Process engineering of demineralisation of moderate to high ash Indian coals through NaOH‑HCl leaching and HF leaching

Chemical leaching of coals would be required to produce cleaner coals for some special applications where physical benefi-ciation may not be effective enough.This would also help in recovering Li and rare earth metals besides in the sequestration of CO_(2).About 20 Indian coals having complexly distributed moderate to high ash contents were sequentially treated with various alkali–acid such as NaOH-HCl,HF,HCl,HCl-HF,and NaOH-HCl-HF leaching.This aimed to establish and design the best stepwise sequential process for the highest degree of demineralisation through a chemical leaching process.Kinetics and process intensification studies were carried out.More than 80%demineralisation of Madhaipur and Neemcha coals was observed using the best sequential treatment designed presently.The repeated stepwise treatment of the alkali and the acid was also studied,which was found to significantly enhance the degree of demineralisation of coals.The integrated process of alkali–acid leaching followed by solvent extraction(Organo-refining)and vice versa of the treated coal was also studied for producing cleaner coals.

Molybdenite alkali fusion and leaching:reactions and mechanism

The production of MoO3 from Sarcheshmeh molybdenite concentrate via a pyro-hydrometallurgical process was studied.The molybdenite concentrate and sodium carbonate were premixed and fused under air atmosphere.Then the fused products were leached in water and the dissolved molybdenum was recovered as ammonium molybdate.The ammonium molybdate was then calcined to produce mo-lybdic oxide.At the fusion stage,the effect of the mass ratio of carbonate to sulfide on the reaction products and the solubility of the products was investigated.The results show that during the fusion,sodium molybdate and sodium sulfate are the final reaction products and sodium sulfide is detected as an intermediate reaction product.By melting at 850℃with 5wt%excess carbonate,the maximum solubility of the products is obtained.The molybdenum is recovered from the solutions as ammonium molybdate.

Efficient separation of alumina and silica in reduction-roasted kaolin by alkali leaching

Alkali leaching was employed to investigate the separation of alumina and silica in roasted kaolin obtained by roasting kaolin alone in air at 1273 K for 60 min and in clinker prepared by roasting the mixed raw meal of kaolin,ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 in reducing atmosphere at 1373 K for 60 min.The thermodynamic analyses and alkali leaching results show that the composition of the Al-Si spinel in roasted kaolin is close to that of 3Al2O3·2SiO2 and the spinel is dissolved with increasing leaching time,resulting in difficulty in deeply separating alumina and silica in kaolin by the traditional roasting-leaching process.On the contrary,the efficient separation of alumina and silica in kaolin can be reached by fully converting kaolinite into insoluble hercynite and soluble free silica,namely quartz solid solution and cristobalite solid solution,during reduction roasting,followed by alkali leaching of the obtained clinker.Furthermore,experimental results from treating high-silica diasporic bauxite indicate that the reduction roasting-alkali leaching process is potential to separate silica and alumina in aluminosilicates.

Study on Solubility of Nb_2O_5 in KOH Solution and Alkali Leaching of Niobite

Solubility of Nb 2O 5 and leaching behaviors of Nb and Ta from niobite in KOH solution have been investigated in order to develop an alkali hydrothermal leaching process of Nb and Ta. The solubility of Nb 2O 5 was measured in the range of 40 ℃ to 200 ℃ at various molar ratios of K 2O to Nb 2O 5 ( n (K 2O)/ n (Nb 2O 5)). It has been found that Nb 2O 5 shows the maximum solubility at the solution composition of n (K 2O)/ n (Nb 2O 5)=4/3 at a given temperature; the rise of temperature increases the solubility of Nb 2O 5 below 120 ℃, but decreases it above 120 ℃. The leaching behaviors of Nb and Ta were studied in the range of 150 ℃ to 250 ℃ and 0.1 MPa to 5 MPa. With the rise of temperature, the leaching degree increases when the leaching temperature is below 200 ℃, but it decreases when the leaching temperature is above 200 ℃. The maximum leaching degree is about 90% at 200 ℃. It was proved that the alkali hydrothermal leaching process is effective for the recovery of Nb and Ta from niobite concentrate.

