CN114702057B - Method for preparing 6N-grade neodymium chloride by fractional extraction separation process - Google Patents
Method for preparing 6N-grade neodymium chloride by fractional extraction separation process Download PDFInfo
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Abstract
The invention relates to a method for preparing 6N grade neodymium chloride by fractional extraction and separation flow, which comprises a saponification section
CePr/NdSm full-load fractionation extraction separation system and saponification section
The device comprises a purification section, an Nd/Sm full-load fractional extraction separation system and a back extraction section. Specifically, 4N-level neodymium chloride aqueous solution is used as feed liquid, and rare earth element impurities cerium, praseodymium and samarium in the feed liquid are separated and removed through a CePr/NdSm full-load fractional extraction separation system and a Nd/Sm full-load fractional extraction separation system, so as to prepare 6N-level neodymium chloride aqueous solution. The purity of neodymium in the 6N grade neodymium chloride aqueous solution of the target product is 99.99991% -99.99998%, and the yield of neodymium is 96% -98%. The invention has the advantages of high product purity, high neodymium yield, good separation effect and the like.
Description
Technical Field
The invention relates to a method for preparing 6N-grade neodymium chloride by a fractional extraction separation process, which specifically takes 4N-grade neodymium chloride aqueous solution as feed liquid, and removes rare earth element impurities cerium, praseodymium and samarium in the 4N-grade neodymium chloride aqueous solution through a CePr/NdSm full-load fractional extraction separation system and a Nd/Sm full-load fractional extraction separation system to prepare the 6N-grade neodymium chloride aqueous solution. The invention belongs to the specific technical field of preparation of 6N-grade neodymium chloride.
Background
The 6N-level neodymium compound has important application in the fields of high-tech materials such as laser materials, magnetic materials, special ceramics and the like. At present, no public report is made about the preparation method of 6N grade neodymium products such as 6N grade neodymium chloride. The 6N-grade neodymium chloride is a basic raw material for preparing other 6N-grade neodymium products, so that the separation and preparation of the 6N-grade neodymium chloride are one of important technologies which are urgently needed currently.
Aiming at the situation that no method for preparing 6N-grade neodymium chloride exists at present, the invention establishes a method for preparing the 6N-grade neodymium chloride aqueous solution by taking 4N-grade neodymium chloride aqueous solution as feed liquid and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (called P507 for short) as extractant through CePr/NdSm full-load fractional extraction separation system and Nd/Sm full-load fractional extraction separation system. Rare earth element impurities in the 4N-level neodymium chloride aqueous solution of the feed liquid mainly comprise cerium, praseodymium and neodymium, and separation and removal of the rare earth element impurities in the 4N-level neodymium chloride aqueous solution are key technical problems in preparing the 6N-level neodymium chloride.
Disclosure of Invention
Aiming at the situation that no method for preparing 6N-grade neodymium chloride exists at present, the invention establishes a method for preparing 6N-grade neodymium chloride aqueous solution by taking 4N-grade neodymium chloride aqueous solution as feed liquid.
The invention relates to a method for preparing 6N-grade neodymium chloride by a fractional extraction separation process, in particular to a method for preparing 6N-grade neodymium chloride aqueous solution by taking 4N-grade neodymium chloride aqueous solution as feed liquid and separating and removing rare earth element impurities cerium, praseodymium and samarium in the feed liquid through a CePr/NdSm full-load fractional extraction separation system and a Nd/Sm full-load fractional extraction separation system. The method comprises a saponification section
CePr/NdSm full-load fractional extraction separation system and saponification section ∈>
The device comprises a purification section, an Nd/Sm full-load fractional extraction separation system and a back extraction section. The purification section is arranged in the saponification section +.>
And Nd/Sm full-load fractional extraction separation system.
The CePr/NdSm full-load fractional extraction separation system adopts a saponification section
The obtained CePrNd-loaded organic phase LOP1 is a rare earth saponification organic phase, and the rare earth saponification organic phase loaded CePrNd organic phase LOP1 enters a CePr/NdSm full-load fractional extraction system from a first stage; taking 4N-level neodymium chloride aqueous solution as feed liquid, and enabling the feed liquid 4N-level neodymium chloride aqueous solution to enter a CePr/NdSm full-load fractional extraction system from a feed stage; the equilibrium aqueous phase neodymium chloride samarium aqueous solution of the feed stage of the Nd/Sm full-load fractional extraction system is taken as a detergent W1, and the detergent W1 neodymium chloride samarium aqueous solution enters the CePr/NdSm full-load fractional extraction system from the last stage. Obtaining cerium praseodymium neodymium chloride enriched aqueous solution from a first-stage outlet aqueous phase of a CePr/NdSm full-load fractional extraction system, and separating the cerium praseodymium neodymium chloride enriched aqueous solution for a saponification section +.>
PreparationLoading CePrNd organic phase LOP1; the loaded NdSm organic phase LOP4 is obtained from the outlet of the last-stage organic phase of the CePr/NdSm full-load fractional extraction system, and the loaded NdSm organic phase LOP4 is used as feed liquid of the Nd/Sm full-load fractional extraction system.
