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CN116272877B - Carbon adsorption material and preparation method and application thereof - Google Patents

Carbon adsorption material and preparation method and application thereof Download PDF

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Publication number
CN116272877B
CN116272877B CN202211093362.0A CN202211093362A CN116272877B CN 116272877 B CN116272877 B CN 116272877B CN 202211093362 A CN202211093362 A CN 202211093362A CN 116272877 B CN116272877 B CN 116272877B
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extractant
carbon
desorption
solid
activated carbon
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CN116272877A (en
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王文萱
许新海
汪印
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Institute of Urban Environment of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • 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
    • C22B58/00—Obtaining gallium or indium
    • 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

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Abstract

The invention relates to a carbon adsorption material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing an extractant and a solvent to obtain an extractant solution; (2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, and carrying out oscillation impregnation to obtain a solid-liquid mixture; (3) And (3) carrying out vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2), and then drying to obtain the carbon adsorption material. The carbon adsorption material provided by the invention has excellent selective separation capability and adsorption capability on the dispersed metal indium and gallium, reduces the loss of an extractant, and has good mechanical strength and recycling stability. The preparation method provided by the invention greatly improves the loading capacity of the extractant, and is simple to operate, low in cost and environment-friendly.

Description

Carbon adsorption material and preparation method and application thereof
Technical Field
The invention relates to the field of electronic waste treatment and disposal, in particular to a carbon adsorption material and a preparation method and application thereof.
Background
Indium and gallium are rare dispersed metal elements, the average content in the crust is low, independent metal ore deposits are difficult to form in nature, and the indium and gallium are often dispersed in other metal minerals in the form of associated ores, so that the global supply is low. Indium and gallium have been widely used in the low-carbon technology fields such as solar cells, electronic semiconductors, and radio by virtue of their unique physicochemical properties. As demand increases, indium and gallium elements will gradually face a shortage problem.
In the market of photovoltaic modules, although the market ratio of the second-generation thin film copper indium gallium selenide (CIGS, chemical formula CuInGaSe 2) solar cells is small, the solar cells have great application potential in the fields of aerospace, photovoltaic buildings and the like by virtue of the advantages of light weight, thinness, flexibility, folding, good weak light performance and the like. The key structure absorption layer of the CIGS photovoltaic module is composed of copper indium gallium selenium alloy, so that the recovery of indium and gallium elements from the abandoned CIGS photovoltaic module has important significance for relieving the supply shortage phenomenon and promoting the sustainable development of low-carbon technical industries such as the photovoltaic industry and the like.
The separation and recovery technique of metal elements can be classified into pyrogenic recovery and wet recovery. At present, more wet recovery technologies are studied, mainly electrodeposition, ion exchange and solvent extraction technologies. The solvent extraction technology is suitable for selectively separating and recovering target metal ions under the condition of low metal ion concentration. However, the liquid-liquid extraction process in wet recovery is easy to cause the problems of emulsification, extractant loss and the like.
CN111321295A discloses a process for separating and purifying nickel and cobalt by using extractant impregnating resin, which uses ethanol or petroleum ether to dilute the extractant (2, 3-dimethyl-butyl) (2, 4' -trimethyl amyl) asymmetric dialkyl phosphinic acid, then impregnates macroporous adsorption resin to prepare extractant impregnating resin, and fills the extractant impregnating resin into a column to obtain a resin column for extraction, and the nickel and cobalt solution is leached to obtain cobalt back extraction solution to realize nickel and cobalt separation. However, the macroporous adsorption resin is adopted as an extractant carrier, so that the problems of poor stability, poor strength, easiness in breaking and aging, short service life, low extractant loading, easiness in loss and the like exist.
CN112206750B discloses a material for selectively adsorbing palladium, a preparation method and application thereof, the method adopts macroporous silica spherical particles as an extractant carrier, the palladium extractant is immersed in holes in the carrier by ultrasound, then the surface of the extractant-immersed silica is coated with polyvinyl alcohol and then immersed in a cross-linking agent solution, the surface polyvinyl alcohol is crosslinked to form a film, and the solid particles are repeatedly heated and cooled to vitrify the surface coating film, thus obtaining the material for selectively adsorbing palladium. The method takes macroporous silica spherical particles as an extractant carrier, the preparation method is complicated, the cost is high, the mechanical strength of the macroporous silica is poor, and the extractant loading capacity is low.
In summary, although the prior researches adopt macroporous adsorption resin, mesoporous silica particles, macroporous silica gel particles and the like as extractant carriers, the prior researches are limited by the stability and pore structure of the carriers, and the mechanical properties of composite adsorption materials obtained by impregnating the carriers with the extractant are generally poor, and the loading amount of the extractant and the recycling performance of the materials are not high.
