Effect of impurity ions on preparation of novel saponifier for rare earth extraction

Magnesium bicarbonate,prepared by the carbonation of magnesium hydroxide slurry,was used as a novel saponifier to eliminate the ammonia nitrogen pollution in the rare earth extraction separation process.The effect of impurity ions introduced by system on the carbonation reaction of magnesium hydroxide was studied in the work.The results showed that the presence of Ca2+ could lead to side reactions so as to reduce the conversion rate of magnesium hydroxide,and a small number of rare earth ions would have great influence on the carbonation reaction.What’s more,there was no influence on carbonation reaction with the low concentration of Na+or Mg2+,the conversion rate of magnesium hydroxide could reach above 96%.This paper showed a practical theory which could provide scientific guidance for the preparation of novel saponifier in rare earth extraction separation process.     

Study on non-saponification extraction process for rare earth separation

The purpose of this study was to overcome the disadvantages of ammonia-nitrogen wastewater pollution and high cost of sodium saponification in rare earth separation process. The study focused on the non-saponification extraction technology with magnesia. The influences of the content and particle size of magnesia, reaction time, reaction temperature, and O/A on cerium extraction rate were also discussed. The results showed that the hydrogen ions of extractant were exchanged by rare earth ions when organic extractant and rare earth solution were mixed with magnesia powder, and then the exchanged hydrogen dissolved magnesia to make the acidity of the system stable. The magnesium ions were not participated in the extraction reaction. Non-saponification extraction process of rare earth had been realized. The cerium extraction rate could reach up to 99% in single stage within the optimal reaction conditions.     

Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507-HCl system

P507 solvent extraction is the main method to separate and purify the rare earth products.The emulsification may be caused by the impurities in process of extracting rare earths,and these result in huge economic loss and decrease the quality of rare earth products.In recent researches,the extractant was prone to emulsification,and aluminum content of rare earth products also increased,while aluminum concentration of feed was higher.Pointing to this problem,the structural change of saponification P507 extracting aluminum and lanthanum was investigated by infrared spectroscopy,and the results showed that Al ions exchanged with H of P-O-H to become P-O-Al.Because aluminum held the characteristic of hydrophilic after extracted in the form of hydroxyl polymer ions and this provided conditions for the formation of micro emulsion.The organic phase and aqueous phase were investigated by polarizing microscope after aluminum was extracted.The results showed that the organic phase was clear when the extraction capacity of Al was less than 5 g/L.If the extraction capacity of Al exceeded 5 g/L,it formed W/O of ME(micro emulsion),leading to form emulsion of the organic phase.When Al concentration of feed was less than 1 g/L,the aqueous phase would form O/W of ME.If aluminum was extracted by saponification P507 firstly,then the the organic phase loading aluminum extracted rare earth continually,the organic and aqueous phase formed emulsification easily.     

Formation mechanism of micro emulsion on aluminum and lanthanum extraction in P507-HCl system

P507 solvent extraction is the main method to separate and purify the rare earth products. The emulsification may be caused by the impurities in process of extracting rare earths, and these result in huge economic loss and decrease the quality of rare earth products. In recent researches, the extractant was prone to emulsification, and aluminum content of rare earth products also increased, while aluminum concentration of feed was higher. Pointing to this problem, the structural change of saponification P507 extracting aluminum and lanthanum was investigated by infrared spectroscopy, and the results showed that Al ions exchanged with H of P-O-H to become P-O-Al. Because aluminum held the characteristic of hydrophilic after extracted in the form of hydroxyl polymer ions and this provided conditions for the formation of micro emulsion. The organic phase and aqueous phase were investigated by polarizing microscope after aluminum was extracted. The results showed that the organic phase was clear when the extraction capacity of Al was less than 5 g/L. If the extraction capacity of Al exceeded 5 g/L, it formed W/O of ME (micro emulsion), leading to form emulsion of the organic phase. When Al concentration of feed was less than 1 g/L, the aqueous phase would form O/W of ME. If aluminum was extracted by saponification P507 firstly, then the the organic phase loading aluminum extracted rare earth continually, the organic and aqueous phase formed emulsification easily.     

