CN111440946A - Rare earth extraction method for realizing recycling of magnesium bicarbonate - Google Patents
Rare earth extraction method for realizing recycling of magnesium bicarbonate Download PDFInfo
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Abstract
The invention belongs to the technical field of rare earth smelting and separation, and particularly relates to a rare earth extraction method for realizing recycling of magnesium bicarbonate. The rare earth extraction method of the invention uses magnesium bicarbonate to saponify the acidic extractant organic phase, and simultaneously recovers the saponification wastewater and CO in the saponification process2The obtained magnesium soap organic phase and rare earth feed liquid are subjected to rare earth saponification treatment to realize extraction of rare earth and prepare rare earth products, and magnesium chloride wastewater generated in the rare earth saponification process is mixed by adding saponification wastewater and amine extractant and utilizing recovered CO2The extraction-carbonization reaction is carried out to convert the magnesium chloride into the magnesium bicarbonate which can be recycled in the saponification process of the acidic extractant, thereby realizing the closed cycle utilization of the magnesium salt, greatly reducing the salt discharge in the rare earth extraction process and having obvious environmental benefit。
Description
Technical Field
The invention belongs to the technical field of rare earth smelting and separation, and particularly relates to a rare earth extraction method for realizing recycling of magnesium bicarbonate.
Background
Rare earth is a general term for 17 elements of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium 15 lanthanoid elements of the third subgroup of the 6 th period of the periodic table of elements and yttrium and scandium of the same group. The rare earth element has various excellent special physical and chemical properties such as magnetism, light, electricity and the like due to the unique electronic layer structure, and the rare earth material is a strategic material which is indispensable or substituted for developing high-precision industries of various countries in the world at present and plays a vital role in improving the traditional industry, is known as vitamins of the modern industry and a new material treasury, and has very wide market prospect and strategic significance.
At present, the separation and purification of rare earth elements mainly adopts an extraction separation technology, the used extractant is mainly acidic extractants such as P507, P204 and the like, the extraction capacity of rare earth is inversely proportional to the third time of water phase equilibrium acidity, in order to improve the production efficiency of rare earth separation, the extractant is firstly saponified by ammonia water or liquid alkali, then the prepared saponified extractant is subjected to extraction reaction with a rare earth solution to generate a rare earth-containing loaded organic phase and an ammonia (sodium) salt solution, the obtained rare earth-containing loaded organic phase is used for the serial extraction separation of rare earth, then a high-purity single rare earth solution is obtained by acid back extraction, and then a rare earth compound product is prepared by ammonium bicarbonate or sodium carbonate and oxalic acid precipitation.
However, the extraction agent saponified with ammonia water or liquid alkali used in the prior art can generate a large amount of ammonia (sodium) salt wastewater in the extraction process. According to statistics, for every 1 ton of rare earth oxide is completely separated, at least about 1 ton of liquid ammonia or 6-8 tons of liquid alkali are used, and more than ten tons of ammonia (sodium) -containing wastewater are discharged. For a large amount of generated ammonia (sodium) -containing wastewater, at present, no efficient treatment method exists, and only an evaporative crystallization process with extremely high energy consumption can be generally adopted for treatment, but the treatment process is high in cost and cannot be borne by most enterprises. Moreover, a large amount of saponification wastewater is generated in the rare earth extraction separation process, high treatment cost is required for enterprises, and serious pollution is caused to the ecological environment due to discharge, so that an environment-friendly saponification and rare earth extraction process is required to be developed.
