CN109395692B - Preparation of modified magnetic perlite adsorbent and method for enriching rare earth from heavy yttrium rare earth wastewater - Google Patents
Preparation of modified magnetic perlite adsorbent and method for enriching rare earth from heavy yttrium rare earth wastewater Download PDFInfo
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- CN109395692B CN109395692B CN201811602700.2A CN201811602700A CN109395692B CN 109395692 B CN109395692 B CN 109395692B CN 201811602700 A CN201811602700 A CN 201811602700A CN 109395692 B CN109395692 B CN 109395692B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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Abstract
The invention relates to a preparation method of a modified magnetic perlite adsorbent and a method for enriching rare earth from heavy yttrium rare earth wastewater, wherein the adsorbent is prepared by mixing modified perlite, ferrous chloride, sodium acetate, polyvinyl alcohol and vinyl alcohol, uniformly dispersing by ultrasonic, then placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining, heating the reaction temperature of the reaction kettle to 200 ℃, reacting for 24 hours at 200 ℃, and cooling. The modified magnetic perlite adsorbent prepared by the invention has magnetism, and can be used for wastewater treatment, wherein the adsorption capacity of heavy yttrium rare earth ions is up to 300-500 mg/g; the invention can realize the recycling of the adsorbent adsorbing the heavy yttrium rare earth ions, the recovery rate is up to more than 98 percent, and the recycled adsorbent still has excellent adsorption performance. Therefore, the invention provides a cheap and efficient method for recovering valuable elements in the rare earth wastewater and deeply treating the rare earth wastewater.
Description
Technical Field
The invention belongs to the technology of treating waste water containing rare earth ions and recovering valuable elements in the mining and smelting industries of rare earth mining areas, and particularly relates to a preparation method of a modified magnetic perlite adsorbent and a method for enriching rare earth from heavy yttrium rare earth waste water.
Background
Rare earth is an important non-ferrous metal mineral resource. The rare earth element has a special electron shell structure, the 4f electron shell of the rare earth element is in an unsaturated state, and rich energy level transition exists between f-f configuration and f-d configuration. Therefore, the rare earth element has unique physical and chemical properties, thereby determining that the rare earth element has special optical, electrical, magnetic and other characteristics. Rare earth is known as industrial vitamin, and is an indispensable strategic resource for developing high and new technology, advanced national defense technology and improving the traditional industry. China has abundant rare earth resources, and mainly takes Mongolia Baiyunebo mixed light rare earth, tetrachuan yak plateau and hamamesite of Shandong micro mountain as well as south ion adsorption type rare earth ores in the west, Guangdong, Fujian, Guangxi and the like as main resources. The rare earth resource in China has five characteristics: large resource reserves, wide mineral distribution, multiple ore deposit types, full mineral varieties, high comprehensive utilization value and the like.
The ionic rare earth ore (weathering crust eluviation type rare earth ore) in south China has the characteristics of large reserves, wide distribution, complete distribution and extremely low radioactivity, and is mainly rich in medium-heavy rare earth elements which are scarce in other rare earth ores, so that the rare earth ore in China has extremely strong market competitiveness. The mining of the ionic rare earth ore in south China successively adopts three different process technologies: tank leaching, heap leaching and in situ leaching. The open pond leaching process and the heap leaching process need to strip, dig and carry surface soil of ore bodies in a large range, and cause serious damage to surface vegetation. After rare earth leaching, a large amount of tailings are generated, which causes serious water and soil loss and environmental pollution. At present, an in-situ leaching process is mainly adopted for extraction, and after the in-situ leaching process is finished, residual rare earth in an ore deposit and rare earth in a downstream ore body can be leached by ammonium sulfate serving as a leaching agent in the ore deposit in the percolation and migration processes, so that underground water and downstream water contain rare earth with certain concentration, rare earth resources are seriously wasted, and a severe environmental pollution problem is caused. In addition, rare earth elements enter water to cause water quality deterioration and pose great threats to animal and plant growth and human health. Therefore, currently, there is an urgent need to develop a practical and effective method for performing advanced treatment on ionic rare earth wastewater and enriching and recovering valuable element rare earth therein.
