WO2013177729A1

WO2013177729A1 - Method for separating rare-earth by coupled recycling of materials

Info

Publication number: WO2013177729A1
Application number: PCT/CN2012/001294
Authority: WO
Inventors: 廖春生; 刘艳; 张玻
Original assignee: 五矿（北京）稀土研究院有限公司
Priority date: 2012-05-28
Filing date: 2012-09-21
Publication date: 2013-12-05
Also published as: CN102676853A; CN102676853B; MY170574A

Abstract

Disclosed is a method for separating a rare-earth by coupled recycling of materials. The method comprises: using an organic phase prepared by mixing an extractant and a rare-earth soap stock and loaded with the rare-earth for a subsequent coupled extraction separation, and re-using same in the dissolution of raw materials after extracting and concentrating the inorganic acid in the remaining water phase or recycling same after precipitating the rare-earth therein with oxalic acid; extracting the rare-earth solution after purification by separation, using oxalic acid to precipitate the rare earth, extracting the precipitated mother solution containing the oxalic acid and the inorganic acid, re-using the extracted oxalic acid to precipitate the rare earth, and using the remaining inorganic acid directly for washing, for a reverse extraction process, or for dissolving raw materials after extraction and concentration. The method can recycle the intermediate materials produced during the rare-earth separation among process sections, can avoid the alkaline saponification of the extractant, and can achieve processes such as dissolution, washing, and reverse extraction of the raw materials by only using the recycled inorganic acid.

Description

物料联动循环利用的稀土分离方法 Rare earth separation method for material linkage recycling

技术领域 Technical field

本发明属于稀土分离技术领域，具体涉及物料联动循环利用的稀土分离方法。背景技术 The invention belongs to the technical field of rare earth separation, and particularly relates to a rare earth separation method for material linkage recycling. Background technique

稀土是钪、钇全部十五个镧系元素的总称，由于化学性质极为相近，在矿物中伴生共存，而各元素优异的光、电、磁、催化的本征特性往往需要单一高纯稀土才能得以充分体现。因此，分离提纯成为稀土材料工业的重要过程。 Rare earth is a general term for all fifteen lanthanides of lanthanum and cerium. Because of their similar chemical properties, they coexist in minerals. The excellent intrinsic properties of light, electricity, magnetism and catalysis of each element often require a single high-purity rare earth. Fully reflected. Therefore, separation and purification have become an important process in the rare earth material industry.

稀土的分离提纯通常采用溶剂萃取分离法，该法具有处理量大、反应速度快、分离效果好的优点，是国内外稀土分离的主要生产方法。稀土萃取分离所用萃取剂主要为酸性磷类萃取剂，如： P204 ( 2-乙基己基磷酸）、 P507 ( 2-乙基己基膦酸单 2-乙基己基酯）和 Cyanex272 (二（ 2, 4, 4-三曱基戊基）膦酸）、 P229 (二（2-乙基己基）膦酸）等）。 The separation and purification of rare earths is usually carried out by solvent extraction and separation. This method has the advantages of large processing capacity, fast reaction speed and good separation effect. It is the main production method for rare earth separation at home and abroad. The extractant used for rare earth extraction and separation is mainly an acidic phosphorus extractant, such as: P204 (2-ethylhexylphosphoric acid), P507 (2-ethylhexylphosphonic acid mono-2-ethylhexyl ester) and Cyanex272 (two (2, 2, 4, 4-trimethylpentyl)phosphonic acid), P229 (bis(2-ethylhexyl)phosphonic acid), etc.).

稀土萃取分离提纯过程主要包括了溶料、萃取分离、沉淀等独立工序。溶料工序主要指将稀土氧化物或碳酸盐用酸溶解的过程，可用下列方程式表示： The separation and purification process of rare earth extraction mainly includes separate processes such as dissolution, extraction and precipitation. The dissolving process mainly refers to the process of dissolving rare earth oxides or carbonates with an acid, which can be expressed by the following formula:

RE₂0₃+6HC1=2REC1₃+3H₂0 (稀土氧化物溶解）（1) RE₂(C0₃)₃+6HC1=2REC1₃+3H₂0+3C0₂† (稀土碳酸盐溶解 ) (2) 为提高分离效率，酸性磷类萃取剂需经氨水或氢氧化钠或碳酸氢铵等碱性物质皂化，皂化后的有机相为稀土皂。皂化反应可用下列方程式表示 (其中 HA表示酸性萃取剂 ) ： RE ₂ 0 ₃ +6HC1=2REC1 ₃ +3H ₂ 0 (rare earth oxide dissolution) (1) RE ₂ (C0 ₃ ) ₃ +6HC1=2REC1 ₃ +3H ₂ 0+3C0 ₂ † (rare earth carbonate dissolution) ( 2) In order to improve the separation efficiency, the acidic phosphorus extractant needs to be saponified by ammonia or an alkaline substance such as sodium hydroxide or ammonium hydrogencarbonate, and the saponified organic phase is a rare earth soap. The saponification reaction can be represented by the following equation (where HA represents an acidic extractant):

HA+NaOH=NaA+H₂0 (钠皂化） (3) 或 HA+NH₄OH=NH₄A+H₂0(氨皂化） (4) 3NaA+RECl₃=REA₃+3NaCl (稀土皂化）（5) 通常使负载难萃组分的有机相在萃取段萃取料液中的易萃组分，获得提纯的难萃组分水溶液，负载易萃组分的有机相在洗涤段再用酸或易萃组分逆流洗涤，获得负载提纯易萃组分的有机相，经酸反萃后获得纯易萃组分水溶液，同时有机相得到再生循环利用。 HA+NaOH=NaA+H ₂ 0 (sodium saponification) (3) or HA+NH ₄ OH=NH ₄ A+H ₂ 0 (ammonia saponification) (4) 3NaA+RECl ₃ =REA ₃ +3NaCl (rare earth saponification) (5) generally extracting the extractable component of the organic phase of the poorly-dissolved component in the extraction section to obtain an aqueous solution of the purified extractable component, and the organic phase supporting the extractable component is further acid or Easy The extract component is subjected to countercurrent washing to obtain an organic phase loaded with the extractable fraction, and after acid stripping, an aqueous solution of the pure extractable component is obtained, and the organic phase is recycled and utilized.

REA₃+3HC1=REC1₃+3HA (洗涤、反萃取）（6) 单一稀土经草酸沉淀（按方程（7 ) )后，再灼烧为稀土氧化物。 _{_{REA 3 + 3HC1 = REC1 3 +}} 3HA ( washed, back extracted) (6) via a single rare earth oxalate precipitate (according to Equation (7)), the re-ignition of a rare earth oxide.

2REC1₃+3H₂C₂0₄=RE₂(C₂0₄)₃+6HC1 (7) 溶料过程中需要消耗无机酸溶解稀土氧化物或碳酸盐，采用酸性磷类萃取剂体系的稀土萃取分离过程的皂化工艺需消耗碱，由此产生相应的含盐皂化废水排放；沉淀工序消耗草酸，产生含草酸和无机酸的高酸度沉淀母液，需大量碱中和后以盐分的形式随废水排放。以年分离 12万吨稀土氧化物计，废水排放量高达 1200万吨以上，盐排放量超过 50万吨，化工原料的大量使用不仅增加了生产成本，而且环保压力巨大。因此，我国的稀土工作者开发了多项稀土清洁制备技术。 2REC1 ₃ +3H ₂ C ₂ 0 ₄ =RE ₂ (C ₂ 0 ₄ ) ₃ +6HC1 (7) In the process of dissolving, it is necessary to consume the inorganic acid to dissolve the rare earth oxide or carbonate, and the rare earth using the acidic phosphorus extractant system The saponification process of the extraction and separation process consumes alkali, thereby producing corresponding salt saponification wastewater discharge; the leaching process consumes oxalic acid, and produces a high acidity precipitation mother liquor containing oxalic acid and inorganic acid, which requires a large amount of alkali to neutralize and then takes the form of salt in the form of salt. emission. With an annual separation of 120,000 tons of rare earth oxides, the discharge of wastewater is as high as 12 million tons and the salt discharge is more than 500,000 tons. The large-scale use of chemical raw materials not only increases the production cost, but also has great environmental pressure. Therefore, China's rare earth workers have developed a number of rare earth clean preparation technologies.

溶料步骤除了用无机酸直接溶解外，还可以采用酸性有机萃取剂直接溶解碳酸盐的方法，用碳酸盐消耗萃取剂中的氢离子使得稀土进入有机萃取剂中。如中国专利申请 "一种碳酸稀土溶剂萃取分离工艺" （申请号： 200810155328.5 ,申请日 2008年 10月 27 日，公开日 2009年 3月 18 曰）、 "一种有机萃取剂的预处理方法及其应用" （申请号： 200710163930.9, 申请日 2007年 10月 11 日，公开日 2008年 9月 10日）、 "一种有机萃取剂的皂化方法" （申请号： 200610001858.5 , 申请日 2006年 1月 24 日，公开日 200年 8月 16日）。以上方法用酸性萃取剂直接溶解稀土，制备负载有混合稀土的有机相取代水相料液进槽，可以利用有机相中的酸，减少原料溶解的酸消耗，但仍需消耗酸碱用于分离过程空白有机相的皂化和负载有机相的洗涤、反萃再生，并相应产生盐排放。 In addition to direct dissolution with a mineral acid, the solution step can also be carried out by directly dissolving the carbonate with an acidic organic extractant, and the hydrogen ions in the extractant are consumed by the carbonate to cause the rare earth to enter the organic extract. Such as the Chinese patent application "a rare earth carbonate solvent extraction separation process" (application number: 200810155328.5, application date October 27, 2008, public day March 18, 2009), "a method of pretreatment of organic extractant and Its application" (application number: 200710163930.9, application date October 11, 2007, publication date September 10, 2008), "Saponification method of an organic extractant" (application number: 200610001858.5, application date January 2006) On the 24th, the public day is August 16th, 200th). The above method uses an acid extractant to directly dissolve the rare earth, and prepares the organic phase loaded with the mixed rare earth to replace the aqueous phase liquid into the tank, and can utilize the acid in the organic phase to reduce the acid consumption of the raw material dissolved, but still needs to consume the acid and alkali for separation. Process saponification of the organic phase and washing of the loaded organic phase, stripping regeneration, and corresponding salt emissions.

