CN113737030B - Method for separating rare earth by using water-soluble polymer complexing agent - Google Patents
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 84
- 239000008139 complexing agent Substances 0.000 title claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920003169 water-soluble polymer Polymers 0.000 title abstract description 9
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 72
- -1 rare earth ions Chemical class 0.000 claims abstract description 56
- 229920001661 Chitosan Polymers 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 230000008929 regeneration Effects 0.000 claims abstract description 5
- 238000011069 regeneration method Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 66
- 101150020229 Apcs gene Proteins 0.000 claims description 49
- 229910052684 Cerium Inorganic materials 0.000 claims description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000026731 phosphorylation Effects 0.000 abstract 1
- 238000006366 phosphorylation reaction Methods 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101150096185 PAAS gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于稀土离子分离领域，尤其涉及一种用水溶性高分子络合剂分离稀土的方法。The invention belongs to the field of rare earth ion separation, in particular to a method for separating rare earth by using a water-soluble polymer complexing agent.
背景技术Background technique
稀土素有“工业维生素”之称，在军工、电子、石油化工等领域中发挥重要作用。溶剂萃取法是目前稀土湿法冶金工业中应用较广的稀土分离方法，具有处理容量大、反应速度快的优点，但该方法也存在一些不足之处，如对稀土的选择性分离效率低；萃取体系级数多，高达几十级甚至上百级；部分萃取剂需在强酸性条件下进行稀土萃取和反萃，酸、碱消耗量大，极易造成二次污染；对有机溶剂的需求量大，使萃取相中化学耗氧量(COD)、生物耗氧量(BOD)较高，后处理困难，同时为了提高萃取能力，通常采用氨水对有机相进行皂化，由此带来的氨氮问题也长期困扰着稀土行业。Rare earths are known as "industrial vitamins" and play an important role in military, electronics, petrochemical and other fields. Solvent extraction is the most widely used rare earth separation method in rare earth hydrometallurgy industry at present. It has the advantages of large processing capacity and fast reaction speed, but this method also has some shortcomings, such as low selective separation efficiency of rare earth; There are many stages in the extraction system, up to dozens or even hundreds of stages; some extractants need to perform rare earth extraction and stripping under strong acid conditions, and the consumption of acids and bases is large, which can easily cause secondary pollution; the demand for organic solvents The amount is large, which makes the chemical oxygen consumption (COD) and biological oxygen consumption (BOD) in the extraction phase higher, and the post-processing is difficult. At the same time, in order to improve the extraction capacity, ammonia water is usually used to saponify the organic phase, resulting in ammonia nitrogen. The problem has also long plagued the rare earth industry.
针对溶剂萃取法的缺点，本发明提出选用络合–超滤结合剪切解络耦合超滤的方法对稀土离子进行分离，以期解决现有的一系列问题。络合–超滤是利用基于含氮、磷、羰基等官能团的水溶性大分子聚合物与溶液中的金属离子络合，选择适宜的超滤膜，通过截留聚合物-金属络合物从而实现对金属离子的截留分离。剪切解络耦合超滤通过在膜室形成剪切场，尤其在靠近膜面趋于产生较大的剪切速率。当膜面剪切速率超过聚合物-稀土络合物的临界剪切速率时，聚合物-稀土络合物会解络产生聚合物络合剂和自由稀土离子，解络出的自由稀土离子则透过超滤膜，聚合物络合剂则被超滤膜截留。由于不同的聚合物-稀土络合物在剪切场中的稳定性不同，因此，采用剪切解络耦合超滤的方法通过控制膜面剪切速率可以精确分离出不同的金属离子。当所有络合物全部解络时，即可实现聚合物络合剂的再生，再生的络合剂可以重新回用于络合–剪切解络–超滤过程。与传统的溶剂萃取相比，该过程在水相中进行，无需有机溶剂，节约成本的同时解决了氨氮污染严重的问题；能实现对稀土的高选择性分离；反应过程在近中性条件下即可进行，大大减少了酸碱消耗，无二次污染，符合绿色化学理念。