Physicochemical and environmental characteristics of alkali leaching residue of wolframite and process for valuable metals recovery

Physicochemical and mineralogical characteristics of an alkali leaching residue of wolframite were studied by XRD,SEM−EDS,chemical phase analysis,mineral liberation analyzer(MLA),and TG−DSC methods.Batch leaching tests,toxicity characteristic leaching procedure(TCLP)tests and Chinese standard leaching tests(CSLT)were conducted to determine the environmental mobility of toxic elements.The results show that,due to the high contents of W,Fe,Mn,Sn,and Nb,the residue is with high resource value,but the content of a toxic element,As,is also high.The existing minerals of the investigated elements mainly occur as monomer particles,but it is difficult to extract these valuable metals by conventional acid leaching due to their mineral properties.The release of As increases over time in acidic environment.The leaching concentration of all investigated harmful elements through TCLP is within the limiting value,while the leaching concentration of As through CSLT exceeds the limiting value by more than 4 times,so the residue is classified as hazardous solid waste based on the Chinese standard.A process for valuable metals recovery from this residue was proposed.Preliminary experimental results indicated that the main valuable metals could be extracted effectively.

Quantifying the impact of mineralogical heterogeneity on reactive transport modeling of CO_(2)+O_(2) in-situ leaching of uranium

CO_(2)+O_(2) in-situ leaching(ISL)of sandstonetype uranium ore represents the third generation of solution mining in China.In this study,reactive transport modeling of the interaction between hydrodynamic and geochemical reactions is performed to enable better prediction and regulation of the CO_(2)+O_(2) in-situ leaching process of uranium.Geochemical reactions between mining solutions and rock,and the kinetic uranium dissolution controlled by O_(2)(aq)and bicarbonate(HCO_(3)-)are considered in the CO_(2)+O_(2) ISL reactive transport model of a typical sandstone-hosted uranium ore deposit in northern China.The reactive leaching of uranium is most sensitive to the spatial distribution of the mineralogical properties of the uranium deposit.Stochastic geostatistical models are used to represent the uncertainty on the spatial distribution of mineral grades.A Monte Carlo analysis was also performed to simulate the uranium production variability over an entire set of geostatistical realizations.The ISL stochastic simulation performed with the selected geostatistical realizations approximates the uranium production variability well.The simulation results of the ISL reactive transport model show that the extent of the uranium plume is highly dependent on mineralogical heterogeneity.The uncertainty analysis suggests the effect of uranium grade heterogeneity was found to be important to improve the accurate capture of the uncertainty.This study provides guidance for the accurate simulation and dynamic regulation of the CO_(2)+O_(2) leaching process of uranium at the scale of large mining areas.

Factors influencing in-situ leaching of uranium mining in a sandstone deposit in Shihongtan, Northwest China

The Shihongtan uranium deposit in northwest China is a sandstone-type deposit suitable for alkaline in-situ leaching exploitation of uranium. Alkaline leaching tends to result in CaCO3 precipitation there by affecting the porosity of the ore-bearing aquifer. CaCO3 deposits can also block pumping and injection holes if the formulation parameters of the leaching solution are not well controlled. However, controlling these parameters to operate the in-situ leaching process is challenging. Our study demonstrates that the dissolved uranium concentration in the leaching solution increases as HCO3-concentration increases. Therefore, the most suitable HCO3-concentration to use as leaching solution is defined by the boundary value of the HCO3-concentration that controls CaCO3 dissolution-precipitation. That is, the dissolution and precipitation of calcite is closely related to pH, Ca2+ and HCO3-concentration. The pH and Ca2+ concentration are the main factors limiting HCO3-concentration in the leaching solution. The higher the pH and Ca2+ concentration, the lower the boundary value of HCO3-concentration, and therefore the more unfavorable to in-situ leaching of uranium.

Recovery of molybdenum from residues by simultaneous ultrafine milling and alkali leaching

A new technology of treating molybdenum residues by simultaneous ultrafine milling and alkali leaching was put forward to recover molybdenum from metallurgical residues. The effects of residue size, milling time, solid content, n (Na 2CO 3)/ n (Mo) and slurry pH value on molybdenum leaching rate were investigated. The results indicate that a simpler process, lower slurry temperature, 50% shorter treating time, 60% decrease of Na 2CO 3 content and 15% increase of molybdenum leaching rate can be obtained by the new technology compared with the traditional process. The leaching kinetic equation was determined, and calculation of active energy ( E =56.2 kJ/mol) shows that the leaching process of molybdenum residues by simultaneous ultrafine milling and alkali leaching is controlled by chemical reaction. Potential exists for the new process to form the basis for an economically viable, environmentally friendly process to recover valuable elements from residues.