The magnesium bicarbonate is an excellent acid balancing agent in the saponification process of the acidic extracting agent, has low impurity content of Fe, Al and the like, can react with the acidic extracting agent and does not generate a three-phase substance, and therefore, has wide application prospect in the rare earth extraction process. During the process of saponifying the acidic extractant with magnesium bicarbonate, magnesium ions exchange with hydrogen ions in the organic phase, and the hydrogen ions promote the hydrolysis of the magnesium bicarbonate to produce CO2And water. And (3) carrying out a rare earth soap process on the magnesium soap organic phase and the rare earth feed liquid, and exchanging magnesium ions with the rare earth ions to obtain the magnesium chloride wastewater. For example, chinese patent CN103382034A discloses a method for extracting agent saponification and rare earth extraction by using magnesium bicarbonate, in the process, magnesite, dolomite or magnesium carbonate is used as raw material after roasting and digestion, and MgCl generated in the saponification process is treated2Preparing Mg (OH) from waste water through alkali conversion reaction2And then with CO recovered during saponification2Preparation of Mg (HCO) by carbonization3)2The solution was used for saponification extraction. But the process is for MgCl2The recycling step of the wastewater needs to adopt caustic soda conversion of light-burned dolomite slurry to obtain Mg (OH)2And CaCl2Consumption of light burned dolomite for Mg (HCO)3)2Is supplied cyclically with CaCl2And also needs to be recycled in a certain way.
Disclosure of Invention
Therefore, the invention aims to provide a rare earth extraction method for realizing recycling of magnesium bicarbonate so as to solve the problem of difficulty in wastewater treatment in the rare earth extraction process in the prior art.
In order to solve the technical problem, the rare earth extraction method for recycling the magnesium bicarbonate is characterized in that magnesium chloride wastewater recovered in the rare earth soap process is mixed with an organic amine extractant and recovered CO2The preparation method of the magnesium bicarbonate solution through extraction-carbonization comprises the following steps:
(1) mixing acidic extractant with magnesium bicarbonate solution for saponification, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant and rare earth feed liquid to perform rare earth soap reaction, and performing extraction separation to obtain magnesium chloride wastewater and required rare earth products respectively;
(3) adding the saponification wastewater collected in the step (1) into the magnesium chloride wastewater collected in the step (2) for dilution, adding an amine extractant for uniformly mixing, and then introducing CO generated in the step (1)2Carrying out carbonization reaction on the gas;
(4) and (3) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution and is circularly used for the saponification reaction in the step (1).
In the step (1), the acidic extractant includes one or more of P507 (2-ethylhexyl phosphate mono 2-ethylhexyl ester), P204(HDEHP), P229 (di (2-ethylhexyl) phosphonic acid, H [ DEHP ]), hbtpmp (di (2,4, 4-trimethylpentyl) phosphonic acid).
In the step (1), the concentration of the magnesium bicarbonate solution is 0.01-0.5 mol/L, preferably 0.05-0.25 mol/L.
In the step (1), the dosage ratio of the acidic extracting agent to the magnesium bicarbonate solution is 0.2: 1-2: 1, preferably 0.5: 1-1.2: 1.
the main reaction process of saponifying the organic phase with magnesium bicarbonate is shown in the following formula, and the saponification process produces H2O and CO2And respectively recovering:
Mg(HCO3)2(aq)+(HL)2(o)→Mg(HL)2(o)+H2O+2CO2(g)。
in the step (2), the concentration of the rare earth feed liquid is 0.5-2 mol/L, and the volume ratio of the saponified extractant to the rare earth feed liquid is 3: 1-15: 1.
In the rare earth soap process, the main reaction process is as follows, the rare earth soap process generates magnesium chloride wastewater, and the magnesium chloride wastewater is recovered for subsequent steps:
3Mg(HL)2(o)+2RECl3(aq)→3MgCl2(aq)+2RE2(HL)3(o)。
in the step (2), the concentration of the magnesium chloride wastewater is adjusted to be 0.1-5 mol/L, and/or the pH of the magnesium chloride wastewater is adjusted to be 2-7.
In the step (3), the volume ratio of the saponified wastewater for dilution to the magnesium chloride wastewater is 5: 1-20: 1, preferably 7: 1-15: 1. because the magnesium chloride concentration obtained in the rare earth soap process is too high, the solubility of the magnesium bicarbonate solution is limited, and the highest magnesium bicarbonate concentration can only reach about 0.4 mol/L, the magnesium chloride wastewater needs to be diluted, and a certain degree of dilution is helpful for converting the magnesium chloride into the magnesium bicarbonate solution.