In view of the shortcomings of the solvent extraction method, the present invention proposes to use the method of complexation-ultrafiltration combined with shear decomplexation coupled ultrafiltration to separate rare earth ions, in order to solve a series of existing problems. Complexation-Ultrafiltration is the use of water-soluble macromolecular polymers based on functional groups such as nitrogen, phosphorus, carbonyl and other functional groups to complex metal ions in solution, select a suitable ultrafiltration membrane, and achieve by blocking polymer-metal complexes. Retention separation of metal ions. Shear decomplexation coupled with ultrafiltration tends to generate larger shear rates by forming a shear field in the membrane chamber, especially near the membrane surface. When the shear rate of the membrane surface exceeds the critical shear rate of the polymer-rare earth complex, the polymer-rare earth complex will decomplex to generate polymer complexing agent and free rare earth ions, and the decomplexed free rare earth ions are After passing through the ultrafiltration membrane, the polymer complexing agent is retained by the ultrafiltration membrane. Since different polymer-rare earth complexes have different stability in shear field, different metal ions can be precisely separated by controlling the shear rate of the membrane surface by adopting the method of shear decomplexation coupled with ultrafiltration. When all the complexes are decomplexed, the regeneration of the polymer complexing agent can be realized, and the regenerated complexing agent can be reused for the complexation-shear decomplexation-ultrafiltration process. Compared with the traditional solvent extraction, the process is carried out in the aqueous phase without organic solvents, which saves costs and solves the problem of serious ammonia nitrogen pollution; it can achieve high selective separation of rare earths; the reaction process is under near-neutral conditions. It can be carried out, which greatly reduces the consumption of acid and alkali, and has no secondary pollution, which is in line with the concept of green chemistry.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种用水溶性高分子络合剂分离稀土的方法，采用的水溶性高分子络合剂为中性磷酰化壳聚糖nPCS和酸性磷酰化壳聚糖aPCS；The purpose of the present invention is to provide a method for separating rare earth by using a water-soluble polymer complexing agent, and the water-soluble polymer complexing agents used are neutral phosphorylated chitosan nPCS and acidic phosphorylated chitosan aPCS;
其中nPCS化学结构式为：The chemical structural formula of nPCS is:
aPCS化学结构式为：
上述结构中n＝1200～3000；In the above structure, n=1200～3000;
磷酰化壳聚糖水合能力强、分子量大，且结构中同时含有P＝O基团和亚氨基，二者协同作用使磷酰化壳聚糖与其他常用的络合剂如聚丙烯酸钠(PAAS)、丙烯酸-马来酸共聚物(PMA)等相比具备更好的稀土络合能力和稀土选择性，是一种性能优良的稀土络合剂；Phosphorylated chitosan has strong hydration ability, large molecular weight, and contains P=O group and imino group at the same time. Compared with PAAS), acrylic acid-maleic acid copolymer (PMA), etc., it has better rare earth complexing ability and rare earth selectivity, and is a rare earth complexing agent with excellent performance;
具体包括以下步骤：Specifically include the following steps:
