CN112176209A - Environment-friendly extraction method of ionic rare earth ore calcium salt system - Google Patents

Environment-friendly extraction method of ionic rare earth ore calcium salt system Download PDF

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CN112176209A
CN112176209A CN202011207902.4A CN202011207902A CN112176209A CN 112176209 A CN112176209 A CN 112176209A CN 202011207902 A CN202011207902 A CN 202011207902A CN 112176209 A CN112176209 A CN 112176209A
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ore
rare earth
leaching
agent
solution
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Inventor
刘聪
钟化云
李纯
叶信宇
李星岚
蔡志华
邹桂添
牛飞
何潇
蓝桥发
李早发
徐星
何花金
庄雪涛
杨幼明
许瑞高
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Longnan Nanyu Rare Earths Resource Integration Utilization Co ltd
Guangsheng Nonferrous Metals Co ltd
Jiangxi University of Science and Technology
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Longnan Nanyu Rare Earths Resource Integration Utilization Co ltd
Guangsheng Nonferrous Metals Co ltd
Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses an ion type rare earth ore calcium salt system green extraction method, which takes calcium salt as an ore leaching agent, calcium oxide as a purification and impurity removal agent and calcium oxide as a precipitating agent, recovers the ore leaching agent, chlorine and heavy metal elements in a fluorine type salt form, has no ammonia nitrogen and high-salt wastewater discharge in the whole process of the system, has smooth process, low product impurity content and small influence on the environment of an ore area after closing the ore, and can realize the ion type rare earth green and environment-friendly exploitation. In addition, the method of the invention takes calcium chloride as a main material, adds a small amount of acid regulating agents such as aluminum chloride, ferric chloride, ammonium chloride and the like, and the formed composite salt mineral leaching agent is a main composition material of the mineral soil.

Description

Environment-friendly extraction method of ionic rare earth ore calcium salt system
Technical Field
The invention relates to the technical field of rare earth hydrometallurgy, in particular to a green extraction method of an ionic rare earth ore calcium salt system.
Background
The rare earth in the ionic rare earth ore is adsorbed on the surface of clay mineral in an ionic state, and the rare earth ions can be exchanged only by using strong electrolyte, so that the ionic rare earth extraction process is invented in China according to the characteristics of the ionic rare earth ore. The ionic rare earth extraction process successively goes through the stages of sodium chloride tank leaching process, ammonium sulfate dump leaching process, ammonium sulfate in-situ leaching process, magnesium sulfate leaching process and the like, and lays a foundation for building an ionic rare earth industrial system in China. The in-situ leaching technology of leaching with ammonium sulfate and crystallizing and precipitating ammonium bicarbonate is applied for decades, and the promotion of in-situ leaching is expected to solve the problem of green and efficient extraction of ionic rare earth resources. However, the problems of low mineral leaching rate, serious pollution of high-salt and high-heavy metal wastewater and the like remained in the extraction process are avoided.
In recent years, an ammonium-free leaching agent mainly based on magnesium sulfate (Wangxiang, Yangming, Yanbin, and the like) is used for extracting ion-adsorption type rare earth [ P ]. Chinese patent application CN103266224A, 2013-08-28.) (Xiaoyanfei, Huangli, Lyanbang, and the like). In Chinese patent application (Schleigh, Zhonghuayun, early-maturing plum, and the like. non-ammonium salt rare earth leaching process for ion-adsorption type rare earth ore [ P ]. China: CN 103436720A, 2013-12-11), a composite salt composed of magnesium salt, calcium salt and sodium salt is taken as an ore leaching agent, three neutral salts, namely magnesium chloride, calcium chloride and sodium chloride, are mainly prepared into the ore leaching agent according to a certain proportion, the ore leaching agent mainly plays a role in ion exchange in the ore leaching process, but the sodium-containing salt ore leaching agent is easy to cause the salt alkalization of soil. In Chinese patent application (Weiruigao, Lixinglan. a process for leaching ion adsorption type rare earth by using potassium aluminum sulfate as a leaching agent [ P ]. China: CN 108998663A, 2018-12-14), potassium aluminum sulfate is used as the leaching agent, the average content of potassium in ore soil is about 1.2%, 0.5-6% of potassium aluminum sulfate solution is injected into an ore body, and a large amount of strong alkaline potassium cations are adsorbed by the ore soil, so that the saline-alkali property of the ore soil is greatly influenced.
