CN113737030B - Method for separating rare earth by using water-soluble polymer complexing agent - Google Patents
Method for separating rare earth by using water-soluble polymer complexing agent Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 86
- 239000008139 complexing agent Substances 0.000 title claims abstract description 44
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 12
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 61
- -1 rare earth ions Chemical class 0.000 claims abstract description 57
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 229920001661 Chitosan Polymers 0.000 claims abstract description 25
- 230000008878 coupling Effects 0.000 claims abstract description 10
- 238000010168 coupling process Methods 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 238000010008 shearing Methods 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 5
- 238000011069 regeneration method Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 69
- 101150020229 Apcs gene Proteins 0.000 claims description 45
- 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
- 238000010668 complexation reaction Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 abstract description 10
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- 230000026731 phosphorylation Effects 0.000 abstract description 2
- 238000006366 phosphorylation reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- 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
- 238000000638 solvent extraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 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
- 235000011114 ammonium hydroxide Nutrition 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
- 230000000368 destabilizing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009854 hydrometallurgy Methods 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
- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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Abstract
The invention discloses a method for separating rare earth by using a water-soluble polymer complexing agent. Uses the Phosphorylation Chitosan (PCS) as the complexing agent, utilizes the difference of the shearing stability of PCS-Re complex compound generated by complexing PCS and different rare earth ions, and adopts shearing decomplexation coupling ultrafiltration to separate the mixed rare earth ion solution. The complex agent phosphorylated chitosan used in the invention has the advantages of large molecular weight, good hydration property, strong rare earth complexing ability and the like. The method for separating the rare earth ion solution has the outstanding advantages of high single-stage selective separation efficiency, green and environment-friendly process, no secondary pollution and the like, and can realize the regeneration of the water-soluble polymer complexing agent while separating the rare earth.
Description
Technical Field
The invention belongs to the field of rare earth ion separation, and particularly relates to a method for separating rare earth by using a water-soluble polymer complexing agent.
Background
Rare earth elements are called industrial vitamins and play an important role in the fields of military industry, electronics, petrochemical industry and the like. The solvent extraction method is a rare earth separation method which is widely applied in the rare earth hydrometallurgy industry at present, has the advantages of large processing capacity and high reaction speed, but has some defects, such as low selective separation efficiency of rare earth; the extraction system has more stages, and the extraction system can reach dozens of stages or even hundreds of stages; part of the extractant needs to be subjected to rare earth extraction and back extraction under a strong acid condition, so that the consumption of acid and alkali is high, and secondary pollution is easily caused; the demand for organic solvent is large, so that the Chemical Oxygen Demand (COD) and the Biological Oxygen Demand (BOD) in the extraction phase are high, the post-treatment is difficult, and meanwhile, in order to improve the extraction capacity, ammonia water is usually adopted to saponify the organic phase, so that the ammonia nitrogen problem also troubles the rare earth industry for a long time.
Aiming at the defects of the solvent extraction method, the invention provides a method for separating rare earth ions by combining complexation-ultrafiltration with shearing and decomplexing coupling ultrafiltration so as to solve a series of existing problems. The complexing-ultrafiltration is to utilize water-soluble macromolecular polymer containing functional groups such as nitrogen, phosphorus, carbonyl and the like to complex with metal ions in a solution, select a proper ultrafiltration membrane and intercept and separate the metal ions by intercepting the polymer-metal complex. Shear-decomplexed ultrafiltration tends to produce large shear rates by creating a shear field in the membrane compartment, especially near the membrane face. When the membrane surface shear rate exceeds the critical shear rate of the polymer-rare earth complex, the polymer-rare earth complex is decomplexed to generate a polymer complexing agent and free rare earth ions, the decomplexed free rare earth ions penetrate through the ultrafiltration membrane, and the polymer complexing agent is intercepted by the ultrafiltration membrane. Because different polymer-rare earth complexes have different stability in a shear field, different metal ions can be accurately separated by adopting a shear decomplexed coupling ultrafiltration method through controlling the membrane surface shear rate. When all the complexes are decomplexed, the regeneration of the polymer complexing agent can be realized, and the regenerated complexing agent can be reused in the complexation-shearing decomplexation-ultrafiltration process. Compared with the traditional solvent extraction, the process is carried out in a water phase, an organic solvent is not needed, the cost is saved, and the problem of serious ammonia nitrogen pollution is solved; the high-selectivity separation of rare earth can be realized; the reaction process can be carried out under a near-neutral condition, so that the consumption of acid and alkali is greatly reduced, secondary pollution is avoided, and the green chemical concept is met.