首先，在pH为3～7条件下，将一定量的中性磷酰化壳聚糖nPCS或酸性磷酰化壳聚糖aPCS加入到含稀土离子的溶液中，搅拌0.5～2.5h，使稀土离子与nPCS或aPCS充分络合，形成PCS-Re络合物；然后，根据不同PCS-Re络合物在一定条件下剪切稳定性的差异，采用剪切解络耦合超滤，实现混合稀土离子的分离和络合剂磷酰化壳聚糖的再生；First, under the condition of pH of 3-7, a certain amount of neutral phosphorylated chitosan nPCS or acidic phosphorylated chitosan aPCS was added to the solution containing rare earth ions, and stirred for 0.5 to 2.5 h to make the rare earth ions. The ions are fully complexed with nPCS or aPCS to form PCS-Re complexes; then, according to the difference in shear stability of different PCS-Re complexes under certain conditions, shear decomplexation coupled with ultrafiltration is used to realize mixed rare earth Separation of ions and regeneration of complexing agent phosphorylated chitosan;
所述的中性磷酰化壳聚糖nPCS或酸性磷酰化壳聚糖aPCS的用量，采用络合–超滤的方法，通过测定络合剂与稀土离子质量比P/Re与稀土离子截留率R的关系来确定：在一定pH条件下进行络合–超滤时，稀土离子截留率随着P/Re的增加而增加，当R达到最大值不再随P/Re的增加而增加时，即为临界的P/Re值，据此确定络合剂的加入量；The dosage of the neutral phosphorylated chitosan nPCS or the acid phosphorylated chitosan aPCS is determined by the method of complexation-ultrafiltration, and the mass ratio P/Re of the complexing agent to the rare earth ion and the interception of the rare earth ion are measured. The relationship between the ratio R to determine: when complexation-ultrafiltration is carried out under a certain pH condition, the rare earth ion rejection increases with the increase of P/Re, and when R reaches the maximum value, it no longer increases with the increase of P/Re , which is the critical P/Re value, according to which the addition amount of the complexing agent is determined;
所述的PCS-Re络合物在一定pH条件下的剪切稳定性大小，采用PCS-Re络合物的临界剪切速率γc(PCS-Re络合物保持稳定所能承受的最大剪切速率)来表示，根据膜面剪切速率与稀土离子截留率的关系来确定：当膜面剪切速率小于PCS-Re络合物的临界剪切速率时，PCS-Re络合物维持稳定，稀土离子的截留率维持不变；当膜面剪切速率大于PCS-Re络合物的临界剪切速率时，PCS-Re络合物解络成聚合物络合剂和自由稀土离子，自由稀土离子可透过超滤膜，稀土离子的截留率急剧下降。The shear stability of the PCS-Re complex under a certain pH condition is determined by the critical shear rate γ c of the PCS-Re complex (the maximum shear rate that the PCS-Re complex can withstand when it remains stable). It is determined according to the relationship between the shear rate of the membrane surface and the rejection rate of rare earth ions: when the shear rate of the membrane surface is less than the critical shear rate of the PCS-Re complex, the PCS-Re complex remains stable. , the retention rate of rare earth ions remains unchanged; when the shear rate of the membrane surface is greater than the critical shear rate of the PCS-Re complex, the PCS-Re complex decomplexes into a polymer complexing agent and free rare earth ions, and the free Rare earth ions can pass through the ultrafiltration membrane, and the rejection rate of rare earth ions drops sharply.
所述的一种用水溶性高分子络合剂分离稀土的方法，其特征在于：用中性磷酰化壳聚糖nPCS作络合剂，根据一定pH和温度条件下，不同nPCS-Re络合物临界剪切速率的差异，通过调整膜面剪切速率耦合超滤实现各稀土离子的有序分离；The method for separating rare earth by using a water-soluble polymer complexing agent is characterized in that: using neutral phosphorylated chitosan nPCS as the complexing agent, according to certain pH and temperature conditions, different nPCS-Re complexed The difference of the critical shear rate of the material can be adjusted, and the orderly separation of rare earth ions can be realized by adjusting the shear rate of the membrane surface and coupled with ultrafiltration;