The Nd/Sm full-load fractional extraction separation system takes a 6N-level loaded neodymium organic phase LOP3 obtained from the last stage of the purification section as a neodymium saponification organic phase, and the neodymium saponification organic phase loaded 6N-level neodymium organic phase LOP3 enters the Nd/Sm full-load fractional extraction separation system from the first stage; taking a loaded NdSm organic phase LOP4 obtained by a CePr/NdSm full-load fractional extraction system as a feed liquid, and feeding the feed liquid loaded NdSm organic phase LOP4 into the Nd/Sm full-load fractional extraction system from a feed stage; the neodymium chloride samarium concentrate aqueous solution obtained in the back extraction section is used as a detergent W2, and the detergent W2 neodymium chloride samarium concentrate aqueous solution enters an Nd/Sm full-load fractional extraction system from the last stage. Obtaining 6N grade neodymium chloride aqueous solution from a first stage outlet water phase of an Nd/Sm full-load fractional extraction system, and separating the 6N grade neodymium chloride aqueous solution for a saponification section
Preparing Nd-loaded organic phase LOP2, and taking 6N-level neodymium chloride aqueous solution as a purifying agent of a purifying section; the equilibrium water phase of the feed stage of the Nd/Sm fully loaded fractional extraction system is neodymium chloride samarium water solution which is used as the detergent W1 of the CePr/NdSm fully loaded fractional extraction system. And obtaining a loaded neodymium-samarium enriched organic phase LOP5 from the outlet of the organic phase of the last stage of the Nd/Sm full-load fractional extraction system, and transferring all the loaded neodymium-samarium enriched organic phase LOP5 into a back extraction section.
The saponification section
Saponifying the unloaded organic phase by using ammonia water to obtain an ammonia saponified organic phase; separating CePr/NdSm full-load fractional extraction separation system to obtain aqueous solution of cerium praseodymium neodymium chloride concentrate, and carrying out exchange reaction on the aqueous solution and an ammonia saponification organic phase to prepare a CePrNd-loaded organic phase LOP1; the CePrNd-loaded organic phase LOP1 is used as a rare earth saponification organic phase of a CePr/NdSm full-load fractional extraction separation system.
The saponification section
Saponifying the unloaded organic phase by using ammonia water to obtain an ammonia saponified organic phase; separating the 6N-level neodymium chloride aqueous solution obtained by the Nd/Sm full-load fractional extraction separation system and the ammonia saponification organic phase to perform exchange reaction to prepare a Nd-loaded organic phase LOP2; the Nd-loaded organic phase LOP2 is completely transferred into a purification section.
The purification section takes a 6N-level neodymium chloride aqueous solution obtained by a Nd/Sm full-load fractional extraction separation system as a purifying agent, a Nd-loaded organic phase LOP2 obtained by a saponification section II enters the purification section from a 1 st level, and a purifying agent 6N-level neodymium chloride aqueous solution enters the purification section from a 6 th level; the 6N-level neodymium organic phase LOP3 is obtained from the 6 th-level outlet organic phase of the purifying section through 6-level countercurrent purification, and the 6N-level neodymium organic phase LOP3 is used as a neodymium saponification organic phase of a Nd/Sm full-load fractional extraction separation system; and (3) obtaining a neodymium chloride aqueous solution from a 1 st-stage aqueous phase outlet of the purifying section, and uniformly mixing the neodymium chloride aqueous solution with a 4N-stage neodymium chloride aqueous solution to be used as feed liquid of the CePr/NdSm full-load fractional extraction separation system.
And the back extraction section adopts an HCl solution with the concentration of 3.0 mol/L as a back extraction agent, and 12-level countercurrent back extraction is carried out on a neodymium-samarium-enriched organic phase LOP5 obtained from an Nd/Sm fully loaded fractional extraction separation system. And (3) obtaining an aqueous solution of the concentrated neodymium samarium chloride from an aqueous phase outlet of the back extraction section, and taking the aqueous solution of the concentrated neodymium samarium chloride as a washing agent W2 of an Nd/Sm full-load fractional extraction separation system. The organic phase outlet of the stripping section obtains a regenerated non-loaded organic phase.
The concentration of rare earth elements in the 4N-level neodymium chloride aqueous solution is Ce 0.70 mg/L-2.8 mg/L, pr 2.0 mg/L-5.6 mg/L, nd 143 g/L-147 g/L, sm 1.5 mg/L-4.5 mg/L respectively.
