Process development for the direct solvent extraction of nickel and cobalt from nitrate solution: aluminum,cobalt, and nickel separation using Cyanex 272

A direct solvent extraction (DSX) process for purifying nickel and cobalt from the nitric acid leach solution of nickel laterite ores was conceived and experimentally probed. The proposed process consists of two solvent extraction (SX) steps but with only one extractant-bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex® 272)-used in both steps. The first extraction step involved the removal of aluminum and zinc, whereas the second extraction step involved the separation of cobalt along with manganese from nickel. The experimental results showed essentially quantitative removal of aluminum (>97%) and zinc (>99%) in a single extraction stage using 20vol% Cyanex 272 at pH 2.1. Some cobalt (32%) and manganese (55%) were co-extracted but were easily scrubbed out completely from the loaded organic phase using dilute sulfuric acid at pH ≤ 1.38. Cobalt and manganese in the first extraction raffinate were extracted completely in four extraction stages at staggered pH values of 4.0, 4.4, 4.5, and 4.0 in the first, second, third, and fourth stages, respectively, using also 20vol% Cyanex 272. A small amount of nickel (up to 6.6%) was co-extracted but was easily scrubbed out completely with dilute sulfuric acid at pH 2.0. A flow diagram showing the input and output conditions and the metals separated under the deduced optimum conditions is presented.     

镍钼矿冶炼渣酸浸液的萃取争化及氧化亚镍的制备

用溶剂萃取的方法从镍钼矿冶炼渣酸浸液中回收镍并制备氧化亚镍粉末.研究结果表明:有机相中萃取剂2-乙基己基膦酸-单-2-乙基己基酯(PC-88A)的添加量、相比(即水与油的体积比)、萃取时间、料液的pH对镍萃取有显著的影响,温度对镍的萃取影响很小.最佳萃取工艺条件如下:萃取剂(PC-88A)体积分数为30%,相比为3:1,料液的pH为6.7,萃取时间为3 min,萃取温度为30℃,在此最佳条件下进行二级错流萃取,镍的萃取率为99.6%.反萃的最佳条件如下:相比为1:3,盐酸的浓度为2 mo1/L,反萃时间为3 min,在此最佳条件下,一级镍的反萃率为99.3%.用反萃得到氯化镍先制备草酸镍,然后煅烧,得到纯度达99%氧化亚镍粉末.     

玻璃基体表面化学镀镍的研究

玻璃镀件通过碱洗、酸洗除去油污及其杂质,再用HF酸进行表面腐蚀,使镀件具有一定的粗糙度.然后控制一定的温度和时间,进行敏化、活化处理.使玻璃基体表面具有催化活性中心,最后将玻璃镀件放入镀镍溶液中进行化学镀镍,控制温度和pH值,进行玻璃的化学镀镍.实验研究了玻璃化学镀镍的操作方法、工艺条件及各种因素对镀层的影响,通过多次试验,确定了玻璃化学镀镍的最佳工艺条件（PH=5.38,温度为85℃）和实验方法.     

Photodegradation of bisphenol a induced by metal ions in aqueous solution in the presence of ascorbic acid

The photodegradation of bisphenol A (BPA) in aqueous solution containing metal ions and ascorbic acid (AsA) was investigated. After strong irradiation, the aqueous solution containing AsA and Cu²⁺ could produce hydroxyl radicals that induced the photodegradation of BPA. The photodegradation efficiency of BPA in the solution containing 70 μmol·L⁻¹ Cu²⁺ and 15 mg·L⁻¹ AsA reached 59% at pH 6.0 after 4 hours irradiation with high pressure mercury lamp. The photodegradation efficiency of BPA reached 10% after 4 hours irradiation with daylight lamp in the presence of 70 μmol·L⁻¹ Cu²⁺ and 15 mg·L⁻¹ ascorbic acid. BPA was not degraded in the aqueous solution only containing AsA or Cu²⁺. The BPA photodegradation in aqueous solution containing AsA and Fe³⁺ was weaker than in aqueous solution that containing AsA and Cu²⁺ at the same concentration. This work showed a new route of the BPA photodegradation in aqueous environment. Biography: PENG Zhang’e (1970–), female, Ph. D. candidate, research direction: aquatic environmental chemistry.     

NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction by coupling combustion with recycling flue gas in iron ore sintering process

A new process called ‘NO _x reduction by coupling combustion with recycling flue gas (RCCRF)’ was proposed to decrease NO _x emission during the iron ore sintering process. The simulation test of NO _x reduction was performed over sintered ore and in the process of coke combustion. Experimentally, NO _x reduction was also carried out by sintering pot test. For sintered ore, the amount of NO _x emission is reduced by 15wt%–25wt% at 400–550°C using 2.0vol% H₂ or 2.0vol% CO, or reduced by 10wt%–30wt% at 560–720°C using 0.15vol% NH₃. NO _x reduction is around 10wt% by coupling combustion of pyrolysis gas and coke, or around 16wt% by recycling flue gas into coke combustion. By RCCRF, the maximum NO _x reduction ratio is about 23wt% in coke combustion experiment and over 40wt% in sintering pot test.     

硼酰化镍的合成及性能

研究了以碳酸镍、硼酸酯和混合羧酸合成新的金属-橡胶粘合促进剂硼酰化镍的方法,系统地考察了各种因素对合成硼酰化镍的影响,优化了合成条件．通过检测,以2-乙基己酸和硼酸三丁酯为有机原料合成的硼酰化镍,其红外光谱数据、应用性能与英国Manobond公司的产品680C的相当,可用作金属-橡胶粘合促进剂．     

铁矾渣微波硫酸化焙烧水浸液的深度除铁

采用微波低温硫酸化焙烧-水浸和针铁矿除铁方法将Zn、Cu等富集到浸出液中,Pb和Ag富集到浸出渣中,使有价金属得到清洁的回收利用.研究了上述工艺中浸出液除铁的优化工艺条件,探究了反应体系的pH值、浸出液单次滴加量、浸出液的铁含量等因素对除铁效果的影响,并采用X射线衍射分析、扫描电子显微镜观察等手段对得到的沉淀渣进行了表征.研究获得的优化实验条件为：以200 mL的0.01 mol·L-1 ZnSO4溶液为底液,晶种添加量为20 g·L-1,除铁体系pH值控制在3左右,温度90℃,每隔5 min滴加3 mL水浸液(保持反应体系中铁的浓度<1 g·L-1).在此条件下,除铁后溶液残铁量仅为0.065 g·L-1,去除率可达99.3%,达到了深度除铁效果.除铁过程中,Zn的损失率仅为4.1%.     

矿浆中和过程中基于模型预估模糊自适应控制

氢氧化镍钴矿浆用已有的中和过程闭环控制方法，在受到随机干扰影响的情况下，常会造成终点pH值偏离目标值，影响后续工艺过程的矿浆沉淀性能，降低镍钴氢氧化物的产品质量.提出模型预估与模糊自适应相结合的控制方法，通过模型预估控制尽量消除大滞后带来的影响，采用模糊自适应控制可以及时、有效地调整石灰石浆流量的设定值，采用PI控制器跟踪其设定值，从而满足pH值的工业过程控制要求.在国外某大型氢氧化镍钴冶炼厂的成功应用，表明该方法有效地解决了中和过程存在的大滞后时变等问题，使得氢氧化镍钴矿浆中和过程稳定运行，提高镍钴金属成分的回收率.     

The test freezing temperature of C2―C6 dicarboxylic acid: The important indicator for ice nucleation processes

The importance of organic compounds as significant constituents of atmospheric aerosols, and cloud condensation nuclei （CCN）, as well as players influencing the tropospheric oxidation and atmospheric energy budget, have been increasingly recognized. Low molecular weight dicarboxylic acids （LMW-DCAs） are significant identified portions of atmospheric condensed matter including aerosols, fog and clouds. Besides the photochemical transformation of DCA, the implication of organic matter in ice nucleation processes has been considered. In this study, we investigated the freezing temperature of pure and mixed （C2-C6） DCA solutions in ultra-pure water and tap water solution droplets using a freezing nucleus counter at different pH, and in different water ionic conditions. The mean freezing temperature of different mixture of LMW-DCA in ultra-pure and tap water solution droplets ranged from -24.1±2.8 to -21.3±3.9℃ and -10.2±2.2 to -9.5±2.2℃, respectively. The mean freezing temperature of the control （ultra-pure and tap） water droplets （-22.6±3.5℃, 11.2±2.4℃） was also measured. The results, and their implications in atmospheric chemistry and physics of the atmosphere will be discussed.     