在常温、pH为5条件下，用nPCS作络合剂时，nPCS与La、Ce、Nd形成的络合物nPCS-La、nPCS-Ce和nPCS-Nd的临界剪切速率分别为8.86×104s-1、9.91×104s-1、1.09×105s-1。先控制膜面剪切速率8.86×104s-1<γ<9.91×104s-1，nPCS-La解络，超滤分离出La；然后控制膜面剪切速率9.91×104s-1<γ<1.09×105s-1，nPCS-Ce解络，超滤分离出Ce；最后控制膜面剪切速率γ>1.09×105s-1，nPCS-Nd解络，超滤分离出Nd，同时获得再生的nPCS，再生的nPCS可继续进行稀土离子的络合；At room temperature and pH 5, when nPCS is used as a complexing agent, the critical shear rates of the complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS with La, Ce, and Nd are 8.86×10 4 s -1 , 9.91×10 4 s -1 , 1.09×10 5 s -1 . First control the shear rate of the membrane surface to 8.86×10 4 s -1 <γ<9.91×10 4 s -1 , nPCS-La decomplexes and separates La by ultrafiltration; then control the shear rate of the membrane surface to 9.91×10 4 s - 1 <γ<1.09×10 5 s -1 , nPCS-Ce decomplexed, and Ce was separated by ultrafiltration; finally, the membrane shear rate was controlled to γ>1.09×10 5 s -1 , nPCS-Nd decomplexed, and ultrafiltration separated Nd is extracted, and regenerated nPCS is obtained at the same time, and the regenerated nPCS can continue to complex rare earth ions;
在常温、pH为6条件下，用nPCS作络合剂时，nPCS与La、Ce、Nd形成的络合物nPCS-La、nPCS-Ce和nPCS-Nd的临界剪切速率分别为1.02×105s-1、1.21×105s-1、1.33×105s-1。先控制膜面剪切速率1.02×105s-1<γ<1.21×105s-1，nPCS-La解络，超滤分离出La；然后控制膜面剪切速率1.21×105s-1<γ<1.33×105s-1，nPCS-Ce解络，超滤分离出Ce；最后控制膜面剪切速率γ>1.33×105s-1，nPCS-Nd解络，超滤分离出Nd，同时获得再生的nPCS，再生的nPCS可继续进行稀土离子的络合；At room temperature and pH 6, when nPCS is used as a complexing agent, the critical shear rates of the complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS with La, Ce, and Nd are 1.02×10 5 s -1 , 1.21×10 5 s -1 , 1.33×10 5 s -1 . First control the shear rate of the membrane surface to 1.02×10 5 s -1 <γ<1.21×10 5 s -1 , nPCS-La decomplexes and separates La by ultrafiltration; then control the shear rate of the membrane surface to 1.21×10 5 s - 1 <γ<1.33×10 5 s -1 , nPCS-Ce decomplexed, and Ce was separated by ultrafiltration; finally, the membrane shear rate was controlled to γ>1.33×10 5 s -1 , nPCS-Nd decomplexed, and ultrafiltration separated Nd is extracted, and regenerated nPCS is obtained at the same time, and the regenerated nPCS can continue to complex rare earth ions;
在常温、pH为7条件下，用nPCS作络合剂时，nPCS与La、Ce、Nd形成的络合物nPCS-La、nPCS-Ce和nPCS-Nd的临界剪切速率分别为1.31×105s-1、1.63×105s-1、1.79×105s-1。先控制膜面剪切速率1.31×105s-1<γ<1.63×105s-1，nPCS-La解络，超滤分离出La；然后控制膜面剪切速率1.63×105s-1<γ<1.79×105s-1，nPCS-Ce解络，超滤分离出Ce；最后控制膜面剪切速率γ>1.79×105s-1，nPCS-Nd解络，超滤分离出Nd，同时获得再生的nPCS，再生的nPCS可继续进行稀土离子的络合。At room temperature and pH 7, when nPCS is used as a complexing agent, the critical shear rates of the complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS with La, Ce, and Nd are 1.31×10 5 s -1 , 1.63×10 5 s -1 , 1.79×10 5 s -1 . First control the shear rate of the membrane surface to 1.31×10 5 s -1 <γ<1.63×10 5 s -1 , nPCS-La decomplexes and separates La by ultrafiltration; then control the shear rate of the membrane surface to 1.63×10 5 s - 1 <γ<1.79×10 5 s -1 , nPCS-Ce decomplexed, and Ce was separated by ultrafiltration; finally, the membrane shear rate was controlled to γ>1.79×10 5 s -1 , nPCS-Nd was decomplexed, and ultrafiltration was performed Nd is extracted, and regenerated nPCS is obtained at the same time, and the regenerated nPCS can continue to complex rare earth ions.
所述的一种用水溶性高分子络合剂分离稀土的方法，其特征在于：用酸性磷酰化壳聚糖aPCS作络合剂，根据一定pH和温度条件下，不同aPCS-Re络合物临界剪切速率的差异，通过调整膜面剪切速率耦合超滤实现各稀土离子的有序分离；The method for separating rare earth by using a water-soluble polymer complexing agent is characterized in that: using acidic phosphorylated chitosan aPCS as the complexing agent, according to certain pH and temperature conditions, different aPCS-Re complexes The difference in critical shear rate, the orderly separation of rare earth ions can be achieved by adjusting the shear rate of the membrane surface coupled with ultrafiltration;