The concentration of rare earth elements in the 6N-level neodymium chloride aqueous solution is 0.0051/mg-0.030 mg/L, pr 0.012.012 mg/L-0.070 mg/L, nd 144 g/L-146 g/L, sm 0.0072 mg/L-0.028 mg/L respectively.
The non-loaded organic phase is the sulfonated kerosene solution of P507, wherein the concentration of P507 is 1.0 mol/L.
The invention has the beneficial effects that: 1) The aqueous solution of neodymium chloride of 6N grade is obtained from the aqueous solution of neodymium chloride of 4N grade. The 6N-level neodymium chloride aqueous solution can be concentrated and crystallized to obtain 6N-level neodymium chloride crystals; the 6N-level neodymium chloride aqueous solution can be precipitated by high-purity ammonia water to obtain 6N-level neodymium hydroxide, and the 6N-level neodymium hydroxide is conveniently converted into other 6N-level neodymium compounds; the 6N-level neodymium chloride aqueous solution can obtain 6N-level neodymium oxalate through refining oxalic acid precipitation, and then the 6N-level neodymium oxide can be obtained through burning; the 6N-grade neodymium oxide can be dissolved by proper acid to prepare a plurality of corresponding 6N-grade neodymium salts; etc. Finally, a series of 6N-grade neodymium compounds can be obtained. 2) The product purity and the yield are high: the purity of neodymium in the 6N grade neodymium chloride aqueous solution of the target product is 99.99991% -99.99998%, and the yield of neodymium is 96% -98%. Obviously, the separation effect is good. 3) The production cost is low: good separation effect and less reagent consumption.
Drawings
Fig. 1: the invention relates to a process flow diagram of a method for preparing 6N-grade neodymium chloride by a fractional extraction separation process;
in the context of figure 1 of the drawings,tfor the number of stages of the purification section,nfor the number of stages of the extraction stage,mfor the washing stage number, 4 nnd represents a 4N grade neodymium chloride aqueous solution; 6 NNd represents a 6N grade neodymium chloride aqueous solution; cePrNd represents an aqueous solution of CePrNd concentrate; ndSm represents an aqueous solution of a samarium chloride concentrate; LOP represents a loaded organic phase, LOP1 is a loaded CePrNd organic phase, LOP2 is a loaded Nd organic phase, LOP3 is a loaded 6N-level neodymium organic phase, LOP4 is a loaded NdSm organic phase, and LOP5 is a loaded neodymium samarium enriched organic phase; w represents a detergent, W1 is an aqueous solution of neodymium chloride samarium, and W2 is an aqueous solution of neodymium chloride samarium concentrate; a sulfonated kerosene solution with no loaded organic phase as extractant P507; solid arrows indicate the flow or transfer direction of the aqueous phase; the dashed arrows indicate the flow or transfer direction of the organic phase.
Detailed Description
The method for preparing 6N-grade neodymium chloride in a fractional extraction separation process according to the invention is further described below with reference to specific examples.
Example 1
The non-loaded organic phase is a sulfonated kerosene solution of P507, wherein the concentration of P507 is 1.0 mol/L.
The concentration of rare earth elements in the 4N-level neodymium chloride aqueous solution of the feed liquid is Ce 2.8 mg/L, pr 5.6.5.6 mg/L, nd 147 g/L, sm 4.5 mg/L respectively.
CePr/NdSm full-load fractional extraction separation system: by saponification section
The obtained CePrNd-loaded organic phase is a rare earth saponification organic phase, and the CePrNd-loaded organic phase of the rare earth saponification organic phase enters a CePr/NdSm full-load fractional extraction system from the 1 st stage; taking 4N-level neodymium chloride aqueous solution as feed liquid, and enabling the feed liquid 4N-level neodymium chloride aqueous solution to enter a CePr/NdSm full-load fractional extraction system from a 56 th level (feed level); the equilibrium aqueous phase neodymium chloride samarium aqueous solution of the feeding stage of the Nd/Sm full-load fractional extraction system is used as a detergent, and the detergent neodymium chloride samarium aqueous solution enters the CePr/NdSm full-load fractional extraction system from the 97 th stage. Obtaining cerium praseodymium neodymium chloride enriched aqueous solution from a 1 st-stage outlet aqueous phase of a CePr/NdSm full-load fractional extraction system, and separating the cerium praseodymium neodymium chloride enriched aqueous solution for a saponification section->
Preparing a CePrNd-loaded organic phase; the loaded NdSm organic phase is obtained from the 97 th-stage organic phase outlet of the CePr/NdSm full-load fractional extraction system, and the loaded NdSm organic phase is used as feed liquid of the Nd/Sm full-load fractional extraction system.