In the step (3):
the amine extractant comprises primary amine, secondary amine or tertiary amine organic amine extractant dissolved in diluent; the amine extractant is preferably N235, N263 and the like;
the diluent comprises benzene, monohydric alcohol, polyhydric alcohol or kerosene; the diluents are preferably mixed in equal amounts;
the main function of the amine extractant is to extract acidic substances in the presence of MgCl2、CO2And amine-based extractants, the following reactions occur:
CO2(g)+H2O→H2CO3；
H2CO3→HCO3 -+2H+；
N3R(o)+H+→N3R·H+(o)；
Mg2++2HCO3→Mg(HCO3)2。
in this reaction system, it is first necessary to have sufficient CO2Partial pressure of CO2And H2The carbonation of O is carried out sufficiently. Secondly, the key to the reaction is Mg2++2HCO3→Mg(HCO3)2The pH value of the process can effectively promote H when the pH value of the reaction system is more than 52CO3Hydrolysis to HCO3 -Further promote the reaction with Mg2+With HCO3Formation of Mg (HCO)3)2The forward reaction of (2) and under the condition of proper concentration, the high-efficiency synthesis of magnesium bicarbonate solution.
The volume ratio of the amine extractant to the diluent is 0.2: 1-2: 1, preferably 0.5: 1-1.5: 1.
in the step (3), the volume ratio of the magnesium chloride wastewater diluted by the saponification wastewater to the amine extractant is 0.2: 1-5: 1, control of CO introduced2The purity is 30-100%, and the carbonization time is 5-300min, preferably 20-80 min. Higher CO2The purity can ensure that the system has enough CO2Partial pressure, promoting the forward direction of the reaction.
In the step (4), a step of adding pure water or the saponification wastewater into the separated organic phase to perform mixed back extraction is further included; the phase ratio of the organic phase to the pure water or the saponified wastewater was 0.5: 1-5: 1, the time of the mixed back extraction is 1-60 min.
The rare earth extraction method for realizing the recycling of the magnesium bicarbonate uses the organic phase of the acidic extractant saponified by the magnesium bicarbonate and simultaneously recovers the saponified wastewater and CO in the saponification process2The obtained magnesium soap organic phase and rare earth feed liquid are subjected to rare earth saponification treatment to realize extraction of rare earth and prepare rare earth products, and magnesium chloride wastewater generated in the rare earth saponification process is added with saponification wastewater and aminesMixing and coarse extracting with extractant, and utilizing recovered CO2Carbonizing to convert magnesium chloride into magnesium bicarbonate for reuse in the saponification of acid extractant, and further back extracting the extracted hydrochloric acid with water or saponified waste water to obtain hydrochloric acid capable of being recovered. In the whole rare earth extraction process, the saponification wastewater and the magnesium chloride wastewater generated in each step can be recycled and then used for carbonizing and synthesizing magnesium bicarbonate, so that the closed cycle utilization of magnesium salts is realized, new other pollution is not introduced, only hydrochloric acid capable of being effectively utilized is generated, the salt discharge in the rare earth extraction process is greatly reduced, and the method has remarkable environmental benefits.
The rare earth extraction method for realizing the recycling of the magnesium bicarbonate can extract H by using the amine extractant+The method is characterized in that the method comprises the steps of firstly diluting magnesium chloride wastewater by using saponified wastewater, mixing the magnesium chloride wastewater with an amine extractant, and simultaneously introducing CO2Performing carbonization reaction, because the amine extractant can extract H+The hydrochloric acid as a product enters the organic phase during the reaction, thereby inhibiting MgCl2-CO2The pH of the reaction water phase system is reduced, and the magnesium chloride and CO are promoted2The carbonization reaction proceeds in the forward direction, so that magnesium chloride and CO are reacted2The reaction generates magnesium bicarbonate solution, has higher reaction yield and further improves the efficiency of the whole process.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a flow diagram of a rare earth extraction process of the present invention.
Detailed Description
In the rare earth extraction method related in the following examples of the present invention, the saponified wastewater of the acidic catalyst refers to the reaction of a magnesium bicarbonate solution with an acidic extractant, magnesium ions exchange with hydrogen ions in an organic phase, and the hydrolysis of the hydrogen bicarbonate generates CO2Then obtaining the saponified wastewater.
