Thermodynamic simulation of stepwise precipitation of NH_4VO_(3)and NaHCO_(3)from carbonating Na_(3)VO_(4)solution

Thermodynamic simulation was conducted to design a new process of stepwise precipitating NH_4VO_(3)and NaHCO_(3)from regulating the CO_(2)carbonation of Na_(3)VO_(4)solution.Firstly,a new V(V)speciation model for the aqueous solution containing vanadate and carbonate is established by using the Bromley-Zemaitis activity coefficient model.Subsequently,thermodynamic equilibrium calculations are conducted to clarify the behavior of vanadium,carbon,sodium,and impurity species in atmospheric or high-pressure carbonation.To ensure the purity and recovery of vanadium products,Na_(3)VO_(4)solution is initially carbonated to the pH of 9.3-9.4,followed by precipitating NH_4VO_(3)by adding(NH_4)_(2)CO_(3).After vanadium precipitation,the solution is deeply carbonated to the final pH of 7.3-7.5 to precipitate NaHCO_(3),and the remaining solution is recycled to dissolve Na_(3)VO_(4)crystals.Finally,verification experiments demonstrate that 99.1%of vanadium and 91.4%of sodium in the solution are recovered in the form of NH_4VO_(3)and NaHCO_(3),respectively.

Conjugated microporous polymers-scaffolded enzyme cascade systems with enhanced catalytic activity

Enhancing catalytic activity of multi-enzyme in vitro through substrate channeling effect is promis-ing yet challenging.Herein,conjugated microporous polymers(CMPs)-scaffolded integrated en-zyme cascade systems(I-ECSs)are constructed through co-entrapping glucose oxidase(GOx)and horseradish peroxidase(HRP),in which hydrogen peroxide(H_(2)O_(2)) is the intermediate product.The interplay of low-resistance mass transfer pathway and appropriate pore wall-H_(2)O_(2) interactions facilitates the directed transfer of H_(2)O_(2),resulting in 2.4-fold and 5.0-fold elevation in catalytic activ-ity compared to free ECSs and separated ECSs,respectively.The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP.Besides,I-ECSs demonstrate excellent stabili-ties in harsh environments and multiple recycling.

煤气化渣制备聚合氯化铝工艺研究

我国煤气化渣(CGR)年产量巨大,但综合利用率低,现有堆存与填埋方式具有较大的环境风险与经济压力,规模化消纳与资源化利用需求迫切。以煤气化渣酸浸液制备聚合氯化铝絮凝剂为目标,考察了铝酸钙粉用量、聚合温度、聚合时间和酸洗液循环次数对聚合氯化铝产品指标的影响。结果表明,煤气化渣酸洗液循环次数达到4次时,液相中铝离子浓度为28 g/L,氧化铝含量可达5. 28%;以该富铝酸液为反应原料,反应温度80℃、反应时间120 min、铝酸钙粉用量12. 50 g/50 m L时,得到的聚合氯化铝产品中氧化铝质量分数为10%～11%,盐基度为44%～50%,且产品中铅、铬、砷等重金属元素含量极低,各项性能指标均符合GB/T 22627—2014中水处理剂聚合氯化铝的制备标准。

Direct extraction of Mo(VI) from acidic leach solution of molybdenite ore by ion exchange resin:Batch and column adsorption studies

The adsorption behavior of ion exchange resin D301 in the extraction of hexavalent molybdenum from high acidic leach solution was investigated. SEM, EDS and Raman spectra analyses were applied to studying the adsorption capacity, reaction kinetics and possible adsorption mechanism in detail. Results showed that the adsorption capacity of D301 resin for molybdenum from high acidic leach solution was up to 463.63 mg/g. Results of the kinetic analysis indicated that the adsorption process was controlled by the particle diffusion with the activation energy 25.47 k J/mol（0.9-1.2 mm） and 20.38 k J/mol（0.6-0.9 mm）. Furthermore, the molybdenum loaded on the resin could be eluted by using 2 mol/L ammonia hydroxide solution. Besides, dynamic continuous column experiments verified direct extraction of molybdenum from acidic leach solutions by ion exchange resin D301 and the upstream flow improved dynamic continuous absorption.