Disclosure of Invention
The invention aims to provide a method for separating rare earth by using a water-soluble polymer complexing agent, which adopts neutral phosphorylated chitosan nPCS and acidic phosphorylated chitosan aPCS as the water-soluble polymer complexing agent;
wherein the chemical structural formula of nPCS is as follows:
aPCS has a chemical structural formula as follows:
in the structure, n is 1200-3000;
the phosphorylated chitosan has strong hydration capability and large molecular weight, and simultaneously contains P ═ O group and imino group in the structure, and the phosphorylation chitosan and other commonly used complexing agents such as sodium Polyacrylate (PAAS), acrylic acid-maleic acid copolymer (PMA) and the like have better rare earth complexing capability and rare earth selectivity under the synergistic action of the P ═ O group and the imino group, so that the phosphorylated chitosan is a rare earth complexing agent with excellent performance;
the method specifically comprises the following steps:
firstly, under the condition that the pH value is 3-7, adding a certain amount of neutral phosphorylated chitosan nPCS or acidic phosphorylated chitosan aPCS into a solution containing rare earth ions, and stirring for 0.5-2.5 h to ensure that the rare earth ions and the nPCS or the aPCS are fully complexed to form a PCS-Re complex; then, according to the difference of the shearing stability of different PCS-Re complexes under certain conditions, the separation of mixed rare earth ions and the regeneration of the complex agent phosphorylated chitosan are realized by adopting shearing decomplexation coupling ultrafiltration;
the dosage of the neutral phosphorylated chitosan nPCS or the acidic phosphorylated chitosan aPCS is determined by measuring the relationship between the mass ratio P/Re of the complexing agent to the rare earth ions and the rare earth ion retention rate R by adopting a complexing-ultrafiltration method: when complexation-ultrafiltration is carried out under a certain pH condition, the rare earth ion retention rate increases with the increase of P/Re, and when the maximum value of R is reached and does not increase with the increase of P/Re, the value is the critical P/Re value, and the addition amount of the complexing agent is determined according to the critical P/Re value;
the PCS-Re complex has the shear stability under certain pH condition, and the critical shear rate gamma of the PCS-Re complex is adoptedc(maximum shear rate that the PCS-Re complex can bear when kept stable) and is determined according to the relationship between the membrane surface shear rate and the rare earth ion rejection rate: when the membrane surface shear rate is less than the critical shear rate of the PCS-Re complex, the PCS-Re complex is kept stable, and the retention rate of rare earth ions is kept unchanged; when the membrane surface shear rate is greater than the critical shear rate of the PCS-Re complex, the PCS-Re complex is decomplexed into the polymer complexing agent and the free rare earth ions, the free rare earth ions can permeate the ultrafiltration membrane, and the rejection rate of the rare earth ions is sharply reduced.