在常温、pH为3条件下，用aPCS作络合剂时，aPCS与La、Ce、Nd形成的络合物aPCS-La、aPCS-Ce和aPCS-Nd的临界剪切速率分别为4.74×104、5.20×104、6.45×104s-1。先控制膜面剪切速率4.74×104s-1<γ<5.20×104s-1，aPCS-La解络，超滤分离出La；然后控制膜面剪切速率5.20×104s-1<γ<6.45×104s-1，aPCS-Ce解络，超滤分离出Ce；最后控制膜面剪切速率γ>6.45×104s-1，aPCS-Nd解络，超滤分离出Nd，同时获得再生的aPCS，再生的aPCS可继续进行稀土离子的络合；At room temperature and pH 3, when aPCS is used as a complexing agent, the critical shear rates of the complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by aPCS with La, Ce and Nd are 4.74×10 4 , 5.20×10 4 , 6.45×10 4 s −1 . First control the shear rate of the membrane surface to 4.74×10 4 s -1 <γ<5.20×10 4 s -1 , aPCS-La decomplexes and separates La by ultrafiltration; then control the shear rate of the membrane surface to 5.20×10 4 s - 1 <γ<6.45×10 4 s -1 , aPCS-Ce decomplexed, and Ce was separated by ultrafiltration; finally, the membrane shear rate was controlled to γ>6.45×10 4 s -1 , aPCS-Nd was decomplexed, and ultrafiltration was performed Nd is extracted, and regenerated aPCS is obtained at the same time, and the regenerated aPCS can continue to complex rare earth ions;
在常温、pH为4条件下，用aPCS作络合剂时，aPCS与La、Ce、Nd形成的络合物aPCS-La、aPCS-Ce和aPCS-Nd的临界剪切速率分别为6.71×104、7.39×104、8.98×104s-1。先控制膜面剪切速率6.71×104s-1<γ<7.39×104s-1，aPCS-La解络，超滤分离出La；然后控制膜面剪切速率7.39×104s-1<γ<8.98×104s-1，aPCS-Ce解络，超滤分离出Ce；最后控制膜面剪切速率γ>8.98×104s-1，aPCS-Nd解络，超滤分离出Nd，同时获得再生的aPCS，再生的aPCS可继续进行稀土离子的络合；At room temperature and pH 4, when aPCS is used as a complexing agent, the critical shear rates of the complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by aPCS with La, Ce and Nd are 6.71×10 4 , 7.39×10 4 , 8.98×10 4 s −1 . First control the shear rate of the membrane surface to 6.71×10 4 s -1 <γ<7.39×10 4 s -1 , aPCS-La decomplexes and separates La by ultrafiltration; then control the shear rate of the membrane surface to 7.39×10 4 s - 1 <γ<8.98×10 4 s -1 , aPCS-Ce decomplexed, and Ce was separated by ultrafiltration; finally, the membrane shear rate was controlled to γ>8.98×10 4 s -1 , aPCS-Nd was decomplexed, and ultrafiltration was performed Nd is extracted, and regenerated aPCS is obtained at the same time, and the regenerated aPCS can continue to complex rare earth ions;
在常温、pH为5条件下，用aPCS作络合剂时，aPCS与La、Ce、Nd形成的络合物aPCS-La、aPCS-Ce和aPCS-Nd的临界剪切速率分别为9.29×104、1.04×105、1.13×105s-1。先控制膜面剪切速率9.29×104s-1<γ<1.04×105s-1，aPCS-La解络，超滤分离出La；然后控制膜面剪切速率1.04×105s-1<γ<1.13×105s-1，aPCS-Ce解络，超滤分离出Ce；最后控制膜面剪切速率γ>1.13×105s-1，aPCS-Nd解络，超滤分离出Nd，同时获得再生的aPCS，再生的aPCS可继续进行稀土离子的络合。At room temperature and pH 5, when aPCS is used as a complexing agent, the critical shear rates of the complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by aPCS with La, Ce, and Nd are 9.29×10 4 , 1.04×10 5 , 1.13×10 5 s −1 . First control the shear rate of the membrane surface to 9.29×10 4 s -1 <γ<1.04×10 5 s -1 , aPCS-La decomplexes and separates La by ultrafiltration; then control the shear rate of the membrane surface to 1.04×10 5 s -1 1 <γ<1.13×10 5 s -1 , aPCS-Ce decomplexed, and Ce was separated by ultrafiltration; finally, the membrane shear rate was controlled to γ>1.13×10 5 s -1 , aPCS-Nd decomplexed, and ultrafiltration separated Nd is extracted, and regenerated aPCS is obtained at the same time, and the regenerated aPCS can continue to complex rare earth ions.