Nd/Sm full fractionation extraction separation system: the neodymium saponification organic phase loaded with 6N grade neodymium organic phase obtained from the 6 th grade of the purification section is taken as the neodymium saponification organic phase, and the neodymium saponification organic phase loaded with 6N grade neodymium organic phase enters a Nd/Sm full-load fractional extraction separation system from the 1 st grade; taking the loaded NdSm organic phase obtained by the CePr/NdSm full-load fractional extraction system as feed liquid, and feeding the feed liquid loaded NdSm organic phase into the Nd/Sm full-load fractional extraction system from the 19 th stage (feeding stage); the aqueous solution of the concentrated neodymium samarium chloride obtained in the back extraction section is used as a detergent, and the aqueous solution of the concentrated neodymium samarium chloride enters a Nd/Sm full-load fractional extraction system from the 28 th stage. Obtaining 6N grade neodymium chloride aqueous solution from 1 st grade outlet water phase of Nd/Sm full-load fractional extraction system, and separating 6N grade neodymium chloride aqueous solution for saponificationSegment(s)
Preparing a Nd-loaded organic phase, and taking a 6N-grade neodymium chloride aqueous solution as a purifying agent of a purifying section; the equilibrium water phase of the 19 th stage (feed stage) of the Nd/Sm full-loaded fractional extraction system is neodymium chloride samarium water solution which is separated and used as a detergent of the CePr/NdSm full-loaded fractional extraction system. And obtaining a loaded neodymium-samarium enriched organic phase from a 28 th-stage organic phase outlet of the Nd/Sm full-load fractional extraction system, and completely transferring the loaded neodymium-samarium enriched organic phase into a stripping section.
Saponification section
: saponifying the unloaded organic phase by ammonia water to obtain an ammonia saponified organic phase; separating CePr/NdSm full-load fractional extraction separation system to obtain aqueous solution of cerium praseodymium neodymium chloride concentrate, and carrying out exchange reaction on the aqueous solution and an ammonia saponification organic phase to prepare a CePrNd-loaded organic phase; the CePrNd-loaded organic phase is used as a rare earth saponification organic phase of a CePr/NdSm full-loaded fractional extraction separation system.
Saponification section
: saponifying the unloaded organic phase by ammonia water to obtain an ammonia saponified organic phase; separating the 6N-level neodymium chloride aqueous solution obtained by the Nd/Sm full-load fractional extraction separation system and the ammonia saponification organic phase to perform exchange reaction so as to prepare a Nd-loaded organic phase; the Nd-loaded organic phase is completely transferred into a purification section.
Purifying section: taking a 6N-level neodymium chloride aqueous solution obtained by a Nd/Sm full-load fractional extraction separation system as a purifying agent, enabling a Nd-loaded organic phase obtained by a saponification section II to enter a purification section from a 1 st level, and enabling a purifying agent 6N-level neodymium chloride aqueous solution to enter the purification section from a 6 th level; the 6N-level neodymium loaded organic phase is obtained from the 6 th-level outlet organic phase of the purifying section through 6-level countercurrent purification, and the 6N-level neodymium loaded organic phase is used as a neodymium saponification organic phase of a Nd/Sm full-load fractional extraction separation system; and (3) obtaining a neodymium chloride aqueous solution from a 1 st-stage aqueous phase outlet of the purifying section, and uniformly mixing the neodymium chloride aqueous solution with a 4N-stage neodymium chloride aqueous solution to be used as feed liquid of the CePr/NdSm full-load fractional extraction separation system.
And (3) back extraction: and adopting HCl solution with the concentration of 3.0 mol/L as a stripping agent, and carrying out 12-level countercurrent stripping to obtain a loaded neodymium-samarium enriched organic phase from the Nd/Sm fully loaded fractionation extraction separation system. And (3) obtaining an aqueous solution of the concentrated neodymium samarium chloride from an aqueous phase outlet of the back extraction section, and taking the aqueous solution of the concentrated neodymium samarium chloride as a washing agent of an Nd/Sm full-load fractional extraction separation system. The organic phase outlet of the stripping section obtains a regenerated non-loaded organic phase.
The concentration of rare earth elements in the 6N-level neodymium chloride aqueous solution is Ce 0.030 mg/L, pr 0.070 mg/L, nd 146 g/L, sm 0.028 mg/L respectively. The purity of neodymium in the 6N grade neodymium chloride aqueous solution of the target product is 99.99991 percent, and the yield of neodymium is 98 percent.
Example 2
The non-loaded organic phase is a sulfonated kerosene solution of P507, wherein the concentration of P507 is 1.0 mol/L.
The concentration of rare earth elements in the 4N-level neodymium chloride aqueous solution of the feed liquid is Ce 1.4 mg/L, pr 4.2.4.2 mg/L, nd 145 g/L, sm 3.0 mg/L respectively.
