湿法炼锌窑渣铁精矿的浸出热力学分析

为实现湿法炼锌窑渣磁选铁精矿(以下简称窑渣铁精矿)中银、铜、铁等有价元素的综合回收,提出一种基于盐酸浸出的新工艺,从理论和实验两方面开展研究。在本研究中介绍新工艺研究的理论部分——浸出热力学分析。物相分析表明:窑渣铁精矿中主要含铁物相为Fe、FeO、FeS、Fe2O3、Fe3O4和FeSiO3。计算绘制了Fe-Cl-H2O系φ—pH优势区图以及FeS、FeO、FeSiO3-H2O系和FeS、FeO、FeSiO3-Cl-H2O系的lg c—pH图,分析窑渣铁精矿盐酸浸出的热力学可行性。结果表明:各含铁物相在盐酸浸出中均能溶解,[Cl]T越高,其溶解度就越大,由于不同阴离子在体系中溶解性质的差异,因此,Cl影响FeO、FeS和FeSiO3溶解的pH范围不同,分别为4.2～10.8、0.4～10.8和0～10.8。     

铅阳极泥碱性加压氧化浸出脱砷过程中As-N-Na-H_2O系的φ-pH图（英文）

为阐明砷在铅阳极泥碱性加压氧化浸出过程(NaNO_3为氧化剂;NaOH为碱性试剂)中的热力学特性,通过热力学计算绘制体系离子质量浓度为0.1 mol/kg,温度为298、373、423和473 K条件下的As-Na-H_2O、N-H_2O和As-N-Na-H_2O系的φ-pH图。结果表明,砷的存在形态与pH值有关。当pH值较低时,砷主要以H_3AsO_4、H_2AsO_4~-、HAsO_4~(2-)、H_2AsO_2~-及As_2O_3的形式存在;当pH11.14时,砷主要以AsO_4~(3-)形式存在,高碱浓度及高温对砷浸出有利。碱性加压氧化浸出实验表明,砷浸出率变化趋势与As-N-Na-H_2O系φ-pH图的热力学分析结果一致,在453K时砷的最佳浸出率为95.85%。     

次氧化锌中砷的物相及砷的浸出(英文)

研究烟化炉次氧化锌中砷的物相类型。结果表明:按砷的物相可将次氧化锌分为3种类型。在一型次氧化锌中砷以As2O3形态存在,而在二型和三型次氧化锌中砷分别以亚砷酸锌(Zn(AsO2)2)和砷酸铅(Pb(As2O6),Pb4As2O9)形态存在。在热力学分析基础上,对二型次氧化锌进行浸出脱砷。结果表明:采用30g/LNaOH溶液,在液固比3、温度20°C的条件下,砷的浸出率在1h内可达到65%～70%,而铅、锌的损失均小于1%。     

含砷污酸资源化回收铜和砷的新工艺

以含砷污酸为原料,通过中和除杂-沉砷-洗涤-浸出-蒸发结晶-溶解制取三氧化二砷,实现含砷污酸的资源化。结果表明：将污酸中和至pH为2,使污酸的酸度降低;在中和液中加入硫酸铜,控制Cu和As的摩尔比为1.5：1,调节体系pH为8沉淀As,得到亚砷酸铜,As的沉淀率达到97.81%;通过洗涤除杂提高亚砷酸铜中As和Cu的含量;采用10%硫酸溶液,在液固比为5：1条件下浸出亚砷酸铜,所得溶液蒸发结晶得到三氧化二砷与硫酸铜的混合物;用水溶解该混合物后过滤得到硫酸铜溶液及符合 YS/T-99-1997As2O3-3号产品标准的三氧化二砷。     

氢氧化钠分解不溶性钼酸盐的浸出热力学

辉钼矿经氧化焙烧转化成MoO3的过程中,伴生的铜铅铁等硫化矿亦被氧化,并与MoO3生成难溶钼酸盐。为减少因难溶钼酸盐带来的钼损失,需要对这些钼酸盐进行再浸出处理。针对这些钼酸盐湿法浸出过程进行热力学分析,绘制了25℃时Me-Mo-H2O(Me:Cu,Pb,Fe)系组分的浓度对数-pH图。利用热力学平衡图对氢氧化钠分解钼酸盐进行热力学分析。结果表明:整个pH值范围可分为H2MoO4的稳定区、难溶钼酸盐的稳定区、Me(OH)n的稳定区。高pH区钼酸盐中的Me转变为稳定的Me(OH)n物相,即实现了钼酸盐的碱分解。而Fe2(MoO4)3、CuMoO4和PbMoO4的碱浸出难度依次递增,达到一定碱度时这3种难溶盐都能很好地分解,并实现Me与Mo的分离。但过高的碱度又使大量的金属以羟基配合物离子的形式进入溶液,增加了后续除杂难度。     

结晶型砷酸镍的合成

为了处理在冶金过程中产生的高镍、砷废液,通常用碱中和废液以形成砷酸镍化合物.采用稀释法在pH值为7,n(Ni):n(As)=1.5,反应温度为22℃,反应时间为2 h的条件下合成了具有较低溶解度的砷酸镍化合物.X射线衍射分析表明产物为结晶型砷酸镍,热重分析和化学分析得出其化学分子式为Ni3(AsO4)2·8H2O,合成的结晶型砷酸镍产物为晶粒尺寸为5～20μm的球形颗粒.     