Remediation of in-situ Leach Mining Contaminated Soil by Amendment-plant Synergism

This study aimed to remediate in-situ leach mining contaminated soil by amendment-plant synergism. The results showed that plant species exhibited ex-tremely significant effects on the concentration of nitrate nitrogen; to be specific, the concentration of nitrate nitrogen in soil planted with wheat was reduced from 692.19 mg/kg to lower than 100 mg/kg; when the mass ratio of amendment to soil reached 3：50 and the amendment particle size was 1-2 mm, the concentration of nitrate ni-trogen in soil planted with wheat was reduced to 43 mg/kg. The amendment type exhibited extremely significant effects on the concentration of ammonium nitrogen; to be specific, when the mass ratio of amendment to soil reached 10：50, the concen-tration of ammonium nitrogen in soil added with 2-3 mm zeolite was reduced from 23 593.75 to 3 300 mg/kg on day 15. Amendments and plants mainly exhibited desorption performance for sulfate radical in soil, and the amendment type extreme-ly significantly affected the concentration of sulfate radical; to be specific, the con-centration of sulfate radical in soil added with limestone increased from 370 mg/kg to 900 mg/kg on day 7.

Enhancing the electrocatalytic performance of nitrate reduction to ammonia by in-situ nitrogen leaching

Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts .Herein, for the first time, nickel foam supported Co_(4) N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy.At the optimal potential, the Co_(4) N/NF catalyst achieves ultra-high Faraday efficiency and NH_(3) selectivity of 95.4% and 99.4%, respectively.Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia.Theoretical calculations confirm that Co_(4) N with abundant nitrogen vacancies can optimize the adsorption energies of NO_(3)^(-) and intermediates, lower the free energy (Δ G ) of the potential-determining step (*NH_(3) to NH_(3) ) and inhibit the formation of N-containing byproducts.In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H_(2) quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate.This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.

Recovery of waste rare earth fluorescent powders by two steps acid leaching

The effects of the acid leaching and alkali fusion on the leaching efficiency of Y,Eu,Ce,and Tb from the waste rare earth fluorescent powders were investigated in this paper.The results show that hydrochloric acid is better than sulfuric acid in the first acid leaching,and NaOH is better than Na2CO3in the alkali fusion.In the first acid leaching,the Wloss is 20.94%when the waste rare earth fluorescent powders are acid leached in H?concentration 3 mol L-1and S/L ratio 1:3 for 4 h due to red powders dissolved.The better results of the alkali fusion can be got at 800℃ for 2 h when the NaOH is used.The blue powders and the green powders can be dissolved into NaAlO2and oxides such as rare earth oxide(REO).The REO can be dissolved in H?concentration 5 mol L-1,S/L1:10 for 3 h in the second acid leaching.The leaching rates of the Y,Eu,Ce,and Tb are 99.06%,97.38%,98.22%,and 98.15%,respectively.The leaching rate of the total rare earth is 98.60%.

Promotion effects of alkali metals on iron molybdate catalysts for CO_(2)catalytic hydrogenation

CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.

碱烧结法回收二次铝灰中氧化铝

二次铝灰中蕴含大量的氧化铝、铝和氮化铝等,还有部分氟化物和氯化物盐类,属于危险废弃物。目前常用的铝回收技术有酸浸法和碱浸法,均存在工艺条件苛刻、回收率低、能耗高、物耗大和产品附加值较低等问题。本研究采用碱烧结法从二次铝灰中回收氧化铝,考察烧结温度对氮化铝转化率的影响,碱铝比、烧结时间和成型方式对氧化铝回收率的影响,得到以下主要结论:在烧结温度1423 K、烧结时间40 min、碱铝比1.1、干压成型的试验条件下,氧化铝溶出率最大为94.23%;通过对二次铝灰铝酸钠熟料浸出渣成分以及物相进行分析,得到二次铝灰经过碱烧结法焙烧后熟料主要成分为Al_(2)O_(3)和Na_(2)O,分别占到49.70%和28.06%,熟料标准浸出后残渣主要成分为CaO、Al_(2)O_(3)和MgO,含量分别为25.46%、20.27%和15.80%;二次铝灰中AlN分解率较高,可达到95%以上,最终浸出渣中氟离子浸出毒性在30 mg/L以下。综上所述,本文采用碱烧结法资源化利用二次铝灰,实现了二次铝灰脱氮固氟的无害化处置,具有环境友好、资源利用率高的优势,为后续大规模工业化推广奠定了理论基础。