The method for separating rare earth by using the water-soluble polymer complexing agent is characterized by comprising the following steps of: using neutral phosphorylated chitosan nPCS as a complexing agent, and realizing the ordered separation of rare earth ions by adjusting membrane surface shear rate coupling ultrafiltration according to the difference of critical shear rates of different nPCS-Re complexes under certain pH and temperature conditions;
under the conditions of normal temperature and pH 5, when nPCS is used as a complexing agent, the critical shear rates of complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS and La, Ce and Nd are respectively 8.86 multiplied by 104s-1、9.91×104s-1、1.09×105s-1. Firstly, controlling the membrane surface shear rate to be 8.86 multiplied by 104s-1<γ<9.91×104s-1nPCS-La decomplexes and La is separated by ultrafiltration; then controlling the membrane surface shear rate to be 9.91 multiplied by 104s-1<γ<1.09×105s-1nPCS-Ce decomplexes and is ultrafiltered to separate Ce; finally controlling the membrane surface shear rate gamma>1.09×105s-1The nPCS-Nd is subjected to decomplexing, Nd is separated by ultrafiltration, and regenerated nPCS is obtained at the same time, and can be used for continuously complexing rare earth ions;
under the conditions of normal temperature and pH 6 and with nPCS as complexing agent, the critical shear rates of nPCS, nPCS-La, nPCS-Ce and nPCS-Nd complexes formed by nPCS and La, Ce and Nd are respectively 1.02 multiplied by 105s-1、1.21×105s-1、1.33×105s-1. Firstly controlling the membrane surface shear rate to be 1.02 multiplied by 105s-1<γ<1.21×105s-1nPCS-La decomplexes, and La is separated by ultrafiltration; then controlling the membrane surface shear rate to be 1.21 multiplied by 105s-1<γ<1.33×105s-1nPCS-Ce decomplexes and is ultrafiltered to separate Ce; finally controlling the membrane surface shear rate gamma>1.33×105s-1The nPCS-Nd is subjected to decomplexing, Nd is separated out through ultrafiltration, and regenerated nPCS is obtained at the same time, and the regenerated nPCS can be used for continuously complexing rare earth ions;
under the conditions of normal temperature and pH value of 7, when nPCS is used as a complexing agent, the critical shear rates of complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS and La, Ce and Nd are respectively 1.31 multiplied by 105s-1、1.63×105s-1、1.79×105s-1. The membrane surface shear rate is firstly controlled to be 1.31 multiplied by 105s-1<γ<1.63×105s-1nPCS-La decomplexes, and La is separated by ultrafiltration; then controlling the membrane surface shear rate to be 1.63105s-1<γ<1.79×105s-1nPCS-Ce decomplexes and is ultrafiltered to separate Ce; finally controlling the membrane surface shear rate gamma>1.79×105s-1And (3) decomplexing nPCS-Nd, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated nPCS which can continue to perform complexation of rare earth ions.
The method for separating rare earth by using the water-soluble polymer complexing agent is characterized by comprising the following steps: using acid phosphorylated chitosan aPCS as a complexing agent, and realizing the ordered separation of rare earth ions by adjusting membrane surface shear rate coupling ultrafiltration according to the difference of different aPCS-Re complex critical shear rates under certain pH and temperature conditions;
under the conditions of normal temperature and pH value of 3, when aPCS is used as a complexing agent, the critical shear rates of complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by the aPCS and La, Ce and Nd are respectively 4.74 multiplied by 104、5.20×104、6.45×104s-1. The membrane surface shear rate is firstly controlled to be 4.74 multiplied by 104s-1<γ<5.20×104s-1Decomplexation of aPCS-La, and ultrafiltration separation of La; then controlling the membrane surface shear rate to be 5.20 multiplied by 104s-1<γ<6.45×104s-1aPCS-Ce is decomplexed and subjected to ultrafiltration separation to obtain Ce; finally controlling the membrane surface shear rate gamma>6.45×104s-1Decomplexing aPCS-Nd, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated aPCS which can continue to perform complexation of rare earth ions;