The traditional treatment method of rare earth mine wastewater and smelting wastewater mainly comprises a chemical precipitation method, a solvent extraction method, an ion exchange method, a membrane separation method, an adsorption method and the like. These methods play an important role in rare earth wastewater treatment, but still have the disadvantages of low recovery rate, long separation time, high toxicity, high price, secondary pollution, poor treatment effect on low-concentration wastewater and the like. Although many important research results are obtained, the development of wastewater treatment technology and process with excellent performance such as high efficiency, rapidness, safety, low price, environmental protection and the like is still urgent.
The adsorption method is based on a physical or chemical adsorption principle, and has a remarkable removal effect on pollutants which are difficult to degrade, and has the advantages of strong selectivity, good adsorption effect, low energy consumption, simple operation, cheap and easily-obtained raw materials and the like, so that the adsorption method has unique advantages in enriching and recovering rare earth ions.
For the above reasons, the present application has been made.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a modified magnetic perlite adsorbent and a method for enriching rare earth from heavy yttrium rare earth wastewater.
In order to achieve the purpose, the invention firstly carries out a series of surface modification on the expanded perlite to make the perlite have magnetism, and then the magnetic perlite obtained by modification is used as an adsorbent to adsorb and recover rare earth elements from the heavy yttrium rare earth ion-containing wastewater. The method can efficiently recover valuable rare earth elements in the rare earth wastewater, and reduces the harm of rare earth ions to the water environment, thereby providing a cheap and efficient method for recovering the valuable elements in the rare earth wastewater and deeply treating the rare earth wastewater.
The first object of the present invention is achieved by the following technical solutions:
a method for preparing a modified magnetic perlite adsorbent, comprising the steps of:
mixing modified perlite with ferrous chloride, sodium acetate, polyvinyl alcohol and vinyl alcohol according to a ratio, placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining after uniformly dispersing by ultrasonic, then heating the reaction temperature of the reaction kettle to 200 ℃, reacting for 24 hours at the temperature of 200 ℃, and cooling to room temperature after the reaction is finished to obtain the modified magnetic perlite adsorbent.
Further, according to the technical scheme, the mass ratio of the modified perlite to the ferrous chloride is 1: 1-2, preferably 1: 1.35; the mass ratio of the modified perlite to the sodium acetate is 1: 3-4, preferably 1: 3.6; the mass ratio of the modified perlite to the polyvinyl alcohol is 1: 0.5-2, preferably 1: 1; the dosage ratio of the modified perlite to the vinyl alcohol is 1 part by mass: 20-60 parts by volume, preferably 1 part by mass: 40 parts by volume, wherein: the mass part and the volume part are as follows: ml is used as a reference.
Further, according to the technical scheme, the modified perlite is prepared by sieving the expanded perlite and then modifying the sieved expanded perlite by the long-chain surfactant and the amino coupling agent in sequence.
Preferably, in the above technical scheme, the long-chain surfactant is any one of sodium dodecyl benzene sulfonate or cetyl trimethyl ammonium bromide; the amino coupling agent is preferably 3-aminopropyltriethoxysilane.
The second purpose of the invention is to provide a method for enriching rare earth from heavy yttrium rare earth wastewater by using the modified magnetic perlite adsorbent prepared by the method.
The method for enriching rare earth from heavy yttrium rare earth wastewater by using the modified magnetic perlite adsorbent comprises the following steps:
(1) keeping the pH value of the heavy yttrium rare earth wastewater at 3.0-5.5;
(2) and (3) mixing the obtained modified magnetic perlite adsorbent according to the mass ratio of (0.1-10000): adding 1L of the mixture into the wastewater obtained in the step (1), uniformly stirring, and then performing constant-temperature vibration adsorption for 10min to 2.5h at normal temperature to enable heavy yttrium rare earth ions in the wastewater to be adsorbed on the surface of a magnetic adsorbent;
(3) and after adsorption, standing the wastewater for 30-60 min, centrifuging, discharging clear liquid after the modified magnetic perlite adsorbent adsorbed with the heavy yttrium rare earth ions is placed on the wall of a wastewater tank by means of an external magnet, recovering the adsorbent adsorbed with the heavy yttrium rare earth ions, performing oscillation desorption by using acid liquid with the mass percentage concentration of 0.5-1 wt%, drying at 60-80 ℃, and then continuously recycling.