改性电解锰渣-矿粉复合胶材料的制备及水化机理

电解锰渣(EMR)是金属锰湿法冶炼过程中产生的一种固体废物,其堆积量大,对环境造成了严重的污染。但电解锰渣中富含硫酸盐,依据其特性,可与矿粉(GGBFS)复合制备胶凝材料。以矿粉为主要原料,电解锰渣为矿粉的硫酸盐激发剂,熟石灰为碱激发剂,制备电解锰渣-矿粉复合胶凝材料。探究电解锰渣、矿粉和熟石灰的最佳配比,并在此基础上对电解锰渣在不同温度下煅烧改性,通过力学测试确定最佳煅烧温度。利用XRD、FT-IR、TG-DTG和SEM等表征方式分析胶凝材料的水化产物及水化机理,同时对硬化体进行毒性测试。结果表明:电解锰渣对矿粉有良好的激发作用,复合胶凝材料中电解锰渣、矿粉、熟石灰最佳质量配比为2∶7∶1,其28 d的抗压强度达到27.2 MPa,电解锰渣经350℃煅烧所制备的复合胶凝材料抗压强度达到30.5 MPa。复合胶凝材料的水化产物主要为钙矾石(AFt)和水化硅酸钙(C-S-H);28 d硬化体浸出液中的重金属浓度均在《生活饮用水卫生标准》(GB 5749—2022)标准限值内,复合胶凝材料具有良好的安全性。

Determination of arsenic speciation in secondary zinc oxide and arsenic leachability

The species of arsenic in secondary zinc oxide generated from fuming furnace were investigated. The results revealed that there are mainly three types of secondary zinc oxide based on three arsenic species. The main phase of As is As2O3 in type Ⅰ, zinc arsenite （Zn（AsO2）2） in type Ⅱ and lead arsenate （Pb（As206）, Pb4As2O9） in type Ⅲ, respectively. Selective leaching of zinc oxide of type Ⅱ was carried out. The leaching rate of As kept at 65%-70% with 30 g/L NaOH and L/S ratio of 3 at 20 ℃ for 1 h, while the losses of Pb and Zn were both below 1%.

二次铝灰湿法除氟工艺及氟化物的转化行为研究

为了研究湿法除氟因素(液固比、时间、温度、溶液种类、溶液浓度)对二次铝灰湿法处理过程中氟化物浸出效率及底渣氟化物浸出的影响规律,分别采用单因素实验测定湿法浸出前后底渣及其浸出液氟化物含量,同时对二次铝灰原样及湿法处理后的底渣进行XRD、SEM-EDS表征。结果表明,两种浸出介质条件下,以上5种因素均对氟化物浸出效率产生影响,常温湿法浸出条件下,NaOH溶液碱浸去除氟化物效果优于去离子水。去离子水浸出氟化物的最佳工艺参数:液固比(体积质量比,mL/g,下同)为30、水解时间为4 h、水解温度为90℃,此时氟化物浸出率为12.98%。常温条件下NaOH溶液浸出氟化物的最佳工艺参数:液固比为10、NaOH溶液浓度为1.5 mol/L、水解时间为30 min,此时氟化物浸出率为65.85%。XRD表征结果反映出湿法处理后二次铝灰中AlN含量有不同程度的减少,SEM-EDS表征结果反映出湿法处理后底渣中氟化物含量均相应减少,上述研究结果为二次铝灰湿法处理过程中氟化物去除提供科学依据。

Leaching kinetics of fluorine during the aluminum removal from spent Li-ion battery cathode materials

