风化壳淋积型稀土矿浸出渗流和传质过程研究现状及展望

风化壳淋积型稀土矿富含中重稀土,主要分布在中国的南方七省,目前主要用硫酸铵作为浸取剂的化学浸出法回收稀土。浸取剂在矿体中的渗流、传质过程直接影响着稀土浸出效率,强化其渗流、传质过程可以提高稀土浸出的有效渗流速度,加快稀土离子交换速率,降低浸取剂用量,缩短生产周期,实现稀土绿色高效回收。本文分析了风化壳淋积型稀土矿渗流、传质过程的研究现状,总结了风化壳淋积型稀土矿渗流、传质过程的强化方法。结果表明,继续探索浸取液在风化壳淋积型稀土矿矿体中的有效渗流扩散规律和找寻促进稀土传质的高效传质规律,并以此为指导筛选浸取剂和助浸剂、改进注液方式、增加外力场将是强化风化壳淋积型稀土矿渗流、传质过程的主要研究方向。     

中国稀土矿稀土配分特征

稀土矿床分为矿物型和风化型两种:我国著名的矿物型稀土矿有白云鄂博铁稀土铌矿、四川攀西冕宁稀土矿和山东微山稀土矿;风化型稀土矿有信丰型稀土矿、龙南型稀土矿和寻乌型稀土矿。对矿物型稀土矿的矿物组成和稀土配分研究发现,它们主要的稀土矿物为氟碳铈矿和独居石,强烈地选择轻稀土配分,轻稀土配分La+Ce+Pr+Nd大于95%。风化型稀土矿中的稀土主要以水合或羟基水合离子吸附于黏土矿物上,稀土配分主要选择中重稀土配分,约占90%,该类型中稀土Sm+Eu+Gd+Tb+Dy配分和约为15%,重稀土配分Ho+Er+Tm+Yb+Lu+Y约为29%,少量选择重稀土配分型,约占8%,其该类型重稀土配分约为75%。从原岩到风化壳矿石,再从风化壳矿石到风化壳淋积型稀土矿的提取产品,稀土配分存在富铕效应和铈亏效应。该结果不仅有利于制定稀土矿的选矿和混合稀土的分离工艺,而且为揭示稀土矿稀土迁移富集成矿规律起到积极的作用。     

广东省大埔县平原矿区稀土矿地质特征及成因探讨

广东省大埔县矿区稀土矿赋存于大埔岩体风化壳中，岩体规模大，成矿条件好，全风化层为主含矿层；属低钇中铕型轻稀土矿。文章通过分析研究该矿床的地质特征矿和矿化富集规律，总结了区内风化壳淋积型轻稀土找矿标志，认为在平原地区周边的大埔岩体风化壳中仍具有较大的找矿前景的结论。     

风化壳淋积型稀土矿的基础研究

文章评述了40年来风化壳淋积型稀土矿的基础研究,包括矿床的成因及特征、稀土矿物的组成及性质,稀土与黏土矿物的关系、稀土在黏土矿物中的吸附及迁移理论,论述了风化壳淋积型稀土矿的稀土元素配分的特征及四大效应,并探讨了稀土浸出机理和风化壳淋积型稀土矿稀土浸取的三代工艺,提出了风化壳淋积型稀土矿基础研究和浸出工艺的发展方向及亟待解决的问题.      

风化壳淋积型稀土矿浸取技术发展现状

对风化壳淋积型稀土矿的浸取技术进行了综述。根据该矿的浸出机理,分析了三种传统浸出工艺的利弊,结合最新研究成果,总结出4种新型浸出方式并指出了浸出工艺的发展趋势。在沉淀稀土工艺方面,重点论述了碳酸氢铵沉淀工艺及镁/钙盐体系下风化壳淋积型稀土沉淀的最新成果,最后提出了风化壳淋积型稀土矿浸取工艺的发展方向。     

风化壳淋积稀土矿浸取动力学基础理论研究

风化壳淋积型稀土开采先后经历了池浸、堆浸和原地浸矿,目前采用原地浸矿法.研究风化壳淋积型稀土浸取动力学有助于从本质上提高浸矿效率和资源回收率,为高效、科学开采风化壳淋积型稀土矿提供理论依据,进一步完善风化壳淋积型稀土的原地浸出理论和技术.为此对风化壳淋积型稀土矿浸取动力学基础理论进行研究,并针对现有浸矿工艺,指出了影响浸取效率的因素,提出了提高风化壳淋积型稀土浸取速度的方法与措施.      