Further, in the technical scheme, the concentration of the heavy yttrium rare earth wastewater in the step (1) is preferably 0.01-1 g/L.
Further, in the above technical scheme, the pH value of the heavy yttrium rare earth wastewater in the step (1) is preferably 5.5.
Further, in the above technical solution, the room temperature in the step (2) is preferably 30 ℃.
Further, in the above technical solution, the adsorption time in the step (2) is preferably 2 hours.
Further, in the technical scheme, the adsorption capacity of the modified magnetic perlite material in the step (2) to the heavy yttrium rare earth ions is 1 mg/g-500 mg/g.
Further, in the above technical solution, the acid solution in the step (2) is preferably any one of dilute hydrochloric acid or dilute nitric acid.
The invention adopts the modified magnetic perlite as the adsorbent, and the functional group selectively modified on the surface of the adsorbent can be coordinated with the rare earth ions, so that the rare earth ions are efficiently enriched.
Compared with the prior art, the preparation of the modified magnetic perlite adsorbent and the method for enriching rare earth from heavy yttrium rare earth wastewater have the following advantages and beneficial effects:
(1) the modified magnetic perlite adsorbent prepared by the invention has magnetism, and can be used for wastewater treatment, wherein the adsorption capacity of heavy yttrium rare earth ions is up to 300-500 mg/g; the adsorbent can be desorbed by a simple acid treatment method, the recycling is realized, the recovery rate is up to more than 98%, and the recycled adsorbent still has excellent adsorption performance.
(2) The modified magnetic perlite adsorbent prepared by the invention has stable properties, and is non-toxic and harmless; the adopted raw materials such as perlite, surfactant, functional group coupling agent and the like are cheap and easily available, and the preparation method and the adsorption method are simple, rapid and efficient, and have good application prospect in the aspect of treatment of heavy yttrium rare earth wastewater.
(3) The modified magnetic perlite adsorbent prepared by the invention can be used for recovering valuable elements in low-concentration rare earth wastewater generated in rare earth mining and smelting processes and providing a new way for advanced treatment of wastewater.
Drawings
FIG. 1 is a graph showing the effect of modified magnetic perlite on the adsorption capacity of heavy yttrium rare earth ions under different pH conditions in example 2 of the present invention;
FIG. 2 is a graph showing the effect of modified magnetic perlite on the adsorption capacity of heavy yttrium rare earth ions under different adsorption time conditions in example 3 of the present invention;
FIG. 3 is a graph showing the effect of varying amounts of modified magnetic perlite on the adsorption capacity of heavy yttrium rare earth ions in example 4 of the present invention;
FIG. 4 is a graph showing the relationship between the adsorption performance of the recycled and regenerated modified perlite to heavy yttrium rare earth ions and the cycle number in example 5 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and a specific operation process are given, but the protection scope of the invention is not limited to the following embodiment.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The starting materials used in the examples described below, unless otherwise specified, were all considered to have been obtained from commercial sources.
Example 1
The preparation method of the modified magnetic perlite adsorbent comprises the following steps:
(1) sieving the expanded perlite with a 200-mesh sieve, and mixing the sieved perlite with a long-chain surfactant (sodium dodecyl benzene sulfonate) in a mass ratio of 3: 1, performing ultrasonic dispersion, then mechanically stirring for 16h at room temperature, performing suction filtration, and then performing vacuum drying for 24h at 60 ℃ to obtain an expanded perlite-surfactant modified product (product 1).
(2) And (2) reacting the product 1 obtained in the step (1) with an ethanol solution of 3-aminopropyltriethoxysilane (coupling agent) with the mass percentage concentration of 2.0 wt% at 60 ℃ for 12h, then performing suction filtration, and performing vacuum drying at 60 ℃ for 24h, so that the silicon hydroxyl on the surface of the perlite is coupled with the amino coupling agent, and thus obtaining the perlite-amino functional group modified product (product 2).
