cr-enrichment were chromium concentration at 0.37 mg/L, culture time of 59 d and il umination intensity of 1 822.22 lx. The predicted value of Cr-content in protocorm was 5.08 mg/kg. [Conclusion] RSM can optimize the techniques for culturing Cr-enriched protocorm of Dendrobium can-didum, provide the optimum process parameters and lay the foundation for further research.
基金Project (NCET-07-0577) supported by New Century Excellent Talents of Ministry of Education, China
文摘The extraction experiments of chromium（W） from aqueous waste solution by predispersed solvent extraction （PDSE） process with extractant （HEHPEHE） and its mixture, including acidic extractant （D2EHPA）, alkaline extractant （TOA） and neutral extractant （TBP） were carried out respectively. It is found that the extractant HEHPEHE exhibited high extraction selectivity to chromium（III） from aqueous waste solution. The colloidal liquid aphrons （CLAs） were successfully generated using kerosene as a solvent, HEHPEHE as an extractant, sodium dodecyl benzene sulphate （SDBS） as a surfactant in aqueous phase and polyoxyethylene sorbitol anhydride monolaurate （Tween-20） in oil phase. To study the extraction efficiency and advantages of the PDSE process in the removal of chromium（III）, the effects of major factors, such as initial chromium（III） concentration, volume of colloidal gas aphrons （CGAs）, HEHPEHE volume fraction, phase ratio （solvent phase to water phase）, mass fraction of dodecyl trimethylammonium bromide （HTAB）, mass fraction of SDBS, mass fraction of Tween-20 and initial pH of aqueous waste solution were also investigated and the appropriate process conditions were obtained. Under the appropriate conditions, the extraction efficiency of chromium（III） above 99.9 % can be achieved and the treated aqueous waste solution can be discharged directly without polluting the environment.
基金financially supported by the National Natural Science Foundation of China (Nos.51674084, 51174051, and 51574082)
文摘The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.
基金supported by Open Fund of State Key Laboratory of Oral Diseases,Sichun University
文摘This paper aims to investigate if the dental restoration of nickel-chromium based alloy(Ni-Cr) leads to the enhanced excretions of Ni and Cr in urine.Seven hundred and ninety-five patients in a dental hospital had single or multiple Ni-Cr alloy restoration recently and 198 controls were recruited to collect information on dental restoration by questionnaire and clinical examination.Urinary concentrations of Ni and Cr from each subject were measure by graphite furnace atomic absorption spectrometry.Compared to the control group,the urinary level of Ni was significantly higher in the patient group of < 1 month of the restoration duration,among which higher Ni excretions were found in those with either a higher number of teeth replaced by dental alloys or a higher index of metal crown not covered with the porcelain.Urinary levels of Cr were significantly higher in the three patient groups of <1,1 to <3 and 3 to <6 months,especially in those with a higher metal crown exposure index.Linear curve estimations showed better relationships between urinary Ni and Cr in patients within 6-month groups.Our data suggested significant increased excretions of urinary Ni and Cr after dental restoration.Potential short- and long-term effects of Ni-Cr alloy restoration need to be investigated.
基金Project(50474083) supported by the National Natural Science Foundation of ChinaProject supported by the Baoshan Iron & Steel Co. Ltd. of China
文摘Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the conditions of COFCC with n(O)-n(C) (molar ratio) as 1.00-0.84 and n(SiO2)-n(CaO) as 1.00-0.39, the samples were heated by 10 kW microwave power to reach the given temperatures and held for different times respectively. The results show that the low-C-Cr ferrochromium metal phase in the reduced materials forms before the high-C-Cr ferrochromium metal phase does. With increasing temperature the C content of ferrochromium metals is in a positive correlation with the content of Cr. The C content of ferrochromium metal in reduced materials is 0-10.07% with an average value of 4.68%. With the increase of holding time the Cr content in ferrochromium metals is in a negative correlation with the content of C, while the content of Fe changes in the contrary way. In the microwave field the kinetic conditions of carburization are closely related with the temperature of microwave heating, holding time and carbon fitting ratio.
基金Supported by the National Basic Research and Development Program of China(973ProgramNo.2013CB632602)the National Natural Science Foundation of China(Nos.51574213,51074150)
文摘A new method by liquid-liquid-liquid three phase system, consisting of acidified primary amine N1923 （abbreviated as A-N1923）, poly（ethylene glycol） （PEG） and （NH4）2S04 aqueous solution, was suggested for the separation and simultaneous extraction of Ⅴ（Ⅴ） and Cr（Ⅵ） from the acidic leach solutions of high- chromium vanadium-titanium magnetite. Experimental results indicated that Ⅴ（Ⅴ） and Cr（Ⅵ） could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while AI（Ⅲ） and other co-existing impurity ions, such as Si（Ⅳ）, Fe（Ⅲ）, Ti（Ⅳ）, Mg（Ⅱ） and Ca（Ⅱ） in acidic leach solutions, could be enriched in the （NH4）2SO4 bottom aqueous phase. During the process for extraction and separation of Ⅴ（Ⅴ） and Cr（Ⅵ）, almost all of impurity ions could be removed. The separation factors between Ⅴ （Ⅴ） and Cr（Ⅵ） could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered Ⅴ（Ⅴ） and Cr（Ⅵ） in the top phase and middle phase respectively were all above 90%. Various effects including aqueous pH, A-N1923 concentration, PEG added amount and （NH4）2SO4 concentration on three-phase partitioning of Ⅴ（Ⅴ） and Cr（Ⅵ） were discussed. It was found that the partition of Cr（Ⅵ） into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of Ⅴ（Ⅴ） by A-N1923 resulted of anion exchange between NO; and H2V10O4-28. Stripping of Ⅴ（Ⅴ） and Cr（Ⅵ） from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NANO3 aqueous solutions and NaOH-（NH4）2SO4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium-titanium magnetite.
基金financially supported by the Innovation Foundation of Shanghai University (Nos. sdcx2012033 and sdcx2012062)the Special Research Foundation for Training and Selecting Outstanding Young Teachers of Universities in Shanghai (No. B.37-0407-12-008)+1 种基金the National Natural Science Foundation of China (Nos. 51072112 and 51272154)the Projects of International Cooperation and Exchanges NSFC (No. 51311130110)
文摘CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were constructed for different tempera- tures. Chromium nitride formed at 700-1200℃ under relatively higher nitrogen and lower oxygen partial pressures. Phases in the products were then investigated using X-ray diffraction （XRD）, and the Cr2N content varied with reaction temperature and holding time. The results indicate that the Cr metal powder nitridation process can be explained by a diffusion model. Further, Cr2N formed as an intermediate product because of an incomplete reaction, which was observed by high-resolution transmission electron microscopy （HRTEM）. After nitriding at 1000℃ for 20 h, CrN powder with an average grain size of 63 nm was obtained, and the obtained sample was analyzed by using a scanning electron microscope （SEM）.
文摘The removal of chromium（Vl） from an aqueous solution using persimmon gel was examined. The amount of chromium（VI） removed was strongly affected by the pH of the solution, with all ehromium（VI） being removed at pH 2 or lower. However, in a solution containing, 15 mg dry weight of immobilized persimmon gel, the amount of removed chromium（VI） decreased as the pH increased. A part of chromium（VI） was reduced another oxidation stage, mainly chromium（III）, by immobilized persimmon gel. The amount of reduced chromium（III） in the solution was increased with decreasing the pH of the solution. As a result, the amount of total chromium removed was maximal at pH 2. The amount of chromium removed were affected by the chromium concentration and the amount of gel. The maximal amount of chromium removed by the column system was also discussed.