CePr/NdSm full-load fractional extraction separation system: by saponification section
The obtained CePrNd-loaded organic phase is a rare earth saponification organic phase, and the CePrNd-loaded organic phase of the rare earth saponification organic phase enters a CePr/NdSm full-load fractional extraction system from the 1 st stage; taking 4N-level neodymium chloride aqueous solution as feed liquid, and enabling the feed liquid 4N-level neodymium chloride aqueous solution to enter a CePr/NdSm full-load fractional extraction system from a 59 th level (feed level); the equilibrium aqueous phase neodymium chloride samarium aqueous solution of the feeding stage of the Nd/Sm full-load fractional extraction system is used as a detergent, and the detergent neodymium chloride samarium aqueous solution enters the CePr/NdSm full-load fractional extraction system from the 101 st stage. Obtaining cerium praseodymium neodymium chloride enriched aqueous solution from a 1 st-stage outlet aqueous phase of a CePr/NdSm full-load fractional extraction system, and separating the cerium praseodymium neodymium chloride enriched aqueous solution for a saponification section->
Preparing a CePrNd-loaded organic phase; from CePrThe grade 101 organic phase outlet of the NdSm full fractionation extraction system obtains a loaded NdSm organic phase which is used as feed liquid of the Nd/Sm full fractionation extraction system.
Nd/Sm full fractionation extraction separation system: the neodymium saponification organic phase loaded with 6N grade neodymium organic phase obtained from the 6 th grade of the purification section is taken as the neodymium saponification organic phase, and the neodymium saponification organic phase loaded with 6N grade neodymium organic phase enters a Nd/Sm full-load fractional extraction separation system from the 1 st grade; taking the loaded NdSm organic phase obtained by the CePr/NdSm full-load fractional extraction system as a feed liquid, and feeding the feed liquid loaded NdSm organic phase into the Nd/Sm full-load fractional extraction system from the 20 th stage (feeding stage); the neodymium chloride and samarium chloride enriched aqueous solution obtained in the back extraction section is used as a detergent, and the detergent neodymium chloride and samarium chloride enriched aqueous solution enters a Nd/Sm full-load fractionation extraction system from the 31 st stage. Obtaining 6N grade neodymium chloride aqueous solution from 1 st grade outlet water phase of Nd/Sm full-load fractional extraction system, and separating 6N grade neodymium chloride aqueous solution for saponification section
Preparing a Nd-loaded organic phase, and taking a 6N-grade neodymium chloride aqueous solution as a purifying agent of a purifying section; the equilibrium water phase of the 20 th stage (feeding stage) of the Nd/Sm full-load fractional extraction system is neodymium chloride samarium water solution which is separated and used as a detergent of the CePr/NdSm full-load fractional extraction system. And obtaining a loaded neodymium-samarium enriched organic phase from a 31 st-stage organic phase outlet of the Nd/Sm full-load fractional extraction system, and completely transferring the loaded neodymium-samarium enriched organic phase into a stripping section.
Saponification section
: saponifying the unloaded organic phase by ammonia water to obtain an ammonia saponified organic phase; separating CePr/NdSm full-load fractional extraction separation system to obtain aqueous solution of cerium praseodymium neodymium chloride concentrate, and carrying out exchange reaction on the aqueous solution and an ammonia saponification organic phase to prepare a CePrNd-loaded organic phase; the CePrNd-loaded organic phase is used as a rare earth saponification organic phase of a CePr/NdSm full-loaded fractional extraction separation system.
Saponification section
: saponifying the unloaded organic phase by ammonia water to obtain an ammonia saponified organic phase; separating the 6N-level neodymium chloride aqueous solution obtained by the Nd/Sm full-load fractional extraction separation system and the ammonia saponification organic phase to perform exchange reaction so as to prepare a Nd-loaded organic phase; the Nd-loaded organic phase is completely transferred into a purification section.
Purifying section: taking a 6N-level neodymium chloride aqueous solution obtained by a Nd/Sm full-load fractional extraction separation system as a purifying agent, enabling a Nd-loaded organic phase obtained by a saponification section II to enter a purification section from a 1 st level, and enabling a purifying agent 6N-level neodymium chloride aqueous solution to enter the purification section from a 6 th level; the 6N-level neodymium loaded organic phase is obtained from the 6 th-level outlet organic phase of the purifying section through 6-level countercurrent purification, and the 6N-level neodymium loaded organic phase is used as a neodymium saponification organic phase of a Nd/Sm full-load fractional extraction separation system; and (3) obtaining a neodymium chloride aqueous solution from a 1 st-stage aqueous phase outlet of the purifying section, and uniformly mixing the neodymium chloride aqueous solution with a 4N-stage neodymium chloride aqueous solution to be used as feed liquid of the CePr/NdSm full-load fractional extraction separation system.