(3) 1.0g of the product 2, 1.35g of ferrous chloride, 3.6g of sodium acetate, 1.0g of polyvinyl alcohol and 40mL of vinyl alcohol are mixed uniformly by ultrasound, then the obtained mixture is placed in a reaction kettle with a polytetrafluoroethylene lining for hydrothermal synthesis reaction, the reaction temperature of the reaction kettle is controlled at 200 ℃, and the reaction time is 24 hours, so that the modified magnetic perlite adsorbent (product 3) is obtained.
In the following methods for enriching rare earth from heavy yttrium rare earth solution related in examples 2 to 4, the used adsorbents are all modified magnetic perlite adsorbents prepared by the method of example 1.
Example 2
A method for enriching rare earth from a heavy yttrium rare earth solution by using a modified magnetic perlite adsorbent comprises the following steps:
(1) taking a plurality of 250mL conical flasks, and respectively preparing heavy yttrium rare earth solutions with pH values of 3.0, 3.5, 4.0, 4.5, 5.0 and 5.5, wherein: the initial concentration of the heavy yttrium rare earth solution is 0.1000 g/L;
(2) the obtained modified magnetic perlite adsorbent is prepared according to the following steps of 10 mg: adding 1L of the mixture into the conical flasks filled with the heavy yttrium rare earth solutions with different pH values in the step (1) respectively, uniformly stirring, and adsorbing for 2 hours in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 30 ℃ to enable heavy yttrium rare earth ions in the solution to be adsorbed on the surface of the magnetic adsorbent;
(3) after adsorption, standing the obtained mixed solution for 30min, centrifuging at a rotation speed of 8000rmp for 10min at 4 ℃, discharging supernatant after the modified magnetic perlite adsorbent adsorbing the heavy yttrium rare earth ions is placed on the wall of a wastewater tank by means of an external magnet, recovering the adsorbent adsorbing the heavy yttrium rare earth ions, oscillating and desorbing by using hydrochloric acid with the mass percentage concentration of 0.5 wt%, drying at 60 ℃, and then continuously recycling.
And (3) taking a certain amount of clear liquid obtained in the step (3), determining the concentration of the rare earth ions in the clear liquid by using an EDTA (ethylene diamine tetraacetic acid) coordination titration method, and calculating the adsorption capacity of the rare earth ions, wherein the adsorption capacity of the modified magnetic perlite under different pH conditions is shown in figure 1.
As can be seen from fig. 1, the adsorption capacity of the modified magnetic perlite to the heavy yttrium rare earth ions increases with increasing pH. The pH is increased from 3.0 to 5.5, and the adsorption capacity of the modified magnetic perlite to the heavy yttrium rare earth ions is increased from 44.8mg/g to 342.3 mg/g. In experiments, the modified magnetic perlite is found to adsorb the heavy yttrium rare earth ions with the optimum pH value of 5.5 because the heavy yttrium rare earth ions in the solution are turbid due to the formation of rare earth hydroxide precipitates when the pH value is more than 5.5.
Example 3
A method for enriching rare earth from a heavy yttrium rare earth solution by using a modified magnetic perlite adsorbent comprises the following steps:
(1) taking a plurality of 250mL conical flasks, and respectively preparing heavy yttrium rare earth solutions with the pH value of 5.5, wherein: the initial concentration of the heavy yttrium rare earth solution is 0.1000 g/L;
(2) the obtained modified magnetic perlite adsorbent is prepared according to the following steps of 10 mg: adding 1L of the heavy yttrium rare earth ions into the conical flasks filled with the heavy yttrium rare earth solution in the step (1) respectively, stirring uniformly, adsorbing in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 30 ℃, and adjusting the adsorption time to be 10min, 20min, 30min, 60min, 90min and 120min respectively to enable the heavy yttrium rare earth ions in the solution to be adsorbed on the surface of a magnetic adsorbent;
(3) after adsorption, standing the obtained mixed solution for 30min, centrifuging at a rotation speed of 8000rmp for 10min at 4 ℃, discharging clear liquid after the modified magnetic perlite adsorbent adsorbing the heavy yttrium rare earth ions is placed on the wall of a wastewater tank by means of an external magnet, recovering the adsorbent adsorbing the heavy yttrium rare earth ions, oscillating and desorbing by using hydrochloric acid with the mass percentage concentration of 0.5 wt%, drying at 60 ℃, and then continuously recycling.