本发明具有以下优点：The present invention has the following advantages:
(1)采用磷酰化壳聚糖作为络合剂分离稀土，磷酰化壳聚糖与常用水溶性高分子络合剂相比，具备优越的稀土络合能力和稀土选择性，将其作为络合剂应用于稀土分离过程，稀土离子截留率可达99％以上，提高了分离效率；(1) Phosphorylated chitosan is used as a complexing agent to separate rare earths. Compared with common water-soluble polymer complexing agents, phosphorylated chitosan has superior rare earth complexing ability and rare earth selectivity. The complexing agent is used in the rare earth separation process, and the rare earth ion retention rate can reach more than 99%, which improves the separation efficiency;
(2)采用络合–超滤结合剪切解络耦合超滤方法进行稀土分离，与传统的溶剂萃取法相比，该方法具有选择性分离效果好，酸碱消耗量小、无二次污染，无需有机溶剂、节约成本的同时减少氨氮污染的优点；(2) Rare earth separation is carried out by complexation-ultrafiltration combined with shear decomplexation coupling ultrafiltration. Compared with the traditional solvent extraction method, this method has good selective separation effect, small acid-base consumption and no secondary pollution. The advantages of eliminating the need for organic solvents, saving costs and reducing ammonia nitrogen pollution;
(3)剪切解络耦合超滤过程能一次性实现混合稀土的选择性分离和络合剂磷酰化壳聚糖的再生，经济环保。(3) The shear decomplexing coupled ultrafiltration process can realize the selective separation of mixed rare earths and the regeneration of the complexing agent phosphorylated chitosan at one time, which is economical and environmentally friendly.
具体实施方式Detailed ways
下面结合实例对本发明做进一步描述。The present invention will be further described below in conjunction with examples.
实施例1Example 1
常温下，配制La、Ce质量浓度均为10mg/L的混合离子溶液，向溶液中加入nPCS，其中nPCS与混合稀土离子质量比为10：1，调节溶液pH为5，搅拌0.5h，得到pH为5、P/Re为10的含nPCS-La和nPCS-Ce络合物的溶液。根据此条件下两种络合物剪切稳定性的差异，先控制膜面剪切速率为8.86×104s-1<γ<9.91×104s-1，nPCS-La失稳解络，nPCS-Ce未解络，超滤分离出La；然后调节膜面剪切速率大于9.91×104s-1，nPCS-Ce络合物解络，超滤分离出Ce，同时获得再生的nPCS，再生的nPCS可继续进行稀土离子的络合。At room temperature, a mixed ion solution with both La and Ce mass concentrations of 10 mg/L was prepared, and nPCS was added to the solution, wherein the mass ratio of nPCS and mixed rare earth ions was 10:1, the pH of the solution was adjusted to 5, and the pH was stirred for 0.5 h to obtain pH A solution containing nPCS-La and nPCS-Ce complexes with a P/Re of 5 and a P/Re of 10. According to the difference in shear stability of the two complexes under these conditions, the shear rate of the membrane surface was first controlled to be 8.86×10 4 s -1 <γ<9.91×10 4 s -1 , and the nPCS-La destabilized and decomplexed, The nPCS-Ce complex was not decomplexed, and La was separated by ultrafiltration; then, the shear rate of the membrane surface was adjusted to be greater than 9.91×10 4 s -1 , the nPCS-Ce complex was decomplexed, Ce was separated by ultrafiltration, and the regenerated nPCS was obtained at the same time. The regenerated nPCS can proceed to complexation of rare earth ions.
实施例2Example 2
常温下，配制Ce、Nd质量浓度均为20mg/L的混合离子溶液，向溶液中加入nPCS，其中nPCS与混合稀土离子质量比为10：1，调节溶液pH为6，搅拌1h，得到pH为6、P/Re为10的nPCS-Ce和nPCS-Nd混合络合物溶液。根据此条件下两种络合物剪切稳定性的差异，先控制膜面剪切速率为1.21×105s-1<γ<1.33×105s-1，nPCS-Ce失稳解络，nPCS-Nd未解络，超滤分离出Ce；然后调节膜面剪切速率至1.33×105s-1以上，nPCS-Nd络合物解络，超滤分离出Nd，同时获得再生的nPCS，再生的nPCS可继续进行稀土离子的络合。At room temperature, a mixed ion solution with a mass concentration of Ce and Nd of 20 mg/L was prepared, and nPCS was added to the solution, wherein the mass ratio of nPCS and mixed rare earth ions was 10:1, the pH of the solution was adjusted to 6, and the solution was stirred for 1 h to obtain a pH of 6. A mixed complex solution of nPCS-Ce and nPCS-Nd with P/Re of 10. According to the difference in shear stability of the two complexes under these conditions, the shear rate of the membrane surface was first controlled to be 1.21×10 5 s -1 <γ<1.33×10 5 s -1 , and the nPCS-Ce destabilized and decomplexed, The nPCS-Nd was not decomplexed, and Ce was separated by ultrafiltration; then, the shear rate of the membrane surface was adjusted to more than 1.33×10 5 s -1 , the nPCS-Nd complex was decomplexed, Nd was separated by ultrafiltration, and the regenerated nPCS was obtained at the same time. , the regenerated nPCS can continue the complexation of rare earth ions.