under the conditions of normal temperature and pH value of 4, when aPCS is used as a complexing agent, the critical shear rates of complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by the aPCS and La, Ce and Nd are respectively 6.71 multiplied by 104、7.39×104、8.98×104s-1. The membrane surface shear rate is firstly controlled to be 6.71 multiplied by 104s-1<γ<7.39×104s-1Decomplexation of aPCS-La, and ultrafiltration separation of La; then controlling the membrane surface shear rate to be 7.39 multiplied by 104s-1<γ<8.98×104s-1aPCS-Ce is decomplexed and subjected to ultrafiltration separation to obtain Ce; finally controlling the membrane surface shear rate gamma>8.98×104s-1The aPCS-Nd is subjected to decomplexing and ultrafiltration separationNd, obtaining regenerated aPCS at the same time, wherein the regenerated aPCS can continuously carry out complexation on rare earth ions;
under the conditions of normal temperature and pH value of 5, when aPCS is used as a complexing agent, the critical shear rates of complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by aPCS and La, Ce and Nd are respectively 9.29 multiplied by 104、1.04×105、1.13×105s-1. The membrane surface shear rate is firstly controlled to be 9.29 multiplied by 104s-1<γ<1.04×105s-1Decomplexation of aPCS-La, and ultrafiltration separation of La; then controlling the membrane surface shear rate to be 1.04 multiplied by 105s-1<γ<1.13×105s-1aPCS-Ce is decomplexed and subjected to ultrafiltration separation to obtain Ce; finally controlling the membrane surface shear rate gamma>1.13×105s-1And (3) decomplexing aPCS-Nd, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated aPCS which can continue to perform complexation of rare earth ions.
The invention has the following advantages:
(1) compared with the common water-soluble polymer complexing agent, the phosphorylated chitosan has superior rare earth complexing ability and rare earth selectivity, and is applied to the rare earth separation process as the complexing agent, so that the rare earth ion retention rate can reach more than 99 percent, and the separation efficiency is improved;
(2) the method has the advantages of good selective separation effect, small acid and alkali consumption, no secondary pollution, no need of organic solvent, cost saving and ammonia nitrogen pollution reduction;
(3) the shearing decomplexing coupling ultrafiltration process can realize the selective separation of the mixed rare earth and the regeneration of the complex agent phosphorylated chitosan at one time, and is economic and environment-friendly.
Detailed Description
The invention is further described below with reference to examples.
Example 1
Preparing mixed ion solution with La and Ce mass concentration of 10mg/L at normal temperature, adding nPCS into the solution, wherein the nPCS is separated from mixed rare earthThe sub-mass ratio is 10: and 1, adjusting the pH value of the solution to be 5, and stirring for 0.5h to obtain a solution containing the nPCS-La and nPCS-Ce complexes, wherein the pH value of the solution is 5, and the P/Re of the solution is 10. According to the difference of the shear stability of the two complexes under the condition, the membrane surface shear rate is firstly controlled to be 8.86 multiplied by 104s-1<γ<9.91×104s-1Destabilizing nPCS-La for decomplexing nPCS-Ce, and ultrafiltering to separate La; then adjusting the membrane surface shear rate to be more than 9.91 multiplied by 104s-1The complex of nPCS-Ce is decomplexed, Ce is separated out by ultrafiltration, and regenerated nPCS is obtained at the same time, and can continue to carry out complexation of rare earth ions.
Example 2
Preparing mixed ion solution with the mass concentration of both Ce and Nd being 20mg/L at normal temperature, and adding nPCS into the solution, wherein the mass ratio of the nPCS to the mixed rare earth ions is 10: and 1, adjusting the pH value of the solution to 6, and stirring for 1h to obtain a mixed complex solution of nPCS-Ce and nPCS-Nd, wherein the pH value of the mixed complex solution is 6, and the P/Re of the mixed complex solution is 10. According to the difference of the shear stability of the two complexes under the condition, the membrane surface shear rate is firstly controlled to be 1.21 multiplied by 105s-1<γ<1.33×105s-1nPCS-Ce is destabilized and decomplexed, nPCS-Nd is not decomplexed, and Ce is separated out by ultrafiltration; then adjusting the membrane surface shear rate to 1.33X 105s-1And (3) decomplexing the nPCS-Nd complex, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated nPCS which can continue to perform complexation of rare earth ions.