Example 1
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.14 mol/L) at volume ratio of 1.79: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 3: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 5.4: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in sec-octanol and kerosene (the volume ratio of the amine extractant to the diluent is 1.5: 1), and the ratio of diluted magnesium chloride to the mixed amine extractant is 2.14: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 60%) to carry out carbonization reaction for 40 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater was 0.5: 1, the time of the mixed back extraction is 60min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 2
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.14 mol/L) at volume ratio of 1.79: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 3: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 5.4: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in sec-octanol and kerosene (the volume ratio of the amine extractant to the diluent is 1: 1), and the ratio of diluted magnesium chloride to the mixed amine extractant is 2.14: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 50%) to carry out carbonization reaction for 20 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the ratio of the organic phase to the pure water or the saponified wastewater is 1: 1, the time of the mixed back extraction is 40min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 3
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) taking the acidic extractant P507 and a magnesium bicarbonate solution (with the controlled concentration of 0.15 mol/L) according to the volume ratio of 1.67: 1Mixing, saponifying at normal temperature, separating solid from liquid, and recovering CO2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 3: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 5.0: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in sec-octanol and kerosene (the volume ratio of the amine extractant to the diluent is 0.5: 1), and the ratio of diluted magnesium chloride to the mixed amine extractant is 2.00: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration of 70%) for carbonization reaction for 80 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 1.5: 1, the time of the mixed back extraction is 30min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 4
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.15 mol/L) at volume ratio of 1.67: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 3: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 5.0: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in sec-octanol and kerosene (the volume ratio of the amine extractant to the diluent is 1.5: 1), and the ratio of diluted magnesium chloride to the mixed amine extractant is 2.00: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 60%) to carry out carbonization reaction for 100 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 3: 1, the time of the mixed back extraction is 60min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 5
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.16 mol/L) at volume ratio of 1.56: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.8 mol/L of rare earth feed liquid according to the feed-liquid ratio of 4.8: 1, carrying out rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 7.5: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in 2-ethyl ethanol and kerosene (the volume ratio of the amine extractant to the diluent is 1: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.88: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 50%) to carry out carbonization reaction for 200 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 4: 1, the time of the mixed back extraction is 30min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 6
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.16 mol/L) at volume ratio of 1.56: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.8 mol/L of rare earth feed liquid according to the feed-liquid ratio of 4.8: 1, carrying out rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 7.5: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in 2-ethyl ethanol and kerosene (the volume ratio of the amine extractant to the diluent is 0.5: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.88: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration of 70%) for 40 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater was 0.5: 1, the time of the mixed back extraction is 30min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 7
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.18 mol/L) at volume ratio of 1.39: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.8 mol/L of rare earth feed liquid according to the feed-liquid ratio of 4.8: 1, carrying out rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 6.7: 1 adding to saidDiluting the saponification wastewater collected in the step (1), adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in 2-ethyl ethanol and kerosene (the volume ratio of the amine extractant to the diluent is 1.5: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.67: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 60%) to carry out carbonization reaction for 20 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the ratio of the organic phase to the pure water or the saponified wastewater is 1: 1, the time of the mixed back extraction is 60min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 8
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.2 mol/L) at a volume ratio of 1.25: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 0.8 mol/L of rare earth feed liquid according to the feed-liquid ratio of 4.8: 1, carrying out rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 6.0: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N263 for uniform mixing, wherein the amine extractant is obtained by dissolving the N263 in 2-ethylEthanol and kerosene (the volume ratio of the amine extractant to the diluent is 1: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.50: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 50%) to carry out carbonization reaction for 80 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 1.5: 1, the time of the mixed back extraction is 40min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 9
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.2 mol/L) at a volume ratio of 1.25: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 1.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 9: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 11.3: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N263 for uniformly mixing, wherein the amine extractant is obtained by dissolving the N263 in 2-ethyl alcohol and kerosene (the volume ratio of the amine extractant to the diluent is 0.5: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.50: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration of 70%) for carbonization reaction for 100 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 3: 1, the time of the mixed back extraction is 30min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 10