共沉淀法制备Co-Y2O3复合粉的热力学分析

为了制备球形颗粒的Co粉和实现在Co粉中添加Y_2O_3的目的,分析了共沉淀法制备Co-Y_2O_3复合粉前驱体的热力学。通过对Co~(2+)-Y~(3+)-NH_3-C_2O_4~(2-)-H_2O沉淀体系的热力学分析,得到了lg[M]T-p H关系图(M为金属元素)。热力学分析表明:增加草酸根总浓度[C]T和铵根总浓度[N]T会促进Co~(2+)离子的络合,而Yz~(3+)离子只受草酸根总浓度[C]T的影响,随着[C]T的升高Y~(3+)离子沉淀率下降。Co~(2+)离子和Y~(3+)离子沉淀的最佳p H值分别为2~2.5和1.5~2.5。当p H值为2.5时,由共沉淀法制备出簇球状Co-Y_2O_3前驱体,经煅烧和还原后得到球形Co-Y_2O_3复合粉,其颗粒尺寸约为5μm。     

纤维状超细银粉前驱体制备热力学分析

根据同时平衡原理和质量平衡原理,从理论上推导出了Ag(Ⅰ)-C2O42--NH3-NH4+-H2体系中金属银离子和草酸盐在水溶液中热力学平衡的数学模型,计算并绘制出该体系的lg[Ag]T-pH图。在此基础上,分析液相沉淀过程中溶液的lg[Ag]T与pH之间的关系并推断出制备纤维状银粉前驱体粉末的理想pH值为5.0~6.0之间,为液相沉淀过程的实验操作提供了理论依据。最后通过验证实验证明了热力学计算结果的准确性。     

水合肼对铜电解液净化的作用

在铜电解液中加入水合肼产生沉淀,使铜电解液中砷、锑、铋杂质得到有效去除。当电解液Cu2+质量浓度为22g/L,硫酸质量浓度为203g/L,反应温度为42℃,反应时间为60mi,n砷、锑、铋质量浓度分别为8.80 g/L、0.36 g/L、0.20 g/L时,按照铜电解液与水合肼体积比为20:1在铜电解液加入水合肼,铜脱除率为97.04%,砷、锑、铋去除率分别为5.28%、37.92%、94.40%。在卤化物作用下,有助电解液中砷的去除。杂质的脱除有一定影响。在铜电解液中加入水合肼产生沉淀有Cu4SO4（OH）6·H2O、Cu2（OH）3NO3、Cu3（AsO4）（OH）3等。     

二段脱铜液还原结晶法脱砷新工艺

对铜电解液脱砷方法进行研究,提出以二段脱铜液为原料,采用SO2还原结晶法脱砷新工艺。在二段脱铜液中通入SO2,将其中的As(Ⅴ)还原成As(Ⅲ),还原后的溶液通过蒸发结晶析出As2O3,达到二段脱铜液脱砷的目的。结果表明:当As(Ⅴ)浓度为12.41 g/L、H2SO4浓度为253.00 g/L、反应温度为60℃时,向二段脱铜液中通入SO290 min后静置90 min,二段脱铜液中As(Ⅴ)的还原率达到94.54%。还原后的溶液进行蒸发结晶,当蒸发前与结晶后的体积比(V0:V1)为3.5时,砷的脱除率达到91.33%,结晶产物为As2O3。与传统脱砷工艺相比,新工艺具有操作简单、成本低廉及砷的脱除效果明显等优势。     

铜电解液净化中铜砷的分离与回收(英文)

经二氧化硫还原、蒸发结晶,使铜电解液中铜、砷、锑和铋得到有效去除。结晶产物经过溶解、氧化、中和、沉淀、过滤和蒸发结晶,得到三氧化二砷和硫酸铜。当采用SO2将铜电解液中As(Ⅴ)充分还原为As(Ⅲ),并加热蒸发浓缩铜电解液中硫酸浓度至645g/L时,铜电解液中铜、砷、锑和铋的去除率分别为87.1 %,83.9 %,21.0 %和84.7%。在温度30℃,将65g结晶产物溶于200mL自来水时,砷的去除率为92.81%。将所得滤液在如下条件下净化:n(Fe):n(As)为1.2,双氧水为理论用量的19倍,氧化温度为45℃,氧化时间为40min,终点pH为3.7,净化后蒸发浓缩结晶,所得硫酸铜溶液中硫酸铜含量达到98.8%。     

A new mixed-valent iron arsenate black crystal

Scorodite (FeAsO₄·2H₂O) is the most popular phase for arsenic (As) immobilization while the reductive dissolution of Fe(III) to Fe(II) will promote As release. In the present study, an equilibrium between Fe(III) and Fe(II) was achieved in scorodite preparation system by introducing certain alcohol (methanol, ethanol, isopropanol or tert-butanol), and thus a new mixed-valent iron arsenate black crystal formulated as Fe(II)_5.2Fe(III)_8.8(HAsO₄)₄(AsO₄)₈·H₂O was prepared. In comparison with scorodite, the black crystal has higher As content (36.4%, mass fraction) and lower crystal water content (0.73%, mass fraction). Additionally, the leaching concentration of As can be lower than the threshold value (5 mg/L) regulated by identification standards for hazardous wastes of China (GB 5080.3–2007). Therefore, this new mixed-valent iron arsenate crystal could be classified as a non-hazardous and promising As-bearing phase in environmental applications.     