Example 3
Preparing a solution with La, Ce and Nd mass concentrations of 15mg/L at normal temperature, and adding nPCS into the solution, wherein the mass ratio of the nPCS to the mixed rare earth ions is 10: and 1, adjusting the pH value of the solution to 7, and stirring for 2.5h to obtain a mixed complex solution of nPCS-La, nPCS-Ce and nPCS-Nd, wherein the pH value of the mixed complex solution is 7, and the P/Re of the mixed complex solution is 10. According to the difference of the shear stability of the three complexes under the condition, the membrane surface shear rate is firstly controlled to be 1.31 multiplied by 105s-1<γ<1.63×105s-1nPCS-La is unstable and complex-released, nPCS-Ce and nPCS-Nd are not complex-released, and La is separated by ultrafiltration; then adjusting the membrane surface shear rate to be 1.63 multiplied by 105s-1<γ<1.79×105s-1nPCS-Ce destabilizing complex, nPCS-Nd not dissolvingComplexing, and ultrafiltering to separate Ce; finally, adjusting the membrane surface shear rate to 1.79X 105s-1And (3) decomplexing the nPCS-Nd complex, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated nPCS which can continue to perform complexation of rare earth ions.
Example 4
Preparing mixed ion solution with La and Ce mass concentration of 10mg/L at normal temperature, and adding aPCS into the solution, wherein the mass ratio of the aPCS to the mixed rare earth ions is 8: 1, adjusting the pH value of the solution to 3, and stirring for 1.5h to obtain a mixed complex solution of aPCS-La and aPCS-Ce, wherein the pH value of the mixed complex solution is 3, and the P/Re of the mixed complex solution is 8. According to the difference of the shear stability of the two complexes under the condition, the membrane surface shear rate is firstly controlled to be 4.74 multiplied by 104s-1<γ<5.20×104s-1Destabilizing aPCS-La for decomplexation, and ultrafiltering aPCS-Ce without decomplexation to separate La; then adjusting the membrane surface shear rate to 5.20X 104s-1In the above step, the aPCS-Ce complex is decomplexed, the Ce is separated by ultrafiltration, and meanwhile, the regenerated aPCS is obtained, and the regenerated aPCS can continue to carry out complexation of rare earth ions.
Example 5
At normal temperature, preparing mixed ion solution with the mass concentration of both Ce and Nd being 15mg/L, and adding aPCS into the solution, wherein the mass ratio of the aPCS to the mixed rare earth ions is 8: and 1, adjusting the pH value of the solution to be 4, and stirring for 2h to obtain a mixed complex solution of aPCS-Ce and aPCS-Nd, wherein the pH value of the mixed complex solution is 4, and the P/Re of the mixed complex solution is 8. According to the difference of the shear stability of the two complexes under the condition, the membrane surface shear rate is firstly controlled to be 7.39 multiplied by 104s-1<γ<8.98×104s-1Destabilizing aPCS-Ce for decomplexing, not decomplexing aPCS-Nd, and ultrafiltering to separate Ce; then adjusting the membrane surface shear rate to 8.98 x 104s-1In the above step, complexing of the aPCS-Nd complex is performed, Nd is separated by ultrafiltration, and meanwhile, regenerated aPCS is obtained, and the regenerated aPCS can be used for continuously complexing rare earth ions.
