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矿石性质及稀土在各粒级上的分布

研究了风化壳淋积型稀土矿矿石性质及稀土在各粒级上的含量。采用热重分析、EDTA容量法、紫外分光光度法、原子吸收分光光度法、甲醛容量法等测试手段,对矿石的多水性、吸附稀土离子的稳定性、原矿的缓冲性、吸附离子的可交换性这四大物理化学性质进行了验证,对稀土在各粒级上的含量进行了测定,为进一步合理利用该矿石资源提供理论指导。     

风化壳淋积型稀土矿浸出液沉淀浮选溶液化学分析

通过对风化壳淋积型稀土矿浸出液沉淀浮选进行溶液化学研究,探讨了体系pH、沉淀剂及浮选剂对沉淀浮选的影响.结果表明,风化壳淋积型稀土矿浸出液杂质可通过优先沉淀浮选以氢氧化物或焦磷酸盐或聚磷酸沉淀形式全部有效除去,最后将优先沉淀浮选除杂后浸出液中和提高pH值,再用沉淀浮选方法有效提取稀土.     

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。     

风化壳淋积型稀土矿浸取过程中基础理论研究现状

对风化壳淋积型稀土矿浸取过程中的浸取水动力学、原地浸出渗流规律、浸取稀土动力学、浸取铝动力学、浸取传质浸取过程选择性等基础理论现状进行了概括和分析.指出了目前浸取过程中存在的一些问题和面临的挑战,特别指出应在浸铝浸取动力学过程研究、浸取过程强化研究、堆浸、原地浸出基础理论研究方面有待进一步加强.      

不同孔隙比下风化壳淋积型稀土矿强度特性

风化壳淋积型稀土开采过程中,孔隙比为影响浸矿效果和矿体稳定性的关键因素.为探索不同孔隙比下风化壳淋积型稀土矿强度特性变化,选取6组重配比的稀土矿样,对不同孔隙比矿样进行了直接剪切实验,探讨孔隙演化对矿体抗剪强度的作用规律,揭示孔隙比对黏聚力和内摩擦角的影响机制.研究表明:不同孔隙比非饱和稀土矿对应着不同的剪切强度,基于试验数据发现剪应力与剪位移呈"类抛物线"变化,并建立了孔隙比与抗剪强度指标的关系模型.机制分析认为,随着孔隙比的增大,结合水膜效应逐渐弱化,粒间接触点数目也随之减少,使矿体抗剪强度减小.      

复合铵盐浸出风化壳淋积型稀土矿的研究

采用复合铵盐作浸出剂浸出风化壳淋积型稀土矿中的稀土。考察浸出剂的配比、浓度、液固比、流速、pH等因素对稀土浸出率的影响。结果表明,NH4Cl、NH4NO3、(NH4)2SO4质量比为4∶5∶6的复合铵盐浸出剂为最佳组合;液固比越大、流速越慢,浸出率越高;当浸出剂浓度为10g/L、pH=3.5时浸出效果最好。     

离子型稀土矿抑杂浸出中抑铝剂的研究

研究了在抑杂浸出过程中添加抑铝剂对稀土浸出的影响，筛选出了适宜的抑铝剂．所筛选出的抑铝剂能适应于我国南方不同类型离子型稀土矿，抑铝剂的添加几乎不影响稀土的浸出率．通过抑杂浸出得到的浸出液中铝离子含量小于2mg／L，去除率达到98％以上，铁离子含量小于0．3mg／L，该浸出液无需净化直接用碳酸氢铵沉淀得到的碳酸沉淀稀土符合生产质量要求．稀土产品质量达到国内现行标准，有效地简化了生产流程，并能减少5％-15％的稀土损失．     