皂化萃取会产生大量的含盐废水，增加生产成本的同时对环境造成较大的污染。有机相不经碱皂化直接进行稀土皂化反应，该反应可表示为： REC1₃+3HA=REA₃+3HC1 (8) 中国专利申请 "一种高浓度稀土溶液非皂化萃取全分离工艺" （申请号 200610076405.9 , 申请日 2006年 4月 25 日，公开日 2006年 12月 20 日）、"一种非皂化体系萃取分离稀土元素的工艺，，（申请号 200610072668.2 , 申请日 2006年 4月 7 日，公开日 2007年 10月 10日）、 "一种非皂化有机相萃取稀土全分离工艺" （申请号 200610057908.1 , 申请日 2006年 2 月 27 日，公开日 2006年 8月 30日）、 "一种非皂化磷类混合萃取剂萃取分离稀土元素的工艺" （申请号 200510137231.8 , 申请日 2005年 12月 31 日，公开日 2006年 7月 19日）均为非皂化体系下的稀土萃取方法。为了降低非皂化后水相中的酸度，又在此过程中添加碱性物质 MgO、 CaO等中和以提高萃取容量。如中国专利申请"溶剂萃取分离提纯稀土元素的工艺方法"（申请号 200710100026.3 , 申请日 2007年 6月 4 日，公开日 2008 年 12月 10 ) 、 "一种萃取剂的皂化方法"（申请号 200610078830.1 , 申请日 2006年 5月 10日，公开日 2006年 12月 6日）。非皂化体系从有机相中置换出来的酸没有回收利用，最终仍需中和，排放含盐废水量与皂化工艺相当。 Saponification extraction will produce a large amount of salty wastewater, which will increase the production cost and cause greater pollution to the environment. The organic phase is directly subjected to rare earth saponification reaction without alkali saponification, and the reaction can be expressed as: REC1 ₃ +3HA=REA ₃ +3HC1 (8) Chinese Patent Application "A High-concentration Rare Earth Solution Non-Saponification Extraction Separation Process" (Application No. 200610076405.9, application date April 25, 2006, public day December 20, 2006), "A process for extracting and separating rare earth elements by a non-saponification system, (Application No. 200610072668.2, application date April 7, 2006, public October 10, 2007), "A non-saponification has Machine phase extraction rare earth separation process" (Application No. 200610057908.1, application date February 27, 2006, publication date August 30, 2006), "A process for extracting and separating rare earth elements by a non-saponified phosphorus-based extractant" ( Application No. 200510137231.8, application date December 31, 2005, publication date July 19, 2006) are rare earth extraction methods under non-saponification system. In order to reduce the acidity in the non-saponified aqueous phase, it is added in the process. Neutralization of alkaline substances such as MgO, CaO, etc. to increase the extraction capacity. For example, the Chinese patent application "Process for Solvent Extraction and Purification of Rare Earth Elements" (Application No. 200710100026.3, Application Date June 4, 2007, Public Date December 10, 2008 ", a method for saponification of extractant" (Application No. 200610078830.1, application date May 10, 2006, publication date December 6, 2006). The acid that is replaced by the non-saponification system from the organic phase is not recycled. In the end, it is still necessary to neutralize, and the amount of discharged salt water is equivalent to the saponification process.

草酸沉淀废水含有草酸与大量无机酸，常规处理方法为石灰中和沉淀处理法。中国专利申请 "一种草酸沉淀的洗涤方法" （申请号： The oxalic acid precipitation wastewater contains oxalic acid and a large amount of inorganic acid, and the conventional treatment method is lime neutralization precipitation treatment. Chinese Patent Application "A Washing Method for Oxalic Acid Precipitation" (Application No.:

201110095141.2申请日： 2011-04-15 , 公开日 2011年 10月 26日）用有机溶剂萃取的方法再生水，并没有考虑盐酸和草酸的循环利用，酸仍需中和，产生含盐废水的排放。 201110095141.2 Application Date: 2011-04-15, Public Date October 26, 2011) The method of extracting water by organic solvent extraction does not consider the recycling of hydrochloric acid and oxalic acid, and the acid still needs to be neutralized to produce the discharge of salty wastewater.

以上方法均针对单一过程，仅能降低某单一环节的试剂消耗或废水排放，没有将分离过程作为一个整体考虑，没有对不同工序试剂的产生和利用进行联动，最终仍然会产生大量含盐废水，无法消除稀土分离所带来的环境压力。发明内容 The above methods are all directed to a single process, which can only reduce the reagent consumption or wastewater discharge of a single link. The separation process is not considered as a whole, and the production and utilization of different process reagents are not linked, and finally a large amount of salty wastewater is still produced. It is impossible to eliminate the environmental stress caused by the separation of rare earths. Summary of the invention

针对现有技术中存在的缺陷，本发明的目的是提供两种物料联动循环利用的稀土分离方法，采用该方法能够使包含原料溶解、萃取分离和草酸沉淀的稀土分离全过程都能进行酸的物料联动循环利用，可避免萃取剂碱皂化过程，仅以循环回收利用的无机酸即可完成原料溶解和洗涤、反萃等过程。稀土分离提纯过程不消耗碱及无机酸，不产生含盐废水，生产成本低，绿色环保。为达到以上目的，本发明采用的技术方案是：物料联动循环利用的稀土分离方法，包括以下步骤： In view of the defects existing in the prior art, the object of the present invention is to provide a rare earth separation method for the coordinated use of two materials, which can perform the acid separation of the rare earth separation process including the raw material dissolution, the extraction separation and the oxalic acid precipitation. The material can be recycled and recycled to avoid the alkali saponification process of the extractant. The inorganic acid can be recycled and washed, and stripped. The rare earth separation and purification process does not consume alkali and inorganic acid, does not produce salty wastewater, and has low production cost and is environmentally friendly. In order to achieve the above objectives, the technical solution adopted by the present invention is: Dilution of material linkage recycling The soil separation method includes the following steps:

( I ) 将稀土碳酸盐或氧化物溶于无机酸溶液得到的混合稀土溶液或硫酸焙烧法得到的混合硫酸稀土水浸液或南方矿离子交换得到的混合稀土水浸液作为待萃取原料； (I) a mixed rare earth solution obtained by dissolving a rare earth carbonate or an oxide in a mineral acid solution or a mixed rare earth water immersion liquid obtained by a sulfuric acid roasting method or a mixed rare earth water immersion liquid obtained by ion exchange of a southern ore as a raw material to be extracted;

( II ) 将稀土皂料与用有机溶剂稀释后的空白萃取剂 A 按体积比为 ( II ) The rare earth soap material and the blank extractant A diluted with an organic solvent are in a volume ratio

0.1-20:1 的比例充分混合，直接进行稀土皂化反应，得到负载稀土的有机相和含酸稀土溶液； The ratio of 0.1-20:1 is fully mixed, and the rare earth saponification reaction is directly carried out to obtain a rare earth-loaded organic phase and an acid-containing rare earth solution;

( in )将步骤（ I )得到的待萃取原料与步骤（ Π )得到的负载稀土的有机相在串级萃取槽中混合进行稀土交换纯化反应，经过多次洗涤、反萃有机相，分别得到单一稀土溶液和空白萃取剂 A, 空白萃取剂 A返回步骤（ II ) 重新利用； (in) mixing the raw material to be extracted obtained in the step (I) with the rare earth-loaded organic phase obtained in the step (( )) in a cascade extraction tank for the rare earth exchange purification reaction, after multiple washings and stripping the organic phase, respectively Single rare earth solution and blank extractant A, blank extractant A is returned to step (II) for reuse;

( IV ) 将步骤（ III )得到的单一稀土溶液与草酸溶液或固体草酸混合沉淀稀土离子，分离、洗涤草酸稀土沉淀物，得到含草酸和无机酸的草酸沉淀废水； (IV) mixing the single rare earth solution obtained in the step (III) with the oxalic acid solution or the solid oxalic acid to precipitate the rare earth ions, separating and washing the rare earth oxalate precipitate to obtain the oxalic acid precipitation wastewater containing the oxalic acid and the inorganic acid;

( V )将步骤（ IV )得到的草酸沉淀废水与用有机溶剂稀释后的萃取剂 B按体积比 0.1-20: 1的比例充分混合，得到负载草酸的有机相以及含无机酸的平衡水相，有机相中的草酸经回收后重新沉淀稀土离子； (V) The oxalic acid precipitation wastewater obtained in the step (IV) and the extractant B diluted with the organic solvent are thoroughly mixed at a volume ratio of 0.1-20:1 to obtain an oxalic acid-loaded organic phase and an aqueous phase containing a mineral acid. , the oxalic acid in the organic phase is recovered and re-precipitated with rare earth ions;

( VI ) 步骤（ V )得到的含无机酸的平衡水相返回步骤（ I )溶解稀土碳酸盐或氧化物，或者返回步骤（ III ) 洗涤、反萃有机相； (VI) Step (V) of the inorganic acid-containing equilibrium aqueous phase is returned to step (I) to dissolve the rare earth carbonate or oxide, or return to step (III) to wash and strip the organic phase;

( ^1 )步骤（ II )中稀土皂化反应后得到的含酸稀土溶液采用步骤（ IV ) 中的方法沉淀稀土离子，并采用步骤（ V ) - ( VI ) 的方法处理草酸沉淀废水。进一步，步骤（ Π ) 中，稀土皂料与用有机溶剂稀释后的空白萃取剂 A的体积比为 1-5:1 , 所述萃取剂 A选自 2-乙基己基磷酸（ P204 ) 、 2-乙基己基膦酸单 2-乙基己基酯（ P507；)、二（ 2,4,4-三曱基戊基）膦酸（ Cyanex272 ) 和二（2-乙基己基）膦酸酯（P229 ) 中的一种或多种，所述有机溶剂选自工业煤油、磺化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种，萃取剂 A的浓度为 0.5-1.8mol/L。进一步，步骤（ Π ) 中的稀土皂料为单一稀土溶液或经萃取分组后得到的稀土溶液，其稀土含量以 REO计为 0.1-2.5mol/L。此处，经萃取分组后得到的稀土溶液优选为经萃取分组后得到的含难萃稀土组分的溶液。 (^1) The rare earth-containing acid solution obtained after the saponification reaction of the rare earth in the step (II) is precipitated with the rare earth ions by the method in the step (IV), and the oxalic acid precipitation wastewater is treated by the method of the step (V) - (VI). Further, in the step ( Π ), the volume ratio of the rare earth soap material to the blank extractant A diluted with the organic solvent is 1-5:1, and the extracting agent A is selected from the group consisting of 2-ethylhexylphosphoric acid (P204), 2 -ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507;), bis(2,4,4-tridecylpentyl)phosphonic acid (Cyanex272) and di(2-ethylhexyl)phosphonate ( One or more of P229), the organic solvent is selected from one or more of industrial kerosene, sulfonated kerosene, mineral spirit oil, isooctanol, and octanol, and the concentration of extractant A is 0.5-1.8. Mol/L. Further, the rare earth soap in the step ( Π ) is a single rare earth solution or a rare earth solution obtained by extracting and grouping, and the rare earth content thereof is 0.1-2.5 mol/L in terms of REO. Here, the rare earth solution obtained by the extraction grouping is preferably a solution containing the intractable rare earth component obtained by the extraction grouping.