Synthesis mechanism of LiNiVO4 by wet chemical method and mixed valence of nickel and vanadium

The single phase LiNiVO₄ has been successfully synthesized by adopting a new mild liquid route with oxalic acid as both complexant and precipitant, and this method is named the CPG method. The products were obtained by sintering the dry gel precursor which was prepared by the CPG method at 200—850℃ for 2—10 h in air. The products were tested by XRD, XPS, ESR and TGA-DTA, and the results indicate that the single phase LiNiVO₄ could be obtained at 450℃ for 2—3 h in air and LiNiVO₄ was still steady at 850℃ for 10 h. The valence analyses show that in LiNiVO₄ the valence of lithium is +1, both nickel and vanadium have the mixed valence, namely +2, +3 for nickel and +4, +5 for vanadium respectively. The LiNiVO₄ can be expressed as LiNi³⁺_xNi²⁺_1-xV⁴⁺_xV⁵⁺_1-xO₄ (0≤x<1). The pyrolysis mechanism of the dry gel is also discussed.     

Extraction behaviours of titanium and other impurities in the decomposition process of ilmenite by highly concentrated KOH solution

To effectively utilize ilmenite and recycle KOH solution, the extraction behaviours of titanium and other associated impurities in the decomposition process of ilmenite by highly concentrated KOH solution were studied. Experiments on the extraction behaviours of titanium as well as other associated impurities of ilmenite such as iron, silicon, calcium, and aluminium were carried out. The effects of various parameters, including reaction temperature, KOH concentration, reaction time, alkali-to-ore mass ratio, and particle size on the extraction rate of titanium and other impurities were examined. When the finely ground ore (58-75 μm) reacted with KOH solution (80wt%) in an alkali-to-ore mass ratio of 7:1 at 260℃ for 60 min, almost complete extraction of titanium was achieved, while the extraction rate of aluminium was 78% and that of other impurities was less than 22%. Moreover, high purity (98.2wt%) TiO₂ with the anatase structure could be gained in the purification process.     

Fabrication of porous alumina templates with a large-scale tunable interpore distance in a H<Subscript>2</Subscript>C<Subscript>2</Subscript>O<Subscript>4</Subscript>-C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH-H<Subscript>2</Subscript>O solution

Highly ordered porous alumina templates with a large-scale tunable interpore distance （100-445 nm） have been successfully fabricated under an electric field of 40-180 V by modifying oxalic acid solution with adequate alcohol. The results under our experimental conditions show that the phenomena of burning and breakdown during the high-field anodization process can be avoided by adding a proper amount of alcohol to the oxalic acid solution. An excellent linear relationship between interpore distance and anodization voltage is obtained under 40-170 V, and the maximum anodization voltage that could be used to avoid burning and breakdown is 180 V.     

Comparison of effective parameters for copper powder production <Emphasis Type="Italic">via</Emphasis> electrorefining and electrowinning cells and improvement using DOE methods

The influences of cupric ion concentration (5–35 g/L), current density (500–2000 A/m²), circulation rate of the electrolyte solution (15–120 mL/min), and temperature (25–60°C) on the physical and chemical properties of copper powders obtained in electrolysis cells were investigated. Two industrial processes, electrorefining (ER) cells with a synthetic electrolyte and electrowinning (EW) cells with an original solution of copper mineral leaching, were utilized to produce copper powders. Finally, the statistical full factorial method of design of experiments (DOE) was employed to investigate the interaction or the main effects of processes. The results show that increasing the copper concentration and temperature can increase the grain size, apparent density, and electrical energy consumption. On the other hand, increasing the current density and circulation rate of the electrolyte can decrease them. This production process is optimized via DOE to control the interactive and main effects to produce copper powders with favorable properties.     

Preparation of titanium dioxide from titania-rich slag by molten NaOH method

Preparing titanium dioxide from titania-rich slag (TiO₂ 73wt%) by molten NaOH method has been developed. The effects of temperature and reaction time on the titanium conversion were investigated. The results showed that temperature had significant influence on the titanium conversion as well as the structure of the product. About 92% of titanium in the titania-rich slag could be converted after reacting with NaOH at 500℃ for 1 h. Metatitanic acid was formed through the steps of washing treatment, acid dissolution, and hydrolysis. Well-dispersed spherical titanium dioxide particles with an average size of 0.1-0.4 μm can be obtained by calcination of metatitanic acid. In addition, the content of titanium dioxide in the product is up to 98.6wt%, which can be used as pigments after further treatment of coating and crushing.     

