CN113667826B - Method for removing calcium and magnesium ions in rare earth solution of calcium-magnesium-containing soap material and purifying calcium and magnesium by extraction method - Google Patents

Method for removing calcium and magnesium ions in rare earth solution of calcium-magnesium-containing soap material and purifying calcium and magnesium by extraction method Download PDF

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CN113667826B
CN113667826B CN202110946598.3A CN202110946598A CN113667826B CN 113667826 B CN113667826 B CN 113667826B CN 202110946598 A CN202110946598 A CN 202110946598A CN 113667826 B CN113667826 B CN 113667826B
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CN113667826A (en
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胡广寿
李虎平
王斌
韩满璇
王兆彦
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Gansu Rare Earth New Material LLC
Lanzhou University
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Lanzhou University
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Abstract

The invention discloses a method for removing calcium and magnesium ions in a calcium-magnesium-containing soap rare earth solution and purifying calcium and magnesium by an extraction method, and belongs to the technical field of rare earth hydrometallurgical extraction. The invention also comprises a saponification control section before the multistage extraction, wherein the multistage extraction consists of an ammonium/magnesium separation control section, a magnesium/calcium separation control section and 3 separation sections before and after the magnesium/calcium/soap rare earth separation control section; the first-stage outlet water phase of the ammonium/magnesium separation control section and the saponification wastewater of the saponification control section are converged and discharged from a saponification control section water outlet; a part of the first-stage water phase of the magnesium/calcium separation control section is discharged and used for preparing a snow-melting agent after evaporation and crystallization, and the other part is used as the water phase of the upper stage; and part of the first-stage water phase of the magnesium-calcium/soap rare earth separation control section is discharged and used for preparing a snow-melting agent after evaporative crystallization, the other part of the first-stage water phase is used as the water phase of the previous stage, and the final-stage organic phase of the magnesium-calcium/soap rare earth separation control section is transformed out to be used as a load organic of a rare earth extraction production line.

Description

Method for removing calcium and magnesium ions in rare earth solution of calcium-magnesium-containing soap material and purifying calcium and magnesium by extraction method
Technical Field
The invention belongs to the technical field of rare earth hydrometallurgical extraction, and particularly relates to a method for removing calcium and magnesium ions in a calcium-magnesium-containing soap rare earth solution and purifying calcium and magnesium by an extraction method.
Background
The rare earth resource generates a large amount of high-salt and high-ammonia nitrogen wastewater in the wet smelting process, and enterprises must treat the rare earth smelting wastewater to reach the standard to protect the environment so as to realize the green development and sustainable development of the rare earth industry. The ammonium chloride wastewater generated in the rare earth wet smelting process is generally divided into two types, one type is precipitation wastewater generated in the rare earth ammonium chloride carbonate precipitation process, and the method is characterized in that the wastewater has low ammonia nitrogen concentration and low impurity content. The other type is saponification wastewater generated by ammonia saponification extraction (rare earth extraction separation line) of rare earth chloride under a chloride system, and the ammonia saponification extraction process of the existing rare earth chloride under the chloride system comprises the following steps: the method comprises the steps of carrying out saponification reaction on a P507 organic phase and industrial ammonia water to obtain a saponification organic phase with a saponification rate of 0.30-0.36, setting multi-stage extraction, taking the saponification organic phase as an initial organic phase of primary extraction, taking a calcium-magnesium soap rare earth solution as an initial aqueous phase of final extraction, taking the organic phase after each stage of extraction as an organic phase of the next stage, taking the aqueous phase after each stage of extraction as an aqueous phase of the previous stage, namely, carrying out the organic phase back-transfer and forward-going processes, finally taking the organic phase out of the final stage of extraction as a load organic phase of a rare earth extraction production line, taking the aqueous phase out of the final stage of extraction as ammonium chloride wastewater, and mainly characterized by higher ammonia nitrogen concentration of the wastewater, but simultaneously higher calcium, magnesium and other impurities and great wastewater treatment difficulty.