Example 6
Preparing a mixed ion solution with La, Ce and Nd mass concentrations of 20mg/L at normal temperature, and adding aPCS into the solution, wherein the mass ratio of the aPCS to the mixed rare earth ions is 8: 1, adjusting the pH of the solution to 5, and stirring for 2.5h to obtain the product with the pH of 5 and the P/Re of 8aPCS-La, aPCS-Ce and aPCS-Nd are mixed with complex solution. According to the difference of the shear stability of the three complexes under the condition, the membrane surface shear rate is firstly controlled to be 9.29 multiplied by 104s-1<γ<1.04×105s-1Destabilizing aPCS-La for decomplexing, wherein aPCS-Ce and aPCS-Nd are not decomplexed, and ultrafiltering to separate La; then adjusting the membrane surface shear rate to be 1.04X 105s-1<γ<1.13×105s-1Destabilizing aPCS-Ce for decomplexing, not decomplexing aPCS-Nd, and ultrafiltering to separate Ce; finally, adjusting the membrane surface shear rate to 1.13X 105s-1In the above step, complexing of the aPCS-Nd complex is performed, Nd is separated by ultrafiltration, and meanwhile, regenerated aPCS is obtained, and the regenerated aPCS can be used for continuously complexing rare earth ions.
Claims (3)
1. A method for separating rare earth by using a water-soluble polymer complexing agent is characterized by comprising the following steps: the adopted water-soluble polymer complexing agents are neutral phosphorylated chitosan nPCS and acidic phosphorylated chitosan aPCS;
wherein the chemical structural formula of nPCS is as follows:
aPCS has a chemical structural formula as follows:
n = 1200-3000 in the structure;
the method comprises the following steps:
firstly, under the condition that the pH value is 3-7, adding a certain amount of neutral phosphorylated chitosan nPCS or acidic phosphorylated chitosan aPCS into a solution containing rare earth ions, and stirring for 0.5-2.5 h to ensure that the rare earth ions and the nPCS or the aPCS are fully complexed to form a PCS-Re complex; then, according to the difference of the shearing stability of different PCS-Re complexes under certain conditions, the separation of mixed rare earth ions and the regeneration of the complex agent phosphorylated chitosan are realized by adopting shearing decomplexation coupling ultrafiltration;
the dosage of the neutral phosphorylated chitosan nPCS or the acidic phosphorylated chitosan aPCS is determined by measuring the relationship between the mass ratio P/Re of the complexing agent to the rare earth ions and the rare earth ion retention rate R by adopting a complexing-ultrafiltration method: when complexation-ultrafiltration is carried out under a certain pH condition, the rare earth ion retention rate increases with the increase of P/Re, and when the maximum value of R is reached and does not increase with the increase of P/Re, the value is the critical P/Re value, and the addition amount of the complexing agent is determined according to the critical P/Re value;
the PCS-Re complex has the shear stability under certain pH condition, and the critical shear rate of the PCS-Re complex is adoptedγ c The maximum shear rate that the PCS-Re complex can bear when the PCS-Re complex is kept stable is determined according to the relationship between the membrane surface shear rate and the rare earth ion rejection rate: when the membrane surface shear rate is less than the critical shear rate of the PCS-Re complex, the PCS-Re complex is kept stable, and the retention rate of rare earth ions is kept unchanged; when the membrane surface shear rate is greater than the critical shear rate of the PCS-Re complex, the PCS-Re complex is decomplexed into a polymer complexing agent and free rare earth ions, the free rare earth ions penetrate through the ultrafiltration membrane, and the rare earth ion rejection rate is sharply reduced.
