某磷灰石浮选精矿磷酸浸出提纯试验研究

为进一步提高磷灰石浮选精矿纯度,创新性地提出了采用磷酸浸出法脱除磷灰石浮选精矿中的方解石和白云石等碳酸盐脉石矿物的方法。酸浸条件对磷灰石提纯效果的影响规律研究表明,在磷灰石粒度为-38μm,稀磷酸浓度为10%,液固比为4∶1,反应温度为20℃,反应时间为240 s条件下进行磷灰石浮选精矿的磷酸浸出试验,可将纯度为86.88%的磷灰石提纯至99.36%。酸浸机理研究表明,磷灰石不与磷酸发生反应,而方解石和白云石均可以与过量的磷酸反应生成溶于水的物质而被脱除;经过磷酸浸出提纯后的磷灰石纯度较高,结晶良好。研究结果对碳酸盐矿物钙质型磷矿的提纯降杂具有重要参考意义。

拜耳法赤泥中钪、钇浸出行为及动力学研究

采用两步酸浸法浸出赤泥中的钪和钇,用磷酸对赤泥进行一段酸浸,实现脱碱和脱硅并富集稀土金属钪、钇;用硫酸对磷酸浸出渣进行二段酸浸,考察了硫酸浓度、液固比、反应温度、反应时间对钪、钇浸出过程的影响,并进行了浸出动力学分析。结果表明,赤泥经磷酸浸出后,脱碱和脱硅效果较好,K、Na、Si浸出率分别为75.62%、87.82%、80.25%;在硫酸浓度2.5 mol/L、液固比7∶1、反应温度70℃、反应时间45 min条件下进行二段硫酸浸出,Sc、Y平均浸出率分别为74.49%、80.02%。Sc和Y的硫酸浸出过程均符合多相液固区域反应模型,受扩散控制,表观反应活化能分别为18.50 kJ/mol和16.74 kJ/mol。

磷酸法从磷矿中分离富集稀土的机理研究

通过试验与理论分析、矿相显微镜、SEM、EDS、XRD、EPMA及化学逐提等方法,研究了磷酸分解法从含稀土磷矿中分离、富集稀土的反应机理。在磷酸分解过程中,氟磷灰石晶体中的磷、大部分钙元素被选择性溶解进入溶液,而氟元素与少部分钙在氟磷灰石晶体内发生原位化学反应形成了类晶质状的氟化钙新相,约95%的稀土以类质同相的形式进入氟化钙物相中与磷分离并得到富集。

污泥4种热处理产物中磷的化学提取-沉淀回收性能

污水处理厂污泥中磷含量较高,对磷进行回收能有效实现磷资源的二次利用。采用磷酸铵镁(MAP)回收法分别对污泥4种热处理产物阴燃灰、掺烧灰、焚烧灰和热解焦的酸浸出液进行磷回收试验,重点分析了各热处理产物在酸浸出-MAP路线下的磷回收性能,包括磷沉淀率、产物中磷和杂质含量,并进一步探究了沉淀产物的环境安全性。结果表明,通过酸浸出-MAP回收法,单位质量沉淀产物磷质量分数达19.82~31.71 mg/g,原污泥中磷回收率达49.25%~65.81%。磷回收性能由高到低依次为焚烧灰、热解焦、阴燃灰、掺烧灰。酸浸出-MAP回收产物中含有大量Ca、Fe、Al和Si杂质,且含有一定量Zn、Pb、Cr、Cu、Cd、As和Ni,其中Zn含量远高于其他重金属含量。产物纯度和环境安全性由高到低依次为焚烧灰、掺烧灰、热解焦、阴燃灰。在沉淀产物的环境安全性方面,阴燃灰、焚烧灰和热解焦的酸浸出-MAP回收产物中重金属含量均符合GB/T 23349—2009《肥料中砷、镉、铅、汞生态指标》和GB 4284—2018《农用污泥污染物控制标准》。掺烧灰的酸浸出-MAP回收产物中Cd质量分数为3.20 mg/kg,超过农用污泥污染物控制标准限值3.00 mg/kg。

Removal of magnesium and calcium from electric furnace titanium slag by H_3PO_4 oxidation roasting-leaching process

H3PO4 oxidation roasting followed by HCl acid leaching was proposed to remove magnesium and calcium from electric furnace titanium slag containing 3.12% MgO and 0.86% CaO. XRF, XRD and SEM techniques were used to characterize the composition, mineral phase component and microstructure of the titanium slag. The H3PO4 oxidation thermodynamic, mineral phase transformation, microstructure, element distribution in titanium slag during H3PO4 oxidation process and leaching process were investigated. The thermodynamic analysis indicated that H3PO4 could promote the decomposition of MgTi2O5 and CaSiO3. The results indicated that H3PO4 could effectively promote the transformation of titanium-bearing mineral to rutile and enrich the impurities in MxTi（3-x）O5 into phosphate which could be removed by acid leaching process. Under the studied conditions, the leaching rates of magnesium and calcium reached 94.68% and 87.19%, respectively. The acid leached slag containing 0.19% MgO and 0.13% CaO（mass fraction） was obtained.

Removal of phosphorus from iron ores by chemical leaching

Alkali-leaching and acid-leaching were proposed for the dephosphorization of Changde iron ore, which contains an average of 1.12% for phosphorus content. Sodium hydroxide, sulfuriced, hydrochloric and nitric acids were used for the preparation of leach solutions. The results show that phosphorus occurring as apatite phase could be removed by alkali-leaching, but those occurring in the iron phase could not. Sulfuric acid is the most effective among the three kinds of acid. 91.61% phosphorus removal was attained with 1% sulfuric acid after leaching for 20 rain at room temperature. Iron loss during acid-leaching can be negligible, which was less than 0.25%.The pH value of solution after leaching with1% sulfuric acid was about 0.86, which means acid would not be exhausted during the process and it could be recycled, and the recycle of sulfuric acid solution would make the dephosphorization process more economical.

