CN113332957A - Preparation method of modified magnetic doping material and method for recovering rare earth elements from rare earth ore wastewater - Google Patents
Preparation method of modified magnetic doping material and method for recovering rare earth elements from rare earth ore wastewater Download PDFInfo
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Abstract
The invention discloses a modified magnetic doping material and a method for recovering rare earth elements from mine wastewater by using the same. The doping material takes reaction products of alkyl orthosilicate, organic alcohol, deionized water and acid as precursors, ferroferric oxide, an extracting agent and strong alkali are introduced into the precursors to form gel, then the organic alcohol in the system is rapidly removed, and finally the modified magnetic doping material with the synergistic effect is obtained. The doping material is used for recovering rare earth ions from rare earth mine wastewater, has good effect, can be recycled on the basis of reducing the total rare earth ion concentration in the wastewater to be below 5ppm, protects the environment while recovering resources, and has wide industrial application prospect.
Description
Technical Field
The invention relates to recovery of rare earth elements, in particular to a method for recovering rare earth elements from rare earth ore wastewater. Meanwhile, relates to a preparation method of the modified magnetic doping material for recovering rare earth elements.
Background
Rare earth is a generic name of seventeen elements and is known as an industrial vitamin in the twenty-first century. They have a plurality of unique physicochemical properties, have important application in the fields of magnetism, luminescence, catalytic materials, semiconductor materials and the like, and are listed as important strategic resources in China. Meanwhile, China is also a large country of rare earth resources, particularly south ion adsorption type rare earth ores, and is a world rare ore species, has the characteristics of high medium-heavy rare earth distribution, easiness in mining and the like, and is a main source of international medium-heavy rare earth.
In the existing ion adsorption type rare earth mining of China, due to the limitation of process technology, after most of rare earth is recovered through impurity removal and precipitation of rare earth leaching mother liquor, a small amount of residual rare earth still exists in supernatant waste liquor of the rare earth leaching mother liquor, in addition, rare earth is detected in seepage waste water around a rare earth mining area, but the waste water cannot be further recycled due to too low rare earth concentration. Rare earth is used as a nonrenewable resource, and the current situation causes resource waste and simultaneously pollutes the environment, which is contrary to the development concept that 'green water mountain is Jinshan mountain silver mountain'.
CN 201811602700.2 discloses a method for enriching rare earth from high-yttrium heavy rare earth wastewater by using a modified magnetic perlite adsorbent, which is synthesized under the condition of high-temperature hydrothermal reaction, so that the reaction conditions are harsh, and the energy consumption is high; in addition, the simulated rare earth wastewater used by the method is 0.10g/L, and the rare earth in the actual wastewater can not reach the concentration, so the technology lacks practical application and popularization value.
CN 202010432708.X discloses a method for recovering rare earth from rare earth secondary resources, which comprises introducing wastewater into a reactor containing sodium hydroxide to obtain rare earth precipitate, wherein the rare earth precipitate is difficult to completely precipitate due to a certain solubility product of the rare earth hydroxide precipitate in water.
Therefore, at present, a method for efficiently recovering rare earth elements in rare earth mine wastewater needs to be researched, so that the environment is protected while rare earth resources are recycled, and sustainable development is realized.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a modified magnetic doping material for recovering rare earth elements from mine wastewater and a preparation method and application thereof. The invention can reduce the total concentration of rare earth ions in the wastewater to below 5ppm and can be recycled; the method protects the ecological environment while recycling the rare earth resources, and has good industrial application prospect.