柠檬酸盐配位浸出风化壳淋积型稀土矿回收稀土的研究

选用柠檬酸盐作为风化壳淋积型稀土矿的浸取剂,并将柠檬酸盐对稀土的浸出效果与硫酸盐和氯化盐等浸取剂进行了对比,考察了柠檬酸铵作为浸取剂时的最佳浸取工艺。实验结果表明,柠檬酸铵作为风化壳淋积型稀土矿浸取剂时,柠檬酸根离子与稀土离子的配位作用,能促进矿石稀土离子交换,提高稀土回收率,降低浸矿剂铵盐的用量,减小氨氮废水的污染。采用柱浸回收稀土的最佳工艺条件为:柠檬酸铵浓度3 g/L,液固比2∶1,浸取剂pH 6.0~8.0,淋洗流速0.5 min/m L,稀土浸出率可达90.01%。     

从风化壳淋积型稀土矿除杂渣中酸浸稀土和铝

研究了用盐酸从风化壳淋积型稀土矿除杂渣中浸出稀土和铝,考察了盐酸浓度、温度、液固体积质量比和浸出时间对稀土、铝及杂质离子浸出率的影响。结果表明:在盐酸浓度1 mol/L、液固体积质量比10/1、温度40℃条件下浸出30 min,镧、钇、铝浸出率分别为85%、66%和48%,杂质离子铁、钾、镁浸出率均较低;酸浸液用100 g/L碳酸氢铵溶液调pH分步沉淀铝和稀土,铝和稀土最终回收率分别为46%和75%。采用该工艺可实现二次资源综合回收,有较好经济效益。     

田菁胶助浸低品位风化壳淋积型稀土矿研究

针对低品位风化壳淋积型稀土矿渗透性存在的问题,采用田菁胶作助浸剂,利用其促渗性能来提高风化壳淋积型稀土矿浸取效率,通过试验考查了田菁胶浓度、浸取剂浓度、浸取流速、浸取固液比对稀土浸取效果的影响.结果表明,田菁胶助浸使稀土的浸取率由87.05 %提高至94.17 %,同时还减少32.56 %浸取剂用量,有效地提高了风化壳淋积型稀土矿的浸取效率.      

风化壳淋积型稀土矿浸取分形动力学研究

风化壳淋积型稀土矿粒径分布特征是影响浸取性能的主要因素之一。以五种重组江西风化壳淋积型稀土矿为研究对象,通过柱浸实验和分形理论相结合的研究手段,探究稀土矿的粒径分布特征与分形维数的关系,以及其对浸取动力学性能的影响规律。结果表明,随着分形维数增大,小粒径颗粒质量含量随之增大,而大粒径颗粒质量含量随之减少,尤其是小于0.150 mm和大于1.400 mm粒径颗粒质量占比变化幅度较大,其余粒径颗粒变化幅度较小。随着分形维数增加,浸出的稀土浓度峰值逐渐增大,浸矿中稀土浓度峰值出现的时间变晚,稀土浸取率达到平衡所需要的时间变长。基于分形理论,构建了风化壳淋积型稀土矿浸取分形动力学模型,并证实了新模型具有较高的准确性,能够较好的定量描述浸矿中不同分形维数的稀土矿样的浸取动力学特性。     

A two-parameter model for ion exchange process of ion-adsorption type rare earth ores

The establishment of a mathematical model for the ion exchange process is key to creating a theoretical basis for the mining of ion-adsorption type rare earth ores. Ore samples from Xinfeng, Xunwu and Anyuan were used as the test ore samples in the present study and equilibrium batch tests of ore sample leaching using various ammonium sulfate concentrations were performed. The results show that, after leaching, there is a negative exponential relationship between the ratio of the solid-phase rare earth ion concentration to the aqueous-phase rare earth ion concentration and the initial ammonium ion concentration. However, there is a linear relationship between the natural logarithm of the ratio of the solid-phase ammonium ion concentration to the aqueous-phase ammonium ion concentration and the initial ammonium ion concentration. Based on the above two functional relationships, a two-parameter model for the equilibrium ion exchange process of ion-adsorption type rare earth ores was established. Using the established model to analyze the test data the model error for the Xunwu ore sample is found to be less than 5%. The proposed model is more accurate compared with the Kerr model. The two-parameter model proposed in this study provides theoretical support for the numerical simulation of column leaching (in-situ leaching) of ion-adsorption type rare earth ores.     