Most rare earth enterprises adopt MVR+triple effect evaporation technology in the treatment process of ammonium chloride wastewater. The ammonium chloride wastewater generated by the precipitation can be directly treated due to lower content of calcium and magnesium impurities, but the ammonium chloride wastewater generated by the extraction is influenced by the purity of rare earth separation raw materials, so that the content of calcium and magnesium impurities is higher, the evaporator is easy to be blocked in the actual production and operation process, and a calcium and magnesium removal procedure is required to avoid scaling, and the commonly adopted calcium and magnesium removal method is an oxalic acid precipitation method and an ammonium bicarbonate precipitation method. The method has high production cost due to the consumption of a large amount of chemical reagents, the generation of a large amount of solid wastes in the calcium removal process and the complicated process.
In order to remove calcium and magnesium, there is also an attempt to perform extraction operation in a wastewater treatment stage, for example, in patent application with publication number of CN105461002a and patent application name of a method for removing calcium and magnesium from rare earth industrial wastewater, the described technical scheme is that "ammonium sulfate wastewater generated by a smelting process of a rare earth acid method is used as a treatment object, P507 with 50% by volume ratio is added with 50% by volume ratio of sulfonated kerosene as an organic extractant, extraction is performed under the conditions that the volume ratio of an organic phase to a liquid phase is 1-2 and the saponification rate is 45% -60%, and standing and layering are performed after extraction", the method uses ammonium sulfate wastewater as a treatment object, and a re-extraction scheme is adopted for the ammonium sulfate wastewater generated by the smelting process of the rare earth acid method, but the method also has obvious technical defects: the saponification P507 is used for extraction again, the process cost is high in the saponification stage, the saponification stage can only exist in a laboratory, the large-scale application is difficult to take place in economic value, in addition, the extraction process also has the condition that calcium is enriched in an extractant, if an optional calcium outlet or an effective calcium dissociation means is not arranged in an extraction production line, the calcium enrichment can be easily caused, when the calcium in the system reaches a certain degree, the calcium overflows from a front-stage water phase outlet of the production line, the calcium removal effect is reduced, and the solid is difficult to popularize and use.
Therefore, in order to solve the problem of difficult treatment of the ammonium chloride wastewater, besides how to treat the wastewater, it is necessary to improve the wastewater conditions in the early wastewater generation stage, thereby fundamentally eliminating the problem of difficult treatment of the ammonium chloride wastewater.
Disclosure of Invention
The invention aims to provide a method for removing calcium and magnesium ions in a rare earth solution of a calcium-magnesium-containing soap material and purifying calcium and magnesium by an extraction method, which is used for solving the technical problem that saponification wastewater generated by ammonia saponification extraction of the existing rare earth chloride under a chloride system is difficult to treat.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the method comprises the steps of setting multistage extraction, taking an ammonia saponification P507 organic phase as an initial organic phase of primary extraction, taking the calcium-magnesium soap rare earth solution as an initial aqueous phase of final extraction, taking the organic phase after each stage of extraction as an organic phase of the next stage, taking the aqueous phase after each stage of extraction as an aqueous phase of the previous stage, and further comprising a saponification control section before the multistage extraction, wherein the multistage extraction consists of an ammonium/magnesium separation control section, a magnesium/calcium separation control section and 3 separation sections before and after the magnesium/calcium soap rare earth separation control section; the first-stage outlet water phase of the ammonium/magnesium separation control section and the saponification wastewater of the saponification control section are converged and discharged from a saponification control section water outlet; a part of the first-stage water phase of the magnesium/calcium separation control section is discharged and used for preparing a snow-melting agent after evaporation and crystallization, and the other part is used as the water phase of the upper stage; and part of the first-stage water phase of the magnesium-calcium/soap rare earth separation control section is discharged and used for preparing a snow-melting agent after evaporative crystallization, the other part of the first-stage water phase is used as the water phase of the previous stage, and the final-stage organic phase of the magnesium-calcium/soap rare earth separation control section is transformed out to be used as a load organic of a rare earth extraction production line.