The preparation method of the modified magnetic doping material comprises the following steps:
(1) mixing alkyl orthosilicate, organic alcohol and deionized water according to a certain proportion at room temperature, and carrying out hydrolysis reaction under the catalysis of acid, wherein the volume ratio of the alkyl orthosilicate to the organic alcohol is 1: 0.5-3, and the volume ratio of the alkyl orthosilicate to the deionized water is 5-25: 1; the molar ratio of the alkyl orthosilicate to the acid catalyst is 2-20: 1;
(2) adding nano ferroferric oxide into the solution obtained in the step (1), and performing ultrasonic treatment to disperse the nano ferroferric oxide to obtain a sol system;
(3) quickly adding an organic alcohol solution containing strong base and an extracting agent into the sol system obtained in the step (2), and continuing ultrasonic dispersion to form gel;
(4) and (4) sequentially drying, washing and drying the gel obtained in the step (3) again to obtain the modified magnetic doped material.
In the step (1), the alkyl orthosilicate is selected from at least one of methyl orthosilicate, tetraethyl orthosilicate, n-propyl orthosilicate, isopropyl orthosilicate, n-butyl orthosilicate and the like; preferably, the alkyl orthosilicate is selected from at least one of tetraethyl orthosilicate and n-propyl orthosilicate.
In the preparation method of the modified magnetic doping material, the volume ratio of the alkyl orthosilicate to the organic alcohol in the step (1) is preferably 1: 1-2; the organic alcohol is at least one selected from methanol, ethanol, isopropanol and the like.
In the preparation method of the modified magnetic doping material, in the step (1), preferably, the volume ratio of the alkyl orthosilicate to the deionized water is 10-15: 1; the acid catalyst is selected from one of concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, formic acid and the like; preferably, the molar ratio of alkyl orthosilicate to acid catalyst is from 8 to 15: 1.
In the step (2), the mass ratio of the alkyl orthosilicate to the ferroferric oxide is 5-25: 1; the preferred mass ratio of the alkyl orthosilicate to the ferroferric oxide is 12-18: 1.
In the step (3), the molar ratio of the alkyl orthosilicate to the extractant is 7-12: 1; preferably, the molar ratio of the alkyl orthosilicate to the extractant is from 8 to 10: 1; the extractant is preferably an extractant with the extraction capacity on rare earth ions, and comprises at least one of bis (2,4, 4-trimethylpentyl) phosphonic acid (C272), 2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester (P507), bis (2-ethylhexyl) phosphoric acid (P204) and tributyl phosphate (TBP); the strong base is selected from one of sodium hydroxide, potassium hydroxide and concentrated ammonia water, and the molar ratio of the strong base to the extracting agent is 2-5: 1.
In the step (4), the drying mode of the gel system comprises two modes of vacuum heat drying and freeze drying, wherein the temperature of the vacuum heat drying is preferably 40-95 ℃, and the heat drying time is preferably 2-10 hours; the dried product was washed several times with deionized water and dried again in a vacuum oven at 75-105 ℃ for 24 hours.
The method for recovering rare earth elements from the rare earth mine wastewater uses the modified magnetic doping material and comprises the following steps:
(a) adding the modified magnetic doping material into the rare earth mine wastewater according to a certain proportion, and oscillating for a certain time at constant temperature at normal temperature to enable the rare earth ions in the water phase to be adsorbed into the doping material;
(b) after adsorption, carrying out solid-liquid separation on the mixture obtained in the step (a) by means of an external magnetic field, discarding supernatant, and recovering solid doped materials;
(c) and (c) adding a desorption solution into the solid doping material in the step (b), fully oscillating, and desorbing the rare earth ions into the solution so as to realize the cyclic utilization of the doping material.
In the method for recovering the rare earth elements from the rare earth mine wastewater, in the step (1), the proportion of the doping material to the rare earth wastewater is 0.5-8 g: 1L; preferably, the proportion of the doping material to the rare earth wastewater is 2-6 g: 1L; the shaking time is 10-180 minutes.
In the step (3), the desorption solution is at least one of hydrochloric acid, nitric acid, sulfuric acid and disodium ethylene diamine tetraacetate, and the ratio of the desorption solution to the doping material is preferably 0.02-0.2 mL: 1 mg.