Comprehensive model for a slag bath in electroslag remelting process with a current-conductive mould

A mathematical model was developed to describe the interaction of multiple physical fields in a slag bath during electroslag remelting (ESR) process with a current-conductive mould. The distributions of current density, magnetic induction intensity, electromagnetic force, Joule heating, fluid flow and temperature were simulated. The model was verified by temperature measurements during remelting 12CrMoVG steel with a slag of 50wt%-70wt% CaF₂, 20wt%-30wt% CaO, 10wt%-20wt% Al₂O₃, and ≤ 10wt% SiO₂ in a 600 mm diameter current-conductive mould. There is a good agreement between the calculated temperature results and the measured data in the slag bath. The calculated results show that the maximum values of current density, electromagnetic force and Joule heating are in the region between the corner electrodes and the conductivity element. The characteristics of current density distribution, magnetic induction intensity, electromagnetic force, Joule heating, velocity patterns and temperature profiles in the slag bath during ESR process with current-conductive mould were analyzed.     

湿法磷酸制牙膏级磷酸氢钙中的脱氟工艺

针对由中低品位磷矿石制得的湿法磷酸,提出采用预脱氟和灰乳中和深度脱氟相结合的工艺路线,使净化后的湿法磷酸达到作为生产牙膏级磷酸氢钙原料酸的指标要求。实验表明,钾盐的脱氟效果与磷酸的浓度有一定关系,同时活性氧化硅有且于氟的进一步脱除;在进一步的净化过程中,用石灰乳中和至一定的ｐＨ值,绝大部分的氟及其它杂质沉淀析出脱除,净化酸达到了牙膏级磷酸氢钙的生产要求。     

高浓度NaOH浸出红土镍矿中SiO_2的研究

研究了红土镍矿高浓度NaOH浸出的条件.探讨了搅拌强度、温度、NaOH初始质量分数、浸出时间和碱矿质量比对SiO2浸出率的影响.结果表明:搅拌强度600 r/min、浸出温度225℃、初始NaOH质量分数85%、浸出时间90 min、碱矿比5∶1时,SiO2的浸出率可达82.77%.碱浸渣中的铁、镁、镍被富集,其中氧化镍的质量分数由1.29%提高到2.15%.     

Use of mesophilic and thermophilic bacteria for the improvement of copper extraction from a low-grade ore

Bioleaching was examined for copper extraction from a low grade ore using mesophilic and moderate thermophilic bacteria. Five equal size columns were used for the leaching of the ore. Sulfuric acid solution with a flow rate of 3.12 L·m-2·h-1 and pH 1.5 passed through each column continuously for 90 d. In the first and the second column, bioleaching was performed without agglomeration of the ore and on the agglomerated ore, respectively. 28wt% of the copper was extracted in the first column after 40 d, while this figure was 38wt% in the second column. After 90 d, however, the overall extractions were almost the same for both of them. Bioleaching with mesophilic bacteria was performed in the third column without agglomeration of the ore and in the fourth column on the agglomerated ore. After 40 d, copper extractions in the third and the fourth columns were 62wt% and 70wt%, respectively. Copper extractions were 75wt% for both the columns after 90 d. For the last column, bioleaching was performed with moderate thermophilic bacteria and agglomerated ore. Copper extractions were 80wt% and 85wt% after 40 and 90 d, respectively. It was concluded that crushing and agglomeration of the ore using bacteria could enhance the copper extraction considerably.     

高铁锌矿的湿法处理

研究高铁锌矿的湿法处理工艺，提出了“硫化锌精矿、软锰矿同时浸出，氧化锌矿中和，锌、二氧化锰分步电解”的工艺制度。试验结果表明：高铁锌矿的全湿法处理在技术上是可行的。     

Evaluation of virus removal in MBR using coliphages T4

A membrane bioreactor (MBR) with gravity drain was tested for domestic wastewater for 65 days. Resultss howed that the effluent quality was excellent, and met with the reuse water standard of China (GB/T 18920-2002). Virus removal in the membrane separation process was investigated by employing coliphages T4 as a tracer. Two microfiltration membrane modules, with pore sizes of 0.22 and 0.1 μm, were used to investigate their effects on virus rejection at the transmembrane pressure of 8.5 kPa. It was found that 0.1 μm membrane had complete rejection of virus, and 0.22 μm membrane had significant rejection of virus. In the longterm operation of this MBR, no significant difference was observed between both pore sizes because the virus concentrations of the effluent in both cases were in the same order. Effluent virus concentration at steady state of MBR running was less than 2 PFU/mL. The removal ratios of coliphage T4 in MF processes were more than 10^5.5. The membrane surface deposits played an important role in the rejection of virus. The formation of cake clay on the membrane surface was the main cause of high rejection of colipbage T4 with MF of 0.22 μm.