实施例3Example 3
常温下，配制La、Ce、Nd质量浓度均为15mg/L的溶液，向溶液中加入一nPCS，其中nPCS与混合稀土离子质量比为10：1，调节溶液pH为7，搅拌2.5h，得到pH为7、P/Re为10的nPCS-La、nPCS-Ce和nPCS-Nd混合络合物溶液。根据此条件下三种络合物剪切稳定性的差异，先控制膜面剪切速率1.31×105s-1<γ<1.63×105s-1，nPCS-La失稳解络，nPCS-Ce和nPCS-Nd未解络，超滤分离出La；然后调节膜面剪切速率为1.63×105s-1<γ<1.79×105s-1，nPCS-Ce失稳解络，nPCS-Nd未解络，超滤分离出Ce；最后调节膜面剪切速率至1.79×105s-1以上，nPCS-Nd络合物解络，超滤分离出Nd，同时获得再生的nPCS，再生的nPCS可继续进行稀土离子的络合。At room temperature, prepare a solution with a mass concentration of La, Ce, and Nd of 15 mg/L, add one nPCS to the solution, wherein the mass ratio of nPCS and mixed rare earth ions is 10:1, adjust the pH of the solution to 7, and stir for 2.5 h to obtain Mixed complex solutions of nPCS-La, nPCS-Ce and nPCS-Nd with pH of 7 and P/Re of 10. According to the difference in shear stability of the three complexes under these conditions, the shear rate of the membrane surface was first controlled to be 1.31×10 5 s -1 <γ<1.63×10 5 s -1 , nPCS-La destabilized and decomplexed, nPCS -Ce and nPCS-Nd were not decomplexed, and La was separated by ultrafiltration; then the shear rate of the membrane surface was adjusted to 1.63×10 5 s -1 <γ<1.79×10 5 s -1 , nPCS-Ce was destabilized and decomplexed, The nPCS-Nd was not decomplexed, and Ce was separated by ultrafiltration; finally, the shear rate of the membrane surface was adjusted to more than 1.79×10 5 s -1 , the nPCS-Nd complex was decomplexed, Nd was separated by ultrafiltration, and the regenerated nPCS was obtained at the same time. , the regenerated nPCS can continue the complexation of rare earth ions.
实施例4Example 4
常温下，配制La、Ce质量浓度均为10mg/L的混合离子溶液，向溶液中加入aPCS，其中aPCS与混合稀土离子质量比为8：1，调节溶液pH为3，搅拌1.5h，得到pH为3、P/Re为8的aPCS-La和aPCS-Ce混合络合物溶液。根据此条件下两种络合物剪切稳定性的差异，先控制膜面剪切速率为4.74×104s-1<γ<5.20×104s-1，aPCS-La失稳解络，aPCS-Ce未解络超滤分离出La；然后调节膜面剪切速率至5.20×104s-1以上，aPCS-Ce络合物解络，超滤分离出Ce，同时获得再生的aPCS，再生的aPCS可继续进行稀土离子的络合。At room temperature, a mixed ion solution with La and Ce mass concentrations of 10 mg/L was prepared, aPCS was added to the solution, wherein the mass ratio of aPCS and mixed rare earth ions was 8:1, the pH of the solution was adjusted to 3, and the pH was stirred for 1.5 h to obtain pH is a mixed complex solution of aPCS-La and aPCS-Ce with a P/Re of 3 and 8. According to the difference in shear stability of the two complexes under these conditions, the shear rate of the membrane surface was controlled to be 4.74×10 4 s -1 <γ<5.20×10 4 s -1 , and aPCS-La destabilized and decomplexed, La was separated by ultrafiltration without decomplexation of aPCS-Ce; then the shear rate of the membrane surface was adjusted to above 5.20×10 4 s -1 , the aPCS-Ce complex was decomplexed, Ce was separated by ultrafiltration, and the regenerated aPCS was obtained at the same time. The regenerated aPCS can proceed to complexation of rare earth ions.