Simultaneous extraction of gold and zinc from refractory carbonaceous gold ore by chlorination roasting process

A novel process based on chlorination roasting was proposed to simultaneously recover gold and zinc from refractory carbonaceous gold ore by using NaCl as chlorination agent.The effects of roasting temperature,roasting time and NaCl content on the volatilization rates of gold and zinc were investigated.The reaction mechanism and the phase transition process were also analyzed by means of SEM,EDS and XRD.The results demonstrated that under the optimal conditions of NaCl content of 10%,roasting temperature of 800℃,roasting time of 4 h and gas flow rate of 1 L/min,the rates of gold and zinc were 92%and 92.56%,respectively.During low-temperature chlorination roasting stage,a certain content of sulfur was beneficial to the chlorination reactions of gold and zinc;and during high-temperature chlorination roasting stage,the crystal structure of vanadium-bearing mica was destroyed,and the vanadium-containing oxides were beneficial to the chlorinating volatilization of gold and zinc.Eventually,the chlorinated volatiles of gold and zinc could be recovered by alkaline solution.

Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

Extraction of valuable metals from Ti-bearing blast furnace slag using ammonium sulfate pressurized pyrolysis−acid leaching processes

A novel method of extracting valuable metals from Ti-bearing blast furnace slag(TBBF slag)via pressure pyrolysis of recyclable ammonium sulfate(AS)−acid leaching process was proposed.The results show that when pressurized roasting at an AS-to-slag mass ratio 3:1 and 370℃for 90 min,the extraction rates of titanium,aluminum and magnesium reached 94.5%,91.9%and 97.4%,respectively.The acid leaching solution was subjected to re-crystallization in a boiling state to obtain a titanium product having a TiO2 content of 94.1%.The above crystallization mother liquor was adjusted to pH=6 and pH≥12.2,respectively,and then qualified Al2O3 and MgO products were obtained.The analysis through XRD and SEM−EDS proves that the main phases in roasted samples were NH4AlSO4,CaSO4 and TiOSO4.The thermodynamic analysis presents that the main minerals of perovskite,spinel and diopside in raw ore could spontaneously react with the intermediate produced by AS under optimal conditions.

Complexation separation for vanadium and chromium by dithiocarbamate and its application in treatment of chromium-vanadium-bearing slag

A novel method for the separation and reclamation of vanadium and chromium from acidic solution was proposed. The principle for the separation is based on selective complexation. In specific, V(V) can be complexated by dithiocarbamate to form VO(R1R2NCS2)3 precipitate, leaving Cr(Ⅲ) remained in the acidic solution. Then the reclamation of V and Cr from VO(R1R2NCS2)3 precipitate and Cr(Ⅲ)-bearing solution can be reached by decomplexation and neutralization, respectively. The kinetics of the complexation reaction was studied. In addition, the precipitation ratio of vanadium reached 97% and the loss of chromium was less than 4% after process optimization. The complexing agent could be regenerated with a high ratio of 99.5%. The method was successfully applied to treating chromium-vanadium-bearing slag produced in conventional vanadium production industry. Vanadium and chromium could be extracted from the slag in the form of calcium vanadate and Cr2O3 product with a purity of over 98%.

Synthesis of isosorbide-based polycarbonates via melt polycondensation catalyzed by quaternary ammonium ionic liquids

A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.

Kinetics of decomposition of mullite and corundum in coal fly ash under highly alkaline condition

Decomposition kinetics of mullite and corundum in coal fly ash with highly alkaline solution was studied.The effects of the reaction temperature and reaction time on decomposition rates of mullite and corundum and alumina extraction efficiency were investigated.The results show that increasing reaction temperature and reaction time increases the decomposition rates of mullite and corundum and alumina extraction efficiency,with the decomposition temperature of mullite lower than that of corundum.After 90 min reaction at 220℃,more than 100 g alumina was extracted when recycling 1 L of alkaline solution.The decomposition processes of mullite and corundum corresponded with the shrinking unreacted core model,and the reaction rate was under chemical reaction control,with the activation energies of mullite and corundum being 67.46 and 161.82 kJ/mol,respectively.