And (4) taking a certain amount of the clear liquid obtained in the step (3), determining the concentration of the rare earth ions in the clear liquid by using an EDTA (ethylene diamine tetraacetic acid) coordination titration method, and calculating the adsorption capacity of the rare earth ions and the adsorption capacity of the modified magnetic perlite with different adsorbent dosages.
It can be seen from fig. 2 that the adsorption capacity of the modified magnetic perlite for rare earth ions decreases with increasing adsorption time. When the adsorption time is increased from 10min to 120min, the adsorption capacity of the modified magnetic perlite for the rare earth ions is increased from 224.2mg/g to 383.6 mg/g. The adsorption time is continuously increased to 150min, and the adsorption capacity is not obviously changed. The optimal time of the modified magnetic perlite for adsorbing the rare earth ions is 120 min.
Example 4
A method for enriching rare earth from a heavy yttrium rare earth solution by using a modified magnetic perlite adsorbent comprises the following steps:
(1) taking a plurality of 250mL conical flasks, and respectively preparing heavy yttrium rare earth solutions with the pH value of 5.5, wherein: the initial concentration of the heavy yttrium rare earth solution is 0.1000 g/L;
(2) respectively mixing the obtained modified magnetic perlite adsorbent according to the weight ratio of 10 mg: 1L, 20 mg: 1L, 40 mg: 1L, 60 mg: 1L, 80 mg: 1L, 100 mg: adding 1L of the mixture into each conical flask filled with the heavy yttrium rare earth solution in the step (1) respectively, uniformly stirring, and adsorbing for 2 hours in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 30 ℃ to enable heavy yttrium rare earth ions in the solution to be adsorbed on the surface of a magnetic adsorbent;
(3) after adsorption, standing the obtained mixed solution for 30min, centrifuging at a rotation speed of 8000rmp for 10min at 4 ℃, discharging clear liquid after the modified magnetic perlite adsorbent adsorbing the heavy yttrium rare earth ions is placed on the wall of a wastewater tank by means of an external magnet, recovering the adsorbent adsorbing the heavy yttrium rare earth ions, performing oscillation desorption by using a hydrochloric acid solution with the mass percentage concentration of 1.0 wt%, drying at 60 ℃, obtaining 9.82mg of recovered and regenerated modified magnetic perlite adsorbent, and continuously recycling.
And (4) taking a certain amount of the supernatant obtained in the step (3), determining the concentration of the rare earth ions in the supernatant by using an EDTA (ethylene diamine tetraacetic acid) coordination titration method, and calculating the adsorption capacity of the rare earth ions and the adsorption capacity of the modified magnetic perlite with different adsorbent dosages.
As can be seen in FIG. 3, the adsorption capacity of the modified magnetic perlite for rare earth ions decreases with increasing sorbent usage. When the dosage of the adsorbent is increased from 10.0mg to 100.0mg, the adsorption capacity of the modified magnetic perlite to the rare earth ions is reduced from 383.6mg/g to 16.1 mg/g. Under the condition of a certain amount of rare earth solution, the dosage of the adsorbent is higher than 20mg, and the adsorption capacity of the modified magnetic perlite to the rare earth ions is obviously reduced along with the increase of the dosage of the adsorbent, which indicates that the adsorption material is not fully adsorbed under the condition. The optimal dosage of the rare earth solution added into the adsorbent is 10 mg.
