半风化离子吸附型稀土的浸取实验

针对龙南某矿山的半风化离子型稀土进行浸取试验研究.矿样中全相品位为 0.11 %,其中离子相稀土含量为 0.083 7 %.考察了浸取剂种类,浸取剂浓度,淋洗液固比以及尾水液固比对浸取的影响,其最佳柱浸浸取条件为:HT-13 浓度 2 %,淋洗液固比（指质量比,下同）为 0.4:1,尾液水液固比为0.6:1, 在此条件下稀土离子相浸出率为 98.06 %. 在放大试验中 HT-13 浸出液中稀土离子浓度为1.14 g/L,铝浓度为 10.8 mg/L,铁浓度为 7.8 mg/L,且 HT-13 可以循环使用.      

离子型稀土尾矿硫酸镁高效淋洗脱除氨氮技术研究

针对赣南地区离子型稀土尾矿残存氨氮带来的长期拖尾问题,通过室内柱浸模拟矿区环境,采用淋洗药剂集中淋洗的方法脱铵,开展了淋洗药剂筛选、淋洗工艺优化、淋洗效果验证及尾矿残留淋洗药剂的脱除等方面的研究。结果表明,硫酸镁是适合赣南地区离子型稀土尾矿氨氮淋洗的药剂;当硫酸镁溶液的浓度为2.5%(质量分数)、pH值为5、注液强度为0.3 mL/min时,淋洗效果较好,淋洗液固比为2.9时,尾矿氨氮淋出率为96.97%。将硫酸镁淋洗尾矿在pH值为5.7的雨水中浸泡60天后,浸泡液氨氮浓度低于15 mg/L的直接排放标准。集中淋洗后的尾矿加注顶水可将尾矿中残留的镁离子淋洗下来循环利用,不会对离子型稀土尾矿矿区造成二次污染。     

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。     

离子型稀土矿渗流溶浸行为研究

离子型稀土矿性质复杂,当前所采用的原地溶浸工艺适应性不强、影响因素较多,为揭示离子型稀土矿原地溶浸过程影响机制,探寻溶浸过程优化调控方法,本文以江西龙南足洞风化离子型稀土矿为研究对象,采用室内柱式溶浸法模拟原地溶浸工艺过程,开展离子型稀土矿溶浸过程影响规律研究,考察浸出过程各工艺因素对离子型稀土矿浸出效率的影响以及稀土原矿浸出前后的物质变化。研究结果表明,调控离子型稀土矿浸出过程原矿含水量4%、矿层高度43 mm,浸出剂浓度4%、浸出剂溶液p H值5.0、浸取过程固液比1.0∶0.8、浸取剂流速5 ml·min-1为最佳浸出条件参数,在原矿REO总量为0.078%的情况下,可获得浸出率为92.87%的稀土母液,母液中稀土平均浓度为1.73g·L-1,效果良好。稀土离子在浸出过程中与浸出剂的电解质NH+4发生了离子交换反应,稀土离子被交换浸出,而阳离子电解质NH+4则保留在浸渣中,整个浸出过程未生成其他新的物质,没有改变离子型稀土矿原有的晶型结构,不会影响稀土离子的渗流溶浸,有利于离子型稀土矿的绿色高效提取。     

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%。     

萃淋树脂法制备超高纯氯化钕工艺研究

以单一盐酸溶液为淋洗剂,采用萃淋树脂法制备超高纯氯化钕溶液。研究了CL-P507、CL-P204、001×7、001×8、D113、D900、DH100等7种树脂对RE3+、Al3+的吸附、解析、分离性能,遴选CL-P507为分离树脂、DH100为除铝树脂。单因素条件试验发现,加液方式、料液浓度、淋洗酸浓度、柱径比对流出液稀土纯度影响不显著,高料液浓度、高淋洗酸浓度、低柱径比可以获得较高浓度的超高纯氯化钕溶液,以正吸附方式加料、料液浓度30.89 g/L、淋洗酸浓度0.3 mol/L、柱径比20︰1为最优工艺条件,制备了纯度＞99.999%的超高纯氯化钕溶液。工艺不使用任何延缓离子,从源头控制非稀土杂质的引入,为超高纯稀土溶液的制备提供了技术参考。     

混合铵盐浸出风化壳淋积型稀土矿中稀土的研究

采用氯化铵和硝酸铵配成的混合铵盐作浸出剂,用柱浸模拟风化壳淋积型稀土矿的浸出过程,考察混合铵盐浸出剂的配比、浓度、液固比、pH和流速等对稀土浸出率的影响。结果表明,这种类型的浸出剂对该稀土矿有较高的稀土浸出率,且能较好地抑制黏土矿物的膨胀,最优工艺条件为:NH4Cl和NH4NO3的质量比8∶2、浸出剂质量浓度10g/L、浸出液pH=4.0、液固比2∶1、流速0.5mL/min,在此条件下稀土浸出率为96.29%,黏土矿物的线膨胀率为2.738%。     