Leaching performance of Al-bearing spent LiFePO_(4) cathode powder in H_(2)SO_(4) aqueous solution

The leaching performance and leaching kinetics of LiFePO_(4)(LFP)and Al in Al-bearing spent LFP cathode powder were systematically studied.The effects of temperature(273−368 K),stirring speed(200−950 r/min),reaction time(0−240 min),acid-to-material ratio(0.1:1−1:1 mL/g)and liquid-to-solid ratio(3:1−9:1 mL/g)on the leaching process were investigated.The results show that the concentration of reactants and the temperature have a greater impact on the leaching of Al.Under the optimal conditions,leaching efficiencies of LFP and Al are 91.53%and 15.98%,respectively.The kinetic study shows that the leaching of LFP is kinetically controlled by mixed surface reaction and diffusion,with an activation energy of 22.990 kJ/mol;whereas the leaching of Al is only controlled by surface chemical reaction,with an activation energy of 46.581 kJ/mol.A low leaching temperature can effectively suppress the dissolving of Al during the acid leaching of the spent LFP cathode material.

An efficient and stable Cu/SiO_2 catalyst for the syntheses of ethylene glycol and methanol via chemoselective hydrogenation of ethylene carbonate

The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate（EC） is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_（cat）^（–1） h^（–1） with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~＋/（Cu^0＋Cu~＋）. Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~＋ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.

Synthesis of propylene glycol ethers from propylene oxide catalyzed by environmentally friendly ionic liquids

A series of acetate ionic liquids were synthesized using a typical two‐step method.The ionic liquids were used as environmentally benign catalysts in the production of propylene glycol ethers from propylene oxide and alcohols under mild conditions.The basic strengths of the ionic liquids were evaluated by determination of their Hammett functions,obtained using ultraviolet‐visible spectroscopy,and the relationship between their catalytic activities and basicities was established.The catalytic efficiencies of the ionic liquids were higher than that of the traditional basic catalyst NaOH.This can be attributed to the involvement of a novel reaction mechanism when these ionic liquids are used.A possible electrophilic‐nucleophilic dual activation mechanism was proposed and confirmed using electrospray ionization quadrupole time‐of‐flight mass spectrometry.In addition,the effects of significant reaction parameters such as concentration of catalyst,molar ratio of alcohol to propylene oxide,reaction temperature,and steric hindrance of the alcohol were investigated in detail.

ZrO_2-modified Ni/LaAl_(11)O_(18) catalyst for CO methanation: Effects of catalyst structure on catalytic performance

We report Ni/LaHA@ZrO2catalysts prepared by a facile modified successive adsorption and reaction method for CO methanation.N2adsorption,X‐ray diffraction,transmission electron microscopy,scanning electron microscopy,thermogravimetric analysis,H2temperature‐programmed reduction,H2temperature‐programmed desorption,X‐ray photoelectron spectroscopy,thermogravimetric analysis,and inductively coupled plasma atomic emission spectrometry were used to characterize the samples.The results indicated that the ZrO2nanoparticles were distributed over the surface of the Ni/LaHA@ZrO2catalyst and even partially covered some Ni particles,resulting in the coating exerting a confinement effect.The excess ZrO2had an adverse effect on the enhancement of CO conversion because of the coverage of the surface Ni particles;however,the Ni/LaHA@ZrO2catalyst displayed much higher CH4selectivity than Ni/LaHA because of the activation of the byproduct CO2molecules by ZrO2species.Therefore,even though20Ni/LaHA@ZrO2‐5exhibited similar CO conversion as20Ni/LaHA,the use of the former resulted in a higher CH4yield than the use of the latter.A107‐h‐lifetime test revealed that the Ni/LaHA@ZrO2catalyst was highly stable with superior anti‐sintering and anti‐coking properties because of its coating structure and the promoter effect of ZrO2.

Decomposition kinetics of zircon sand in NaOH sub-molten salt solution

Sub-molten salt was applied to the decomposition of zircon sand(ZrSiO4).The kinetics of the decomposition of zircon sand and the effects of reaction temperature,reaction time,NaOH content,agitation speed,and the NaOH/ore mass ratio on the decomposition rate of zircon sand in NaOH sub-molten salt were investigated.The results indicate that the decomposition rate of zircon sand increases with the increase in the reaction temperature,reaction time,and NaOH content.The shrinking-core model with surface chemical reaction-controlled process is the most applicable for the decomposition of zircon sand,with the apparent activation energy of 77.98 kJ/mol.The decomposition product is sodium zirconium silicate(Na2ZrSiO5),and the decomposition rate is higher than 99%under the optimal conditions.