The modified magnetic doping material can obviously increase the specific surface area because a large amount of ethanol is introduced in the preparation process. And various saponified extractants are doped into the magnetic silicon material with the microporous structure by a simple sol-gel method to obtain the modified magnetic doped material with the synergistic effect. The doped material prepared by the method has magnetism while selectively adsorbing rare earth ions, and the solid-liquid separation efficiency in the later period is obviously improved. The rare earth ion recycling agent has a good effect of recycling rare earth elements from low-concentration rare earth mine wastewater, can reduce the total concentration of rare earth ions in the wastewater to be below 5ppm, can be recycled, saves water resources while recycling rare earth resources, protects the ecological environment, and has a good industrial application prospect.
Drawings
FIG. 1 shows the recovery rate of rare earth ions in wastewater by the modified magnetic doping material under different liquid-solid ratio conditions.
FIG. 2 shows the adsorption capacity of the modified magnetic doped material for lutetium ions at different oscillation times.
Detailed Description
The invention is further illustrated with reference to the following figures and specific examples.
The preparation method of the modified magnetic doping material comprises the following steps:
(1) at room temperature, mixing alkyl orthosilicate, organic alcohol and deionized water according to a certain proportion, and carrying out hydrolysis reaction under the catalysis of acid;
(2) adding nano ferroferric oxide into the solution obtained in the step (1), and performing ultrasonic treatment to disperse the nano ferroferric oxide to obtain a sol system;
(3) quickly adding an organic alcohol solution containing strong base and an extracting agent into the sol system obtained in the step (2), and continuing ultrasonic dispersion to form gel;
(4) and (4) sequentially drying, washing and drying the gel obtained in the step (3) again to obtain the modified magnetic doped material.
The method for recovering rare earth elements from the rare earth mine wastewater uses the modified magnetic doping material and comprises the following steps:
(a) adding the modified magnetic doping material into the rare earth mine wastewater according to a certain proportion, and oscillating for a certain time at constant temperature at normal temperature to enable the rare earth ions in the water phase to be adsorbed into the doping material;
(b) after adsorption, carrying out solid-liquid separation on the mixture obtained in the step (a) by means of an external magnetic field, discarding supernatant, and recovering solid doped materials;
(c) and (c) adding a desorption solution into the solid doping material in the step (b), fully oscillating, and desorbing the rare earth ions into the solution so as to realize the cyclic utilization of the doping material.
Example 1
Preparing a modified magnetic doping material:
(1) accurately, 5ml of tetraethyl orthosilicate was weighed into a round-bottom flask, and 8ml of absolute ethanol, 0.3ml of deionized water, and 0.15ml of concentrated hydrochloric acid were sequentially added thereto, followed by stirring at room temperature for 8 hours.
(2) And (3) adding 0.3g of nano ferroferric oxide into the mixed solution in the step (1), and performing ultrasonic treatment for 10 minutes to completely disperse the nano ferroferric oxide.
(3) 1mmol of 2- (2,4, 4' -trimethylpentyl) phosphonic acid (C272) extractant, 1mmol of 2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester (P507) and 0.6ml of concentrated ammonia water are dissolved in 2.5ml of ethanol solution to obtain completely saponified mixed extractant solution, and the completely saponified mixed extractant solution is quickly added into the mixed solution of the step (2) and continues to be subjected to ultrasonic treatment.
(4) And (4) after the mixed solution in the step (3) forms gel, placing the gel in a vacuum drying oven at 60 ℃, taking out the gel after drying for 12 hours, washing the gel for 6-10 times by using deionized water, and placing the gel in the vacuum drying oven again for drying for 12 hours at 90 ℃.
Recovering rare earth from rare earth wastewater by using the modified doping material:
(1) the ion adsorption type rare earth mining area seepage wastewater is taken as a raw material, 8mg, 20mg, 30mg, 40mg and 50mg of the modified magnetic doping material are respectively placed in a centrifuge tube containing 8ml of mining area seepage wastewater, and the centrifuge tube is vibrated for 90 minutes at room temperature.