实施例5Example 5
常温下，配制Ce、Nd质量浓度均为15mg/L的混合离子溶液，向溶液中加入aPCS，其中aPCS与混合稀土离子质量比为8：1，调节溶液pH为4，搅拌2h，得到pH为4、P/Re为8的aPCS-Ce和aPCS-Nd混合络合物溶液。根据此条件下两种络合物剪切稳定性的差异，先控制膜面剪切速率为7.39×104s-1<γ<8.98×104s-1，aPCS-Ce失稳解络，aPCS-Nd未解络，超滤分离出Ce；然后调节膜面剪切速率至8.98×104s-1以上，aPCS-Nd络合物解络，超滤分离出Nd，同时获得再生的aPCS，再生的aPCS可继续进行稀土离子的络合。At room temperature, a mixed ion solution with both Ce and Nd mass concentrations of 15 mg/L was prepared, aPCS was added to the solution, wherein the mass ratio of aPCS and mixed rare earth ions was 8:1, the pH of the solution was adjusted to 4, and stirred for 2 hours to obtain a pH of 4. APCS-Ce and aPCS-Nd mixed complex solution with P/Re of 8. According to the difference in shear stability of the two complexes under this condition, the shear rate of the membrane surface was first controlled to be 7.39×10 4 s -1 <γ<8.98×10 4 s -1 , the aPCS-Ce destabilized and decomplexed, The aPCS-Nd was not decomplexed, and Ce was separated by ultrafiltration; then the shear rate of the membrane surface was adjusted to over 8.98×10 4 s -1 , the aPCS-Nd complex was decomplexed, Nd was separated by ultrafiltration, and the regenerated aPCS was obtained at the same time. , the regenerated aPCS can continue the complexation of rare earth ions.
实施例6Example 6
常温下，配制La、Ce、Nd质量浓度均为20mg/L的混合离子溶液，向溶液中加入aPCS，其中aPCS与混合稀土离子质量比为8：1，调节溶液pH为5，搅拌2.5h，得到pH为5、P/Re为8的aPCS-La、aPCS-Ce和aPCS-Nd混合络合物溶液。根据此条件下三种络合物剪切稳定性的差异，先控制膜面剪切速率9.29×104s-1<γ<1.04×105s-1，aPCS-La失稳解络，aPCS-Ce和aPCS-Nd未解络，超滤分离出La；然后调节膜面剪切速率为1.04×105s-1<γ<1.13×105s-1，aPCS-Ce失稳解络，aPCS-Nd未解络，超滤分离出Ce；最后调节膜面剪切速率至1.13×105s-1以上，aPCS-Nd络合物解络，超滤分离出Nd，同时获得再生的aPCS，再生的aPCS可继续进行稀土离子的络合。At room temperature, a mixed ion solution with La, Ce, and Nd mass concentrations of 20 mg/L was prepared, aPCS was added to the solution, wherein the mass ratio of aPCS and mixed rare earth ions was 8:1, the pH of the solution was adjusted to 5, and the solution was stirred for 2.5 h. A mixed complex solution of aPCS-La, aPCS-Ce and aPCS-Nd with a pH of 5 and a P/Re of 8 was obtained. According to the difference in shear stability of the three complexes under this condition, the shear rate of the membrane surface was controlled to be 9.29×10 4 s -1 <γ<1.04×10 5 s -1 , aPCS-La destabilized and decomplexed, aPCS -Ce and aPCS-Nd were not decomplexed, and La was separated by ultrafiltration; then the shear rate of the membrane surface was adjusted to 1.04×10 5 s -1 <γ<1.13×10 5 s -1 , aPCS-Ce destabilized and decomplexed, aPCS-Nd was not decomplexed, and Ce was separated by ultrafiltration; finally, the shear rate of the membrane surface was adjusted to more than 1.13×10 5 s -1 , the aPCS-Nd complex was decomplexed, Nd was separated by ultrafiltration, and the regenerated aPCS was obtained at the same time. , the regenerated aPCS can continue the complexation of rare earth ions.
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