Example 5
A method for recovering a regenerated modified magnetic perlite adsorbent for enriching rare earths from a heavy yttrium rare earth solution, said method comprising the steps of:
(1) taking one 250mL conical flask, preparing a heavy yttrium rare earth solution with the pH value of 5.5, wherein: the initial concentration of the heavy yttrium rare earth solution is 0.1000 g/L;
(2) adding the regenerated 9.82mg modified magnetic perlite adsorbent recovered in the example 4 into the conical flask filled with the heavy yttrium rare earth solution in the step (1), uniformly stirring, and then adsorbing for 2 hours in a constant-temperature water bath shaking table with the rotation speed of 200r/min at the temperature of 30 ℃ to make heavy yttrium rare earth ions in the solution adsorbed on the surface of the magnetic adsorbent;
(3) after adsorption, standing the obtained mixed solution for 30min, centrifuging at a rotation speed of 8000rmp for 10min at 4 ℃, discharging clear liquid after the modified magnetic perlite adsorbent adsorbing the heavy yttrium rare earth ions is placed on the wall of a wastewater tank by means of an external magnet, recovering the adsorbent adsorbing the heavy yttrium rare earth ions, oscillating and desorbing 1.0 wt% of hydrochloric acid, drying at 60 ℃, and then continuously recycling.
And (4) taking a certain amount of the supernatant obtained in the step (3), determining the concentration of the rare earth ions in the supernatant by using an EDTA (ethylene diamine tetraacetic acid) coordination titration method, and calculating the adsorption capacity of the rare earth ions. Then, the steps (1) to (3) were repeated 5 times to calculate the adsorption capacity of the recovered and regenerated adsorbent, and the adsorption capacity of the cycle test was shown in FIG. 4. As can be seen in fig. 4, the adsorption capacity of the modified magnetic perlite for rare earth ions decreases with increasing number of adsorbent cycles. The adsorption capacity of the recovered modified magnetic perlite to the rare earth ions is reduced from 388.4mg/g to 354.2 mg/g. Although the adsorption capacity of the recovered adsorbent is reduced and still kept at 350mg/g, the adsorbent recovered and regenerated by the method still has excellent adsorption performance.
Claims (6)
1. A method for enriching rare earth from heavy yttrium rare earth wastewater by using a modified magnetic perlite adsorbent is characterized by comprising the following steps: the method comprises the following steps:
(1) keeping the pH value of the heavy yttrium rare earth wastewater at 3.0-5.5;
(2) and (2) mixing the obtained modified magnetic perlite adsorbent according to the weight ratio of (10-100) mg: adding 1L of the mixture into the wastewater obtained in the step (1), uniformly stirring, and then performing constant-temperature vibration adsorption for 10min to 2.5h at normal temperature to enable heavy yttrium rare earth ions in the wastewater to be adsorbed on the surface of a magnetic adsorbent;
(3) after adsorption, standing the wastewater for 30-60 min, centrifuging, discharging clear liquid after the modified magnetic perlite adsorbent adsorbed with the heavy yttrium rare earth ions is placed on the wall of a wastewater tank by means of an external magnet, recovering the adsorbent adsorbed with the heavy yttrium rare earth ions, performing oscillation desorption by using acid liquid with the mass percentage concentration of 0.5-1 wt%, drying at 60-80 ℃, and then continuously recycling;
wherein: the modified magnetic perlite adsorbent is prepared by adopting the following method, and the method comprises the following steps:
mixing modified perlite with ferrous chloride, sodium acetate, polyvinyl alcohol and vinyl alcohol according to a ratio, placing the obtained mixture into a reaction kettle with a polytetrafluoroethylene lining after uniformly dispersing by ultrasonic, then heating the reaction temperature of the reaction kettle to 200 ℃, reacting for 24 hours at the temperature of 200 ℃, and cooling to room temperature after the reaction is finished to obtain the modified magnetic perlite adsorbent; the mass ratio of the modified perlite to the ferrous chloride is 1: 1-2; the mass ratio of the modified perlite to the sodium acetate is 1: 3-4; the mass ratio of the modified perlite to the polyvinyl alcohol is 1: 0.5 to 2; the dosage ratio of the modified perlite to the vinyl alcohol is 1 part by mass: 20-60 parts by volume, wherein: the mass part and the volume part are as follows: ml is taken as a benchmark; the modified perlite is prepared by sieving expanded perlite and then modifying the sieved expanded perlite by a long-chain surfactant and an amino coupling agent in sequence.