The principle of the invention is to utilize the extraction balance difference of ammonium ion, magnesium ion, calcium ion and rare earth ion in the extractant to realize the separation of ammonium/magnesium/calcium/soap material rare earth under the P507-HCl system, so that the generated rare earth soap wastewater calcium and magnesium ion both meet the wastewater treatment requirement and the enrichment and purification of element calcium and magnesium, and the atom economy is effectively realized.
Preferably, the ammonium/magnesium separation control section is provided with at least 3 stages.
Preferably, the magnesium/calcium separation control section is provided with at least 4 stages.
Preferably, the magnesium-calcium/soap stock rare earth separation control section is provided with at least 4 stages.
Preferably, the ammonia saponification P507 organic phase is prepared by mixing P507 and sulfonated kerosene, and then fully clarifying after industrial ammonia water saponification, wherein the saponification degree is 30% -36%.
Further, the concentration of the industrial ammonia water is 6.0-6.5 mol/L.
Preferably, the concentration of the relevant elements of the calcium-magnesium-containing soap stock rare earth solution serving as the initial aqueous phase is respectively as follows: ca (Ca) 2+ Ion concentration is 4-5 g/L, mg 2+ The ion concentration is 2.5-3 g/L, NH 4 + The ion concentration is not more than 0.005g/L, and the rare earth concentration is 250-300 g/L.
Further, the magnesium calciumThe concentration of water phase related elements of the first stage of the soap stock rare earth separation control section is respectively as follows: ca (Ca) 2+ Ion concentration is 4-5 g/L, mg 2+ The ion concentration is 2.5-3.0 g/L, NH 4 + Not more than 0.01g/L and rare earth concentration not more than 0.1g/L.
Further, the concentration of the water phase related elements of the first stage of the magnesium/calcium separation control section is respectively as follows: ca (Ca) 2+ Ion concentration of not more than 0.01g/L, mg 2+ The ion concentration is 2.0-2.5 g/L, NH 4 + The ion concentration is not more than 0.015g/L, and the rare earth concentration is not more than 0.01g/L.
More preferably, the concentrations of the water phase related elements of the first stage of the ammonium/magnesium separation control section are respectively as follows: ca (Ca) 2+ Ion concentration of not more than 0.005g/L, mg 2+ Ion concentration of not more than 0.005g/LL, NH 4 + The ion concentration is 150-160 g/L, and the rare earth concentration is not more than 0.005g/L.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the original saponification rare earth soap section function is increased by coupling the existing extraction production line process, the traditional organic phase saponification and the preparation of the loaded rare earth organic phase are realized without additional consumption of other chemical reagents, and the existing separation work of the production line is utilized to separate and remove redundant calcium and magnesium ions of the whole separation line and produce the snow-melting agent consisting of magnesium chloride and calcium magnesium chloride; according to the method, a precipitation method calcium and magnesium removal procedure in a wastewater treatment process is omitted, other reagents are not required to be introduced to pretreat waste liquid, the current situation that the production cost of the traditional precipitation method calcium and magnesium removal is high can be effectively solved, purified magnesium chloride and calcium and magnesium chloride can be used as products for export to realize reduction and recycling of waste residues, the atom economy is effectively improved, and the problem of serious equipment blockage in the wastewater treatment process can be effectively avoided in ammonium chloride wastewater with calcium and magnesium removed;
(2) Compared with the traditional transformation separation line process, the invention has the advantages that on the basis of original actual consumption, no other reagent is added, only the extraction stage number is increased, the difficulty of wastewater treatment is reduced on the premise of zero consumption of the reagent, part of wastewater treatment is pre-arranged, and meanwhile, the wastewater of a saponification section is combined to obtain wastewater with higher ammonia content, so that the wastewater is convenient for evaporation and crystallization treatment.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
Detailed Description
Referring to fig. 1, a schematic process flow of the present invention is shown, and the present invention is further described with reference to the accompanying drawings and examples, which include but are not limited to the following examples.