2. The method according to claim 1, wherein the rare earth is separated by a water-soluble polymeric complexing agent, wherein: using neutral phosphorylated chitosan nPCS as a complexing agent, and realizing the ordered separation of rare earth ions by adjusting membrane surface shear rate coupling ultrafiltration according to the difference of critical shear rates of different nPCS-Re complexes under certain pH and temperature conditions;
under the conditions of normal temperature and pH value of 5, when nPCS is used as a complexing agent, the critical shear rates of complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS and La, Ce and Nd are respectively 8.86 multiplied by 104 s-1、9.91×104 s-1、1.09×105 s-1(ii) a Firstly controlling the membrane surface shear rate to be 8.86 multiplied by 104 s-1 < γ < 9.91×104 s-1nPCS-La decomplexes, and La is separated by ultrafiltration; then controlling the membrane surface shear rate to be 9.91 multiplied by 104 s-1 < γ < 1.09×105 s-1nPCS-Ce decomplexes and is ultrafiltered to separate Ce; finally controlling the membrane surface shear rateγ > 1.09×105 s-1The nPCS-Nd is subjected to decomplexing, Nd is separated by ultrafiltration, regenerated nPCS is obtained at the same time, and the regenerated nPCS continues to carry out complexation of rare earth ions;
under the conditions of normal temperature and pH 6, when nPCS is used as a complexing agent, the critical shear rates of complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS and La, Ce and Nd are respectively 1.02 multiplied by 105、1.21×105、1.33×105 s-1(ii) a Firstly controlling the membrane surface shear rate to be 1.02 multiplied by 105 s-1 < γ < 1.21×105 s-1nPCS-La decomplexes, and La is separated by ultrafiltration; then controlling the membrane surface shear rate to be 1.21 multiplied by 105 s-1 < γ < 1.33×105 s-1nPCS-Ce decomplexes and is ultrafiltered to separate Ce; finally controlling the membrane surface shear rateγ > 1.33×105 s-1The nPCS-Nd is subjected to decomplexing, Nd is separated by ultrafiltration, regenerated nPCS is obtained at the same time, and the regenerated nPCS continues to carry out complexation of rare earth ions;
under the conditions of normal temperature and pH value of 7, when nPCS is used as a complexing agent, the critical shear rates of complexes nPCS-La, nPCS-Ce and nPCS-Nd formed by nPCS and La, Ce and Nd are respectively 1.31 multiplied by 105、1.63×105、1.79×105 s-1(ii) a The membrane surface shear rate is firstly controlled to be 1.31 multiplied by 105 s-1 < γ < 1.63×105 s-1nPCS-La decomplexes, and La is separated by ultrafiltration; then controlling the membrane surface shear rate to be 1.63 multiplied by 105 s-1 < γ < 1.79×105 s-1nPCS-Ce decomplexes and is ultrafiltered to separate Ce; finally controlling the membrane surface shear rateγ > 1.79×105 s-1And (3) decomplexing nPCS-Nd, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated nPCS which continues to perform complexation of rare earth ions.
3. The method according to claim 1, wherein the rare earth is separated by a water-soluble polymeric complexing agent, wherein: using acid phosphorylated chitosan aPCS as a complexing agent, and realizing the ordered separation of rare earth ions by adjusting membrane surface shear rate coupling ultrafiltration according to the difference of different aPCS-Re complex critical shear rates under certain pH and temperature conditions;
under the conditions of normal temperature and pH value of 3, when aPCS is used as a complexing agent, the critical shear rates of complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by the aPCS and La, Ce and Nd are respectively 4.74 multiplied by 104 s-1、5.20×104 s-1、6.45×104 s-1(ii) a The membrane surface shear rate is firstly controlled to be 4.74 multiplied by 104 s-1 < γ < 5.20×104 s-1Decomplexation of aPCS-La, and ultrafiltration separation of La; then controlling the membrane surface shear rate to be 5.20 multiplied by 104 s-1 < γ < 6.45×104 s-1aPCS-Ce is decomplexed and subjected to ultrafiltration separation to obtain Ce; finally controlling the membrane surface shear rateγ > 6.45×104 s-1Decomplexing aPCS-Nd, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated aPCS, and continuously performing complexation of rare earth ions by the regenerated aPCS;