In the process of leaching ore, the invention provides a method for adding acetate (Burunan plum Johnxus Shih. aluminum-inhibiting leaching weathering crust leaching type rare earth ore [ P ] into sulfate leaching agent]China: CN 103526014 a, 2014-01-22), using ionization of weak acid salt to generate OH-With Al3+Formation of Al (OH)3Thereby fixing partial ion-state aluminum in the mineral soil and reducing the leaching rate of impurity aluminum. Patent (Wangliao spring young Yangming, etc.. leaching method for raising leaching rate of ion-adsorption type rare earth ore [ P)]China: CN106702181A, 2017-05-24) utilizes weak acid and weak acid salt to promote the agglomeration of clay minerals, thereby properly increasing the permeability of the mineral soil and improving the leaching rate of rare earth. There are also patents (Xiaoyanfei, Huangli, Xushifeng, an auxiliary leaching agent for ion type rare earth ore leaching and ore leaching method [ P)]China: CN 105087925A, 2015-11-25) adopts EDTA to complex rare earth, thereby improving the leaching rate of the rare earth. However, the leaching aids are different from the used mineral leaching agents, have undefined influence on the pH value and the saline-alkali property of the mineral body, and bring new pollution hidden troubles to the surrounding environment of the mineral body and an underground water system.
Aiming at the problems of impurity removal and precipitation of leachate, non-ammonia reagents such as magnesium salt and calcium salt are mainly developed in non-ammonia leaching systems such as magnesium sulfate and the like to purify and recover rare earth (Mayongman, Ruidan, Haoshenmin. magnesium oxide is used in the production process of a rare earth solution precipitator [ P ]. Chinese patent applications: CN101037219A, 20070919) and (calcium oxide is used in the production process of a rare earth solution precipitator [ P ]. Chinese: CN101475202, 20090708.). However, basic magnesium salts such as magnesium oxide, magnesium hydroxide, magnesium carbonate and the like are insoluble in water, soluble magnesium bicarbonate is extremely unstable, the process is difficult to control, and the content of magnesium impurities carried in rare earth products is high.
In addition, after closing the mine in the mining area, the amount of the waste water remained in the mining area is large, the waste water mainly comes from recycled ore leaching tail liquid, impurity removal and precipitation waste water and the like, the content of valuable elements is low, the treatment and recycling cost is high, and the waste water is often directly discharged into the surrounding environment without being treated. The content of salt substances in the wastewater is high, so that the rare earth mining area and the peripheral soil are acidified, hardened and the like, and the ecological restoration cost is high. The waste water also contains a low-concentration mineral leaching agent, so that the waste of resources is caused by direct discharge, and the waste water contains a small amount of heavy metals such as lead, zinc, copper and the like, so that the content of the heavy metal elements in the surrounding environment is over standard even if the waste water is not treated for discharge.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a green extraction method of an ionic rare earth ore calcium salt system.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ion type rare earth ore calcium salt system green extraction method comprises the following steps:
s1, rare earth leaching: taking ion type rare earth ore as a raw material, determining the grade of the rare earth, calculating the dosage of the required ore leaching agent according to the mass ratio of the total amount of the rare earth in the ore soil to the ore leaching agent of 1: 11.6-75.5, wherein the ore leaching agent comprises calcium salt and an acid regulating agent, the mass ratio of the calcium salt to the acid regulating agent is 4-19: 1, preparing an ore leaching agent solution with the mass concentration of the ore leaching agent of 4-5%, adding the ore leaching agent solution into the ore soil for leaching, and collecting the ore leaching solution; the acid regulating agent is one or a combination of more of aluminum chloride, ferric chloride and ammonium chloride;
s2, purifying and removing impurities: adding lime slurry into the mineral leaching solution, stirring, controlling the pH value of the solution to be 4.0-5.0, and purifying and removing impurities;
s3, rare earth precipitation: adding lime slurry into the ore leaching solution after impurity removal, stirring, controlling the pH value of the solution to be 7.5-8.5, performing rare earth precipitation, and washing the precipitate product to obtain a rare earth hydroxide product;
s4, closed ore wastewater treatment: adding calcium salt and aluminum salt to the wastewater generated after the completion of step S3 until Ca is reached2+∶Al3+∶Cl-The mass ratio of (9-12) to (1.5-2.0) to 1, filtering to obtain a freund salt precipitate, decomposing with hydrochloric acid to obtain a solution containing calcium chloride and aluminum chloride, and returning to the next ore site to be used as an ore leaching agent.