Example 1
The organic phase of P507 is a solution prepared by P507 and sulfonated kerosene according to a certain volume ratio, wherein the concentration of P507 is 1.0mol/L.
The saponifier ammonia water is a solution prepared by liquid ammonia and pure water according to a certain proportion, wherein the concentration of the ammonia water is 6.0mol/L.
The concentration of the relevant elements of the rare earth solution of the calcium-magnesium-containing soap material to be treated is respectively as follows: ca (Ca) 2+ Ion concentration of 4.26g/L, mg 2+ Ion concentration of 2.51g/L, NH 4 + The ion concentration is 0.004g/L, and the rare earth concentration is 274.85g/L.
After the original rare earth extraction separation line treatment, the concentrations of the related elements of the generated ammonium chloride wastewater containing calcium and magnesium ions are respectively as follows: ca (Ca) 2+ ＝4.15g/L、Mg 2+ ＝2.44g/L、NH 4 Cl＝154g/L。
The processing method according to this embodiment is specifically as follows:
step 1, saponification control section: controlling the saponification rate of the P507 organic phase to be 0.30, adding the P507 organic phase and industrial ammonia water into a saponification section mixer-settler 1 level according to the saponification rate requirement, enabling an equilibrium water phase of the ammonium/magnesium separation control section 1 level in the step 2 to enter into wastewater of a saponification control section from the section 2 level, collecting all wastewater by the saponification control section 1 level, enabling an outlet water phase to be ammonium chloride wastewater meeting the calcium and magnesium content requirement of the wastewater, and enabling an outlet organic phase of the saponification control section 2 level to be an ammonium saponification P507 organic phase. The obtained ammonium soaping P507 organic phase is used as the extraction organic phase of the ammonium/magnesium separation control stage of step 2. The generated wastewater is an ammonium chloride solution with calcium and magnesium ions meeting wastewater treatment requirements, and can be directly used for recycling ammonium chloride in a wastewater evaporation system, and the recycled ammonium chloride can be sold as an agricultural chemical fertilizer.
Step 2, ammonium/magnesium separation control section: the organic phase of the ammonium saponification P507 obtained in the 2 nd stage of the saponification control section in the step 1 is used as a balance load, and the balance water phase obtained in the 1 st stage of the magnesium/calcium separation section in the step 3 is used as a washing liquid. The equilibrium aqueous phase of the magnesium/calcium separation control stage of step 3 enters the ammonium/magnesium separation stage from the last 1 stage of the stage. An ammonium chloride solution with the target purity of calcium and magnesium meeting the subsequent wastewater treatment index is obtained from the water phase at the 1 st grade outlet of the ammonium/magnesium separation control section and enters the step 1 to be converged with the saponification wastewater of the saponification control section; obtaining magnesium loaded P507 organic phase from the ammonium/magnesium separation control stage 3 rd stage outlet organic phase provides separation work for the stage 3 magnesium/calcium separation control stage.
Step 3, magnesium/calcium separation control section: taking the magnesium-containing load P507 organic phase obtained in the stage 3 of the ammonium/magnesium separation control section in the step 2 as balance load, and enabling the balance water phase of the magnesium-calcium/soap rare earth separation control section in the step 4 to enter the magnesium/calcium separation section from the final stage 1. The magnesium chloride solution obtained from part of the water phase at the 1 st stage outlet of the magnesium/calcium separation control section is partially led out and then is concentrated to be used as a product for export, and the dosage is calculated partially according to the concentration and the volume of ammonium ions in the front section and is used for washing liquid of the ammonium/magnesium separation control section in the step 2; obtaining the magnesium-calcium loaded P507 organic phase from the magnesium/calcium separation control stage 4 grade outlet organic phase provides separation work for the magnesium/calcium separation control stage of step 4.