HDEHP在硫酸溶液中萃取分离轻稀土性能研究

研究了 HDEHP在硫酸溶液中萃取分离轻稀土离子时有机相浓度、皂化剂类型、有机相皂化率、料液酸度对萃取饱和容量、分配比、分离系数的影响 ,确定了最佳萃取工艺参数 ,测定了轻稀土离子的分配比和分离系数。     

Effect of loaded organic phase containing mixtures of silicon and aluminum, single iron on extraction of lanthanum in saponification P507-HCl system

Emulsification troubled normal extraction process of rare earths due to the existence of non-rare earth impurities,especially Si,Al and Fe.Against this background,the effect of emulsification caused by Si,Al and Fe on the La extraction with saponification P507(2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester) in chloride medium was systematically investigated.A series of experiments were carried out to study the relationship of the extraction capacity of La and the concentration of impurities.ZPM-203 polarizing microscope was applied to investigate the morphology of emulsification,and the cation exchange extraction mechanism of Fe and Al as well as La was clarified by IR spectra.The results showed that a low concentration of Si in organic phase would aggravate the emulsification with Al,and the formation of ME(micro emulsion) and club-shaped polymer would result in emulsification in the extraction of mixtures of Si and Al,single Fe,respectively.Furthermore,the accumulation of impurity such as Si,Al and Fe in the organic phase would severely reduce the extraction capacity of La simultaneously.     

Extraction and separation of yttrium from other rare earths in chloride medium by phosphorylcarboxylic acids

Two phosphorylcarboxylic acids, 3-((bis(2-ethylhexyloxy))phosphoryl)propanoic acid (PPA) and 3-((bis(2-ethylhexyloxy))phosphoryl)-3-phenylpropanoic acid (PPPA), were synthesized for separating yttrium from other rare earths in the chloride feed of ion-adsorption type rare earth concentrate. The effect of the factors such as pH_1/2, temperature, saponification degree and phase modifiers was investigated. The separation efficiencies of PPA and PPPA are obviously better than the typical extractants such as sec-octylphenoxy acetic acid (CA-12) and naphthenic acid (NA). The extraction process of rare earths by PPA and PPPA is a cation exchanging reaction, which is similar to those of CA-12 and NA. The loaded rare earths in both PPA and PPPA systems can be effectively back-extracted by 0.5 mol/L HCl or higher concentration. A cascade extraction process for separating yttrium from other rare earths was developed using PPPA as the extractant. The yttrium product with the purity of 97.20 wt% was obtained by 35 stages of extraction and 12 stages of scrubbing.     

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.     

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.     

Preparation of high-purity neodymium chloride by solvent extraction in the mixer-settlers:A pilot-scale investigation

A novel purification process based on mixer-settlers for high-purity NdCl_3 was developed. Acidic solution and pure NdCl_3 solution were compared to scrub the less-extractable rare earths(REs)(La, Ce, and Pr)from loaded organic phase. The extractant with low-degree saponification was evaluated to remove the more-extractable element(Sm). Then the RE impurities(La, Ce, Pr, and Sm) in Nd were purified by an integrated process. Furthermore, effect of smuggling behavior on the purification of NdCl_3 in mixersettlers was studied. Based on the investigation mentioned above, the pilot-scale purification process for NdCl_3 with a purity of 99.999% was developed, and the total recovery was about 99%.     

萃取流量参数对稀土槽分布的影响

以国内某稀土厂生产萃取线A的La/CePr/Nd萃取过程为研究对象,通过采集和分析萃取槽各级有机相和水相中稀土元素的含量,明确不同皂化有机相流量、料液流量、酸流量等条件对各级稀土元素含量分布和稀土总量的影响。适当提高皂化有机相流量、料液流量和酸流量,可使水相出口处La的含量较高,从而保证出口产品纯度,但会使55级有机相出口处有机相中Ce组分含量较高,Pr、Nd组分含量较低,增加下一系列分离Pr、Nd的压力。     