Further, in step S4, the calcium salt is lime, and the aluminum salt is sodium metaaluminate.
Further, in steps S2 and S3, the mass concentration of lime in the lime slurry is 5%.
The invention has the beneficial effects that:
1. according to the method, calcium salt is used as an ore leaching agent, calcium oxide is used as a purification and impurity removal agent, calcium oxide is used as a precipitating agent, the ore leaching agent, chlorine and heavy metal elements are recovered in a fluorine type salt form, ammonia nitrogen and high-salt wastewater is not discharged in the whole process of the system, the process is smooth, the content of product impurities is low, the influence on the environment of a mining area after ore closing is small, and the environment-friendly mining of the ionic rare earth can be realized.
2. The method of the invention takes calcium chloride as a main material, adds a small amount of acid regulating agents such as aluminum chloride, ferric chloride, ammonium chloride and the like, and the formed composite salt mineral leaching agent is a main composition material of the mineral soil.
Detailed Description
The present invention will be further described below, and it should be noted that the present embodiment is based on the technical solution, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the present embodiment.
Example 1
The embodiment provides a green extraction method of an ionic rare earth ore calcium salt system, which comprises the following steps:
(1) leaching rare earth: taking the Guangdong Xinfeng ion type rare earth ore as a sample, determining that the ion phase rare earth grade of the ore soil is 0.054%, taking 1.8kg of the ore soil containing 0.972g of rare earth, and filling the ore soil into a glass column with the diameter of 66mm, wherein the height of the ore soil in the column is 32.8 cm. The total amount of the required mineral leaching agent is 14.4g calculated according to 14.8 times of the weight of the rare earth in the mineral soil. Aluminum chloride is used as an acid regulating agent, calcium chloride and the acid regulating agent are prepared into an ore leaching agent according to the weight ratio of 9: 1, and 360ml of ore leaching agent solution with the mass concentration of the ore leaching agent being 4% is prepared. Adding the mineral leaching agent solution into ore soil for leaching, and collecting mineral leaching liquid. The volume of the leachate was measured at 970mL and the rare earth and impurity concentrations are shown in table 1. The rare earth leaching rate is 113.77% by analysis.
(2) Purifying and removing impurities: mixing lime according to the mass concentration of 5%, adding the lime into mineral leaching liquid, stirring, controlling the pH value of the solution to be 4.8, purifying and removing impurities, adding 5mL of 5% lime slurry, determining the volume of the mineral leaching liquid to be 970mL, determining the concentrations of rare earth and impurities to be shown in Table 1, analyzing the loss rate of the rare earth after impurity removal to be 5.26%, and removing the impurity rate of impurity aluminum to be 95.7%;
(3) rare earth precipitation: mixing lime according to the mass concentration of 5%, adding the lime into ore leaching liquid after impurity removal, stirring, controlling the pH value of the solution to be 7.5, precipitating rare earth, washing the precipitated product to obtain a rare earth hydroxide product, determining the rare earth content of the product to be 92%, and respectively determining the impurity content in the product to be: al (Al)2O30.8 percent, 0.08 percent of Fe, 2.01 percent of Si, 1.23 percent of Ca and 1.82 percent of Mg, and the impurity content in the product is lower;
(4) closed ore wastewater treatment: taking 0.85L of precipitation wastewater, measuring the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the wastewater as shown in Table 2, adding 78g of lime and 32g of sodium metaaluminate to the wastewater until Ca is obtained2+∶Al3+∶Cl-The mass ratio of the components is 12: 2: 1, stirring the components for reaction, and filtering the mixture; the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the filtrate are determined As shown in Table 2, the contents of Ca, Mg and Cl ions in the wastewater are greatly reduced, the contents of heavy metal ions such As Zn, Cd, Pb, Cu, As, Cr, Mn and the like are all less than 0.05Mg/L, and the discharge requirement is met. The reason why the aluminum concentration in the wastewater rises is as follows: sodium metaaluminate is added during wastewater treatment, and a small amount of aluminum is not completely precipitated during preparation of the freund salt, so that the concentration of aluminum is increased to some extent, but the concentration is about 20mg/L and is lower. And the aluminosilicate is a main component of the ionic rare earth mineral, so that the emission of a small amount of aluminum ions and calcium ions in the wastewater has no influence on the environment.