Leaching kinetics of calcium molybdate with hydrochloric acid in presence of phosphoric acid

Calcium molybdate(CaMoO4)is the main component of powellite and is a predominant intermediate in the pyrometallurgical and hydrometallurgical process of molybdenum.The extraction of Mo from CaMoO4 by a combination of phosphoric acid and hydrochloric acid was investigated.For further understanding of the leaching mechanism,the effects of five key factors were studied to describe the leaching kinetics.The results indicated that the dissolution rate of CaMoO4 was independent of the stirring speed.Mo extraction significantly increased with increasing HCl concentration and temperature,but decreased with increasing particle size.A shrinking core model with surface chemical reaction was found to withstand the dissolution of CaMoO4.The apparent activation energy was calculated to be 70.879 kJ/mol,and a semi-empirical equation was derived for the rate of reaction.

Selective recovery of lithium from spent lithium iron phosphate batteries using oxidation pressure sulfuric acid leaching system

Oxidation pressure leaching was proposed to selectively dissolve Li from spent LiFePO_(4) batteries in a stoichiometric sulfuric acid solution.Using O_(2) as an oxidant and stoichiometric sulfuric acid as leaching agent,above 97% of Li was leached into the solution,whereas more than 99% of Fe remained in the leaching residue,enabling a relatively low cost for one-step separation of Li and Fe.And then,by adjusting the pH of leachate,above 95% of Li was recovered in the form of the Li_(3)PO_(4) product through iron removal and chemical precipitation of phosphate.

Extraction of germanium(IV) from acid leaching solution with mixtures of P204 and TBP

Solvent extraction experiments were conducted from acidic solutions containing germanium（IV） and other metal ions, such as Ga3＋, Fe3＋, Zn2＋ and Fe2＋ in hydrometallurgical process of zinc. The purpose of this work was to enhance the efficiency of the extraction and stripping processes and the selectivity of germanium and other metals, while making the method as simple as possible. Germanium was recovered from sulfuric acid, using di-（2-ethylhexyl） phosphoric acid （P2O4） as an extractant, tributyl phosphate （TBP） as modifier diluted in sulfonate kerosene and stripped by NaOH aqueous solution. Extraction studies were carried out under different acid concentrations and solvent concentrations, and optimized conditions were determined. The numbers of stages required for extraction and stripping of metal ions were determined from the McCabe-Thiele plot. The results show that the extracting and stripping efficiencies are 94.3% and 100%, respectively, through two-stage extraction and two-stage strip. Moreover, the synergistic effect of TBP on the system P2O4/kerosense/Ge4＋ is revealed with respect to the extraction of germanium.

Process for recycle of spent lithium iron phosphate battery via a selective leaching-precipitation method

Applying spent lithium iron phosphate battery as raw material,valuable metals in spent lithium ion battery were effectively recovered through separation of active material,selective leaching,and stepwise chemical precipitation.Using stoichiometric Na2S2O8 as an oxidant and adding low-concentration H2SO4 as a leaching agent was proposed.This route was totally different from the conventional methods of dissolving all of the elements into solution by using excess mineral acid.When experiments were done under optimal conditions(Na2S2O8-to-Li molar ratio 0.45,0.30 mol/L H2SO4,60℃,1.5 h),leaching efficiencies of 97.53% for Li^+,1.39%for Fe^3+,and 2.58% for PO4^3−were recorded.FePO4 was then recovered by a precipitation method from the leachate while maintaining the pH at 2.0.The mother liquor was concentrated and maintained at a temperature of approximately 100℃,and then a saturated sodium carbonate solution was added to precipitate Li2CO3.The lithium recovery yield was close to 80%.

Leaching kinetics of scheelite concentrate with sodium hydroxide in the presence of phosphate

The reaction kinetics for the leaching of low-grade scheelite concentrate was investigated in an autoclave with sodium hydroxide in the presence of phosphate. The effects of stirring speed (300-600 r/min), reaction temperature (353-383 K), sodium hydroxide concentration (1.69-6.76 mol/L) and phosphate concentration (0.68-1.69 mol/L) on the WO3 dissolution ratio were studied. The results showed that the WO3 dissolution ratio was practically independent of stirring speed, while it increased with increasing the reaction temperature, and the concentrations of sodium hydroxide and phosphate. The experimental data were consistent with the shrinking core model, with a surface chemical reaction as the leaching rate-determining step. The apparent activation energy was calculated as 49.56 kJ/mol, and the reaction orders with respect to the concentrations of sodium hydroxide and phosphate were determined as 0.27 and 0.67, respectively. The kinetics equation of the leaching process was established.

Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid

A hydrometallurgical process for tungsten extraction and recovery from scheelite is reported.The technology includes leaching scheelite using phosphoric acid as chelating agent in nitric acid solutions,extracting tungsten by solvent extraction and reusing leaching agent.In the leaching process,affecting factors,such as temperature,leaching time,nitric acid and dosage of phosphoric acid,were examined on recovery of tungsten.Results show that more than 97%of tungsten could be extracted under conditions of leaching temperature of 80-90°C,HNO3 concentration of 3.0-4.0 mol/L,liquild-to-soild ratio of 10:1,H3PO4 dosage of 3 stoichiometric ratio and leaching time of 3 h.Solvent extraction was then employed for the W recovery from the leachate with a organic system of 40%(v/v)N235,30%(v/v)TBP,and 30%sulfonated kerosene.Approximately 99.93%of W was extracted and ammonium tungstate solution containing 193 g/L W was obtained with a stripping rate of 98.10%under the optimized conditions.