再进一步，步骤（ Π ) 中的稀土皂料为单一稀土溶液时，步骤（VII ) 中，稀土皂化反应得到的含酸稀土溶液与步骤（ III )得到的同种单一稀土溶液合并后采用步骤（ IV ) 中的方法沉淀稀土离子。进一步，步骤（ V ) 中，草酸沉淀废水与用有机溶剂稀释后的萃取剂 B的体积比为 0.5-5: 1 , 萃取剂 B为磷酸三丁酯（TBP )和 /或曱基磷酸二曱庚酯（P350 ) , 所述有机溶剂选自工业煤油、磺化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种，萃取剂 B的浓度为 0.1-1.8mol/L。进一步，步骤（ V ) 中回收草酸时，使用水反萃负载草酸的有机相，得到草酸溶液，草酸返回做步骤（ IV ) 沉淀稀土离子；或使用稀土溶液反萃负载草酸的有机相，得到草酸稀土沉淀物；或使用氨水或氢氧化钠溶液反萃负载草酸的有机相，得到草酸铵或草酸钠副产品。进一步，步骤（VI ) 中，含无机酸的平衡水相返回步骤（ I )使用之前，预先使含无机酸的平衡水相与用有机溶剂稀释后的萃取剂 C按体积比 0.1-20: 1的比例混合萃取浓缩，经浓缩后的无机酸返回步骤（ I )使用，水相作溶料的底水或配制草酸溶液的底水或草酸稀土沉淀物的洗水循环使用。 Further, when the rare earth soap in the step ( Π ) is a single rare earth solution, in step (VII), the rare earth acid-containing solution obtained by the saponification of the rare earth is combined with the same single rare earth solution obtained in the step (III), and the step is adopted ( The method in IV) precipitates rare earth ions. Further, in the step (V), the volume ratio of the oxalic acid precipitation wastewater to the extractant B diluted with the organic solvent is 0.5-5:1, and the extractant B is tributyl phosphate (TBP) and/or bismuth subruthenium phosphate. The heptyl ester (P350), the organic solvent is selected from one or more of industrial kerosene, sulfonated kerosene, mineral spirits, isooctyl alcohol, and octanol, and the concentration of the extractant B is 0.1-1.8 mol/L. Further, in the step (V), when the oxalic acid is recovered, the oxalic acid-containing organic phase is back-extracted with water to obtain an oxalic acid solution, and the oxalic acid is returned to the step (IV) to precipitate the rare earth ions; or the rare earth solution is used to back-extract the organic phase supporting the oxalic acid to obtain the oxalic acid. Rare earth precipitate; or back-extracting the organic phase loaded with oxalic acid using ammonia or sodium hydroxide solution to obtain ammonium oxalate or sodium oxalate by-product. Further, in the step (VI), the aqueous phase containing the inorganic acid is returned to the step (I) before the use of the mineral acid-containing equilibrium aqueous phase and the organic solvent-diluted extractant C by volume ratio of 0.1-20:1 The ratio of the mixed extract is concentrated, and the concentrated inorganic acid is returned to the step (I), and the aqueous phase is used as the bottom water of the solution or the water of the oxalic acid solution or the oxalic acid rare earth precipitate is used for the water washing cycle.

再进一步，所述萃取剂 C选自仲碳伯胺（N1923 ) 、三烷基曱胺、 N- 十二烯（三烷基曱基）胺、二（ 1-异丁基 -3,5-二曱基己基）胺、二（ 1-曱基庚基）胺、 Ν,Ν-二（1-曱基庚基）乙酰胺、三正辛胺、三异辛胺、三辛烷基叔胺（Ν235 ) 、三月桂胺和三（2-乙基己基胺）中的一种或多种，所述有机溶剂选自工业煤油、磺化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种，萃取剂 C的浓度为 0.1-1.8mol/L。本发明提供的另一种物料联动循环利用的稀土分离方法，包括溶料、萃取分离、草酸沉淀和洗涤工序，萃取分离工序包括皂化负载稀土和稀土交换纯化步骤，将萃取分离、草酸沉淀和洗涤工序产生的无机酸溶液或含无机酸的稀土溶液与用有机溶剂稀释后的萃取剂 C按体积比 0.1-20:1的比例充分混合，萃取浓缩无机酸，经浓缩后的无机酸返回溶料工序循环使用，含稀土的低酸水相返回皂化负载稀土步骤，不含稀土的低酸水相作溶料的底水或配制草酸溶液的底水或草酸稀土沉淀物的洗水循环使用。 Still further, the extracting agent C is selected from the group consisting of primary carbon primary amine (N1923), trialkyl decylamine, N-decadiene (trialkyl decyl) amine, and bis(1-isobutyl-3,5- Dimercaptohexyl)amine, bis(1-fluorenylheptyl)amine, hydrazine, hydrazine-bis(1-decylheptyl)acetamide, tri-n-octylamine, triisooctylamine, trioctyl tertiary amine (Ν235), one or more of trilaurylamine and tris(2-ethylhexylamine), the organic solvent being selected from the group consisting of industrial kerosene, sulfonated kerosene, mineral spirits, isooctyl alcohol, and octanol One or more of the extractant C has a concentration of 0.1 to 1.8 mol/L. Another rare earth separation method utilizing the material linkage recycling provided by the invention includes a solvent, Extraction separation, oxalic acid precipitation and washing process, the extraction and separation process comprises saponification loading rare earth and rare earth exchange purification step, and the inorganic acid solution or the rare earth solution containing inorganic acid produced by extraction separation, oxalic acid precipitation and washing process is diluted with organic solvent The extracting agent C is thoroughly mixed according to the volume ratio of 0.1-20:1, and the concentrated inorganic acid is extracted and extracted, and the concentrated inorganic acid is returned to the dissolving step for recycling, and the rare earth-containing low acid aqueous phase is returned to the saponification supporting rare earth step, and the rare earth is not contained. The low acid aqueous phase is used as a bottom water for the solution or a water rinse for the bottom water of the oxalic acid solution or the rare earth oxalate precipitate.

该方法提及的 "无机酸溶液或含无机酸的稀土溶液" 是指不含草酸而含无机酸的溶液，无机酸主要为盐酸和 /或硝酸和 /或石 A酸。 The "mineral acid solution or rare earth solution containing inorganic acid" referred to in the method means a solution containing no oxalic acid and containing an inorganic acid, and the inorganic acid is mainly hydrochloric acid and/or nitric acid and/or sulphuric acid.

上述 "无机酸溶液或含无机酸的稀土溶液" 包括稀土皂化步骤产生的稀土皂化后含酸稀土溶液、草酸沉淀步骤中稀土过量情况下产生的含无机酸的稀土溶液以及洗涤步骤中采用低浓度酸除杂时产生的无机酸溶液，等等。进一步，所述萃取剂 C选自仲碳伯胺（N1923 ) 、三烷基曱胺、 Ν-十二烯（三烷基曱基）胺、二（ 1-异丁基 -3,5-二曱基己基）胺、二（ 1-曱基庚基）胺、 Ν,Ν-二（ 1-曱基庚基）乙酰胺、三正辛胺、三异辛胺、三辛烷基叔胺（Ν235 ) 、三月桂胺和三（2-乙基己基胺）中的一种或多种，萃取剂 C的浓度为 0.1-1.8mol/L, 所述有机溶剂选自工业煤油、礒化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种。进一步，皂化负载稀土步骤采用稀土皂料与用有机溶剂稀释后的空白萃取剂 A按体积比为 1-20:1的比例充分混合，直接进行稀土皂化反应；所述萃取剂 A选自 2-乙基己基磷酸、 2-乙基己基膦酸单 2-乙基己基酯、二 ( 2,4,4-三曱基戊基）膦酸和二（2-乙基己基）膦酸酯中的一种或多种，萃取剂 A的浓度为 0.5-1.8mol/L。 The above "inorganic acid solution or rare earth solution containing inorganic acid" includes a rare earth acid-containing rare earth solution after saponification of rare earth generated by a rare earth saponification step, a rare earth solution containing inorganic acid generated in an excess of rare earth in the oxalic acid precipitation step, and a low concentration in the washing step. A mineral acid solution produced by acid removal, and the like. Further, the extracting agent C is selected from the group consisting of primary carbon primary amine (N1923), trialkyl decylamine, decane-dodecene (trialkyl decyl) amine, and bis(1-isobutyl-3,5-di Amidinoyl, bis(1-indenylheptyl)amine, hydrazine, hydrazine-bis(1-decylheptyl)acetamide, tri-n-octylamine, triisooctylamine, trioctylalkyl tertiary amine一种 235 ), one or more of trilaurylamine and tris(2-ethylhexylamine), the concentration of extractant C is 0.1-1.8 mol/L, and the organic solvent is selected from the group consisting of industrial kerosene, sulphurized kerosene, One or more of solvent oil, isooctanol, and octanol. Further, the saponification loading rare earth step is carried out by directly mixing the rare earth soap material with the blank extractant A diluted with the organic solvent at a volume ratio of 1-20:1, and directly performing the rare earth saponification reaction; the extracting agent A is selected from the group consisting of 2- Ethylhexylphosphoric acid, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, bis(2,4,4-tridecylpentyl)phosphonic acid and di(2-ethylhexyl)phosphonate One or more of the extractant A has a concentration of 0.5 to 1.8 mol/L.