under the conditions of normal temperature and pH value of 4, when aPCS is used as a complexing agent, the critical shear rates of complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by the aPCS and La, Ce and Nd are respectively 6.71 multiplied by 104 s-1、7.39×104 s-1、8.98×104 s-1(ii) a The membrane surface shear rate is firstly controlled to be 6.71 multiplied by 104 s-1 < γ < 7.39×104 s-1Decomplexation of aPCS-La, and ultrafiltration separation of La; then controlling the membrane surface shear rate to be 7.39 multiplied by 104 s-1 < γ < 8.98×104 s-1aPCS-Ce is decomplexed and subjected to ultrafiltration separation to obtain Ce; finally controlling the membrane surface shear rateγ > 8.98×104 s-1Decomplexing aPCS-Nd, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated aPCS, and continuously performing complexation of rare earth ions by the regenerated aPCS;
under the conditions of normal temperature and pH value of 5, when aPCS is used as a complexing agent, the critical shear rates of complexes aPCS-La, aPCS-Ce and aPCS-Nd formed by the aPCS and La, Ce and Nd are respectively 9.29 multiplied by 104、1.04×105、1.13×105 s-1(ii) a The membrane surface shear rate is firstly controlled to be 9.29 multiplied by 104 s-1 < γ < 1.04×105 s-1aPCS-La decomplexes and La is separated by ultrafiltration; then controlling the membrane surface shear rate to be 1.04 multiplied by 105 s-1 < γ < 1.13×105 s-1aPCS-Ce is decomplexed and subjected to ultrafiltration separation to obtain Ce; finally controlling the membrane surface shear rateγ > 1.13×105 s-1And (3) decomplexing aPCS-Nd, performing ultrafiltration to separate Nd, and simultaneously obtaining regenerated aPCS which continues to perform complexation of rare earth ions.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5708152A (en) * | 1992-03-27 | 1998-01-13 | Ciba Specialty Chemicals Corporation | N-substituted chitosan derivatives in a process for their preparation |
| US5777091A (en) * | 1994-11-24 | 1998-07-07 | Ciba Specialty Chemicals Corporation | Phosphonomethylated chitosans |
| CN1317496A (en) * | 2000-04-11 | 2001-10-17 | 海南大学 | Generation and control degradation of chitosan-metal metches |
| JP2007146178A (en) * | 2007-02-01 | 2007-06-14 | Seikagaku Kogyo Co Ltd | Chitosan derivative and crosslinked chitosan |
| CN107255604A (en) * | 2017-06-28 | 2017-10-17 | 中南大学 | A kind of device and method for determining polymer heavy metal complex shear stability |
| CN108623707A (en) * | 2017-03-21 | 2018-10-09 | 广西大学 | The method that microwave and complexing synergistic oxidation prepare chitosan oligosaccharide-rare-earth complex |
-
2021
- 2021-08-30 CN CN202111000622.0A patent/CN113737030B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5708152A (en) * | 1992-03-27 | 1998-01-13 | Ciba Specialty Chemicals Corporation | N-substituted chitosan derivatives in a process for their preparation |
| US5777091A (en) * | 1994-11-24 | 1998-07-07 | Ciba Specialty Chemicals Corporation | Phosphonomethylated chitosans |
| CN1317496A (en) * | 2000-04-11 | 2001-10-17 | 海南大学 | Generation and control degradation of chitosan-metal metches |
| JP2007146178A (en) * | 2007-02-01 | 2007-06-14 | Seikagaku Kogyo Co Ltd | Chitosan derivative and crosslinked chitosan |
| CN108623707A (en) * | 2017-03-21 | 2018-10-09 | 广西大学 | The method that microwave and complexing synergistic oxidation prepare chitosan oligosaccharide-rare-earth complex |
| CN107255604A (en) * | 2017-06-28 | 2017-10-17 | 中南大学 | A kind of device and method for determining polymer heavy metal complex shear stability |
Non-Patent Citations (2)
| Title |
|---|
| 《"旋转盘剪切辅助络合-超滤处理含Cr3+废水》;张强等;《矿冶工程》;20180630;第38卷(第3期);第104-107页 * |
| 《羧甲基壳聚糖对稀土离子吸附性能的研究》;于昆等;《化学试剂》;20030331;第31卷(第3期);第218-220页 * |
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