Step 4, a magnesium-calcium/soap stock rare earth separation control section: taking the magnesium-calcium-containing load P507 organic phase obtained in the stage 4 of the magnesium/calcium separation control section in the step 3 as balance load, and feeding a balance water phase (raffinate) of the extraction section of the rare earth extraction production line from the final 1-stage magnesium-calcium/rare earth separation control section. The water phase at the 1 st stage outlet of the magnesium-calcium/rare earth separation control section obtains calcium-magnesium chloride solution with certain purity after separating ammonium/rare earth, part of the solution is led out and then is concentrated to be used as a snow-melting agent for export, and the amount of the solution is calculated according to the concentration and the volume of ammonium ions in the front stage section and is used for washing liquid of the magnesium-calcium separation control section in the step 3; the P507 organic phase of loaded soap stock rare earth obtained from the 5 th grade outlet organic phase of the magnesium-calcium/rare earth separation section is used as the loaded organic phase of the rare earth extraction production line to enter the separation section.
The concentrations of relevant elements in the ammonium chloride wastewater after the operation and treatment according to the embodiment are respectively as follows: ca (Ca) 2+ ＝0.0038g/L、Mg 2+ ＝0.0034g/L、NH 4 Cl is about 153.51g/L, and compared with the original rare earth extraction separation line treatment, the magnesium and calcium ions in the wastewater obtained by extraction in the embodiment are greatly reduced.
The concentrations of relevant elements in the magnesium chloride wastewater are respectively as follows: NH (NH) 4 + ＝0.013g/L、Ca 2+ ＝0.0087g/L。
The concentrations of relevant elements in the calcium chloride magnesium wastewater are respectively as follows: NH (NH) 4 + ＝0.047g/L、RE0＝0.053g/L。
Example 2
The organic phase of P507 is a solution prepared by P507 and sulfonated kerosene according to a certain volume ratio, wherein the concentration of P507 is 1.5mol/L.
The saponifier ammonia water is a solution prepared by liquid ammonia and pure water according to a certain ratio, wherein the concentration of the ammonia water is 6.5mol/L.
The concentration of the relevant elements of the rare earth solution of the calcium-magnesium-containing soap material to be treated is respectively as follows: ca (Ca) 2+ Ion concentration of 4.87g/L, mg 2+ Ion concentration of 2.74g/L, NH 4 + The ion concentration is 0, and the rare earth concentration is 285g/L.
The concentration of the relevant elements of the ammonium chloride wastewater containing calcium and magnesium ions generated by the original rare earth extraction separation line is respectively as follows: ca (Ca) 2+ ＝4.15g/L、Mg 2+ ＝2.74g/L、NH 4 Cl＝157g/L。
Step 1, saponification control section: controlling the saponification rate of the P507 organic phase to be 0.36, adding the P507 organic phase and industrial ammonia water into a saponification section mixer-settler 1 level according to the saponification rate requirement, enabling an equilibrium water phase of the ammonium/magnesium separation control section 1 level in the step 2 to enter into wastewater of a saponification control section from the section 2 level, collecting all wastewater by the saponification control section 1 level, enabling an outlet water phase to be ammonium chloride wastewater meeting the calcium and magnesium content requirement of the wastewater, and enabling an outlet organic phase of the saponification control section 2 level to be an ammonium saponification P507 organic phase. The obtained ammonium soaping P507 organic phase is used as the extraction organic phase of the ammonium/magnesium separation control stage of step 2. The generated wastewater is an ammonium chloride solution with calcium and magnesium ions meeting wastewater treatment requirements, and can be directly used for recycling ammonium chloride in a wastewater evaporation system, and the recycled ammonium chloride can be sold as an agricultural chemical fertilizer.
Step 2, ammonium/magnesium separation control section: the organic phase of the ammonium saponification P507 obtained in the 2 nd stage of the saponification control section of the step 1 is used as a balance load, and the balance water phase obtained in the 1 st stage of the magnesium/calcium separation control section of the step 3 is used as a washing liquid. The equilibrium aqueous phase of the magnesium/calcium separation control stage of step 3 enters the ammonium/magnesium separation stage from the last 1 stage of the stage. An ammonium chloride solution with the target purity of calcium and magnesium meeting the subsequent wastewater treatment index is obtained from the water phase at the 1 st grade outlet of the ammonium/magnesium separation control section and enters the step 1 to be converged with the saponification wastewater of the saponification control section; obtaining magnesium loaded P507 organic phase from the ammonium/magnesium separation control stage 3 rd stage outlet organic phase provides separation work for the stage 3 magnesium/calcium separation control stage.