The total amount of the filtered freund salt precipitate after pressure filtration is 136g, and the solution containing calcium chloride and aluminum chloride can be obtained by decomposing the hydrochloric acid and is returned to the next ore site to be used as an ore leaching agent.
TABLE 1 concentration of rare earths and impurity ions before and after impurity removal of the leaching solution
Figure BDA0002755527580000061
Figure BDA0002755527580000071
TABLE 2 concentration of impurity ions before and after wastewater treatment
Figure BDA0002755527580000072
Example 2
The embodiment provides a green extraction method of an ionic rare earth ore calcium salt system, which comprises the following steps:
(1) leaching rare earth: taking the Guangdong Xinfeng ion type rare earth ore as a sample, determining that the ion phase rare earth grade of the ore soil is 0.069%, taking 3.6kg of the ore soil, wherein the ore soil contains 2.484g of rare earth, and filling the ore soil into a glass column with the diameter of 64mm, wherein the height of the ore soil in the column is 69.99 cm. The total amount of the required mineral leaching agent is 28.8g calculated according to 11.6 times of the weight of the rare earth in the mineral soil. Aluminum chloride is used as an acid regulating agent, calcium chloride and the acid regulating agent are prepared into an ore leaching agent according to the weight ratio of 9: 1, and 720ml of ore leaching agent solution with the mass concentration of the ore leaching agent being 4% is prepared. Adding the mineral leaching agent solution into ore soil for leaching, and collecting mineral leaching liquid. The volume of the leachate was measured to be 2.18L and the rare earth and impurity concentrations are shown in table 3. The leaching rate of rare earth is 128% by analysis.
(2) Purifying and removing impurities: mixing lime according to the mass concentration of 5%, adding the lime into ore leaching solution, stirring, controlling the pH value of the solution to be 4.0, purifying and removing impurities, adding 11.5mL of 5% lime slurry, determining the volume of the ore leaching solution to be 2.18L, determining the concentrations of rare earth and impurities to be shown in Table 3, analyzing the loss rate of the rare earth after impurity removal to be 6.85%, and removing the impurity rate of impurity aluminum to be 95.65%;
(3) rare earth precipitation: mixing lime according to 5% mass concentration, adding into the ore leaching solution after impurity removal, stirring, controlling the pH value of the solution to be 7.5 to precipitate rare earth, and precipitating the productWashing to obtain a rare earth hydroxide product, and determining that the rare earth content of the product is 92.1 percent, wherein the impurity content in the product is respectively as follows: al (Al)2O30.8 percent of Fe, 0.06 percent of Si, 1.85 percent of Ca, 1.2 percent of Mg and 1.8 percent of Mg, and the impurity content in the product is lower;
(4) closed ore wastewater treatment: 1.5L of the mineral leaching comprehensive wastewater is taken, and the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the wastewater are measured and are shown in Table 4. Adding 54.5g of lime and 21g of sodium metaaluminate into the wastewater until Ca is obtained2+∶Al3+∶Cl-The mass ratio of the components is 9: 1.5: 1, stirring the components for reaction and filtering the mixture; the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the filtrate are determined As shown in Table 4, the contents of Ca, Mg and Cl ions in the wastewater are greatly reduced, and the contents of heavy metal ions such As Zn, Cd, Pb, Cu, As, Cr, Mn and the like are all less than 0.05Mg/L, so that the discharge requirement is met; the total amount of the filtered and obtained freund salt precipitate is 87.5g after pressure filtration, and the solution containing calcium chloride and aluminum chloride can be obtained by decomposing the hydrochloric acid and is returned to the next ore site to be used as an ore leaching agent.