从锌冶炼净化渣中回收高品位铜精矿

锌冶炼净化渣先进行高温浸出,使锌、钴、镉等有价金属进入浸出液,而铜留在渣中,所得铜渣再经高酸浸出及水洗后得到铜精矿。结果表明,最佳高温浸出条件为:液固比(6⁷)∶1,始酸浓度100g/L、终点pH=3.0、807)∶1,始酸浓度100g/L、终点pH=3.0、80⁸5℃浸出8h;高酸洗涤最佳条件为:液固比(485℃浸出8h;高酸洗涤最佳条件为:液固比(4⁶)∶1,终点酸度50g/L,706)∶1,终点酸度50g/L,70⁸0℃浸出6080℃浸出60⁹0min。铜精矿含铜65%以上、含锌小于2%。     

基于正交设计法的西藏玉龙铜矿酸浸工艺研究

为了提高西藏玉龙铜矿铜氧化矿的酸浸效率,采用正交设计法优化了酸浸过程中的各项参数,以期提高铜浸出效率,为中试及工程化生产提供理论依据.首先研究了氧化铜矿硫酸浸出的单因素最佳区间,然后针对温度、初始酸浓度、浸出时间、液固比和磨矿细度等多因素进行了正交优化.结果表明:这些因素对浸出过程均有影响,其中温度影响最大.通过参数优化,最终确定搅拌浸出最优工艺条件为:温度30℃、初始酸浓度100 g/L、浸矿时间2 h、液固比(指质量比)2∶1、磨矿细度为粒径≤74μm的物粒占65%.此时,铜氧化矿中铜浸出率可以达到79.45%.     

废旧稀土荧光粉除铝渣二段酸浸回收稀土的研究

以废旧稀土荧光粉经酸浸、苛性钠焙烧、水洗除铝后的除铝渣为原料,采用二段酸浸并进行正交实验优化酸浸条件。结果表明,一段酸浸时,各因素对稀土浸出影响顺序为:液固比盐酸浓度浸出时间浸出温度H_2O_2添加量。在液固比6∶1、盐酸浓度6 mol/L、浸出时间60 min、浸出温度60℃、H_2O_2添加8%(体积分数)优化条件下,稀土总浸出率为95.48%,残酸浓度为2.18 mol/L,杂质Al含量高达134 mmol/L,Fe含量为1.78 mmol/L,Si含量达到3.89 mmol/L;二段酸浸在浸出温度60℃、浸出时间60 min下,通过添加新鲜除铝渣调节浸出液终点pH值为4,二段酸浸液杂质Al、Fe、Si含量降低到24.1 mmol/L、0.09 mmol/L、3.89 mmol/L,满足后续萃取要求。     

Leaching of rare earth elements from contaminated soils using saponin and rhamnolipid bio-surfactant

The effective leaching of rare earth elements(La, Ce, Y and Eu) from simulated contaminated soil using bio-surfactant was investigated in a lab-scale column leaching experiment, where anionic biosurfactant rhamnolipid and non-ionic biosurfactant saponin were used as washing solutions. Soil properties and the rare earth element fractions were analysed to define the effect of leaching on soil and elemental speciation. Column leaching results showed that saponin solution was more effective than rhamnolipid in the removal of the four rare earth elements tested, with the accumulative removal efficiency of La, Ce, Y and Eu following flushing with 400 mL of 25 g/L saponin, reaching 35.258%, 26.072%, 31.476% and 30.849%, respectively. The change in REE speciation showed that REE removed from soils were mainly derived from the acid-soluble and residual fractions released when rhamnolipid solution was used as a leaching agent. However, for saponin leaching, removed REE amounts were derived from acid-soluble and reducible fractions. Complexation interactions were identified between saponin and REEs, according to infrared spectroscopy and ion exchange data, with saponin complexing with La, Ce, Y, and Eu at a complex ratio of 1:1.     

羧酸盐复合浸取剂对中重稀土浸出强化研究

以缅甸稀土矿与福建稀土矿为研究对象,采用柱浸工艺方法,研究风化壳淋积型稀土矿的矿石性质,分析乙酸铵添加浓度对风化壳淋积型稀土矿轻、中重稀土浸出的影响。结果表明,缅甸和福建稀土矿分别属于中钇型中重稀土选择型稀土矿和富铕轻稀土选择型稀土矿,并且均存在铈负异常和铕负异常现象。乙酸铵最佳添加浓度为0.04mol/L,稀土浸出可达到浸出平衡,浸出率提升到95%,同时乙酸铵主要通过增强钇元素的浸出,使缅甸稀土矿轻/中重稀土比值从1.04下降到0.98,福建稀土矿轻/中重稀土比值从1.65下降到1.47,表明乙酸铵能够明显提高中重稀土的浸出。     

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.     