And (3) back extraction: and adopting HCl solution with the concentration of 3.0 mol/L as a stripping agent, and carrying out 12-level countercurrent stripping to obtain a loaded neodymium-samarium enriched organic phase from the Nd/Sm fully loaded fractionation extraction separation system. And (3) obtaining an aqueous solution of the concentrated neodymium samarium chloride from an aqueous phase outlet of the back extraction section, and taking the aqueous solution of the concentrated neodymium samarium chloride as a washing agent of an Nd/Sm full-load fractional extraction separation system. The organic phase outlet of the stripping section obtains a regenerated non-loaded organic phase.
The rare earth element concentration in the 6N-level neodymium chloride aqueous solution is Ce 0.012 mg/L, pr 0.042 mg/L, nd 145 g/L, sm 0.016 mg/L respectively. The purity of neodymium in the 6N grade neodymium chloride aqueous solution of the target product is 99.99995%, and the yield of neodymium is 97%.
Example 3
The non-loaded organic phase is a sulfonated kerosene solution of P507, wherein the concentration of P507 is 1.0 mol/L.
The concentration of rare earth elements in the 4N-level neodymium chloride aqueous solution of the feed liquid is Ce 0.70 mg/L, pr 2.0 mg/L, nd 143 g/L, sm 1.5 mg/L respectively.
CePr/NdSm full-load fractional extraction separation system: by saponification section
The obtained CePrNd-loaded organic phase is a rare earth saponification organic phase, and the CePrNd-loaded organic phase of the rare earth saponification organic phase enters a CePr/NdSm full-load fractional extraction system from the 1 st stage; taking 4N-level neodymium chloride aqueous solution as feed liquid, and enabling the feed liquid 4N-level neodymium chloride aqueous solution to enter a CePr/NdSm full-load fractional extraction system from a 62 th level (feed level); the equilibrium aqueous phase neodymium chloride samarium aqueous solution of the feed stage of the Nd/Sm full-load fractional extraction system is used as a detergent, and the detergent neodymium chloride samarium aqueous solution enters the CePr/NdSm full-load fractional extraction system from the 118 th stage. Obtaining cerium praseodymium neodymium chloride enriched aqueous solution from a 1 st-stage outlet aqueous phase of a CePr/NdSm full-load fractional extraction system, and separating the cerium praseodymium neodymium chloride enriched aqueous solution for a saponification section->
Preparing a CePrNd-loaded organic phase; the NdSm-loaded organic phase is obtained from the 118 th organic phase outlet of the CePr/NdSm full-loaded fractional extraction system and is used as feed liquid of the Nd/Sm full-loaded fractional extraction system.
Nd/Sm full fractionation extraction separation system: the neodymium saponification organic phase loaded with 6N grade neodymium organic phase obtained from the 6 th grade of the purification section is taken as the neodymium saponification organic phase, and the neodymium saponification organic phase loaded with 6N grade neodymium organic phase enters a Nd/Sm full-load fractional extraction separation system from the 1 st grade; taking the loaded NdSm organic phase obtained by the CePr/NdSm full-load fractional extraction system as feed liquid, and feeding the feed liquid loaded NdSm organic phase into the Nd/Sm full-load fractional extraction system from the 26 th stage (feeding stage); the aqueous solution of the concentrated neodymium samarium chloride obtained in the back extraction section is used as a detergent, and the aqueous solution of the concentrated neodymium samarium chloride enters a Nd/Sm full-load fractional extraction system from the 37 th level. Obtaining 6N grade neodymium chloride aqueous solution from 1 st grade outlet water phase of Nd/Sm full-load fractional extraction system, and separating 6N grade neodymium chloride aqueous solution for saponification section
Preparing a Nd-loaded organic phase, and taking a 6N-grade neodymium chloride aqueous solution as a purifying agent of a purifying section; the equilibrium water phase of the 26 th stage (feeding stage) of the Nd/Sm full-load fractional extraction system is neodymium chloride samarium water solution which is separated and used as CePr/NdSm is fully loaded with detergents for fractionation extraction systems. And obtaining a loaded neodymium-samarium enriched organic phase from a 37 th-stage organic phase outlet of the Nd/Sm full-load fractional extraction system, and completely transferring the loaded neodymium-samarium enriched organic phase into a stripping section.
Saponification section
: saponifying the unloaded organic phase by ammonia water to obtain an ammonia saponified organic phase; separating CePr/NdSm full-load fractional extraction separation system to obtain aqueous solution of cerium praseodymium neodymium chloride concentrate, and carrying out exchange reaction on the aqueous solution and an ammonia saponification organic phase to prepare a CePrNd-loaded organic phase; the CePrNd-loaded organic phase is used as a rare earth saponification organic phase of a CePr/NdSm full-loaded fractional extraction separation system.