TABLE 3 concentration of rare earths and impurity ions before and after impurity removal of the leaching solution
Figure BDA0002755527580000091
TABLE 4 impurity ion content before and after wastewater treatment
Figure BDA0002755527580000092
Example 3
The embodiment provides a green extraction method of an ionic rare earth ore calcium salt system, which comprises the following steps:
(1) taking the Guangdong Xinfeng ion type rare earth ore as a sample, determining that the ion phase rare earth grade of the ore soil is 0.054%, taking 1.8kg of the ore soil, wherein the ore soil contains 0.972g of rare earth, and filling the ore soil into a glass column with the diameter of 100mm, wherein the height of the ore soil in the column is 143 mm. The total amount of the required calcium salt and the acid regulating agent is calculated to be 18g according to 18.5 times of the weight of the rare earth in the ore soil, ferric chloride is used as the acid regulating agent, and the calcium chloride and the acid regulating agent are mixed according to the proportion of 19: 1 is prepared into an ore leaching agent, and 360ml of ore leaching agent solution with the mass concentration of the ore leaching agent being 5 percent is prepared. The mineral leaching agent solution was added to the ore soil for leaching, the mineral leaching solution was collected, the volume of the mineral leaching solution was determined to be 0.84L, and the rare earth and impurity concentrations were as shown in table 5. The rare earth leaching rate is 109.70% by analysis.
(2) Purifying and removing impurities: mixing lime according to the mass concentration of 5%, adding the lime into mineral leaching liquid, stirring, controlling the pH value of the solution to be 5.0, purifying and removing impurities, adding 5mL of 5% lime slurry, determining the volume of the mineral leaching liquid to be 0.84L, determining the concentrations of rare earth and impurities to be shown in Table 5, analyzing the loss rate of the rare earth after impurity removal to be 4.72%, and removing the impurity rate of impurity aluminum to be 91.12%;
(3) rare earth precipitation: mixing lime according to the mass concentration of 5%, adding the lime into ore leaching liquid after impurity removal, stirring, controlling the pH value of the solution to be 8.5, precipitating rare earth, washing the precipitated product to obtain a rare earth hydroxide product, determining the rare earth content of the product to be 92%, and respectively determining the impurity content in the product to be: al (Al)2O30.4 percent of Fe, 0.10 percent of Si, 1.88 percent of Ca, 1.07 percent of Mg and 1.64 percent of Mg, and the impurity content in the product is lower;
(4) closed ore wastewater treatment: taking 0.8L of precipitation wastewater, measuring the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the wastewater as shown in Table 6, adding 57g of lime and 28g of sodium metaaluminate into the wastewater until Ca is obtained2+∶Al3+∶Cl-The mass ratio of the components is 10: 2: 1, stirring the components for reaction, and filtering the mixture; the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the filtrate are determined As shown in Table 6, the contents of Ca, Mg and Cl ions in the wastewater are greatly reduced, and the contents of heavy metal ions such As Zn, Cd, Pb, Cu, As, Cr, Mn and the like are all less than 0.05Mg/L, so that the discharge requirement is met; the total amount of filtered free salt precipitates after pressure filtration is 118g, and the solution containing calcium chloride and aluminum chloride can be obtained by decomposing the salt with hydrochloric acid and is returned to the next ore site to be used as an ore leaching agent.
TABLE 5 concentrations of rare earths and impurity ions before and after impurity removal of the leach liquor
Figure BDA0002755527580000111
TABLE 6 concentration of impurity ions before and after wastewater treatment
Figure BDA0002755527580000112
Example 4
The embodiment provides a green extraction method of an ionic rare earth ore calcium salt system, which comprises the following steps:
(1) taking the Guangdong Xinfeng ion type rare earth ore as a sample, determining that the ion phase rare earth grade of the ore soil is 0.053%, taking 0.5kg of the ore soil containing 0.265g of rare earth, and filling the ore soil into a glass column with the diameter of 80mm, wherein the height of the ore soil in the column is 99 mm. The total amount of the required calcium salt and the acid regulating agent is calculated to be 20g according to 75.5 times of the weight of the rare earth in the ore soil, ammonium chloride is used as the acid regulating agent, calcium chloride and the acid regulating agent are used for preparing the ore leaching agent according to the proportion of 4: 1, and the total amount of the prepared ore leaching agent solution with the mass concentration of the ore leaching agent being 4% is 500 ml. The mineral leaching agent solution was added to the ore soil for leaching, the mineral leaching solution was collected, the volume of the mineral leaching solution was determined to be 430mL, and the rare earth and impurity concentrations are shown in table 7. The rare earth leaching rate is 111.63% by analysis.