Step 3, magnesium/calcium separation control section: taking the magnesium-containing load P507 organic phase obtained in the stage 3 of the ammonium/magnesium separation control section in the step 2 as balance load, and enabling the balance water phase of the magnesium-calcium/soap rare earth separation control section in the step 4 to enter the magnesium/calcium separation section from the final stage 1. The magnesium chloride solution obtained from part of the water phase at the 1 st stage outlet of the magnesium/calcium separation control section is partially led out and then is concentrated to be used as a product for export, and the dosage is calculated partially according to the concentration and the volume of ammonium ions in the front section and is used for washing liquid of the ammonium/magnesium separation control section in the step 2; obtaining the magnesium-calcium loaded P507 organic phase from the magnesium/calcium separation control stage 4 grade outlet organic phase provides separation work for the magnesium/calcium separation control stage of step 4.
Step 4, magnesium-calcium/soap stock rare earth separation section: taking the magnesium-calcium-containing load P507 organic phase obtained in the stage 4 of the magnesium/calcium separation control section in the step 3 as balance load, and feeding a balance water phase (raffinate) of the extraction section of the rare earth extraction production line from the final 1-stage magnesium-calcium/rare earth separation control section. The water phase at the 1 st stage outlet of the magnesium-calcium/rare earth separation control section obtains calcium-magnesium chloride solution with certain purity after separating ammonium/rare earth, part of the solution is led out and then is concentrated to be used as a snow-melting agent for export, and the amount of the solution is calculated according to the concentration and the volume of ammonium ions in the front stage section and is used for washing liquid of the magnesium-calcium separation control section in the step 3; the P507 organic phase of loaded soap stock rare earth obtained from the 5 th grade outlet organic phase of the magnesium-calcium/rare earth separation section is used as the loaded organic phase of the rare earth extraction production line to enter the separation section.
The concentrations of relevant elements in the ammonium chloride wastewater after the operation and treatment according to the embodiment are respectively as follows: ca (Ca) 2+ ＝0.0038g/L、Mg 2+ ＝0.0034g/L、NH 4 Cl is about 156.51g/L, and compared with the original rare earth extraction separation line treatment, the magnesium and calcium ions in the wastewater obtained by extraction in the embodiment are greatly reduced.
The concentrations of relevant elements in the magnesium chloride wastewater are respectively as follows: NH (NH) 4 + ＝0.013g/L、Ca 2+ ＝0.0087g/L。
The concentrations of relevant elements in the calcium chloride magnesium wastewater are respectively as follows: NH (NH) 4 + ＝0.047g/L、RE0＝0.053g/L。
Example 3
The organic phase of P507 is a solution prepared by P507 and sulfonated kerosene according to a certain volume ratio, wherein the concentration of P507 is 1.5mol/L.
The saponifier ammonia water is a solution prepared by liquid ammonia and pure water according to a certain proportion, wherein the concentration of the ammonia water is 6.5mol/L.