Saponification section
: saponifying the unloaded organic phase by ammonia water to obtain an ammonia saponified organic phase; separating the 6N-level neodymium chloride aqueous solution obtained by the Nd/Sm full-load fractional extraction separation system and the ammonia saponification organic phase to perform exchange reaction so as to prepare a Nd-loaded organic phase; the Nd-loaded organic phase is completely transferred into a purification section.
Purifying section: taking a 6N-level neodymium chloride aqueous solution obtained by a Nd/Sm full-load fractional extraction separation system as a purifying agent, enabling a Nd-loaded organic phase obtained by a saponification section II to enter a purification section from a 1 st level, and enabling a purifying agent 6N-level neodymium chloride aqueous solution to enter the purification section from a 6 th level; the 6N-level neodymium loaded organic phase is obtained from the 6 th-level outlet organic phase of the purifying section through 6-level countercurrent purification, and the 6N-level neodymium loaded organic phase is used as a neodymium saponification organic phase of a Nd/Sm full-load fractional extraction separation system; and (3) obtaining a neodymium chloride aqueous solution from a 1 st-stage aqueous phase outlet of the purifying section, and uniformly mixing the neodymium chloride aqueous solution with a 4N-stage neodymium chloride aqueous solution to be used as feed liquid of the CePr/NdSm full-load fractional extraction separation system.
And (3) back extraction: and adopting HCl solution with the concentration of 3.0 mol/L as a stripping agent, and carrying out 12-level countercurrent stripping to obtain a loaded neodymium-samarium enriched organic phase from the Nd/Sm fully loaded fractionation extraction separation system. And (3) obtaining an aqueous solution of the concentrated neodymium samarium chloride from an aqueous phase outlet of the back extraction section, and taking the aqueous solution of the concentrated neodymium samarium chloride as a washing agent of an Nd/Sm full-load fractional extraction separation system. The organic phase outlet of the stripping section obtains a regenerated non-loaded organic phase.
The rare earth element concentration in the 6N-level neodymium chloride aqueous solution is Ce 0.0051 mg/L, pr 0.012 mg/L, nd 144 g/L, sm 0.0072 mg/L respectively. The purity of neodymium in the 6N grade neodymium chloride aqueous solution of the target product is 99.99998%, and the yield of neodymium is 96%.
Claims (8)
1. A method for preparing 6N-grade neodymium chloride by a fractional extraction separation process is characterized by comprising the following steps: the method takes 4N-level neodymium chloride aqueous solution as feed liquid, and rare earth element impurities cerium, praseodymium and samarium in the feed liquid are separated and removed through a CePr/NdSm full-load fractional extraction separation system and a Nd/Sm full-load fractional extraction separation system to prepare 6N-level neodymium chloride aqueous solution; the method comprises a saponification section I, a CePr/NdSm full-load fractional extraction separation system, a saponification section II, a purification section, an Nd/Sm full-load fractional extraction separation system and a back extraction section; the purification section is arranged between the saponification section II and the Nd/Sm full-load fractionation extraction separation system;
the CePr/NdSm full-load fractional extraction separation system takes a CePrNd-loaded organic phase LOP1 obtained in a saponification section I as a rare earth saponification organic phase, and the CePrNd-loaded organic phase LOP1 of the rare earth saponification organic phase enters the CePr/NdSm full-load fractional extraction system from a first stage; taking 4N-level neodymium chloride aqueous solution as feed liquid, and enabling the feed liquid 4N-level neodymium chloride aqueous solution to enter a CePr/NdSm full-load fractional extraction system from a feed stage; taking an equilibrium aqueous phase neodymium chloride samarium aqueous solution of a feed stage of an Nd/Sm full-load fractional extraction system as a detergent W1, wherein the detergent W1 neodymium chloride samarium aqueous solution enters the CePr/NdSm full-load fractional extraction system from a final stage; obtaining a cerium praseodymium neodymium chloride enriched aqueous solution from a first-stage outlet aqueous phase of a CePr/NdSm fully-loaded fractional extraction system, and separating the cerium praseodymium neodymium chloride enriched aqueous solution for preparing a CePrNd-loaded organic phase LOP1 in a saponification section I; obtaining a loaded NdSm organic phase LOP4 from an organic phase outlet of the last stage of the CePr/NdSm full-load fractional extraction system, wherein the loaded NdSm organic phase LOP4 is used as feed liquid of the Nd/Sm full-load fractional extraction system;
the Nd/Sm full-load fractional extraction separation system takes a 6N-level loaded neodymium organic phase LOP3 obtained from the last stage of the purification section as a neodymium saponification organic phase, and the neodymium saponification organic phase loaded 6N-level neodymium organic phase LOP3 enters the Nd/Sm full-load fractional extraction separation system from the first stage; taking a loaded NdSm organic phase LOP4 obtained by a CePr/NdSm full-load fractional extraction system as a feed liquid, and feeding the feed liquid loaded NdSm organic phase LOP4 into the Nd/Sm full-load fractional extraction system from a feed stage; taking the aqueous solution of the neodymium chloride and samarium chloride enrichment obtained in the back extraction section as a detergent W2, wherein the aqueous solution of the neodymium chloride and samarium chloride enrichment of the detergent W2 enters a Nd/Sm full-load fractional extraction system from the last stage; obtaining a 6N-level neodymium chloride aqueous solution from a first-stage outlet aqueous phase of an Nd/Sm full-load fractional extraction system, separating the 6N-level neodymium chloride aqueous solution for preparing a Nd-loaded organic phase LOP2 in a saponification section II, and separating the 6N-level neodymium chloride aqueous solution for being used as a purifying agent in a purification section; the equilibrium water phase of the feeding stage of the Nd/Sm full-load fractional extraction system is neodymium chloride samarium water solution which is used as a detergent W1 of the CePr/NdSm full-load fractional extraction system; and obtaining a loaded neodymium-samarium enriched organic phase LOP5 from the outlet of the organic phase of the last stage of the Nd/Sm full-load fractional extraction system, and transferring all the loaded neodymium-samarium enriched organic phase LOP5 into a back extraction section.