2. The method for enriching rare earth from heavy yttrium rare earth wastewater by using the modified magnetic perlite adsorbent according to claim 1, wherein the modified magnetic perlite adsorbent is prepared by the following steps: the concentration of the heavy yttrium rare earth wastewater in the step (1) is 0.01-1 g/L.
3. The method for enriching rare earth from heavy yttrium rare earth wastewater by using the modified magnetic perlite adsorbent according to claim 1, wherein the modified magnetic perlite adsorbent is prepared by the following steps: the pH value of the heavy yttrium rare earth wastewater in the step (1) is 5.5.
4. The method for enriching rare earth from heavy yttrium rare earth wastewater by using the modified magnetic perlite adsorbent according to claim 1, wherein the modified magnetic perlite adsorbent is prepared by the following steps: the adsorption time in the step (2) is 2 h.
5. The method for enriching rare earth from heavy yttrium rare earth wastewater by using the modified magnetic perlite adsorbent according to claim 1, wherein the modified magnetic perlite adsorbent is prepared by the following steps: the modified magnetic perlite material in the step (2) has the adsorption capacity of 16.1-383.6 mg/g for heavy yttrium rare earth ions.
6. The method for enriching rare earth from heavy yttrium rare earth wastewater by using the modified magnetic perlite adsorbent according to claim 1, wherein the modified magnetic perlite adsorbent is prepared by the following steps: and (3) the acid solution in the step (2) is dilute hydrochloric acid or dilute nitric acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658782A (en) * | 2009-08-24 | 2010-03-03 | 淮阴师范学院 | Method for preparing adsorbent by modifying attapulgite clay |
| KR20120080512A (en) * | 2011-01-07 | 2012-07-17 | 주식회사 코캣 | Adsorbents for exhaust gas and method for treating exhaust gas using the same |
| CN103230802A (en) * | 2013-04-12 | 2013-08-07 | 广东工业大学 | Preparation method of composite photocatalyst with visible light response and arsenic removing method |
| CN106975443A (en) * | 2017-05-02 | 2017-07-25 | 宝鸡文理学院 | A kind of preparation method and application of magnetic modified bentonite adsorbent |
| CN107262066A (en) * | 2017-07-27 | 2017-10-20 | 广州市番禺盛达穗南有限公司 | Preparation method for the perlite adsorbent of heavy-metal ion removal |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2675323C (en) * | 2008-08-13 | 2017-02-21 | Contech Stormwater Solutions Inc. | Thermally treated expanded perlite |
-
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- 2018-12-26 CN CN201811602700.2A patent/CN109395692B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658782A (en) * | 2009-08-24 | 2010-03-03 | 淮阴师范学院 | Method for preparing adsorbent by modifying attapulgite clay |
| KR20120080512A (en) * | 2011-01-07 | 2012-07-17 | 주식회사 코캣 | Adsorbents for exhaust gas and method for treating exhaust gas using the same |
| CN103230802A (en) * | 2013-04-12 | 2013-08-07 | 广东工业大学 | Preparation method of composite photocatalyst with visible light response and arsenic removing method |
| CN106975443A (en) * | 2017-05-02 | 2017-07-25 | 宝鸡文理学院 | A kind of preparation method and application of magnetic modified bentonite adsorbent |
| CN107262066A (en) * | 2017-07-27 | 2017-10-20 | 广州市番禺盛达穗南有限公司 | Preparation method for the perlite adsorbent of heavy-metal ion removal |
Non-Patent Citations (3)
| Title |
|---|
| Haiyan Xu et al..Novel and recyclable demulsifier of expanded perlite grafted by magnetic nanoparticles for oil separation from emulsified oil wastewaters.《Chemical Engineering Journal》.2017,第337卷 * |
| Novel and recyclable demulsifier of expanded perlite grafted by magnetic nanoparticles for oil separation from emulsified oil wastewaters;Haiyan Xu et al.;《Chemical Engineering Journal》;20171218;第337卷;第11-12页 * |
| Synthesis and characterization of a new low-cost composite for the adsorption of rare earth ions from aqueous solutions;Recep Akkaya;《Chemical Engineering Journal》;20120619;第200卷;第187-188页 * |
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