渗流作用下风化壳淋积型稀土矿细观孔隙结构演化特征

为研究风化壳淋积型稀土矿浸出过程中溶液渗流作用对孔隙结构的影响,以去离子水为溶浸液开展浸矿实验。对浸出前后矿样进行显微CT扫描,获取了试样内部结构图像,利用阈值分割算法得到了浸出前后稀土矿样的孔隙结构图像。进而,研究了溶液渗流作用下试样孔隙结构的变化特征,分析了渗流作用对试样孔隙率、孔隙体积、孔隙长度、孔隙宽度和孔隙方位角等参数的影响。结果表明:稀土矿孔隙形状和尺寸在渗流作用下发生显著变化,且在粗细颗粒接触区最为明显;溶液渗流作用使得稀土矿孔隙率增大,孔隙总数量减少,孔隙总体积增大。渗流作用下矿样中小孔隙数量减少,大孔隙数量增多,各尺寸区间的孔隙数量变化率随孔隙尺寸的增大呈现先增大后减小的趋势。溶液渗流作用下孔隙长宽比分布更加集中,孔隙方位角在各角度区间的分布更加均匀,孔隙各向异性增强。      

Enhanced Leachability of a Lean Weathered Crust Elution-Deposited Rare-Earth Ore: Effects of Sesbania Gum Filter-Aid Reagent

The enhanced leachability of rare-earth ore from the lean weathered crust elution-deposited rare-earth ores with ammonium sulfate solution as lixiviant and sesbania gum as a filter-aid reagent was elucidated and optimized with chromatographic plate theory. The effects of the flow rate, the concentration of lixiviant, the sesbania gum filter-aid reagent, and the lixiviant consumption on the leaching process were examined with column elution. The results show that the sesbania gum has a positive effect on the leaching process; the relationship between the height equivalent to a theoretical plate (HETP) and the leaching flow rate can be described by the van Deemter equation. There is an optimum flow rate in the leaching process. The optimum concentration of the sesbania gum in lixiviant was discovered. Moreover, sesbania gum added in lixiviant also reduces lixiviant consumption and promotes the optimum leaching flow rate. It provides a new approach to leaching the lean weathered crust elution-deposited rare-earth ores with high efficiency and low reagent consumption. The approach also can reduce the NH₄ ⁺-N pollution.     

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原地浸矿负压收液研究

为了探求风化壳淋积型稀土矿原地浸取工艺中负压收液的可能性及其效果,通过浸矿剂渗透规律及负压收液机理的研究,对负压收液影响因素及边界范围、负压收液试验方法、负压值与收液率的关系、负压收液工艺及其抽取方式进行了探究.优化了收液方式和条件,得出了收液率与负压值基本上呈线性关系,最佳的抽液方式为停机时间10 min,开机时间50 min,三孔联抽,负压值维持在2.66×104Pa以上.随后进行了万吨级矿块工业试验,以进一步验证优化条件,获得了理想的试验结果及技术经济指标,其中REO浸取率达77.5%.     

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.     

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.      

非离子型表面活性剂对风化壳淋积型稀土矿浸出过程的影响

为了缓解风化壳淋积型稀土矿浸取过程存在的浸取周期长、浸出剂用量大和稀土拖尾等问题,以非离子型表面活性剂为助浸剂,氯化镁为浸出剂,对稀土浸出过程进行研究,研究复配浸出剂溶液性质,分析浸矿前后矿物粒径分布,探讨表面活性剂的促渗机理。研究结果显示,加入表面活性剂后,稀土浸出率提高,渗透速度加快,溶液的表面张力和接触角均减小,黏度增大,矿物颗粒的中值粒径明显减小,矿物表面Zeta电位增大,其中加入吐温40后稀土浸出率提高至86.38%,表面张力减小19.00%,接触角减小53.19%,溶液黏度减小4.29%,溶液性质变化最大。加入表面活性剂后可使溶液更容易润湿矿物,进入孔隙的阻力变小,扩散层厚度减小,黏土矿物的膨胀受到抑制,使得溶液浸出稀土的效果更好,其中吐温40对溶液浸出稀土的渗流效果影响最大,助渗效果最好。     