(2) After the oscillation is finished, placing the neodymium iron boron permanent magnet on the outer wall of the centrifugal tube to quickly realize solid-liquid separation; the supernatant was collected and the total concentration of rare earth ions was determined, and the results are shown in FIG. 1.
As can be seen from fig. 1, as the solid-to-liquid ratio increases, the higher the adsorption rate of the rare earth, the less the rare earth ions remain in the wastewater.
Example 2
Preparing a modified magnetic doping material:
(1) accurately, 5ml of tetraethyl orthosilicate was weighed into a round-bottom flask, and 8ml of absolute ethanol, 0.3ml of deionized water, and 0.15ml of concentrated hydrochloric acid were sequentially added thereto, followed by stirring at room temperature for 8 hours.
(2) And (3) adding 0.3g of nano ferroferric oxide into the mixed solution in the step (1), and performing ultrasonic treatment for 10 minutes to completely disperse the nano ferroferric oxide.
(3) 1mmol of 2- (2,4, 4' -trimethylpentyl) phosphonic acid (C272) extractant, 1mmol of 2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester (P507) and 0.6ml of concentrated ammonia water are dissolved in 2.5ml of ethanol solution to obtain completely saponified mixed extractant solution, and the completely saponified mixed extractant solution is quickly added into the mixed solution of the step (2) and continues to be subjected to ultrasonic treatment.
(4) And (3) after the mixed solution in the step (3) forms gel, freezing the gel in a refrigerator at minus 20 ℃ for 10 hours, drying the gel in a freeze dryer for 12 hours, washing the gel for 6 to 10 times by using deionized water, and drying the gel in a vacuum drying oven for 12 hours at 90 ℃.
Recovering rare earth from rare earth wastewater by using the modified doping material:
(1) the ion adsorption type rare earth ore mother liquor precipitation wastewater is used as a raw material, 40mg of the modified magnetic doping material is placed in a centrifugal tube containing 8ml of mine area seepage wastewater, and the centrifugal tube is vibrated for 90 minutes at room temperature.
(2) After the oscillation is finished, placing the neodymium iron boron permanent magnet on the outer wall of the centrifugal tube to quickly realize solid-liquid separation; collecting supernatant and determining the total rare earth concentration.
Example 3
Preparing a modified magnetic doping material:
(1) accurately, 5ml of tetraethyl orthosilicate was weighed into a round-bottom flask, and 8ml of absolute ethanol, 0.3ml of deionized water, and 0.15ml of concentrated hydrochloric acid were sequentially added thereto, followed by stirring at room temperature for 8 hours.
(2) And (3) adding 0.3g of nano ferroferric oxide into the mixed solution in the step (1), and performing ultrasonic treatment for 10 minutes to completely disperse the nano ferroferric oxide.
(3) 1.5mmol of 2- (2,4, 4' -trimethylpentyl) phosphonic acid (C272) extractant, 1.5mmol of bis (2-ethylhexyl) phosphoric acid (P204) and 0.9ml of concentrated ammonia water were dissolved in 3ml of ethanol solution to obtain a completely saponified mixed extractant solution, which was rapidly added to the mixed solution of the above (2), and the sonication was continued.
(4) And (4) after the mixed solution in the step (3) forms gel, placing the gel in a vacuum drying oven at 60 ℃, taking out the gel after drying for 12 hours, washing the gel for 6-10 times by using deionized water, and placing the gel in the vacuum drying oven again for drying for 12 hours at 90 ℃.
Recovering rare earth from rare earth wastewater by using the modified doping material:
(1) the ion adsorption type rare earth mining area seepage wastewater is used as a raw material, 40mg of the modified magnetic doping material is placed in a centrifugal tube containing 8ml of mining area seepage wastewater, and the centrifugal tube is vibrated for 90 minutes at room temperature.