The high content of aluminum(Al)impurity in the recycled cathode powder seriously affects the extraction efficiency of Nickel,Cobalt,Manganese,and Lithium resources and the actual commercial value of recycled materials,so Al removal is crucially important to conform to the industrial standard of spent Li-ion battery cathode materials.In this work,we systematically investigated the leaching process and optimum conditions associated with Al removal from the cathode powder materials collected in a wet cathode-powder peeling and recycling production line of spent Li-ion batteries(LIBs).Moreover,we specifically studied the leaching of fluorine(F)synergistically happened along with the removal process of Al,which was not concerned about in other studies,but one of the key factors affecting pollution prevention in the recovery process.The mechanism of the whole process including the leaching of Al and F from the cathode powder was indicated by using NMR,FTIR,and XPS,and a defluoridation process was preliminarily investigated in this study.The leaching kinetics of Al could be successfully described by the shrinking core model,controlled by the diffusion process and the activation energy was 11.14 kJ/mol.While,the leaching of F was attributed to the dissolution of LiPF6and decomposition of PVDF,and the kinetics associated was described by Avrami model.The interaction of Al and F is advantageous to realize the defluoridation to some degree.It is expected that our investigation will provide theoretical support for the large-scale recycling of spent LIBs.

含砷固废高值利用探索:砷碱浸出渣无害化制备高强陶粒

砷碱浸出渣与陶粒主要组分SiO_(2)、Al_(2)O_(3)和碱性金属氧化物的原料组成具有一定相似性,其火法脱砷工艺与陶粒烧制工艺也极为相近。提出砷碱浸出渣脱砷收无害化制备陶粒的思路,通过还原焙烧将碑、锑挥发脱除后在烟气中进行捕集,捕集产物可直接返回锑冶炼系统,并在此基础上进行陶粒制备工艺探索。研究结果表明:在控制石英与氧化铝质量比Si/Al=6.5,碱性金属氧化物(Na_(2)O、CaO、Fe_(2)O_(3)、K_(2)O、MgO,下同)在陶粒原料(指砷碱浸出渣、石英、氧化铝)中的质量总占比为15%,外配炭量质量分数5%时,采用随炉升温、随炉降温的方式在氩气气氛中970℃保温30min,最终得到表观密度1022kg/m^(3),压裂力为461N的陶粒,、残留量分别为0.020%和0.44%,砷、锑挥发率分别达到99.19%和92.50%。研究结果为砷碱浸出渣及其他含砷固废的高值化利用提供了借鉴。

碱激发粉煤灰基铜尾砂充填膏体试块性能与环境效应研究

为促进矿产资源的可持续利用,保护矿山生态环境,采用一定掺量的碱激发粉煤灰替代水泥制备铜尾砂充填体,通过开展系统的力学、渗透和重金属析出试验,评估了铜尾砂充填膏体试块的强度、抗渗性能和环境效应,结合X射线衍射和扫描电镜结果分析了胶凝材料的矿物组成和充填膏体试块的微观结构特征,揭示了碱激发粉煤灰对充填膏体试块综合性能的影响及其微观作用机理。结果表明,碱激发可以显著提高粉煤灰的活性,在1 mol/L的Na OH碱激发剂作用下,掺量20%的粉煤灰基铜尾砂充填膏体试块经过28 d养护,其抗压强度较水泥胶凝试块提高了17.8%,渗透系数降低了68.0%,综合胶结效果显著;碱激发粉煤灰的掺入减少了铜尾砂充填膏体试块硬化过程中的重金属析出,有助于控制地下水资源的污染;利用粉煤灰的微细颗粒填充效应和复合胶凝效应,可有效降低铜尾砂的孔隙率,并形成新的水化产物,增强尾砂颗粒间的结合力,从而提高材料的强度和稳定性。

碱激发螯合生活垃圾焚烧飞灰力学性能和毒性浸出特性

生活垃圾焚烧飞灰螯合固化后,仍存在一定环境隐患,填埋会占用大量土地,将其再利用可以减缓填埋场的压力。本文采用碱激发技术制备螯合飞灰-矿粉基碱激发胶凝材料,除探讨碱激发螯合飞灰的可行性以外,还研究了氧化钙掺量对胶凝材料性能的影响。结果表明,在氧化钙掺量为4%(质量分数)时,固化体的抗压强度最高,而当氧化钙掺量超过4%时,固化体的抗压强度则会缓慢减小。氧化钙的加入促进了C-S-H凝胶水化产物的形成,显著提高了材料的抗压强度。同时,通过浸出试验发现掺入氧化钙的固化体的重金属浸出浓度低于未掺氧化钙的固化体,并且满足规定《生活垃圾填埋场污染控制标准》(GB 16889—2008)限制值。