Leaching hydrodynamics of weathered elution-deposited rare earth ore with ammonium salts solution

In order to reveal the permeability rule of leaching agent solution and the effects of anions in the leaching process of weathered crust elution-deposited rare earth(RE) ores, the effects of ammonium concentration, temperature, particle size and porosity on the permeability were discussed in detail with(NH_4)2_SO_4, NH_4Cl and NH_4NO_3 as the leaching agent. It was found that the permeation velocity of ammonium salts increased linearly with the increase of hydraulic gradient. The seepage of ammonium salts solution in the RE ores followed Darcy's law and displayed a laminar flow. The properties of the leaching agent solution and RE ores were the main factors that affect the permeability of RE ores. With the decrease of ammonium concentration and increase of temperature, the viscosity of solution decreased and the permeability coefficients of RE ores increased. And the effects of temperature on the viscosity and permeability were larger than ammonium concentration. The permeability of RE ores became worse with the decrease of particle size and porosity, and the particle size played a more important role compared with porosity. The permeability coefficient of RE ores increased and the viscosity of ammonium salts solution decreased in the order of(NH_4)_2SO_4, NH_4Cl and NH_4NO_3, implying that the penetrating power of anions increased in the order of SO_4~(2-), Cl~- and NO_3~-. The results may play a vital role in improving the permeability of weathered crust elution-deposited RE ores.     

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。     

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.     

Anti-swelling mechanism of DMDACC on weathered crust elution-deposited rare earth ore

In order to inhibit the swelling of the clay minerals in the in-situ leaching process of weathered crust elution-deposited rare earth ores (WCE-DREO), diallyl dimethyl ammonium chloride (DMDACC) was introduced as an anti-swelling agent and combined with (NH₄)₂SO₄ as a novel composite leaching agent. It can be found that the novel composite leaching agent exhibits a good anti-swelling performance and leaching capacity of rare earth, and has great potential on the actual exploitation of WCE-DREO. The anti-swelling mechanism of DMDACC was studied by characterization analysis. The results show that DMDACC with positive charges can be adsorbed on the clay particles by the electrostatic attraction and hydrogen bonds, and neutralize the negative charge of the clay particles. The double electrical layers are suppressed and the repulsion force between clay sheets decreases. It causes the clay particles prone to aggregate. Moreover, DMDACC can enter the interlayer and expel out the water molecules in interlayer. The interlayer spacing is decreased and the hydration swelling of the clay particles is weakened. It can provide a theoretical basis for the development of novel anti-swelling agents.     

Reduction leaching of rare earth from ion-adsorption type rare earths ore with ferrous sulfate

The practice of in-situ leaching of the ion-adsorption type rare earths ore with ammonium sulfate could only leach most of rare earth in ion-exchangeable phase,but not the colloidal sediment phase.Therefore,the reduction leaching of rare earth from the ion-adsorption type rare earths ore with ferrous sulfate was innovatively put forward.The soak leaching process and the column leaching process were investigated in the present study.It was determined that ion-exchangeable phase could be released,and part of colloidal sediment phase rare earth could be reduction leached by the cations with reduction properties.The mechanism of reduction leaching was discussed with the Eh-pH diagram of cerium.Moreover,the stronger reduction of reductive ions,the greater acidity of leaching agent solution,and the higher reductive ion concentration,could result in the higher rare earth efficiency and the bigger cerium partition in the leaching liquor.In the ferrous sulfate column leaching process,the rare earth leaching rate and the rare earth efficiency were a little higher than with(NH_4)_2SO_4 agent,and the rare earth efficiency and the partitioning of cerium in leaching liquor could be about 102% and 5.31%,respectively.However,the ferrous sulfate leaching process revealed some problems,so compound leaching with magnesium sulfate and a small amount of ferrous sulfate was proposed to an excellent alternative leaching agent for further studies,which may realize efficiency extraction and be environment-friendly.