(2) Purifying and removing impurities: mixing lime according to the mass concentration of 5%, adding the lime into mineral leaching liquid, stirring, controlling the pH value of the solution to be 4.8, purifying and removing impurities, adding 3mL of 5% lime slurry, determining the volume of the mineral leaching liquid to be 430mL, determining the concentrations of rare earth and impurities to be shown in Table 7, analyzing the loss rate of the rare earth after impurity removal to be 2.62%, and removing the impurity rate of impurity aluminum to be 85.2%;
(3) rare earth precipitation: mixing lime according to the mass concentration of 5%, adding the lime into ore leaching liquid after impurity removal, stirring, controlling the pH value of the solution to be 8.5, precipitating rare earth, washing the precipitated product to obtain a rare earth hydroxide product, determining the rare earth content of the product to be 92.5%, and respectively determining the impurity content in the product to be: al (Al)2O30.4 percent of Fe, 0.16 percent of Si, 1.71 percent of Ca, 1.14 percent of Mg and 1.41 percent of Mg, and the impurity content in the product is low;
(4) closed ore wastewater treatment: taking 650mL of the mixture of the precipitation wastewater and the washing wastewater, measuring the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the wastewater as shown in Table 8, and adding 52.7g of lime and 28g of sodium metaaluminate into the wastewater until the concentration of Ca reaches the value of 52.7g2+∶Al3+∶Cl-The mass ratio of the components is 9: 2: 1, stirring the components for reaction and filtering the mixture; the concentrations of rare earth ions, chloride ions, calcium ions and aluminum ions and the concentrations of other non-rare earth ions and heavy metal ions in the filtrate are determined As shown in Table 8, the contents of Ca, Mg and Cl ions in the wastewater are greatly reduced, and the contents of heavy metal ions such As Zn, Cd, Pb, Cu, As, Cr, Mn and the like are all less than 0.05Mg/L, so that the discharge requirement is met; the filtered freund salt precipitates and is filtered by pressure, the total amount of the filtered freund salt precipitates is 117g, a solution containing calcium chloride and aluminum chloride can be obtained by decomposing the filtered freund salt with hydrochloric acid, and the solution is returned to the next ore site to be used as an ore leaching agent.
TABLE 7 concentration of rare earths and impurity ions before and after impurity removal of the leaching solution
Figure BDA0002755527580000131
TABLE 8 concentration of impurity ions before and after wastewater treatment
Figure BDA0002755527580000132
Figure BDA0002755527580000141
Various corresponding changes and modifications can be made by those skilled in the art based on the above technical solutions and concepts, and all such changes and modifications should be included in the protection scope of the present invention.

Claims (3)

1. The green extraction method of the ionic rare earth ore calcium salt system is characterized by comprising the following steps:
s1, rare earth leaching: taking ion type rare earth ore as a raw material, determining the grade of the rare earth, calculating the dosage of the required ore leaching agent according to the mass ratio of the total amount of the rare earth in the ore soil to the ore leaching agent of 1: 11.6-75.5, wherein the ore leaching agent comprises calcium salt and an acid regulating agent, the mass ratio of the calcium salt to the acid regulating agent is 4-19: 1, preparing an ore leaching agent solution with the mass concentration of the ore leaching agent of 4-5%, adding the ore leaching agent solution into the ore soil for leaching, and collecting the ore leaching solution; the acid regulating agent is one or a combination of more of aluminum chloride, ferric chloride and ammonium chloride;
s2, purifying and removing impurities: adding lime slurry into the mineral leaching solution, stirring, controlling the pH value of the solution to be 4.0-5.0, and purifying and removing impurities;
s3, rare earth precipitation: adding lime slurry into the ore leaching solution after impurity removal, stirring, controlling the pH value of the solution to be 7.5-8.5, performing rare earth precipitation, and washing the precipitate product to obtain a rare earth hydroxide product;
s4, closed ore wastewater treatment: adding calcium salt and aluminum salt to the wastewater generated after the completion of step S3 until Ca is reached2+∶Al3+∶Cl-The mass ratio of (9-12) to (1.5-2.0) to 1, filtering to obtain a freund salt precipitate, decomposing with hydrochloric acid to obtain a solution containing calcium chloride and aluminum chloride, and returning to the next ore site to be used as an ore leaching agent.
2. The method for green extraction of ionic rare earth ore calcium salt system according to claim 1, wherein in step S4, the calcium salt is lime and the aluminum salt is sodium metaaluminate.
3. The method for green extraction of ionic rare earth ore calcium salt system according to claim 1, wherein the mass concentration of lime in the lime slurry is 5% in steps S2 and S3.
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