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.22 mol/L) at volume ratio of 1.14: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 1.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 9: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 10.2: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N263 for uniformly mixing, wherein the amine extractant is obtained by dissolving the N263 in 2-ethyl alcohol and kerosene (the volume ratio of the amine extractant to the diluent is 1.5: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.36: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 60%) to carry out carbonization reaction for 200 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 4: 1, the time of the mixed back extraction is 60min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 11
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P507 and magnesium bicarbonate solution (with concentration controlled at 0.25 mol/L) at volume ratio of 1.00: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 1.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 9: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 9.0: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N263 for uniform mixing, wherein the amine extractant is obtained by dissolving the N263 in kerosene (the volume ratio of the amine extractant to the diluent is 1: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.20: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 50%) to carry out carbonization reaction for 40 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater was 0.5: 1, the time of the mixed back extraction is 40min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 12
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P204 and magnesium bicarbonate solution (with concentration controlled at 0.13 mol/L) at volume ratio of 1.92: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 1.5 mol/L of rare earth feed liquid according to a feed-liquid ratio of 9: 1, carrying out a rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 17.3: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N263 for uniformly mixing, wherein the amine extractant is obtained by dissolving the N263 in kerosene (the volume ratio of the amine extractant to the diluent is 0.5: 1), and the ratio of diluted magnesium chloride to the mixed amine extractant is 2.31: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration of 70%) for 20 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the ratio of the organic phase to the pure water or the saponified wastewater is 1: 1, the time of the mixed back extraction is 30min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 13
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P204 and magnesium bicarbonate solution (with concentration controlled at 0.2 mol/L) at a volume ratio of 1.25: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 1.3 mol/L of rare earth feed liquid according to the feed-liquid ratio of 7.8: 1, carrying out rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 9.8: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in sec-octanol and kerosene (the volume ratio of the amine extractant to the diluent is 1.5: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.50: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 60%) to carry out carbonization reaction for 80 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 1.5: 1, the time of the mixed back extraction is 60min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 14
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant P229 and magnesium bicarbonate solution (with concentration controlled at 0.22 mol/L) at a volume ratio of 1.14: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 1.3 mol/L of rare earth feed liquid according to the feed-liquid ratio of 7.8: 1, carrying out rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 8.9: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in sec-octanol and kerosene (the volume ratio of the amine extractant to the diluent is 1: 1), and the ratio of the diluted magnesium chloride to the mixed amine extractant is 1.36: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration is 50%) to carry out carbonization reaction for 100 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 3: 1, the time of the mixed back extraction is 40min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
Example 15
As shown in the process flow diagram of fig. 1, the rare earth extraction method for recycling magnesium bicarbonate in this embodiment includes the following steps:
(1) mixing acidic extractant HBTMP and magnesium bicarbonate solution (with concentration controlled at 0.15 mol/L) at a volume ratio of 1.67: 1, performing saponification reaction at room temperature, performing solid-liquid separation, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant separated in the step (1) with 1.3 mol/L of rare earth feed liquid according to the feed-liquid ratio of 7.8: 1, carrying out rare earth soap reaction for 5min, carrying out extraction separation to respectively obtain magnesium chloride wastewater and required rare earth products, and further precipitating and roasting to obtain rare earth oxides;
(3) and (3) mixing the collected magnesium chloride wastewater according to the following steps: magnesium chloride volume ratio 13.0: 1, adding the saponification wastewater collected in the step (1) for dilution, adding an amine extractant N235, and uniformly mixing, wherein the amine extractant is obtained by dissolving the N235 in sec-octanol and kerosene (the volume ratio of the amine extractant to the diluent is 0.5: 1), and the ratio of diluted magnesium chloride to the mixed amine extractant is 2.00: 1, followed by introduction of CO produced in said step (1)2Gas (CO)2Gas concentration of 70%) for carbonization reaction for 200 min;
(4) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution; the obtained magnesium bicarbonate solution can be recycled for the saponification reaction in the step (1); and the organic phase can be subjected to mixed back extraction by adding pure water or the saponified wastewater obtained in the step (1) into the organic phase; the phase ratio of the organic phase to the pure water or the saponified wastewater is 4: 1, the time of the mixed back extraction is 30min, and the collected water phase is hydrochloric acid obtained by the back extraction and is recovered.