The concentration of the relevant elements of the rare earth solution of the calcium-magnesium-containing soap material to be treated is respectively as follows: ca (Ca) 2+ Ion concentration of 4.87g/L, mg 2+ Ion concentration of 2.91g/L, NH 4 + Ion concentration is 0.0042, rare earth concentration is 296.49g/L,
the concentration of the relevant elements of the ammonium chloride wastewater containing calcium and magnesium ions generated by the original rare earth extraction separation line is respectively as follows: ca (Ca) 2+ ＝4.93g/L、Mg 2+ ＝2.84g/L、NH 4 Cl＝157.32g/L。
Step 1, saponification control section: controlling the saponification rate of the P507 organic phase to be 0.36, adding the P507 organic phase and industrial ammonia water into a saponification section mixer-settler 1 level according to the saponification rate requirement, enabling an equilibrium water phase of the ammonium/magnesium separation control section 1 level in the step 2 to enter into wastewater of a saponification control section from the section 2 level, collecting all wastewater by the saponification control section 1 level, enabling an aqueous phase to be ammonium chloride wastewater meeting the calcium and magnesium content requirement of the wastewater, and enabling an organic phase at an outlet of the saponification control section 3 level to be an ammonium saponification P507 organic phase. The obtained ammonium soaping P507 organic phase is used as the extraction organic phase of the ammonium/magnesium separation control stage of step 2. The generated wastewater is an ammonium chloride solution with calcium and magnesium ions meeting wastewater treatment requirements, and can be directly used for recycling ammonium chloride in a wastewater evaporation system, and the recycled ammonium chloride can be sold as an agricultural chemical fertilizer.
Step 2, ammonium/magnesium separation: the organic phase of the ammonium saponification P507 obtained in the 3 rd stage of the saponification control section of the step 1 is used as a balance load, and the balance water phase obtained in the 1 st stage of the magnesium/calcium separation control section of the step 3 is used as a washing liquid. The equilibrium aqueous phase of the magnesium/calcium separation control stage of step 3 enters the ammonium/magnesium separation stage from the last 1 stage of the stage. An ammonium chloride solution with the target purity of calcium and magnesium meeting the subsequent wastewater treatment index is obtained from the water phase at the 1 st grade outlet of the ammonium/magnesium separation control section and enters the step 1 to be converged with the saponification wastewater of the saponification control section; obtaining magnesium loaded P507 organic phase from the ammonium/magnesium separation control stage 4 stage outlet organic phase provides separation work for the magnesium/calcium separation control stage of step 3.
Step 3, magnesium/calcium separation section: taking the magnesium-containing load P507 organic phase obtained in the stage 4 of the ammonium/magnesium separation control stage 2 as balance load, and enabling the balance water phase of the magnesium-calcium/soap rare earth separation control stage in the stage 4 to enter the magnesium/calcium separation stage from the final stage 1. The magnesium chloride solution obtained from partial water phase at the 1 st stage outlet of the magnesium/calcium separation control section is partially led out and then is concentrated to be used as a product for export, and the partial solution is used for washing liquid of the ammonium/magnesium separation control section in the step 2 according to the ammonium ion concentration and the volume calculation dosage of the front section; obtaining the P507 organic phase loaded with magnesium and calcium from the 5-stage outlet organic phase of the magnesium/calcium separation control section provides separation work for the magnesium/calcium separation control section of step 4.
Step 4, a magnesium-calcium/soap stock rare earth separation control section: taking the magnesium-calcium-containing load P507 organic phase obtained in the stage 4 of the magnesium/calcium separation control section in the step 3 as balance load, and feeding a balance water phase (raffinate) of the extraction section of the rare earth extraction production line from the final 1-stage magnesium-calcium/rare earth separation control section. The water phase at the 1 st stage outlet of the magnesium-calcium/rare earth separation control section obtains calcium-magnesium chloride solution with certain purity after separating ammonium/rare earth, part of the solution is led out and then is concentrated to be used as a snow-melting agent for export, and the amount of the solution is calculated according to the concentration and the volume of ammonium ions in the front stage section and is used for washing liquid of the magnesium-calcium separation control section in the step 3; the P507 organic phase loaded with soap stock rare earth obtained from the 6 th grade outlet organic phase of the magnesium-calcium/rare earth separation section is used as the loading organic phase of the rare earth extraction production line to enter the separation section.
The concentrations of relevant elements in the ammonium chloride wastewater after the operation and treatment according to the embodiment are respectively as follows: ca (Ca) 2+ ＝0.0021g/L、Mg 2+ ＝0.0024g/L、NH 4 Cl is about 158.51g/L, and compared with the original rare earth extraction separation line treatment, the magnesium and calcium ions in the wastewater obtained by extraction in the embodiment are greatly reduced.