Neodymium naphthenate-loaded organic phase stripping using sodium oxalate

Neodymium naphthenate-loaded organic phase stripping using sodium oxalate solution was studied to explore the feasibility of synchronous rare earth-loaded organic phase stripping, rare earth precipitation, and blank organic phase saponification. Experimental results show that loaded organic phase stripping, rare earth precipitation, and blank organic phase saponification can be realized simultaneously. When using 20% excess of sodium oxalate over the stoichiometry with the volume ratio of organic phase to aqueous phase of 1:1 at 25 °C for 40 min, the single stage stripping rate and saponification value are about 40% and 0.29 mol/L, respectively. After 16 stages of countercurrent continuous stripping, the stripping rate of neodymium can reach 99%, the saponification value is 0.42 mol/L, the Nd³⁺ concentration in saponified organic phase is less than 0.0020 mol/L, and the main phase in precipitation is Nd₂(C₂O₄)₃·10H₂O. Afterwards, this saponified organic phase can be used in the extraction of NdCl₃ solution, and then the loaded organic phases (neodymium naphthenate) with 0.16 mol/L Nd³⁺ can be retrieved. The morphology, particle size distribution, and composition of the Nd₂(C₂O₄)₃·10H₂O products are similar to those of the current direct precipitation products. The neodymium oxide prepared by continuous calcination of neodymium oxalate meets the national standard of China (GB/T 5240?2015). These results prove the feasibility of stripping neodymium naphthenate-loaded organic phase by using sodium oxalate solution. Sodium oxalate can serve as a stripping agent, a saponifier, and a precipitator, thereby simplifying rare earth extraction and separation. This study provides theoretical and technical support for the development of a novel method for rare earth extraction and separation.     

离子型稀土萃取分离工艺技术现状及发展方向

对我国离子型稀土萃取分离工艺中,现有的模糊联动萃取新技术的概念及基本技术经济特征;洗液、反液共用新技术的优势及在工艺设计中应采取的有效措施;稀土皂技术使用的目的及控制好稀土皂饱和度的关键技术;有机相各种皂化技术的技术经济特点;有机相溶料技术的特点及适用范围;C272+P507双溶剂萃取技术特点等进行了系统的分析讨论.对进一步加强稀土萃取分离工艺优化研究;稀土分离产品高纯化、物理性能优良化的指标控制技术的研发;提高萃取过程的装备和自动化水平;节能减排、环境保护、实现清洁生产等方面提出了今后努力的方向.     

Separation of trivalent rare earths from nitrate medium using solvent extraction with a novel extractant 2-ethylhexyl ((2-ethylhexylamino)methyl) phosphonic acid

By introducing the amine group into the structure of P227, a novel extractant 2-ethylhexyl ((2-ethylhexylamino)methyl) phosphonic acid (EEAMPA, abbreviated as HA) was synthesized for the extraction and separation of trivalent rare earths (REs) from nitrate medium. The influence factors including extractant concentration, equilibrium time, HNO₃ concentration, separation factors, cycle regeneration, stripping acidity, and actual leach liquor of metal ions, were studied systematically. The results show that the extraction ability of EEAMPA for REs decreases with increasing acidity. A possible extraction mechanism is proposed and the extracted species as REHA₃(NO₃) are confirmed by the slope analysis method. The extraction equilibrium can reach faster than P227. It shows good chemical stability and cycling regeneration. Stripping studies show that HCl is an excellent stripping agent and REs can be effectively stripped from the organic phase.     

Solvent extraction-separation of La(III), Eu(III) and Er(III) ions from aqueous chloride medium using carbamoyl-carboxylic acid extractants

N,N-dibutyldiglycol amic acid(HLI) and N,N-dioctyldiglycol amic acid(HLII) were synthesized and characterized by conventional spectroscopic methods. These molecules were examined as extractants for extraction-separation of La(III), Eu(III) and Er(III), as representative ions of light, middle and heavy rare earths, from aqueous chloride solutions. The analysis of the extraction equilibria revealed that the extracted species of lanthanum and europium ions by both of the extractants had a 1:3 metal to ligand ratio. It was suggested that erbium ions were extracted into the organic phase via the formation of Er(LI or II)2Cl complexes. The effect of the organic diluents on the extraction-separation efficiency of the studied rare earths by HLI and HLII was investigated by comparing the results obtained in dichloromethane and carbon tetrachloride. Regardless to the diluent used, the order of selectivity presented by the investigated extractants was Er(III)Eu(III)La(III). It is noteworthy that, a significant enhancement in separation of the studied rare earths by the extractants was achieved in their competitive extraction experiments with respect to that obtained in single component extraction experiments. Applicability of the extractants for the removal of rare earth ions from spent Ni-MH batteries was tested by removal of La(III), Eu(III) and Er(III) ions from simulated leach solution of such batteries.     