Therefore, it is of great importance to provide a composite adsorbent material which has stable performance and excellent selective separation effect.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the carbon adsorption material and the preparation method and application thereof, and compared with the prior art, the carbon adsorption material provided by the invention has excellent selectivity and material stability, can be used for high-selectivity separation of dispersed metal indium ions and gallium ions, and has the advantages of simple operation, low cost and capability of remarkably improving the loading capacity of an extractant.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a carbon adsorption material, the method comprising the steps of:
(1) Mixing an extractant and a solvent to obtain an extractant solution;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, and carrying out oscillation impregnation to obtain a solid-liquid mixture;
(3) And (3) carrying out vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2), and then drying to obtain the carbon adsorption material.
According to the preparation method of the carbon adsorption material, the interaction of the coconut shell activated carbon and the extractant is adopted, the mutual coordination is adopted, and the molecular size of the extractant is comprehensively considered, so that on one hand, the unique pore structure of the coconut shell activated carbon is utilized to fully load the extractant, and the loading capacity of the extractant is greatly improved; on the other hand, the system is powered by the vibration impregnation mode, organic molecules are forced to enter the active carbon pores, further vacuum rotary evaporation is adopted, the organic molecules are forced to be fully loaded in the active carbon pores in a vacuumizing mode, and meanwhile solvent evaporation is promoted. Compared with the preparation method adopting bamboo-based active carbon and fruit shell-based active carbon, the preparation method provided by the invention has the advantages that the loading capacity of the extractant is improved by more than 6 times, the loading capacity of the extractant can be improved by more than 1.4 times, the extractant hardly runs off from the carrier, the material performance is more stable, and the material can be recycled for more than 7 times.
In the invention, before the mixing in the step (2), the coconut shell activated carbon is generally repeatedly washed by distilled water until filtrate is clear, and then is dried.
Preferably, the extractant comprises a phosphine-based extractant.
Preferably, the phosphine based extractant comprises any one or a combination of at least two of P204, P507 or TBP, wherein typical but non-limiting combinations include a combination of P204 and P507 or a combination of P507 and TBP, preferably P507.
Preferably, the solvent comprises any one or a combination of at least two of ethanol, methylene chloride or diethyl ether, wherein typical but non-limiting combinations include a combination of ethanol and methylene chloride or a combination of methylene chloride and diethyl ether.
Preferably, the volume ratio of extractant to solvent is (0.04-0.3): 4, which may be, for example, 0.04:4, 0.08:4, 0.1:4, 0.12:4, 0.14:4, 0.16:4, 0.18:4, 0.2:4, 0.22:4, 0.24:4, 0.26:4, 0.28:4 or 0.3:4, although other non-enumerated values within the numerical range are equally applicable, preferably (0.1-0.15): 4.
The invention preferably controls the volume ratio of the extractant to the solvent in a specific range, and can promote the sufficient loading of the extractant and avoid the agglomeration of the activated carbon.
Preferably, the coconut shell activated carbon in the step (2) is a mesoporous activated carbon, and the pore size is 2-50nm, for example, 2nm, 4nm, 6nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the BJH desorption pore diameter of the coconut shell activated carbon is 5-15nm, for example, 5nm, 6nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm or 15nm, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The BJH desorption pore diameter of the coconut shell activated carbon is preferably controlled within a specific range, a freely flowing pore channel can be provided for extractant macromolecules, the extractant can conveniently enter the inner pores of the activated carbon rapidly and efficiently, and the loading capacity of the extractant is improved; meanwhile, sufficient contact area and reaction space can be provided for extractant molecules and metal ions in the solution, so that the metal ion adsorption capacity of the adsorption material is improved.
Preferably, the particle size of the coconut shell activated carbon is 212 to 550. Mu.m, for example, 212 μm, 220 μm, 240 μm, 260 μm, 280 μm, 300 μm, 320 μm, 340 μm, 360 μm, 380 μm, 400 μm, 420 μm, 440 μm, 460 μm, 500 μm, 520 μm or 550 μm, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 250 to 270 μm.
Preferably, the solid-to-liquid ratio of the coconut shell activated carbon to the solvent is (0.1-0.3): 4g/mL, for example, 0.1:4g/mL, 0.15:4g/mL, 0.2:4g/mL, 0.25:4g/mL or 0.3:4g/mL, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the rotation speed of the oscillation impregnation is 130-150r/min, for example 130r/min, 132r/min, 134r/min, 136r/min, 138r/min, 140r/min, 142r/min, 144r/min, 146r/min, 148r/min or 150r/min, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the temperature of the oscillation impregnation is 5 to 35 ℃, for example, 5 ℃, 8 ℃,10 ℃, 12 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃ or 35 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable, preferably 20 to 25 ℃.