(2) After the oscillation is finished, placing the neodymium iron boron permanent magnet on the outer wall of the centrifugal tube to quickly realize solid-liquid separation; collecting supernatant and determining the total rare earth concentration.
(3) The adsorbing material in (2) above was analyzed with 4ml of 0.4mol/L hydrochloric acid solution, and the total rare earth ion concentration in the desorption solution was measured.
Example 4
Preparing a modified magnetic doping material:
(1) accurately, 5ml of tetraethyl orthosilicate was weighed into a round-bottom flask, and 8ml of absolute ethanol, 0.3ml of deionized water, and 0.15ml of concentrated hydrochloric acid were sequentially added thereto, followed by stirring at room temperature for 8 hours.
(2) And (3) adding 0.3g of nano ferroferric oxide into the mixed solution in the step (1), and performing ultrasonic treatment for 10 minutes to completely disperse the nano ferroferric oxide.
(3) 1mmol of 2- (2,4, 4' -trimethylpentyl) phosphonic acid (C272) extractant, 1mmol of 2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester (P507) and 0.6ml of concentrated ammonia water are dissolved in 2.5ml of ethanol solution to obtain completely saponified mixed extractant solution, and the completely saponified mixed extractant solution is rapidly added into the mixed solution of the step (2) and continues to be subjected to ultrasonic treatment.
(4) And (4) after the mixed solution in the step (3) forms gel, placing the gel in a vacuum drying oven at 60 ℃, taking out the gel after drying for 12 hours, washing the gel for 6-10 times by using deionized water, and placing the gel in the vacuum drying oven again for drying for 12 hours at 90 ℃.
Recovering rare earth from rare earth wastewater by using the modified doping material:
using 0.001mol/L lutetium chloride solution prepared in a laboratory as a raw material, respectively putting 40mg of modified magnetic doping material into 8ml of lutetium chloride solution, respectively shaking for 5, 15, 30, 45, 60, 75, 90, 105 and 120 minutes at room temperature, measuring the lutetium ion concentration in the supernatant, and calculating the adsorption capacity, as shown in FIG. 2.
As can be seen from FIG. 2, the adsorption amount increases rapidly with the adsorption time in the first 15 minutes, the adsorption amount increases slowly in 15 to 75 minutes, and after 75 minutes, the adsorption amount does not change with time, which indicates that the adsorption has reached equilibrium after 75 minutes of oscillation.
Comparative example
The modified magnetic doped material was prepared as in example 1, except that in step (3), no extractant was added to obtain an unmodified magnetic doped material, which was used to adsorb rare earth ions from the rare earth mine field leachate.
TABLE 1
Table 1 summarizes the concentrations of rare earth elements in the wastewater before and after the treatment of examples 1-3 and comparative example, and it can be seen that the modified magnetic doping material can adsorb residual rare earth elements of about nine percent in the wastewater, and the wastewater can be repeatedly put into use after being treated.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the modified magnetic doping material is characterized by comprising the following steps:
(1) mixing alkyl orthosilicate, organic alcohol and deionized water according to a certain proportion at room temperature, and carrying out hydrolysis reaction under the catalysis of acid, wherein the volume ratio of the alkyl orthosilicate to the organic alcohol is 1: 0.5-3, and the volume ratio of the alkyl orthosilicate to the deionized water is 5-25: 1; the molar ratio of the alkyl orthosilicate to the acid catalyst is 2-20: 1;
(2) adding nano ferroferric oxide into the solution obtained in the step (1), and performing ultrasonic treatment to disperse the nano ferroferric oxide to obtain a sol system;
(3) quickly adding an organic alcohol solution containing strong base and an extracting agent into the sol system obtained in the step (2), and continuing ultrasonic dispersion to form gel;
(4) and (4) sequentially drying, washing and drying the gel obtained in the step (3) again to obtain the modified magnetic doped material.