阳离子交换纤维分离重稀土工艺方法的研究

介绍了离子交换纤维分离重稀土元素的方法，提出了小口径多端同时出口的分离方案，这对缩短分离时间，富集次要成分。提高分离效率及收率，不失为一种多效分离措施。以EDTA作为淋洗剂，同时采用NH4^＋作排代剂，达到了用Cu^2＋作为延缓离子分离重稀土元素的目的。作为溶剂萃取法一个补充手段，本法不失其应急之需，可作为小批量生产提供分析用基准试剂，科研息需高纯重稀土等需求之用。同时验证了阳离子交换纤维分离重稀土是完全可行的。     

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。     

Extraction of vanadium from direct acid leach solution of converter vanadium slag

Direct acid leaching of converter vanadium slag by titanium dioxide waste is eco-friendly and efficient, but with low selectivity. This novel technique can result in a vanadium solution which contains chromium(III), aluminium(III), magnesium(II), manganese(II) and high amount of iron(II) and iron(III). Bis (2-ethylhexyl) phosphoric acid (D2EHPA) and tri-butyl-phosphate (TBP) diluted with sulphonated kerosene were applied for vanadium extraction from the multi-element leach solution. The effects of the initial pH, concentration of D2EHPA, ratio of organic to aqueous phase, and the extraction time on the extraction efficiency of vanadium were investigated in saponification and unsaponifiable systems, respectively. The results showed that the vanadium extraction percentage can be up to 97% and the iron extraction percentage can be less than 10% in a thirteen-stage counter-current simulation test and the separation coefficient between vanadium and iron can reach to 109.8. Furthermore, vanadium(IV) can also be separated from other impurities such as aluminium(III), magnesium(II), manganese(II), chromium(III) efficiently. The loaded organic phase was stripped by 184?g?L^?1 sulphuric acid solution in a three-stage counter-current stripping process and with the total vanadium stripping percentage of greater than 99.5%. In the end, the vanadium pentoxide products with a purity of 99.14% were obtained.     

P507-N235载酸有机相分解稀土的试验研究

P507-N235复合有机相能很好的萃取分离稀土元素.为有效利用P507-N235复合有机相中的余酸,对载酸有机相分解稀土的试验进行了研究.结果表明,分解碳酸钕时,较优的工艺参数为料浆浓度72.5 g/L、浸出时间30 min、相比V_O:V_A=1:1（有机相与水相的体积比, 下同）,在此条件下,30%P507+25%N235+45%煤油体系对Nd的萃取容量为20.16 g/L(按REO计,下同),有机相中余酸利用率为52.6%,且体系分相效果较好;分解氢氧化钕时,较优的工艺参数为料浆浓度73.3 g/L、浸出时间50 min、相比V_O:V_A=1:1,此时Nd的萃取容量可达21.6 g/L,有机相中余酸利用率为53.7%.实验证明了此方案的可行性,有机相中的残酸利用效果较好,可以实现载酸有机相的循环使用.      

环烷酸萃取分离稀土料液中铝的研究

采用环烷酸-异辛醇-煤油体系,研究去除高浓度稀土料液中铝离子杂质的最佳工艺条件。通过改变有机相皂化度、相比(O/A)等条件,对铝含量高达1.16mg/mL的稀土料液进行除杂试验。经过反复实验,最终确定环烷酸萃取分离稀土料液中铝离子的最佳工艺条件为:环烷酸/异辛醇/煤油=1∶1∶3体积比、皂化度0.10以及相比(O/A)=1.5/1。