再进一步，稀土皂料为单一稀土溶液或经萃取分组后得到的稀土溶液，其稀土含量以 REO计为 0.1-2.5mol/L。本发明提供的物料联动循环利用的稀土分离方法，使得各独立过程能够在充分达到过程目标的前提下，得以统一协调进行。从分离过程各个阶段的反应方程可以看到：稀土原料溶解所需要的盐酸与稀土草酸沉淀产生的盐酸是对应的（见反应（1 ) 、（2 )和反应（7 ) ) ；皂化、萃取步骤反应（3 ) 、（4 ) ( 5 ) 可以合并为直接进行稀土皂化反应（8 ) ；酸性萃取剂萃取稀土置换出来的盐酸与洗涤和反萃取所需的盐酸是匹配的（见反应 ( 6 ) 、（8 ) ) 。在保证萃取效率的情况下，如取消碱皂化过程（见反应 ( 3 ) 、（4 ) ) , 代之以直接稀土皂化过程（见反应（8 ) ) , 并将产生的无机酸回收利用；同时将现行工艺需中和排放的草酸沉淀母液中的酸（见方程（7 ) )加以适当处理后回用，应可恰好满足原料溶解、萃取分离过程对于酸的需求，可实现原料溶解、萃取分离，稀土沉淀洗涤等过程中间物料进行全流程范围的联动循环利用，这样稀土分离全过程相当于方程（ 9 ), 只需要消耗等当量的草酸： Further, the rare earth soap material is a single rare earth solution or a rare earth solution obtained by extracting and grouping, and the rare earth content thereof is 0.1-2.5 mol/L in terms of REO. The rare earth separation method utilizing the material linkage cycle provided by the invention enables the independent processes to be uniformly coordinated under the premise of fully meeting the process objectives. From the various stages of the separation process The reaction equation of the section can be seen: The hydrochloric acid required for the dissolution of the rare earth raw material corresponds to the hydrochloric acid produced by the precipitation of rare earth oxalic acid (see reactions (1), (2) and reaction (7)); saponification, extraction step reaction (3) (4) (5) can be combined to directly carry out the rare earth saponification reaction (8); the acid extractant extracts the rare earth displaced hydrochloric acid to match the hydrochloric acid required for washing and stripping (see reactions (6), (8) ). In the case of ensuring the extraction efficiency, such as the elimination of the alkali saponification process (see reactions (3), (4)), the direct rare earth saponification process (see reaction (8)) is used, and the produced inorganic acid is recycled; The acid in the oxalic acid precipitation mother liquor that needs to be neutralized and discharged in the current process (see equation (7)) should be properly treated and reused. It should meet the acid demand of the raw material dissolution and extraction separation process, and the raw material can be dissolved and extracted. The intermediate materials in the process of rare earth precipitation washing are used in the whole process, so that the whole process of rare earth separation is equivalent to equation (9), and only equivalent equivalent of oxalic acid is consumed:

RE₂(C0₃)₃+3H₂C₂0₄=RE₂(C₂0₄)₃+3H₂0+3C0₂† ( 9 ) 。采用本发明所述的方法，与现有技术相比，具有如下优点： RE ₂ (C0 ₃ ) ₃ +3H ₂ C ₂ 0 ₄ =RE ₂ (C ₂ 0 ₄ ) ₃ +3H ₂ 0+3C0 ₂ † ( 9 ). Compared with the prior art, the method described in the present invention has the following advantages:

1 )采用本发明所述的物料联动的分离方法，在整体物料联动循环利用过程中，采用直接制备稀土负载有机相的方式，以及将皂化和沉淀母液中分离出的酸全部循环回用于稀土分离过程，使包含原料溶解、萃取分离和草酸沉淀的稀土分离全过程消耗的化工试剂仅有草酸，其氢离子用于溶解原料，草酸根用于沉淀稀土离子。 1) using the material linkage separation method according to the present invention, in the process of the overall material linkage recycling, the method of directly preparing the rare earth loaded organic phase, and recycling all the acid separated in the saponification and precipitation mother liquor for the rare earth In the separation process, the chemical reagent consumed in the whole process of rare earth separation including raw material dissolution, extraction separation and oxalic acid precipitation is only oxalic acid, the hydrogen ion is used for dissolving the raw material, and the oxalate is used for precipitating rare earth ions.

2 )将稀土皂化、草酸沉淀、洗涤等环节生成的废酸循环利用，废酸经萃取回收后应用于生产环节，整个稀土分离过程从溶矿到萃取、反萃均不需要额外添加无机酸，也相应的省去了为中和酸性废水而加入的碱，大幅降低了生产中的试剂成本。 2) recycling the waste acid generated by the saponification of rare earth, oxalic acid precipitation, washing, etc. The waste acid is extracted and recovered and used in the production process. The entire rare earth separation process does not require additional inorganic acid from the dissolution to the extraction and stripping. Correspondingly, the alkali added for neutralizing the acidic wastewater is omitted, and the reagent cost in production is greatly reduced.

3 )直接制备负载稀土的有机相，含酸水相分离回用，解决了常规方法直接非皂化的萃取容量低的问题，同时也不产生含盐的皂化废水。 3) Directly preparing the rare earth-loaded organic phase, and separating the acid-containing aqueous phase to solve the problem of low extraction capacity of the conventional non-saponification process, and no salty saponification wastewater.

4 )草酸沉淀废水回收利用，分别回收盐酸、草酸，无需常规方法中耗碱中和沉淀废水的步骤，相应避免了含盐废水的排放。 4) The oxalic acid precipitation wastewater is recycled and recovered, and hydrochloric acid and oxalic acid are separately recovered, and the step of neutralizing the precipitated wastewater by the conventional method is not required, and the discharge of the salty wastewater is correspondingly avoided.

5 ) 草酸沉淀废水、皂化废水、萃取洗涤水均经提取草酸和 /或无机酸后循环使用，提高水利用率，减少生产过程的单位用水量。 5) The oxalic acid precipitation wastewater, the saponification wastewater, and the extraction washing water are recycled after the extraction of oxalic acid and/or inorganic acid to improve the water utilization rate and reduce the unit water consumption in the production process.

6 )不产生皂化废水和沉淀废水，相应的也不产生 NaCl、NH₄Cl、CaCl₂、 MgCl₂、草酸盐等盐的排放。本工艺无需进行任何末端污染治理，实现从源头防止污染，对环境保护有着明显的效果。 6) No saponification wastewater and sedimentation wastewater are produced, and corresponding discharges of NaCl, NH ₄ Cl, CaCl ₂ , MgCl ₂ , and oxalate are not produced. This process does not require any end contamination treatment, The source prevents pollution and has a significant effect on environmental protection.

本工艺在追求环境保护的同时，也实现了经济的最优化，是一个革新性的稀土绿色分离生产工艺。附图说明 This process, while pursuing environmental protection, also achieves economic optimization and is an innovative rare earth green separation production process. DRAWINGS

图 1是本发明提供的物料联动循环利用的稀土分离方法的流程图。具体实施方式 1 is a flow chart of a rare earth separation method utilizing the material linkage recycling provided by the present invention. detailed description

下面结合附图和具体实施方式对本发明作进一步描述。实施例 1 The invention is further described below in conjunction with the drawings and specific embodiments. Example 1

用盐酸溶解的镧饰碳酸盐（La、 Ce摩尔比为 60:40 ) , 溶解得到的溶液作为待萃取原料，采用 P204为萃取剂，在 60级 30L主萃取槽中进行 La/Ce 分离，有机相流量为 6L/min, 浓度为 1.5mol/L (采用 30%仲辛醇 +70%磺化煤油的混合有机溶剂稀释）。另设 10级 30L副萃取槽进行酸的萃取回收，采用三烷基曱胺作为萃取剂，流量 5L/min,浓度 1.0mol/L(采用磺化煤油稀释）。两个萃取槽的有机相均自前向后流动。 The bismuth carbonate dissolved in hydrochloric acid (La, Ce molar ratio is 60:40), the solution obtained by dissolution is used as the raw material to be extracted, and P204 is used as the extracting agent, and La/Ce separation is carried out in a 60-stage 30 L main extraction tank. The organic phase flow rate was 6 L/min and the concentration was 1.5 mol/L (diluted with a mixed organic solvent of 30% octanol + 70% sulfonated kerosene). Another 10 grade 30L sub-extraction tank was used for acid extraction and recovery. Trialkyl decylamine was used as the extractant at a flow rate of 5 L/min and a concentration of 1.0 mol/L (diluted with sulfonated kerosene). The organic phases of the two extraction tanks flow from front to back.

主萃取槽中 (LaCe)Cl₃料液浓度为 lmol/L, 以 1.5L/min的流量自第 30级加入， 3.0mol/L的洗酸以 0.4L/min自第 50级加入， 3.0mol/L反萃酸以 0.7L/min 自第 60级加入。易萃组分 Ce进入有机相，经多次萃取、洗酸洗涤纯化，经反萃酸反萃后从第 51 级总计流出 0.7 L /min 氯化铈溶液，稀土浓度约 0.89mol/L, 酸度 0.33mol/L; 难萃组分留在水相中，经萃取纯化后在第 11级总计流出 1.9L/min氯化镧溶液，其中稀土含量约 0.9mol/L, 酸度 0.3mol/L; 水相均自后向前流动。 The concentration of (LaCe)Cl _{3 in the} main extraction tank is 1 mol/L, and is added from the 30th stage at a flow rate of 1.5 L/min, and the 3.0 mol/L washing acid is added from the 50th stage at 0.4 L/min, 3.0 mol. The /L stripping acid was added from the 60th stage at 0.7 L/min. The easy-to-extract component Ce enters the organic phase, and is purified by multiple extractions and acid washing. After stripping acid stripping, a total of 0.7 L / min cerium chloride solution is discharged from the 51st stage, and the rare earth concentration is about 0.89 mol/L. 0.33mol/L; the difficult-to-extract component remains in the aqueous phase, and after extraction and purification, a total of 1.9L/min barium chloride solution is eluted in the 11th stage, wherein the rare earth content is about 0.9mol/L, and the acidity is 0.3mol/L; The phases flow from the back to the front.