Leaching of chromite ore in concentrated KOH by catalytic oxidation using CuO as catalyst

CuO was used as a catalyst in the concentrated KOH solution to enhance the leaching of chromium from the chromite ore.The impacts of temperature,KOH-to-chromite ore mass ratio,CuO-to-chromite ore mass ratio,and gas flow rate on the chromiumleaching rate were investigated.The results indicated that CuO played an important role in improving the chromium leaching rate.The leaching rate reached98%after leaching for6h when CuO was applied,whereas it was only60.8%without CuO under thesame reaction conditions:temperature230°C,KOH-to-ore mass ratio6:1,stirring speed700r/min,gas flow rate1L/min.Accordingto the kinetics study,the catalytic oxidation was controlled by surface chemical reaction and the activation energy was calculated tobe15.79kJ/mol when the temperature was above230°C.In contrast,without CuO,the rate-determining step was external diffusionand the apparent activation energy was38.01kJ/mol.

Preparation of titanium mineral from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching

Titanium mineral was prepared from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching.The leaching behaviors of elements like Fe,V,Mn,Al,Mg,Ca,and Si were highly related to the reduction degree.The phase compositions of the reduced materials and the leached residues were analyzed by XRD to identify the effect of reduction degree on the leaching mechanisms.The results showed that the concentrates were reduced to iron metal and titanomagnetite at 800-1000°C for 0.5 h,and the above elements of Fe and impurities were easily leached.Deeper reduction led to the formation of ilmenite and Mg-Al spinel,which hindered leaching.Mg-bearing anosovite appeared in the further reduced materials,and the leaching rates of impurities became much lower.An upgraded titanium mineral with a normalized TiO_(2) grade of 70.3%was achieved by H_(2) reduction at 850°C for 0.5 h and acid leaching,which is a satisfactory Ti resource for the preparation of titanium oxide by sulfate process.

Preparation of hexagonal and amorphous chromium oxyhydroxides by facile hydrolysis of K_xCrO_y

The hydrolysis process and mechanisms of unique as-prepared KCrO2 and K3 CrO4 were systematically investigated. The characterization results of XRD, IR and SEM show that the hydrolysis reaction can be realized at a low reaction temperature of 80 ℃ and a reaction time of 24 h. Moreover, the greyish-green α-CrOOH with a hexagonal plate-like morphology and a large size of 10 μm is formed via the hydrolysis of the single-phase hexagonal KCrO2, while the green sol-gel of amorphous Cr(OH)3 with a lumpy aggregate morphology is generated through the hydrolysis of a cubic K3 CrO4. It is a facile and rapid method to synthesize pure-phase chromium oxyhydroxide via the above hydrolysis.

Pickering interfacial biocatalysis with enhanced diffusion processes for CO_(2) mineralization

Utilization of carbon dioxide(CO_(2))has become a crucial and anticipated solution to address environmental and ecological issues.Enzymes such as carbonic anhydrase(CA)can efficiently convert CO_(2) into various platform chemicals under ambient conditions,which offers a promising way for CO_(2) utilization.Herein,we constructed a Pickering interfacial biocatalytic system(PIBS)stabilized by CA‐embedded MOFs(ZIF‐8 and ZIF‐L)for CO_(2) mineralization.Through structure engineering of MOFs and incorporation of Pickering emulsion,the internal and external diffusion processes of CO_(2) during the enzymatic mineralization were greatly intensified.When CO_(2) was ventilated at a flow rate of 50 mL min^(–1) for 1 h,the pH value of PIBS dropped from~8.00 to~6.50,while the average pH value of free system only dropped to~7.15,indicating that the initial reaction rate of CO_(2) mineralization of PIBS is nearly twice that of the free system.After the 8^(th) cycle reaction,PIBS can still produce more than 9.8 mg of CaCO_(3) in 5 min,realizing efficient and continuous mineralization of CO_(2).

镍钴湿法冶金污染源解析及防治建议

镍、钴应用领域广泛,是新型储能材料中的重要组成部分,生产工艺以湿法冶金工艺为主。随着需求端和原料端的变化,镍、钴冶金中产生的污染物逐渐复杂化,对环境的威胁不断增大。本文介绍了镍、钴常用的湿法冶金路线及污染节点,并进一步介绍了主要污染物的组成及防治措施。简要介绍了清洁生产技术发展趋势,并对镍钴湿法冶金清洁生产改造提出建议。