Preferably, the time of the shaking impregnation is 30s-48h, for example, 30s, 1min, 2min, 4min, 6min, 8min, 10min, 1h, 2h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h or 48h, but not limited to the recited values, other non-recited values in the numerical range are equally applicable, preferably 1-10min, further preferably 5-10min.
Preferably, the vacuum degree of the vacuum rotary evaporation in the step (3) is 0.05-0.08MPa, for example, 0.05MPa, 0.055MPa, 0.06MPa, 0.065MPa, 0.07MPa, 0.075MPa or 0.08MPa, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The invention preferably controls the vacuum degree in a specific range, can promote the extractant to enter the active carbon pore canal and promote the solvent to be discharged, and further improves the selective adsorption effect of the adsorption material.
Preferably, the drying temperature is not less than 40 ℃, for example, 40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the values listed, other non-listed values within the range of values are equally applicable, preferably not less than 50 ℃, further preferably 60-70 ℃.
Preferably, the drying time is 8h or more, for example, 8h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 8 to 24h, and more preferably 10 to 12h.
As a preferred technical solution of the first aspect of the present invention, the preparation method includes the following steps:
(1) 4, mixing the phosphine extractant and the solvent according to the volume ratio of (0.04-0.3) to obtain an extractant solution;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, wherein the coconut shell activated carbon is mesoporous activated carbon, the aperture is 2-50nm, the BJH desorption aperture is 5-15nm, the particle size is 212-550 mu m, the solid-to-liquid ratio of the coconut shell activated carbon to the solvent is (0.1-0.3): 4g/mL, and then oscillating and impregnating for 5-10min at the temperature of 20-25 ℃ at the rotating speed of 130-150r/min to obtain a solid-liquid mixture;
(3) And (3) performing vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2) under the vacuum degree of 0.05-0.08MPa, and then drying at the temperature of 60-70 ℃ for 10-12h to obtain the carbon adsorption material.
In a second aspect, the present invention provides a carbon adsorbing material obtained by the production method according to the first aspect of the present invention; the carbon adsorption material comprises a coconut shell activated carbon carrier and an extractant loaded on the coconut shell activated carbon carrier.
The carbon adsorption material provided by the invention adopts the coconut shell activated carbon to load the extractant molecules, and the coconut shell activated carbon has very stable physical and chemical properties, has a larger specific surface area and a more developed pore structure, can load more extractant, is more tightly combined with the extractant, and reduces the loss of the extractant. The carbon adsorption material provided by the invention has high adsorption selectivity, excellent mechanical property and good recycling property.
Preferably, the loading of the extractant in the carbon adsorption material is (0.3-0.35) mL/g, and may be, for example, 0.3mL/g, 0.31mL/g, 0.32mL/g, 0.33mL/g, 0.34mL/g, or 0.35mL/g, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a third aspect, the present invention provides the use of a carbon adsorbing material according to the second aspect of the present invention for selectively separating and recovering a dispersed metal element in a solution; the rare earth metal element comprises indium and/or gallium.
The carbon adsorption material provided by the invention can realize high-efficiency selective adsorption of indium ions and gallium ions by adjusting the acidity condition of adsorption, and can realize separate desorption of indium ions and gallium ions by adjusting the acidity condition of desorption, thereby realizing high-selectivity separation and recovery of indium and gallium.
Preferably, the solution comprises an pickle liquor of a copper indium gallium diselenide photovoltaic module.
The carbon adsorption material provided by the invention can be used for recycling electronic waste, such as pickle liquor of waste copper indium gallium selenium photovoltaic modules, so that the purpose of separating and recycling indium and gallium in the waste photovoltaic modules is achieved, the problem of supply shortage of indium element and gallium element can be relieved, and sustainable development of the photovoltaic industry is promoted.