自主萃取槽第 11级流出 1.9L/min氯化镧溶液，其中 0.9L/min氯化镧溶液作为稀土皂料与空白有机相进行皂化反应（即图 1所示的皂化负载稀土步骤，下同），同时，对皂化后这部分含酸稀土溶液进行萃取浓缩无机酸的过程。具体操作为：在主萃取槽、副萃取槽的前 10级中， 0.9L/min氯化镧溶液首先与副萃取槽第 10级的三烷基曱胺接触进行萃取后，再与主萃取槽第 10级的 P204接触进行萃取，自萃取主槽第 10级流出的氯化镧溶液再依次与副萃取槽第 9级的三烷基曱胺、主萃取槽第 9级的 P204接触进行萃取，依次类推，直到自主萃取槽第 1级输出 0.9L/min基本不含稀土、 PH值约为 4的水溶液，回收利用。在上述皂化过程中， P204有机相负载了 La, 三烷基曱胺有机相负载了 0.54mol/L的盐酸。 In the 11th stage of the self-extraction tank, 1.9L/min lanthanum chloride solution is discharged, wherein 0.9L/min lanthanum chloride solution is used as a rare earth soap material to carry out saponification reaction with the blank organic phase (ie, the saponification loading rare earth step shown in FIG. 1 , the same At the same time, the process of extracting and concentrating the inorganic acid by the acid-containing rare earth solution after saponification. The specific operation is as follows: In the first 10 stages of the main extraction tank and the auxiliary extraction tank, the 0.9 L/min ruthenium chloride solution is firstly contacted with the trialkyl decylamine of the 10th stage of the auxiliary extraction tank for extraction, and then with the main extraction tank. The P204 of the 10th stage is contacted for extraction, and the cerium chloride solution flowing out from the 10th stage of the main extraction tank is sequentially followed by the secondary extraction tank. The tertiary tridecylamine of the ninth stage and the P204 of the ninth stage of the main extraction tank are contacted for extraction, and so on, until the first stage of the autonomous extraction tank outputs 0.9 L/min of an aqueous solution substantially free of rare earth and having a pH of about 4. recycle and re-use. In the above saponification process, the organic phase of P204 was loaded with La, and the organic phase of the trialkylguanamine was loaded with 0.54 mol/L of hydrochloric acid.

主萃取槽第 11级产出的另夕卜 1.OL/min氯化镧溶液（即图 1所示的皂化负载稀土步骤产生的另一部分含酸稀土溶液）用固体草酸沉淀，草酸沉淀废水与 1.5mol/L磷酸三丁酯（采用仲辛醇稀释）按 20:1的相比混合，萃取回收其中少量草酸后，得到 l.OL/min酸度为 3.0mol/L的水溶液，其中 0.4L/min作为洗酸返回主萃取槽，剩余 0.6L/min的盐酸与副萃取槽中经三烷基曱胺提取的盐酸一起进行碳酸镧铈溶解，得到待萃取分离的氯化镧铈溶液，具体操作流程见图 1。 The 11th grade of the main extraction tank produces an additional 1.OL/min ruthenium chloride solution (ie, another portion of the acid-containing rare earth solution produced by the saponification loading rare earth step shown in Figure 1) precipitated with solid oxalic acid, oxalic acid precipitated wastewater and 1.5 mol/L tributyl phosphate (diluted with sec-octanol) was mixed with 20:1, and a small amount of oxalic acid was extracted and extracted to obtain an aqueous solution of 1.0 OL/min acidity of 3.0 mol/L, of which 0.4 L/ Min is returned to the main extraction tank as acid washing, and the remaining 0.6 L/min of hydrochloric acid is dissolved in cesium carbonate together with hydrochloric acid extracted by trialkylguanamine in the auxiliary extraction tank to obtain a cerium chloride solution to be extracted and separated, and the specific operation is carried out. The process is shown in Figure 1.

自主萃取槽第 51 级总计流出 0.7 L /min 氯化铈溶液，稀土浓度约 0.89mol/L, 酸度 0.33mol/L, 采用固体草酸沉淀后，草酸沉淀废水与 0.5mol/L 磷酸三丁酯（采用仲辛醇稀释）按 0.5:1 的相比混合，萃取回收其中少量草酸后，得到 0.7L/min 3.0mol/L盐酸，用作反萃酸，具体操作流程见图 1。磷酸三丁酯中的草酸加水洗潦后得到草酸溶液，有机相得以再生。实施例 2 In the 51st stage of the self-extraction tank, a total of 0.7 L / min lanthanum chloride solution was discharged, the rare earth concentration was about 0.89 mol/L, and the acidity was 0.33 mol/L. After the solid oxalic acid was precipitated, the oxalic acid precipitation wastewater and 0.5 mol/L tributyl phosphate ( The mixture was diluted with octyl octanol and mixed with 0.5% of oxalic acid to obtain 0.7 L/min of 3.0 mol/L hydrochloric acid for use as a stripping acid. The specific operation scheme is shown in Figure 1. The oxalic acid in tributyl phosphate was washed with water to obtain an oxalic acid solution, and the organic phase was regenerated. Example 2

用盐酸溶解镧 4市碳酸盐（La、 Ce摩尔比为 60:40 ) , 得到的溶液作为待萃取原料，采用 60% P204和 40% P507为萃取剂，在 60级 30L主萃取槽中进行 La/Ce分离，有机流量为 6L/min, 浓度为 1.2mol/L (采用 200号溶剂油稀释）。另设 10级 30L副萃取槽进行酸的萃取回收，采用 Ν,Ν-二（ 1-曱基庚基）乙酰胺作为萃取剂，流量 5L/min, 浓度 O.8mol/L (采用 20%200号溶剂油 +40%异辛醇 +40%工业煤油稀释 )。两萃取槽的有机相均自前向后流动。 Dissolve 镧4 municipal carbonate (hydrogen ratio of La and Ce 60:40) with hydrochloric acid, and obtain the solution as the raw material to be extracted, using 60% P204 and 40% P507 as extractant, in 60-stage 30L main extraction tank. La/Ce separation, organic flow rate of 6 L/min, concentration of 1.2 mol/L (diluted with solvent oil No. 200). Another 10 grade 30L sub-extraction tank is used for acid extraction and recovery, using hydrazine, hydrazine-bis(1-decylheptyl)acetamide as the extractant, flow rate 5L/min, concentration O.8mol/L (using 20%200) Solvent oil + 40% isooctanol + 40% industrial kerosene diluted). The organic phases of both extraction tanks flow from front to back.

反萃酸、洗酸的加入和 La、 Ce料液的出口以及稀土皂化过程与实施例 1 相同，氯化镧皂料与空白 P204/P507混合萃取剂进行皂化反应， P204/P507有机相负载了 La, Ν,Ν-二（ 1-曱基庚基）乙酰胺有机相负载了盐酸。 The addition of stripping acid, acid addition and La, Ce liquid solution and rare earth saponification process are the same as in Example 1. The cerium chloride soap material is mixed with the blank P204/P507 mixed extractant for saponification reaction, and the P204/P507 organic phase is loaded. The organic phase of La, Ν, Ν-bis(1-decylheptyl)acetamide is loaded with hydrochloric acid.

萃取分离后的稀土溶液采用草酸沉淀后，草酸沉淀废水与 O.5mol/L曱基磷酸二曱庚酯（采用异辛醇稀释）按 1:1的相比混合，萃取回收其中少量草酸后，水相盐酸及 Ν,Ν-二（ 1-曱基庚基）乙酰胺有机相提取的盐酸同实施例 1 方式处理，曱基磷酸二曱庚酯中的草酸加稀土反萃得到草酸稀土，有机相得以再生。实施例 3 After the extraction and separation of the rare earth solution is precipitated with oxalic acid, the oxalic acid precipitation wastewater is mixed with 0.5 mol/L didecyl heptyl phosphate (diluted with isooctyl alcohol) according to 1:1, and a small amount of oxalic acid is extracted and recovered. Water phase hydrochloric acid and hydrazine, hydrazine-bis(1-fluorenylheptyl) acetamide organic phase extracted hydrochloric acid same as the examples 1 Method treatment, oxalic acid and rare earth stripping in didecyl heptyl phosphate to obtain rare earth oxalate, and the organic phase can be regenerated. Example 3

以硝酸溶解镧铈氧化物（La、 Ce摩尔比为 60:40 ) , 得到的溶液作为待萃取原料，采用 P507为萃取剂，萃取剂浓度 1.8mol/L (采用 20%200号溶剂油 +40%工业煤油 +40%仲辛醇稀释），在 60级 30L主萃取槽中进行 La/Ce 分离，有机流量为 6L/min。另设 10级 30L副萃取槽进行酸的萃取回收，采用三月桂胺作为萃取剂，流量 5L/min, 浓度 1.5mol/L (采用 20%200号溶剂油 +80%礒化煤油稀释）。两萃取槽的有机相均自前向后流动。 The niobium oxide is dissolved in nitric acid (La, Ce molar ratio is 60:40), and the obtained solution is used as the raw material to be extracted, and P507 is used as the extracting agent, and the concentration of the extracting agent is 1.8 mol/L (using 20% No. 200 solvent oil + 40) % industrial kerosene + 40% octanol diluted), La/Ce separation in a 60-stage 30L main extraction tank with an organic flow rate of 6 L/min. Another 10 grade 30L sub-extraction tank was used for acid extraction and recovery, using trilaurylamine as extractant, flow rate 5L/min, concentration 1.5mol/L (diluted with 20% solvent oil + 80% kerosene kerosene). The organic phases of both extraction tanks flow from front to back.

主萃取槽中 (LaCe)(N0₃)₃料液浓度 lmol/L, 以 1.5L/min的流量自第 30级加入， 3.0mol/L洗酸以 0.4L/min的流量自第 50级加入， 3.0mol/L反萃酸以 0.7L/min的流量自第 60级加入。易萃组分 Ce进入有机相，多次萃取、洗酸洗涤纯化，经反萃酸反萃后从第 51级总计流出 0.7 L /min硝酸饰溶液，稀土浓度约 0.89mol/L, 酸度 0.33mol/L; 难萃组分留在水相中，经萃取纯化后在第 11级总计流出 1.9L/min硝酸镧溶液，其中稀土含量约 0.9mol/L,酸度 0.3mol/L; 水相均自后向前流动。 In the main extraction tank (LaCe) (N0 ₃ ) ₃ feed liquid concentration lmol / L, at a flow rate of 1.5L / min from the 30th stage, 3.0mol / L wash acid at a flow rate of 0.4L / min from the 50th level 3.0 mol/L of the stripping acid was added from the 60th stage at a flow rate of 0.7 L/min. The easy-to-extract component Ce enters the organic phase, and is extracted by multiple extractions and washed with acid. After stripping acid stripping, a total of 0.7 L / min nitric acid solution is eluted from the 51st grade. The rare earth concentration is about 0.89 mol/L, and the acidity is 0.33 mol. /L; The difficult-to-extract component remains in the aqueous phase. After extraction and purification, a total of 1.9 L/min lanthanum nitrate solution is eluted in the 11th stage, wherein the rare earth content is about 0.9 mol/L, and the acidity is 0.3 mol/L; It flows backwards.