The carbonization rates of the processes described in examples 1-15 above were measured and calculated and the results reported are shown in table 1 below.
TABLE 1 carbonization ratio of the processes of the examples
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The rare earth extraction method for realizing recycling of magnesium bicarbonate is characterized in that magnesium chloride wastewater recovered in the rare earth soap process is mixed with organic amine extractant and recovered CO2The preparation method of the magnesium bicarbonate solution through extraction-carbonization comprises the following steps:
(1) mixing acidic extractant with magnesium bicarbonate solution for saponification, and recovering CO generated in saponification process2And saponifying the waste water for later use;
(2) uniformly mixing the saponified extractant and rare earth feed liquid to perform rare earth soap reaction, and performing extraction separation to obtain magnesium chloride wastewater and required rare earth products respectively;
(3) adding the saponification wastewater collected in the step (1) into the magnesium chloride wastewater collected in the step (2) for dilution, adding an amine extractant for uniformly mixing, and then introducing CO generated in the step (1)2Carrying out carbonization reaction on the gas;
(4) and (3) after the carbonization is finished, clarifying and phase splitting the reaction liquid, wherein the obtained organic phase is an extract compound containing the amine extractant and hydrochloric acid, and the obtained water phase is the required magnesium bicarbonate solution and is circularly used for the saponification reaction in the step (1).
2. The rare earth extraction method for realizing recycling of magnesium bicarbonate according to claim 1, wherein in the step (1), the acidic extractant comprises one or more of P507, P204, P229 and HBTBPP.
3. The rare earth extraction method for realizing the recycling of the magnesium bicarbonate according to the claim 1 or 2, characterized in that in the step (1), the concentration of the magnesium bicarbonate solution is 0.01-0.5 mol/L.
4. The rare earth extraction method for realizing the recycling of the magnesium bicarbonate according to any one of claims 1 to 3, wherein in the step (1), the dosage ratio of the acidic extracting agent to the magnesium bicarbonate solution is 0.2: 1-2: 1.
5. the method for extracting rare earth for recycling magnesium bicarbonate according to any one of claims 1 to 4, wherein in the step (2), the concentration of the rare earth feed liquid is 0.5-2 mol/L, and the volume ratio of the saponified extractant to the rare earth feed liquid is 3: 1-15: 1.
6. The rare earth extraction method for realizing the recycling of the magnesium bicarbonate according to any one of claims 1 to 5, characterized in that the step (2) further comprises the step of adjusting the concentration of the magnesium chloride wastewater to be 0.1 to 5 mol/L, and/or the step of adjusting the pH of the magnesium chloride wastewater to be 2 to 7.
7. The rare earth extraction method for realizing the recycling of magnesium bicarbonate according to any one of claims 1 to 6, wherein in the step (3), the volume ratio of the saponified wastewater for dilution to the magnesium chloride wastewater is 5: 1-20: 1.
8. the rare earth extraction method for realizing recycling of magnesium bicarbonate according to any one of claims 1-7, wherein in the step (3):
the amine extractant comprises primary amine, secondary amine or tertiary amine organic amine extractant dissolved in diluent;
the diluent comprises benzene, monohydric alcohol, polyhydric alcohol or kerosene;
the volume ratio of the amine extractant to the diluent is 0.2: 1-2: 1.
9. the rare earth extraction method for realizing the recycling of the magnesium bicarbonate according to any one of claims 1 to 8, wherein in the step (3), the volume ratio of the magnesium chloride wastewater diluted by the saponified wastewater to the amine extractant is 0.2: 1-5: 1, control of CO introduced2The purity is 30-100%, and the carbonization time is 5-300 min.