废旧镍氢电池负极板中稀土的回收

采用湿法冶金工艺,回收废旧镍氢电池负极板中的稀土（RE）元素,用硫酸浸出负极板中的有价金属,分析硫酸浓度、浸出温度、浸出时间等因素对稀土元素浸出率的影响,在硫酸浓度为2.0 mol/L、浸出温度为60℃、浸出时间120 min下,RE的浸出率为92.31%.采用磷酸二异辛酯（P204）为萃取剂萃取浸出液中的稀土,当P204在煤油中的比率为20%时,萃取率为92.86%.用硫酸钠沉淀溶液中的稀土,浸出液中稀土元素回收率可达98.78%.采用XRD和SEM分析表征回收的稀土氧化物的物相和表面形貌,结果表明,回收产物为铈系稀土氧化物,为立方晶系,呈面心立方结构,表面形貌为棱柱形.     

纳滤浓缩稀土母液沉淀上清液的实验研究

以赣州某稀土公司浸矿所得稀土母液经NH₄HCO₃除杂沉淀后的上清液为处理对象,主要研究纳滤技术对原液中稀土离子的浓缩效率,以及对NH₃-N分离回收情况,以期能够为工业化分离应用提供借鉴.实验表明,当原液中稀土离子浓度为142.9 mg/L,氨氮浓度为346.1 mg/L时,在操作压力为0.8 MPa,进水pH值为6.49,运行温度为25 ℃的条件下,浓缩液侧稀土离子截留率达到95 %以上,Ca2+、Mg2+、Mn2+、Zn2+等杂质离子截留率能够达到75 %~90 %,透过液侧氨氮浓度为原浓度的60 %左右,有一定的浓缩效果;6.0 L的稀土母液沉淀上清液浓缩至0.6 L时,RE3+浓度升高至1 242.0 mg/L,浓缩了近8.69倍.      

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.     

从钕铁硼废料中提取稀土工艺研究

采用氧化焙烧-盐酸分解法,研究从钕铁硼废料中提取稀土的工艺条件,探讨了焙烧温度和时间对铁的氧化率的影响,在浸出过程中考察了盐酸浓度、反应时间、反应温度以及液固比对稀土浸出率的影响,并分析了pH值和陈化时间对浸出液除杂效果的影响.结果表明:在700℃焙烧1.5 h,铁的氧化率最高,铁基本完全氧化成三价铁,在最佳浸出条件下稀土浸出率高达到99.33%,浸出液中和除杂时,调节pH值为3.5,陈化时间大于2 h,料液中非稀土杂质含量低,特别是铁仅为0.0014 g/L,浸出液完全达到稀土萃取的要求.      

Kinetics study on leaching of rare earth and aluminum from polishing powder waste using hydrochloric acid

In this study,a novel hydrometallurgical process consisting of hydrochloric acid three-stage countercurrent leaching and solvent extraction was proposed to recover rare earth oxide(REO) from the rare earth polishing powder waste(REPPW).The effects of HCI concentration,liquid-solid ratio(L/S ratio),temperature and time on the leaching yields of rare earths(in REO) and aluminum(in Al_2O_3) were studied.The result shows that the leaching yields of REO and Al_2O_3 are 90.96% and 43.89% respectively under the optimum leaching parameters of HCl concentration=8.00 mol/L,L/S ratio=4 mL/g,leaching temperature=353 K and leaching time=180 min.Meanwhile,the leaching kinetics of REO and Al_2O_3 were investigated in this study.The leaching behaviors of REO and Al_2O_3 follow a shrinking sphere/core model and the general leaching process is controlled by the surface chemical reaction.The leaching activation energies of REO and Al_2O_3 are 9.86 and 13.68 kJ/mol,respectively.The leaching yield of each substance in three-stage countercurrent leaching is improved substantially compared with single-stage leaching,with a change from 90.96% to 95.38% for REO and from 43.89% to 46.22% for Al_2O_3,respectively.Especially,the total concentration of REO in three-stage countercurrent leaching solution is greatly increased to above 300 g/L,and the acidity of which is decreased to ca.pH=2,which is conducive to subsequent solvent extraction directly.High purity REO(99.92%) is obtained by solvent extraction separation,oxalate precipitation and calcination.The total recovery yield of REO is 85.13%.     

从低品位钼铅矿中提取钼的试验研究

研究了从氧化钼矿石中回收钼,考察了NaOH质量浓度、温度、时间、液固体积质量比对钼浸出率的影响。试验结果表明:在NaOH质量浓度80g/L、温度95℃、液固体积质量比3∶1条件下浸出矿石120min,钼浸出率达80%以上;浸出液先以Na2S溶液沉铅,再以HCl溶液调节pH=8除硅,然后再用HCl溶液调节pH=2.5,用D314大孔弱碱性阴离子交换树脂吸附钼,用10%NaOH溶液在40℃下解吸钼,钼吸附率及解吸率分别达到95%和97%。