Progress in green and efficient enrichment of rare earth from leaching liquor of ion adsorption type rare earth ores

Ion adsorption type rare earth ores (IATREOs) are a valuable strategic mineral resource in China, which feature a complete composition of fifteen rare earth elements and are rich in medium and heavy rare earth (RE) elements. In the leaching process for recovering rare earth elements from IATREOs, many impurities will be leached together with rare earth elements and enter the leaching liquor. An impurity removal-precipitation enrichment technique is currently applied to selectively recovery rare earth elements from the leaching liquor with the high content of impurities and low concentration of rare earth elements by using ammonium bicarbonate in the industry. However, a high loss of rare earth elements and severe ammonia nitrogen pollution are caused by this process. Therefore, more beneficial impurities removal technologies, mainly for aluminum, and green enrichment technologies with lower pollution are now urgently needed. For this purpose, this paper analyzed two aspects of research progress in recent decades: the green separation of rare earth elements and aluminum from leaching liquor and the green and efficient enrichment of rare earth elements. Finally, an approach for the high-efficiency and green enrichment of rare earth elements from leaching liquor of the IATREOs is proposed in several aspects, including impurity inhibition leaching, neutralization and impurity removal, alkaline calcium and magnesium salt precipitation enrichment, and centrifugal extraction enrichment.     

离子型稀土不同浸出剂柱浸对比试验

针对离子型稀土原地浸出工艺现有氨氮污染问题,考察镁盐、铝盐等非铵浸出剂对稀土浸出过程的影响。以赣州稀土矿样为研究对象,选择硫酸镁与硫酸铵通过柱浸的方式进行对比试验,同时考察铝盐与铵盐、镁盐联合浸出效果的影响,测定浸出液成分,分析不同浸出剂浸出效果的差异。结果表明：相同质量分数的硫酸铵和硫酸镁浸出效率相当,硫酸铵可达91.37%,硫酸镁可达89.22%;添加铝盐后的稀土浸出率仅76%左右,铝盐的添加不能促进稀土浸出效率的提升;铵盐柱浸顶水洗涤后铵根离子可降低至76 mg/L,镁盐柱浸顶水洗涤后镁离子可降低至27 mg/L,镁离子比铵根离子更容易洗涤去除。硫酸镁作为浸出剂能够从根本上解决离子型稀土矿山氨氮污染问题。     

离子型稀土矿硫酸镁柱浸过程中水、稀土和硫酸镁的平衡研究

采用柱浸方法研究无氨浸矿剂硫酸镁浸出离子型稀土矿,考察了浸矿过程中H2O、REO、Mg2+、SO2-4走向。结果表明,每千克稀土原矿吸水量约为344mL,稀土元素浸出率在99%以上,全过程损失率仅为0.045%,有0.24%的镁离子残留于矿体中,浸出液中镁离子总量增加4.7%,平衡率为98.76%,硫酸根总体升高0.52%。硫酸镁作为浸取剂,杂质Fe、Si的浸出率分别由硫酸铵浸矿时的0.435%、0.703%降低到0.03%、0.13%,杂质Al的浸出率基本保持不变。     

Recovery of rare earths from ion-absorbed rare earths ore with MgSO4-ascorbic acid compound leaching agent

The magnesium sulfate leaching technology for the ion-absorbed rare earths ore can solve the ammonia pollution problem existing in ammonium sulfate leaching process. However, the leaching capacity of magnesium sulfate is slightly weaker than that of ammonium sulfate, resulting in a bigger consumption of magnesium sulfate. In this paper, the MgSO_4-ascorbic acid compound leaching agent had been demonstrated to deal with the ion-absorbed rare earths ore. The ascorbic acid could form a stable coordination with rare earth ions, so that it can strengthen the leaching of ion-exchangeable phase.Moreover, ascorbic acid has a strong reductive property, it can leach the colloidal sediment phase rare earth as well. The present study investigates the effect of the initial pH and the composition of leaching agent on the rare earth leaching. It is determined that the rare earth leaching efficiency is 107.5% under the condition of pH 2.00,0.15 mol/L magnesium sulfate and 1.0 g/L ascorbic acid in leaching agent. In this case, the content of the ion-exchangeable phase and colloidal sediment phase rare earth in the leaching residues are both only 0.02‰. The leaching efficiency of colloid sediment phase rare earth can be 85.7%,so that the Ce partition in the leaching liquor increases to be 5.77%. The magnesium-ascorbic acid compound leaching agent is proposed to be a promising choice to deal with the ion-absorbed rare earths ore, which can realize the efficient leaching, low consumption of MgSO_4 and environmentally friendly leaching.     

Kinetics model for leaching of ion-adsorption type rare earth ores

This paper aims to establish a mathematical model that can analyze the whole leaching kinetics process of ion-adsorption type rare earth ores. This leaching process is composed of three steps: (1) ammonium ions arrive at the ore particle surface through the diffusion layer; (2) ammonium ions exchange with rare earth ions; and (3) rare earth ions enter into the external solution through the diffusion layer. In the leaching process, it is hypothesized that the ore particle size remains constant. The process of ammonium ions and rare earth ions passing through the diffusion layer was described by the Fick law, and the reversible ion exchange process between ammonium ions and rare earth ions was described by the Kerr model. A leaching kinetics model of rare earth ions by ammonium ions was constructed. Accuracy of this kinetics model was verified with laboratory tests. It is found that the correlation coefficients of all data are greater than 0.9000. The proposed kinetics model is therefore feasible for kinetics analysis throughout the leaching process.     