10. The rare earth extraction method for realizing the recycling of the magnesium bicarbonate according to claim 8, wherein the step (4) further comprises the step of adding pure water or the saponification wastewater into the separated organic phase for mixed back extraction; the phase ratio of the organic phase to the pure water or the saponified wastewater was 0.5: 1-5: 1, the time of the mixed back extraction is 1-60 min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960799A (en) * | 2021-02-02 | 2021-06-15 | 福建省长汀金龙稀土有限公司 | Rare earth soap wastewater purification and reuse method |
| CN114150155A (en) * | 2021-12-20 | 2022-03-08 | 中国科学院过程工程研究所 | Optimization method for extraction process for simultaneously recovering battery-grade cobalt salt and nickel salt |
| CN115522051A (en) * | 2022-08-27 | 2022-12-27 | 萍乡鑫森新材料有限责任公司 | Method for saponifying and extracting rare earth |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329286A (en) * | 1976-08-31 | 1978-03-18 | Mitsubishi Heavy Ind Ltd | Recovering method for flocculant from sludge precipitated by flocculation |
| CN103382532A (en) * | 2012-05-04 | 2013-11-06 | 有研稀土新材料股份有限公司 | Comprehensive utilization method for extraction separation of dolomite in rare earth |
| CN103382034A (en) * | 2012-05-04 | 2013-11-06 | 有研稀土新材料股份有限公司 | Preparation and comprehensive utilization method of magnesium bicarbonate solution |
| CN105861828A (en) * | 2015-01-23 | 2016-08-17 | 有研稀土新材料股份有限公司 | Rare earth composite compound containing rare earth hydroxide and rare earth carbonate and preparation method thereof |
| AU2016203453A1 (en) * | 2015-05-26 | 2016-12-15 | Grirem Advanced Materials Co., Ltd | Hydrometallurgy and separation method of rare earth ores |
| CN106277417A (en) * | 2015-05-26 | 2017-01-04 | 有研稀土新材料股份有限公司 | The method that smelting waste water comprehensive containing magnesium reclaims |
| CN106756012A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | A kind of method of P204/P507 calcium and magnesiums saponification |
-
2019
- 2019-01-17 CN CN201910045284.9A patent/CN111440946B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5329286A (en) * | 1976-08-31 | 1978-03-18 | Mitsubishi Heavy Ind Ltd | Recovering method for flocculant from sludge precipitated by flocculation |
| CN103382532A (en) * | 2012-05-04 | 2013-11-06 | 有研稀土新材料股份有限公司 | Comprehensive utilization method for extraction separation of dolomite in rare earth |
| CN103382034A (en) * | 2012-05-04 | 2013-11-06 | 有研稀土新材料股份有限公司 | Preparation and comprehensive utilization method of magnesium bicarbonate solution |
| CN105861828A (en) * | 2015-01-23 | 2016-08-17 | 有研稀土新材料股份有限公司 | Rare earth composite compound containing rare earth hydroxide and rare earth carbonate and preparation method thereof |
| AU2016203453A1 (en) * | 2015-05-26 | 2016-12-15 | Grirem Advanced Materials Co., Ltd | Hydrometallurgy and separation method of rare earth ores |
| CN106277417A (en) * | 2015-05-26 | 2017-01-04 | 有研稀土新材料股份有限公司 | The method that smelting waste water comprehensive containing magnesium reclaims |
| CN106756012A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | A kind of method of P204/P507 calcium and magnesiums saponification |
Non-Patent Citations (4)
| Title |
|---|
| HAO LV 等: "Extraction kinetics of neodymium from chloride medium using HEH/EHP saponified with magnesium bicarbonate solution", 《JOURNAL OF RARE EARTHS》 * |
| 王明等: "离子型稀土矿分离的工艺设计", 《稀有金属与硬质合金》 * |
| 王猛等: "稀土萃取分离废水制备氢氧化镁工艺研究", 《稀土》 * |
| 赵永志: "稀土冶炼过程三废处理技术专利分析及保护策略", 《稀土信息》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960799A (en) * | 2021-02-02 | 2021-06-15 | 福建省长汀金龙稀土有限公司 | Rare earth soap wastewater purification and reuse method |
| CN114150155A (en) * | 2021-12-20 | 2022-03-08 | 中国科学院过程工程研究所 | Optimization method for extraction process for simultaneously recovering battery-grade cobalt salt and nickel salt |
| CN115522051A (en) * | 2022-08-27 | 2022-12-27 | 萍乡鑫森新材料有限责任公司 | Method for saponifying and extracting rare earth |
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