Thermodynamic equilibrium calculation on preparation of copper oxalate precursor powder

According to the principles of simultaneous equilibrium and mass balance, a series of thermodynamic equilibrium equations of Cu^2＋-C2O4^2--NH3-NH4^＋＋-H2O system at ambient temperature were deduced theoretically and the logarithm concentration versus pH value （lg[Cu^2＋]T--pH） diagrams at different solution compositions were drawn. The results show that when pH is below 5.0, copper ion reacts with C2O4^2- directly and the morphology of copper precursor powder is of pie-shape, when pH is above 5.0, copper ion coordinates with ammonia, and the precipitation proceeds slowly accompanying with the release of copper ions fi＇om the multi-coordinated Cu（NH3）n^2＋（n =1, 2,…, 5） and the morphologies of copper precursor powder are respectively of rod aggregation shape （when 5.0〈pH〈8.0） and of rod-shape （when pH〉8.0）. Some experiments were performed to confirm the relation between the total concentration of copper ion and pH value. It is shown that the thermodynamic mathematical model is correct and the calculated values are basically accurate.     

Synthesis and Structural Determination of Nine-coordinate K_2[Y~Ⅲ(dtpa)(H_2O)]·7H_2O

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氢在Gasar工艺常用纯金属中的溶解度

对于氢在纯金属巾的溶解度,文献中的大量数据存在分散性,不便选用.本文搜集到了大量氢在Gasar工艺常用的五种纯金属Al,Mg,Cu,Ni和Fe中的溶解度数据及其经验公式,按照lg[H]=-A/T B 0.5lg(pH2/101325)统一形式与单位后,考虑其溶解度常数A和B的波动,选择溶解度比较接近的数据,对其A和B值求平均,得到了新的溶解度计算公式,作为Gasar试样气孔率预测、浓度场计算、气孔生长数值模拟及多元合金中气体溶解度计算等工作的基础.     

Bio-oxidation of arsenopyrite

Oxidation of arsenopyrite with Acidithiobacillus ferrooxidans was studied. The electrochemical results show that arsenopyrite is firstly oxidized to As2S2 at the potential of 0.2-0.3 V （vs SHE） and As2S2 covers the electrode and retards the process continuously. While at higher potential over 0.3 V （vs SHE）, AszS2 is oxidized to H3AsO3, and H3AsO3 is then oxidized to H3AsO4 at 0.8 V （vs SHE）. The leaching results show that the addition of FeS2 can promote the oxidation of As^3＋ to As^5＋ and increase the activity of the bacteria. The best bio-oxidation technical parameters are the initial pH of 1.8-2.0, particle sizes less than 0.074 mm, temperature in the range of 25-30℃ and rotating speed of the orbital incubator of 100-160 r/min. The results provide theoretical and technological supports of bio-oxidation arsenopyrite for pretreating refractory arsenic gold ores.     

Thermodynamic analysis on sodium carbonate decomposition of calcium molybdenum

According to the principle of mass balances and thermodynamic data, 1g [Me]-pH diagrams （Me=Ca, Mo） for Ca-Mo-CO3-H2O system at 25 ℃ were presented with total dissolved carbon-containing ions concentrations of 0.01 mol/L and 1 mol/L, and 1g [Me]-pH diagram for Ca-Mo-H2O system at 25 ℃ was also depicted. The effects of system pH value and total dissolved carbon-containing ions concentrations on the concentrations of the species in Ca-Mo-CO3-H2O system were studied. The results show that the stability region of CaMoO4 reduces significantly in the presence of sodium carbonate. In order to achieve effective leaching of molybdenum from CaMoO4, a certain concentration of sodium carbonate is necessary. High total dissolved carbon-containing ions concentrations and high pH values facilitate to the leaching of CaMoO4 and dissolved sodium carbonate is an efficient leaching agent for decomposing CaMoO4.     

Optimization of separation processing of copper and iron of dump bioleaching solution by Lix 984N in Dexing Copper Mine

The effects of the concentration of Lix 984N, phase ratio, initial pH value of aqueous phase and extraction time on the extraction of copper and iron under the condition of low Cu^2＋/Fe^3＋ ratio in dump bioleaching solution of Dexing Copper Mine were explored. The optimal conditions of extraction are as follows： the concentration of Lix 984N 10%; the phase ratio （O/A） 1：1; the initial pH value of aqueous phase 1.5 and the mixing time 2 min. The stripping experiments show that H2SO4 solution could efficiently recover copper from the organic phase under the optimal conditions.     

Corrosion electrochemical mechanism ofchemical mechanical polishing of copper in K3Fe（CN）6 solution

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