自主萃取槽第 11级流出 1.9L/min硝酸镧溶液，取 1.5L/min作为稀土皂料与空白有机相进行皂化反应，同时，对皂化后这部分含酸稀土溶液进行萃取浓缩无机酸的过程。具体操作为：在主萃取槽、副萃取槽的前 10级中， 1.5L/min 硝酸镧溶液首先在副萃取槽第 10级被三月桂胺萃取其中的余酸后，在主萃取槽第 10级和 P507接触进行萃取，自主萃取槽第 10级流出的硝酸镧溶液再依次与副萃取槽、主萃取槽的第 9级有机相接触进行萃取，依次类推，最终 P507有机相负载了 0.135mol/L的镧，三月桂胺有机相负载了 0.53mol/L的硝酸。从主萃取槽第 1 级流出 1.5L/min 皂化后含酸稀土溶液，其中硝酸镧 0.36mol/L, S史度 0.15mol/L。 In the 11th stage of the self-extraction tank, the 1.9L/min lanthanum nitrate solution was discharged, and 1.5L/min was taken as the rare earth soap material to carry out the saponification reaction with the blank organic phase. At the same time, the process of extracting and concentrating the inorganic acid from the acid-containing rare earth solution after saponification was carried out. . The specific operation is as follows: in the first 10 stages of the main extraction tank and the auxiliary extraction tank, the 1.5 L/min lanthanum nitrate solution is firstly extracted in the 10th stage of the auxiliary extraction tank by trilaurylamine, and 10 times in the main extraction tank. The phase is contacted with P507 for extraction. The cerium nitrate solution flowing out of the 10th stage of the autonomous extraction tank is sequentially contacted with the secondary phase tank of the secondary extraction tank and the 9th organic phase of the main extraction tank for extraction, and so on. Finally, the P507 organic phase is loaded with 0.135 mol/ The lanthanum of L, the laurylamine organic phase was loaded with 0.53 mol/L of nitric acid. From the first stage of the main extraction tank, 1.5 L/min of saponified acid-containing rare earth solution, wherein cerium nitrate is 0.36 mol/L, and S history is 0.15 mol/L.

皂化后含酸稀土溶液采用草酸沉淀，并用磷酸三丁酯回收草酸沉淀废水中的草酸后，水相为 1.5L/min的硝酸，浓度 1.23mol/L。此硝酸与三月桂胺提取的硝酸合并溶解氧化镧铈，得到待萃取的硝酸镧铈料液。主萃取槽第 11级产出的另外 0.4L/min硝酸镧溶液，用固体草酸沉淀，草酸沉淀废水与 1.0mol/L磷酸三丁酯按 10: 1的相比混合，萃取回收其中少量草酸后, 得到 0.4L/min酸度为 3.0mol/L的水溶液，作为洗酸进返回主萃取槽。 After the saponification, the acid-containing rare earth solution is precipitated with oxalic acid, and after the oxalic acid in the oxalic acid precipitation wastewater is recovered by using tributyl phosphate, the aqueous phase is 1.5 L/min of nitric acid at a concentration of 1.23 mol/L. This nitric acid is combined with the nitric acid extracted with trilaurylamine to dissolve the cerium oxide to obtain a cerium nitrate solution to be extracted. The other 0.4L/min cerium nitrate solution produced in the 11th stage of the main extraction tank is precipitated with solid oxalic acid, and the oxalic acid precipitation wastewater is mixed with 1.0 mol/L tributyl phosphate in a ratio of 10:1, and a small amount of oxalic acid is extracted and recovered. An aqueous solution having an acidity of 3.0 mol/L of 0.4 L/min was obtained, and the acid was fed back to the main extraction tank.

自主萃取槽第 51 级总计流出 0.7 L /min 硝酸铈溶液，稀土浓度约 0.89mol/L, 酸度 0.33mol/L, 采用固体草酸沉淀后，草酸沉淀废水与 1.0mol/L 磷酸三丁酯按 0.2: 1 的相比混合，萃取回收其中少量草酸后，得到 0.7L/min 3.0mol/L盐酸，用作反萃酸。磷酸三丁酯中的草酸加水洗潦后得到草酸溶液，有机相得以再生。实施例 4 In the 51st stage of the self-extraction tank, a total of 0.7 L / min lanthanum nitrate solution was discharged. The rare earth concentration was about 0.89 mol/L, and the acidity was 0.33 mol/L. After the solid oxalic acid was precipitated, the oxalic acid precipitation wastewater and 1.0 mol/L tributyl phosphate were 0.2. : 1 compared to mixing, after extracting a small amount of oxalic acid to obtain 0.7 L / min of 3.0 mol / L hydrochloric acid, used as a stripping acid. The oxalic acid in tributyl phosphate was washed with water to obtain an oxalic acid solution, and the organic phase was regenerated. Example 4

稀土皂料为包头混合稀土矿经硫酸焙烧、水浸除杂后得到的硫酸稀土浸出液经萃取分离后得到的难萃组分，其中 REO含量 15g/L, pH为 3 , 主成分为含 La、 Ce的稀土溶液。 The rare earth soap material is a difficult-to-extract component obtained by the extraction and separation of the rare earth leaching solution obtained by roasting sulfuric acid and water leaching of the Baotou mixed rare earth ore. The REO content is 15g/L, the pH is 3, and the main component is La. A rare earth solution of Ce.

将稀土皂料与以 P204空白有机相混合进行稀土皂化反应， P204浓度 1.2mol/L (采用 200号溶剂油稀释）。稀土皂化过程采用 8级萃取槽串联逆流萃取，水相与油相的体积比为 2: 1 , 此过程有机相中的氢离子被稀土交换进入水相，水中大部分稀土进入有机相中，最终稀土皂化后得到的含酸稀土溶液中含 H+ 0.27mol/L、 REO 0.5g/L, 流出的有机相为负载稀土的有机相，进入稀土萃取分离槽进行后续的联动萃取分离。 The rare earth soap material was mixed with P204 blank organic phase to carry out rare earth saponification reaction, and the concentration of P204 was 1.2 mol/L (diluted with solvent oil No. 200). The rare earth saponification process uses 8-stage extraction tank in series countercurrent extraction. The volume ratio of water phase to oil phase is 2:1. In this process, the hydrogen ions in the organic phase are exchanged into the water phase by rare earth, and most of the rare earth in the water enters the organic phase. The rare earth-containing rare earth solution obtained by saponification of rare earth contains H+0.27mol/L and REO 0.5g/L, and the organic phase flowing out is the rare earth-loaded organic phase, and enters the rare earth extraction separation tank for subsequent linkage extraction separation.

向稀土皂化后得到的含酸稀土溶液中加入草酸溶液沉淀稀土离子，控制沉淀终点草酸过量，过滤，洗涤，得到含有 H+ 0.08mol/L 的石充酸和 0.01mol/L草酸的草酸沉淀废水。 To the acid-containing rare earth solution obtained by saponification of rare earth, an oxalic acid solution is added to precipitate rare earth ions, and an excess of oxalic acid is controlled at the end of the precipitation, filtered, and washed to obtain an oxalic acid precipitation wastewater containing H+ 0.08 mol/L of rock-filled acid and 0.01 mol/L of oxalic acid.

草酸沉淀废水与曱基磷酸二曱庚酯萃取剂按照体积比 10: 1 的比例混合萃取草酸，曱基磷酸二曱庚酯浓度 0.5mol/L (采用 260号溶剂油稀释）。经过 5级逆流萃取分离，负载草酸的平衡有机相用 Imol/L NaOH溶液反萃得到草酸钠溶液，平衡水相为稀^ L酸溶液。 The oxalic acid precipitation wastewater and the decyl heptyl phosphate extractant were mixed to extract oxalic acid in a ratio of 10:1 by volume, and the concentration of dinonyl heptyl phosphate was 0.5 mol/L (diluted with solvent oil No. 260). After 5 stages of countercurrent extraction and separation, the equilibrium organic phase loaded with oxalic acid was back extracted with Imol/L NaOH solution to obtain sodium oxalate solution, and the equilibrium aqueous phase was dilute acid solution.

将分离得到的上述稀酸溶液与 1.8mol/L 伯胺 N1923(采用礒化煤油稀释）按照 20: 1的体积比混合，经 2级逆流萃取，硫酸被胺类萃取剂萃取进入有机相，水得以再生循环作为硫酸焙烧矿的水浸液；经萃取浓缩后的硫酸用于溶解 40\¥1%的包头矿混合碳酸稀土，得到 30g/L的混合硫酸稀土料液。实施例 5 The separated dilute acid solution is mixed with 1.8 mol/L primary amine N1923 (diluted with deuterated kerosene) in a volume ratio of 20:1, and subjected to a second-stage countercurrent extraction, and the sulfuric acid is extracted into the organic phase by the amine extractant, water The regeneration cycle can be used as the water immersion liquid of the sulfuric acid roasting ore; the extracted and concentrated sulfuric acid is used to dissolve 40% of the Baotou ore mixed rare earth carbonate to obtain 30 g/L of mixed rare earth sulfate. Liquid. Example 5

将萃取分离后得到的 1.5mol/L 的 SmCl₃溶液与以 P507为萃取剂的空白有机相混合进行稀土皂化反应， P507浓度为 0.5mol/L (采用 10%异辛醇 +90%礒化煤油的混合有机溶剂进行稀释）。稀土皂化过程采用 4级萃取槽串联逆流萃取，水相与油相的体积比为 20: 1 , 此过程有机相中的氢离子被稀土交换进入水相，流出的水相为含 H⁺ 0.01mol/L的含酸稀土溶液，流出的有机相为负载稀土的有机相，进入稀土萃取分离槽进行后续的联动萃取分离。 The 1.5 mol/L SmCl ₃ solution obtained after extraction and separation was mixed with the blank organic phase with P507 as extractant to carry out rare earth saponification reaction. The concentration of P507 was 0.5 mol/L (using 10% isooctanol + 90% deuterated kerosene) The mixed organic solvent is diluted). The rare earth saponification process uses a 4-stage extraction tank in series countercurrent extraction. The volume ratio of the aqueous phase to the oil phase is 20:1. In this process, the hydrogen ions in the organic phase are exchanged into the aqueous phase by the rare earth, and the aqueous phase flowing out contains H ⁺ 0.01 mol. /L of the acid-containing rare earth solution, the organic phase flowing out is the rare earth-loaded organic phase, and enters the rare earth extraction separation tank for subsequent linkage extraction separation.