The concentrations of relevant elements in the magnesium chloride wastewater are respectively as follows: NH (NH) 4 + ＝0.011g/L、Ca 2+ ＝0.0064g/L。
The concentrations of relevant elements in the calcium chloride magnesium wastewater are respectively as follows: NH (NH) 4 + ＝0.032g/L、RE0＝0.021g/L。
The above embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or color changes made in the main design concept and spirit of the present invention are still consistent with the present invention, and all the technical problems to be solved are included in the scope of the present invention.

Claims (3)

1. The method for removing calcium and magnesium ions in rare earth solution of calcium-magnesium-containing soap material and purifying calcium and magnesium by using an extraction method is characterized in that multistage extraction is arranged, an ammonia saponification P507 organic phase is used as an initial organic phase of primary extraction, the calcium-magnesium-containing soap material rare earth solution is used as an initial aqueous phase of final extraction, organic phases after each stage of extraction are used as organic phases of next stage, and aqueous phases after each stage of extraction are used as aqueous phases of previous stage, and the method is characterized in that: the multistage extraction is composed of an ammonium/magnesium separation control section, a magnesium/calcium separation control section and 3 separation sections before and after the magnesium/calcium/soap rare earth separation control section; the first-stage outlet water phase of the ammonium/magnesium separation control section and the saponification wastewater of the saponification control section are converged and discharged from a saponification control section water outlet, and the ammonium/magnesium separation control section is at least provided with 3 stages; a part of the first-stage water phase of the magnesium/calcium separation control section is discharged and used for preparing a snow-melting agent after evaporation and crystallization, and the other part of the first-stage water phase is used as the water phase of the upper stage, and the magnesium/calcium separation control section is at least provided with 4 stages; a part of the first-stage water phase of the magnesium-calcium/soap-stock rare earth separation control section is discharged and used for preparing a snow-melting agent after evaporation and crystallization, and the other part of the first-stage water phase is used as the water phase of the previous stage, and the final-stage organic phase of the magnesium-calcium/soap-stock rare earth separation control section is converted to be used as a load organic of a rare earth extraction production line, wherein the magnesium-calcium/soap-stock rare earth separation control section is at least provided with 4 stages;
the concentration of the related elements of the calcium-magnesium-containing soap stock rare earth solution serving as the initial aqueous phase is respectively as follows: ca (Ca) 2+ Ion concentration is 4-5 g/L, mg 2+ The ion concentration is 2.5-3 g/L, NH 4 + The ion concentration is not more than 0.005g/L, and the rare earth concentration is 250-300 g/L;
the concentration of water phase related elements of the first stage of the magnesium-calcium/soap stock rare earth separation control section is respectively as follows: ca (Ca) 2+ Ion concentration is 4-5 g/L, mg 2+ The ion concentration is 2.5-3 g/L, NH 4 + Ion concentration is not more than 0.01g/L, and rare earth concentration is not more than 0.1g/L;
the concentration of the water phase related elements of the first stage of the magnesium/calcium separation control section is respectively as follows: ca (Ca) 2+ Ion concentration of not more than 0.01g/L, mg 2+ The ion concentration is 2.0-2.5 g/L, NH 4 + Ion concentration is not more than 0.015g/L, and rare earth concentration is not more than 0.01g/L;
the concentration of the water phase related elements of the first stage of the ammonium/magnesium separation control section is respectively as follows: ca (Ca) 2+ Ion concentration of not more than 0.005g/L, mg 2+ Ion concentration of not more than 0.005g/LL, NH 4 + The ion concentration is 150-160 g/L, and the rare earth concentration is not more than 0.005g/L.
2. The method of claim 1, wherein the ammonia saponification P507 organic phase is prepared by mixing P507 with sulfonated kerosene, and then fully clarifying the mixture after industrial ammonia water saponification, and the saponification degree is 30% -36%.
3. The method according to claim 2, wherein the concentration of the industrial aqueous ammonia is 6.0 to 6.5mol/L.
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