2. The method for preparing a modified magnetic doping material according to claim 1, wherein in step (1), the alkyl orthosilicate is selected from at least one of methyl orthosilicate, tetraethyl orthosilicate, n-propyl orthosilicate, isopropyl orthosilicate, n-butyl orthosilicate, and the like; preferably, the alkyl orthosilicate is selected from at least one of tetraethyl orthosilicate and n-propyl orthosilicate.
3. The method for preparing a modified magnetic dopant material according to claim 1, wherein the volume ratio of the alkyl orthosilicate to the organic alcohol in step (1) is preferably 1: 1-2; the organic alcohol is at least one selected from methanol, ethanol, isopropanol and the like.
4. The method for preparing the modified magnetic doping material according to claim 1, wherein in the step (1), the volume ratio of the alkyl orthosilicate to the deionized water is preferably 10-15: 1; the acid catalyst is selected from one of concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, formic acid and the like; preferably, the molar ratio of alkyl orthosilicate to acid catalyst is from 8 to 15: 1.
5. The method for preparing the modified magnetic doping material according to the claim 1, wherein in the step (2), the mass ratio of the alkyl orthosilicate to the ferroferric oxide is 5-25: 1; the preferred mass ratio of the alkyl orthosilicate to the ferroferric oxide is 12-18: 1.
6. The method for preparing a modified magnetic dopant material according to claim 1, wherein in step (3), the molar ratio of the alkyl orthosilicate to the extractant is 7-12: 1; preferably, the molar ratio of the alkyl orthosilicate to the extractant is from 8 to 10: 1; the extractant is preferably an extractant with the extraction capacity on rare earth ions, and comprises at least one of bis (2,4, 4-trimethylpentyl) phosphonic acid (C272), 2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester (P507), bis (2-ethylhexyl) phosphoric acid (P204) and tributyl phosphate (TBP); the strong base is selected from one of sodium hydroxide, potassium hydroxide and concentrated ammonia water, and the molar ratio of the strong base to the extracting agent is 2-5: 1.
7. The method for preparing the modified magnetic doping material according to claim 1, wherein in the step (4), the drying manner for the gel system comprises using vacuum heat drying and freeze drying, wherein the temperature of vacuum heat drying is preferably 40-95 ℃, and the heat drying time is 2-10 hours; the dried product was washed several times with deionized water and dried again in a vacuum oven at 75-105 ℃ for 24 hours.
8. A method for recovering rare earth elements from rare earth mine wastewater, characterized in that it uses the modified magnetic doping material prepared according to any of claims 1 to 7 and comprises the steps of:
(a) adding the modified magnetic doping material into the rare earth mine wastewater according to a certain proportion, and oscillating for a certain time at constant temperature at normal temperature to enable the rare earth ions in the water phase to be adsorbed into the doping material;
(b) after adsorption, carrying out solid-liquid separation on the mixture obtained in the step (a) by means of an external magnetic field, discarding supernatant, and recovering solid doped materials;
(c) and (c) adding a desorption solution into the solid doping material in the step (b), fully oscillating, and desorbing the rare earth ions into the solution so as to realize the cyclic utilization of the doping material.
9. The method for recovering rare earth elements from rare earth mine wastewater according to claim 8, wherein in the step (a), the ratio of the doping material to the rare earth wastewater is 0.5-8 g: 1L; preferably, the proportion of the doping material to the rare earth wastewater is 2-6 g: 1L; the shaking time is 10-180 minutes.
10. The method for recovering rare earth elements from rare earth mine wastewater according to claim 8, wherein in the step (c), the desorption solution is at least one of hydrochloric acid, nitric acid, sulfuric acid and disodium ethylenediamine tetraacetic acid, and the ratio of the desorption solution to the doping material is preferably 0.02-0.2 mL: 1 mg.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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