将稀土皂化后得到的含酸稀土溶液与 1.8mol/L 三辛烷基叔胺萃取剂 (橫化煤油稀释）按照 20: 1的体积比混合，经 2级逆流萃取，盐酸被胺类萃取剂萃取进入有机相，水相为 pH等于 4的 SmCl₃溶液，循环用作配制稀土皂的稀土皂料。 The rare earth acid-containing solution obtained by saponifying the rare earth is mixed with a 1.8 mol/L trioctyl tertiary amine extractant (diluted with kerosene) in a volume ratio of 20:1, and subjected to a second-stage countercurrent extraction, and the hydrochloric acid is extracted with an amine extractant. The solution is extracted into an organic phase, and the aqueous phase is a SmCl ₃ solution having a pH of 4, which is recycled as a rare earth soap material for preparing a rare earth soap.

经三辛烷基叔胺萃取剂萃取浓缩后的盐酸用于溶解南方矿混合氧化稀土（REO含量 92% ) , 稀土被溶解得到 64g/L的混合稀土料液。实施例 6 The concentrated hydrochloric acid extracted by the trioctyl tertiary amine extractant is used to dissolve the southern ore mixed oxidized rare earth (REO content 92%), and the rare earth is dissolved to obtain a mixed rare earth liquid of 64 g/L. Example 6

向萃取分离得到的单一稀土溶液 Dy(N0₃)₃溶液中加入草酸沉淀稀土离子，控制沉淀过程稀土过量，得到含 HNO₃0.5mol/L、 Dy(N0₃)₃ 0.1mol/L 的草酸沉淀废水。 Adding oxalic acid to precipitate rare earth ions in a single rare earth solution Dy(N0 ₃ ) ₃ solution obtained by extraction and separation, and controlling the excess of rare earth in the precipitation process to obtain an oxalic acid precipitate containing HNO ₃ 0.5 mol/L and Dy(N0 ₃ ) ₃ 0.1 mol/L. Waste water.

草酸沉淀废水与 0.3mol/L二（ 1-异丁基 -3,5-二曱基己基 )胺萃取剂（采用仲辛醇稀释）按照 0.5: 1 的体积比混合，经 2级逆流萃取，硝酸被胺类萃取剂萃取进入有机相，水相为 pH等于 4的 Dy(N0₃)₃溶液，循环至草酸沉淀步骤。经二（ 1-异丁基 -3,5-二曱基己基）胺萃取剂萃取浓缩后的硝酸用于溶解南方矿混合碳酸稀土（REO含量 30% ) , 稀土被溶解得到 20g/L 的混合稀土料液。实施例 7 The oxalic acid precipitation wastewater was mixed with 0.3 mol/L bis(1-isobutyl-3,5-didecylhexyl)amine extractant (diluted with octanol) in a volume ratio of 0.5:1, and subjected to a 2-stage countercurrent extraction. The nitric acid is extracted into the organic phase by an amine extractant, and the aqueous phase is a Dy(N0 ₃ ) ₃ solution having a pH of 4, which is recycled to the oxalic acid precipitation step. The concentrated nitric acid is extracted by di(1-isobutyl-3,5-dimercaptohexyl)amine extractant to dissolve the rare earth carbonate (REO content of 30%), and the rare earth is dissolved to obtain a mixture of 20g/L. Rare earth liquid. Example 7

将自捞钇洗钙萃取槽（利用低浓度盐酸将负载捞钇的有机相中的钙反萃）得到的含有 HC1 lmol/L、 CaCl₂ O.lmol/L的酸性废水与 1.5mol/L二（ 1- 曱基庚基）胺（采用 200号溶剂油稀释）萃取剂按照 1:1的体积比混合，盐酸被胺类萃取剂萃取进入有机相，经萃取浓缩后的盐酸用于溶解南方矿混合氧化稀土（ REO含量 92% ) 。上述实施例只是对本发明的举例说明，本发明也可以以其它的特定方式或其它的特定形式实施，而不偏离本发明的要旨或本质特征。因此，描述的实施方式从任何方面来看均应视为说明性而非限定性的。本发明的范围应由附加的权利要求说明，任何与权利要求的意图和范围等效的变化也应包含在本发明的范围内。 Will be self-salted calcium extraction tank (using low concentration of hydrochloric acid will load the calcium in the organic phase of the fishing Extracted acidic wastewater containing HC1 lmol/L, CaCl ₂ O.lmol/L and 1.5 mol/L bis(1-decylheptyl)amine (diluted with solvent oil No. 200) extractant according to 1:1 The volume ratio is mixed, hydrochloric acid is extracted into the organic phase by the amine extractant, and the hydrochloric acid after extraction and concentration is used to dissolve the rare earth mixed rare earth oxide (REO content 92%). The above-described embodiments are merely illustrative of the invention, and the invention may be embodied in other specific forms or other specific forms without departing from the spirit or essential characteristics of the invention. Accordingly, the described embodiments are to be considered in all respects The scope of the invention is to be construed as being limited by the scope of the appended claims.

Claims

权利要求 Rights request

1、一种物料联动循环利用的稀土分离方法，包括以下步骤： 1. A rare earth separation method for material linkage recycling, including the following steps:

( I ) 将稀土碳酸盐或氧化物溶于无机酸溶液得到的混合稀土溶液或硫酸焙烧法得到的混合硫酸稀土水浸液或南方矿离子交换得到的混合稀土水浸液作为待萃取原料； (1) A mixed rare earth solution obtained by dissolving rare earth carbonates or oxides in an inorganic acid solution or a mixed rare earth sulfate aqueous solution obtained by sulfuric acid roasting or a mixed rare earth aqueous solution obtained by ion exchange of Nanfang Mine as the raw material to be extracted;

( II ) 将稀土皂料与用有机溶剂稀释后的空白萃取剂 A 按体积比为 0.1-20:1 的比例充分混合，直接进行稀土皂化反应，得到负载稀土的有机相和含酸稀土溶液； (II) Thoroughly mix the rare earth soap material and the blank extractant A diluted with an organic solvent in a volume ratio of 0.1-20:1, and directly perform a rare earth saponification reaction to obtain a rare earth-loaded organic phase and an acid-containing rare earth solution;

( III )将步骤（ I )得到的待萃取原料与步骤（ Π )得到的负载稀土的有机相在串级萃取槽中混合进行稀土交换纯化反应，经过多次洗涤、反萃有机相，分别得到单一稀土溶液和空白萃取剂 A, 空白萃取剂 A返回步骤（ II ) 重新利用； (III) Mix the raw material to be extracted obtained in step (I) and the rare earth-loaded organic phase obtained in step (Π) in a cascade extraction tank to perform a rare earth exchange purification reaction. After multiple washings and back-extraction of the organic phase, the respective Single rare earth solution and blank extractant A, blank extractant A returns to step (II) for reuse;

( IV )将步骤（ III )得到的单一稀土溶液与草酸混合沉淀稀土离子，分离、洗涤草酸稀土沉淀物，得到含草酸和无机酸的草酸沉淀废水； (IV) Mix the single rare earth solution obtained in step (III) with oxalic acid to precipitate rare earth ions, separate and wash the oxalic acid rare earth precipitate, and obtain oxalic acid precipitation wastewater containing oxalic acid and inorganic acid;

( V )将步骤（ IV )得到的草酸沉淀废水与用有机溶剂稀释后的萃取剂 B按体积比 0.1-20: 1的比例充分混合，得到负载草酸的有机相以及含无机酸的平衡水相，有机相中的草酸经回收后重新沉淀稀土离子； (V) Thoroughly mix the oxalic acid precipitation wastewater obtained in step (IV) and the extraction agent B diluted with an organic solvent in a volume ratio of 0.1-20:1 to obtain an oxalic acid-loaded organic phase and a balanced aqueous phase containing inorganic acid. , the oxalic acid in the organic phase is recovered and re-precipitates rare earth ions;

( VI ) 步骤（ V )得到的含无机酸的平衡水相返回步骤（ I )溶解稀土碳酸盐或氧化物，或者返回步骤（ III ) 洗涤、反萃有机相； (VI) The equilibrium aqueous phase containing inorganic acid obtained in step (V) is returned to step (I) to dissolve the rare earth carbonate or oxide, or returned to step (III) to wash and strip the organic phase;

( 11 )步骤（ II )中稀土皂化反应后得到的含酸稀土溶液采用步骤（ IV ) 中的方法沉淀稀土离子，并采用步骤（ V ) - ( VI ) 的方法处理草酸沉淀废水。 2、根据权利要求 1所述的一种物料联动循环利用的稀土分离方法，其特征在于，步骤（ II ) 中，稀土皂料与用有机溶剂稀释后的空白萃取剂 A 的体积比为 1-5: 1 ,所述萃取剂 A选自 2-乙基己基磷酸、 (11) The acid-containing rare earth solution obtained after the rare earth saponification reaction in step (II) is used to precipitate rare earth ions using the method in step (IV), and the oxalic acid precipitation wastewater is treated using the methods in steps (V)-(VI). 2. A rare earth separation method for material linkage recycling according to claim 1, characterized in that in step (II), the volume ratio of the rare earth soap material and the blank extraction agent A diluted with an organic solvent is 1- 5: 1, the extraction agent A is selected from 2-ethylhexyl phosphoric acid,

2-乙基己基膦酸单 2-乙基己基酯、二（2,4,4-三曱基戊基）膦酸和二（2-乙基己基）膦酸酯中的一种或多种，所述有机溶剂选自工业煤油、磺化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种，萃取剂 A的浓度为 0.5-1.8mol/L。 One or more of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, di(2,4,4-trimethylpentyl)phosphonic acid and di(2-ethylhexyl)phosphonate ester , the organic solvent is selected from one or more types of industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, and sec-octanol, and the concentration of the extraction agent A is 0.5-1.8 mol/L.