2. The method for preparing 6N-grade neodymium chloride by using a fractional extraction separation process according to claim 1, which is characterized in that: the saponification section I adopts ammonia water to saponify the unloaded organic phase to obtain an ammonia saponified organic phase; separating CePr/NdSm full-load fractional extraction separation system to obtain aqueous solution of cerium praseodymium neodymium chloride concentrate, and carrying out exchange reaction on the aqueous solution and an ammonia saponification organic phase to prepare a CePrNd-loaded organic phase LOP1; the CePrNd-loaded organic phase LOP1 is used as a rare earth saponification organic phase of a CePr/NdSm full-load fractional extraction separation system.
3. The method for preparing 6N-grade neodymium chloride by using a fractional extraction separation process according to claim 1, which is characterized in that: the saponification section II adopts ammonia water to saponify the unloaded organic phase to obtain an ammonia saponified organic phase; separating the 6N-level neodymium chloride aqueous solution obtained by the Nd/Sm full-load fractional extraction separation system and the ammonia saponification organic phase to perform exchange reaction to prepare a Nd-loaded organic phase LOP2; the Nd-loaded organic phase LOP2 is completely transferred into a purification section.
4. The method for preparing 6N-grade neodymium chloride by using a fractional extraction separation process according to claim 1, which is characterized in that: the purification section takes a 6N-level neodymium chloride aqueous solution obtained by a Nd/Sm full-load fractionation extraction separation system as a purifying agent, a Nd-loaded organic phase LOP2 obtained by a saponification section enters the purification section from a 1 st level, and the purifying agent 6N-level neodymium chloride aqueous solution enters the purification section from a 6 th level; and 6-stage countercurrent purification is carried out, and a 6N-stage loaded neodymium organic phase LOP3 is obtained from a 6-stage outlet organic phase of the purification section, wherein the 6N-stage loaded neodymium organic phase LOP3 is used as a neodymium saponification organic phase of a Nd/Sm full-load fractional extraction separation system.
5. The method for preparing 6N-grade neodymium chloride by using a fractional extraction separation process according to claim 1, which is characterized in that: the back extraction section adopts HCl solution with the concentration of 3.0 mol/L as a back extraction agent, 12-level countercurrent back extraction is carried out on a neodymium-samarium-enriched organic phase LOP5 obtained from a Nd/Sm fully loaded fractionation extraction separation system; the water phase outlet of the back extraction section obtains a neodymium chloride samarium concentrate water solution which is used as a washing agent W2 of an Nd/Sm full-load fractional extraction separation system; the organic phase outlet of the stripping section obtains a regenerated non-loaded organic phase.
6. The method for preparing 6N-grade neodymium chloride by using a fractional extraction separation process according to claim 1, which is characterized in that: the concentration of rare earth elements in the 4N-level neodymium chloride aqueous solution is Ce 0.70 mg/L-2.8 mg/L, pr 2.0 mg/L-5.6 mg/L, nd 143 g/L-147 g/L, sm 1.5 mg/L-4.5 mg/L respectively.
7. The method for preparing 6N-grade neodymium chloride by using a fractional extraction separation process according to claim 1, which is characterized in that: the concentration of rare earth elements in the 6N-level neodymium chloride aqueous solution is 0.0051/mg-0.030 mg/L, pr 0.012.012 mg/L-0.070 mg/L, nd 144 g/L-146 g/L, sm 0.0072 mg/L-0.028 mg/L respectively.
8. The method for preparing 6N-grade neodymium chloride by using a fractional extraction separation process according to claim 2, which is characterized in that: the non-loaded organic phase is the sulfonated kerosene solution of P507, wherein the concentration of P507 is 1.0 mol/L.
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