Local concentration of middle and heavy rare earth elements in the col on the weathered crust elution-deposited rare earth ores

This present study focused on investigating the content and relative enrichment multiple of rare earth elements(REEs) in different terrain of weathered ore body, and the value of light rare earth elements/middle and heavy rare earth elements(LREEs/HREEs), in order to understand the mobilization and redistribution of HREEs, Furthermore, the abrasion pH was investigated as well, The results show that the average contents of HREEs in the knap, ridge and col are 37.26, 61.71, and 271.3 μg/g, respectively. The value of LREEs/HREEs is decreased from 16.78 to 7.914 between knap and col and the relative enrichment multiple of HREEs is as follows: C_(Col-HREEs) C_(Ridge-HREEs) 0. It is indicated the HREEs is concentrated in the col and the enrichment degree of HREEs is stronger than the ridge and the knap. Rare earth elements fractionation is exhibited in the different terrain of weathered ore body. Based on this study, the finding that HREEs concentrate in the lower terrain of weathered crust elution-deposited rare earth ores, such as in the col, would become a marker or indicator to search for middle and heavy rare earth enriched zone.     

采用固氟氯化法从氟碳铈矿中提取稀土氯化动力学的研究进展

针对我国主要的稀土矿物氟碳铈稀土矿目前在分解回收中主要采用浓硫酸焙烧法产生氟化氢污染环境的问题,清华大学核能与新能源研究院从1998年以来开展了氧化镁固氟、氯化铵选择性氯化提取氟碳铈中稀土及其动力学的研究。选择我国典型的稀土矿物包头混合型稀土矿及山东氟碳铈稀土矿展开研究,确定了适宜的工艺条件、氯化选择性和氟的转化形态。稀土以氯化稀土形式被浸取,对于两种稀土矿物稀土浸出回收率均在85%以上。氯化铵氯化稀土的氯化动力学符合Bagdasarym提出的多相区域反应动力学模型,氯化反应的速率αRE遵从Erofeev方程。氯化铵氯化不同形态氧化稀土氯化反应表观活化能的大小顺序为:EaLa2O3+CeO2相似文献   

Mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore

Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth ore. The development condition of the weathered crust, weathering degree and mineral composition of these ores will be different because of the differences between their parent rocks and weathered crust causes of mineralogy path. Therefore, mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore from Chongzuo(CZ), Guangxi province were investigated. It was found that the CZ rare earth ore was a typical mid-yttrium and rich-europium ore, with the overall rare earth(REE) grade in ion-exchangeable phase of 0.15%. Partide size classification showed that finer particle had a higher REE grade. Column leaching tests showed that the leaching efficiency of REE was above 94% with leaching agent concentration of 0.20 mol/L, liquid-solid ratio of 4:3, flow rate of 0.60 mL/min, and initial pH value around 5.67. Compared to ammonium sulfate leaching, magnesium sulfate leaching was advantaged by nearly zero ammonia nitrogen emission while their REE leaching was almost equivalent.     

聚乙二醇对风化壳淋积型稀土矿浸出的影响

针对氯化铵作为浸取剂浸取风化壳淋积型稀土时,稀土浸取速率较低和浸出周期长等问题,使用聚乙二醇(PEG)为添加剂,通过柱浸试验模拟工业生产中的原地浸出工艺,探究不同聚合度的聚乙二醇对稀土矿渗透性和稀土浸出的影响。结果表明,聚乙二醇400、聚乙二醇1000和聚乙二醇4000溶液在稀土浸出过程中表现出较好的渗透效果。采用质量分数2.00%的聚乙二醇400、聚乙二醇1000、聚乙二醇4000分别与0.20mol/L的氯化铵复配,复配浸取剂溶液在稀土矿样中的渗透速率随着水力梯度的增大呈线性增大,符合达西定律。PEG400+NH_4Cl、PEG1000+NH_4Cl、PEG4000+NH_4Cl以及NH_4Cl溶液的稀土浸出率分别为82.61%、89.12%、70.67%和88.06%,且当聚乙二醇1000作为助浸剂时,渗流速率最大,渗透效果最佳。添加了聚乙二醇1000的复配浸取剂溶液,在浸取风化壳淋积型稀土矿中稀土的反应过程符合内扩散动力学模型。研究结果对提升复配浸取剂溶液在稀土矿体中的渗流速率有重要意义。