3、根据权利要求 1或 2所述的一种物料联动循环利用的稀土分离方法，其特征在于，步骤（ II ) 中的稀土皂料为单一稀土溶液或经萃取分组后得到的稀土溶液，其稀土含量以 REO计为 0.1-2.5mol/L。 3. A rare earth separation method for material linkage recycling according to claim 1 or 2, characterized in that the rare earth soap material in step (II) is a single rare earth solution or a rare earth solution obtained after extraction and grouping, and The rare earth content is 0.1-2.5 mol/L in terms of REO.

4、根据权利要求 3所述的一种物料联动循环利用的稀土分离方法，其特征在于，步骤（ II ) 中的稀土皂料为单一稀土溶液时，步骤（VII ) 中，稀土皂化反应得到的含酸稀土溶液与步骤（ III )得到的同种单一稀土溶液合并后采用步骤（ IV ) 中的方法沉淀稀土离子。 4. A rare earth separation method for material linkage recycling according to claim 3, characterized in that when the rare earth soap material in step (II) is a single rare earth solution, in step (VII), the rare earth soap material obtained by the rare earth saponification reaction The acid-containing rare earth solution is combined with the same single rare earth solution obtained in step (III), and then the rare earth ions are precipitated using the method in step (IV).

5、根据权利要求 1或 2所述的一种物料联动循环利用的稀土分离方法，其特征在于，步骤（ V ) 中，草酸沉淀废水与用有机溶剂稀释后的萃取剂 B的体积比为 0.5-5: 1 , 萃取剂 B为磷酸三丁酯和 /或曱基磷酸二曱庚酯，所述有机溶剂选自工业煤油、磺化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种，萃取剂 B的浓度为 0.1-1.8mol/L。 5. A rare earth separation method for material linkage recycling according to claim 1 or 2, characterized in that, in step (V), the volume ratio of the oxalic acid precipitation wastewater and the extraction agent B diluted with an organic solvent is 0.5 -5: 1, the extraction agent B is tributyl phosphate and/or dimethylheptyl methyl phosphate, and the organic solvent is selected from industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, and sec-octanol. One or more kinds, the concentration of extraction agent B is 0.1-1.8mol/L.

6、根据权利要求 1或 2所述的一种物料联动循环利用的稀土分离方法，其特征在于，步骤（ V ) 中回收草酸时，使用水反萃负载草酸的有机相，得到草酸溶液，草酸返回做步骤（ IV ) 沉淀稀土离子；或使用稀土溶液反萃负载草酸的有机相，得到草酸稀土沉淀物；或使用氨水或氢氧化钠溶液反萃负载草酸的有机相，得到草酸铵或草酸钠副产品。 6. A rare earth separation method for material linkage recycling according to claim 1 or 2, characterized in that when recovering oxalic acid in step (V), water is used to strip the organic phase loaded with oxalic acid to obtain an oxalic acid solution, oxalic acid Return to step (IV) to precipitate rare earth ions; or use a rare earth solution to back-extract the organic phase loaded with oxalic acid to obtain a rare earth oxalate precipitate; or use ammonia or sodium hydroxide solution to back-extract the organic phase loaded with oxalic acid to obtain ammonium oxalate or sodium oxalate By-products.

7、根据权利要求 1或 2所述的一种物料联动循环利用的稀土分离方法，其特征在于，步骤（VI ) 中，含无机酸的平衡水相返回步骤（ I )使用之前，预先使含无机酸的平衡水相与用有机溶剂稀释后的萃取剂 C按体积比 0.1-20: 1的比例混合萃取浓缩，经浓缩后的无机酸返回步骤（ I )使用，水相作溶料的底水或配制草酸溶液的底水或草酸稀土沉淀物的洗水循环使用。 7. A rare earth separation method for material linkage recycling according to claim 1 or 2, characterized in that in step (VI), the balanced aqueous phase containing inorganic acid is returned to step (I) before use. The equilibrium aqueous phase of the inorganic acid and the extractant C diluted with the organic solvent are mixed, extracted and concentrated in a volume ratio of 0.1-20:1. The concentrated inorganic acid is returned to step (I) for use, and the aqueous phase is used as the base of the dissolved material. Water or the bottom water for preparing the oxalic acid solution or the washing water for the oxalic acid rare earth precipitate are recycled.

8、根据权利要求 7所述的一种物料联动循环利用的稀土分离方法，其特征在于，所述萃取剂 C选自仲碳伯胺、三烷基曱胺、 N-十二烯（三烷基曱基）胺、二（ 1-异丁基 -3,5-二曱基己基）胺、二（ 1-曱基庚基）胺、 Ν,Ν- 二（ 1-曱基庚基）乙酰胺、三正辛胺、三异辛胺、三辛烷基叔胺、三月桂胺和三（2-乙基己基胺）中的一种或多种，所述有机溶剂选自工业煤油、磺化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种，萃取剂 C的浓度为 0.1-1.8mol/L。 8. A rare earth separation method for material linkage recycling according to claim 7, wherein It is characterized in that the extraction agent C is selected from secondary carbon primary amine, trialkyl methylamine, N-dodecene (trialkyl methyl) amine, di(1-isobutyl-3,5-dimethyl) Hexyl)amine, di(1-methylheptyl)amine, N,N-bis(1-methylheptyl)acetamide, tri-n-octylamine, triisooctylamine, trioctyl tertiary amine, laurel One or more of amine and tris(2-ethylhexylamine), the organic solvent is selected from one or more of industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, and sec-octanol, The concentration of extraction agent C is 0.1-1.8mol/L.

9、一种物料联动循环利用的稀土分离方法，包括溶料、萃取分离、草酸沉淀和洗涤工序，萃取分离工序包括皂化负载稀土和稀土交换纯化步骤，其特征在于，将萃取分离、草酸沉淀和洗涤工序产生的无机酸溶液或含无机酸的稀土溶液与用有机溶剂稀释后的萃取剂 C按体积比 0.1-20: 1的比例充分混合，萃取浓缩无机酸，经浓缩后的无机酸返回溶料工序循环使用，含稀土的低酸水相返回皂化负载稀土步骤，不含稀土的低酸水相作溶料的底水或配制草酸溶液的底水或草酸稀土沉淀物的洗水循环使用。 9. A rare earth separation method for material linkage recycling, including the steps of dissolving materials, extraction and separation, oxalic acid precipitation and washing. The extraction and separation process includes saponification loaded rare earth and rare earth exchange purification steps. It is characterized in that the extraction and separation, oxalic acid precipitation and The inorganic acid solution or rare earth solution containing inorganic acid produced in the washing process is fully mixed with the extraction agent C diluted with an organic solvent in a volume ratio of 0.1-20:1, and the inorganic acid is extracted and concentrated. The concentrated inorganic acid is returned to the solution. The low-acid aqueous phase containing rare earths is recycled in the saponification step of loading rare earths, and the low-acid aqueous phase containing rare earths is used as bottom water for dissolving materials or for preparing oxalic acid solutions or washing water for oxalic acid rare earth precipitates.

10、根据权利要求 9所述的一种物料联动循环利用的稀土分离方法，其特征在于，所述萃取剂 C选自仲碳伯胺、三烷基曱胺、 N-十二烯（三烷基曱基）胺、二（ 1-异丁基 -3,5-二曱基己基）胺、二（ 1-曱基庚基）胺、 Ν,Ν-二（ 1-曱基庚基）乙酰胺、三正辛胺、三异辛胺、三辛烷基叔胺、三月桂胺和三（ 2-乙基己基胺）中的一种或多种，萃取剂 C 的浓度为 0.1-1.8mol/L, 所述有机溶剂选自工业煤油、礒化煤油、溶剂油、异辛醇、仲辛醇中的一种或多种。 10. A rare earth separation method for material linkage recycling according to claim 9, characterized in that the extraction agent C is selected from the group consisting of secondary carbon primary amines, trialkyl methylamines, N-dodecene (triane (methylmethyl)amine, bis(1-isobutyl-3,5-dimethylhexyl)amine, bis(1-methylheptyl)amine, Ν,Ν-bis(1-methylheptyl)ethyl One or more of amide, tri-n-octylamine, triisooctylamine, trioctyl tertiary amine, trilaurylamine and tris(2-ethylhexylamine), the concentration of extraction agent C is 0.1-1.8 mol /L, the organic solvent is selected from one or more types of industrial kerosene, chemical kerosene, solvent oil, isooctyl alcohol, and sec-octanol.

11、根据权利要求 9或 10所述的一种物料联动循环利用的稀土分离方法，其特征在于，皂化负载稀土步骤采用稀土皂料与用有机溶剂稀释后的空白萃取剂 A按体积比为 1-20:1的比例充分混合，直接进行稀土皂化反应；所述萃取剂 A选自 2-乙基己基磷酸、 2-乙基己基膦酸单 2-乙基己基酯、二 ( 2,4,4-三曱基戊基）膦酸和二（2-乙基己基）膦酸酯中的一种或多种，萃取剂 A的浓度为 0.5-1.8mol/L。 11. A rare earth separation method for material linkage recycling according to claim 9 or 10, characterized in that the saponification loading rare earth step adopts rare earth soap material and blank extractant A diluted with an organic solvent in a volume ratio of 1 -Mix thoroughly at a ratio of 20:1, and directly perform rare earth saponification reaction; The extraction agent A is selected from 2-ethylhexylphosphoric acid, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, di(2,4, One or more of 4-trimethylpentyl)phosphonic acid and di(2-ethylhexyl)phosphonate, the concentration of extractant A is 0.5-1.8mol/L.

12、根据权利要求 11所述的一种物料联动循环利用的稀土分离方法, 其特征在于，稀土皂料为单一稀土溶液或经萃取分组后得到的稀土溶液，其稀土含量以 REO计为 0.1-2.5mol/L。 12. A rare earth separation method for material linkage recycling according to claim 11, characterized in that the rare earth soap material is a single rare earth solution or a rare earth solution obtained after extraction and grouping, and its rare earth content is 0.1-0.1 in REO. 2.5mol/L.