Preferably, the use comprises the steps of:
(a) Acid leaching is carried out on the copper indium gallium selenide photovoltaic module by adopting nitric acid to obtain acid leaching liquid;
(b) Mixing the pickle liquor obtained in the step (a) with a carbon adsorption material under the condition that the pH value is 0.9-1.1, performing primary adsorption, performing solid-liquid separation to obtain a first filtrate and a first filter residue, mixing the first filtrate with the carbon adsorption material again, performing secondary adsorption, and performing solid-liquid separation to obtain a second filtrate and a second filter residue;
(c) Mixing the second filtrate obtained in the step (b) with a carbon adsorption material under the condition that the pH is 1.9-2.1, performing three-time adsorption, performing solid-liquid separation to obtain a third filtrate and a third filter residue, mixing the third filtrate with the carbon adsorption material again, performing four-time adsorption, and performing solid-liquid separation to obtain a separated solution and a fourth filter residue;
(d) Immersing the first filter residue and the second filter residue obtained in the step (b) and the third filter residue and the fourth filter residue obtained in the step (c) into 0.05-0.15mol/L nitric acid solution for primary desorption, then performing solid-liquid separation to obtain a first desorption material, immersing the first desorption material into 0.05-0.15mol/L nitric acid solution for secondary desorption, and then performing solid-liquid separation to obtain a second desorption material; the filtrate obtained by solid-liquid separation after the primary desorption and the secondary desorption is gallium nitrate solution;
(e) Immersing the second desorption material obtained in the step (d) into 3.9-4.1mol/L nitric acid solution for three times of desorption, then performing solid-liquid separation to obtain a third desorption material, immersing the third desorption material into 3.9-4.1mol/L nitric acid solution for four times of desorption, and then performing solid-liquid separation to obtain a completely desorbed carbon adsorption material; and the filtrate obtained by solid-liquid separation after the three desorption and four desorption is an indium nitrate solution.
The method of solid-liquid separation in the present invention is not particularly limited, and may be any method of solid-liquid separation commonly used in the art, for example, filtration or centrifugation.
The carbon adsorption material completely desorbed in the invention can be reused as an adsorption material in the adsorption process, realizes recycling, and has good use stability.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with liquid-liquid extraction, bamboo-based or fruit shell-based active carbon composite extraction materials and macroporous adsorption resin composite extraction materials, the carbon adsorption material provided by the invention has the advantages that the selective separation capacity and adsorption capacity of rare-dispersed metal indium and gallium are greatly improved, the loss of the extractant is reduced, and in addition, the carbon adsorption material has good mechanical strength and recycling stability.
(2) The preparation method of the carbon adsorption material provided by the invention fully utilizes the excellent specific surface area and developed pore structure of the coconut shell activated carbon, and combines the means of vibration impregnation, vacuum rotary evaporation and the like to force the organic macromolecule extractant to enter the pores of the activated carbon, so that the organic macromolecule extractant is loaded on the coconut shell activated carbon carrier more uniformly and dispersedly, the loading amount of the extractant is greatly improved, the loading amount of the extractant of the carbon adsorption material can reach more than 0.08mL/g, and can reach more than 0.31mL/g under the optimal condition; when the pH is 1, the indium adsorption rate can reach more than 52.9 percent, and can reach more than 87.9 percent under the better condition; when the pH is 2, the adsorption rate of gallium can reach more than 50.1 percent, and under the optimal condition, the adsorption rate of gallium can reach more than 84.9 percent, and the method is simple to operate, low in cost and environment-friendly.
(3) The carbon adsorption material provided by the invention has an excellent metal ion contact area, can be used for recycling the scattered metal elements indium and gallium in the solution with high selectivity, is especially suitable for efficient separation and high-purity recycling of indium and gallium in the waste CIGS photovoltaic module pickle liquor, is green and pollution-free, can relieve the problem of supply shortage of the indium element and the gallium element, and promotes the sustainable development of the photovoltaic industry.
Drawings
FIG. 1 is a graph showing the results of adsorption of metal ions by the carbon adsorbent material according to example 1 of the present invention;
FIG. 2 is a graph showing the result of adsorption of each metal ion by the adsorption material according to comparative example 1 of the present invention;
Fig. 3 is a flowchart of the carbon adsorption material of application example 1 of the invention for treating waste copper indium gallium selenide photovoltaic module pickle liquor.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a carbon adsorption material, which comprises the following steps:
(1) Mixing 0.12mL of extractant P507 and 4mL of ethanol with a volume ratio of 0.12:4 to obtain an extractant solution;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, wherein the BJH desorption aperture of the coconut shell activated carbon is 9.44nm, the particle size is 212-250 mu m, the solid-liquid ratio of the coconut shell activated carbon to ethanol is 0.2:4g/mL, and then oscillating and impregnating for 7min at the temperature of 22 ℃ at the rotating speed of 140r/min to obtain a solid-liquid mixture;
(3) And (3) carrying out vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2) under the vacuum degree of 0.06MPa, and then drying for 11 hours at the temperature of 65 ℃ to obtain the carbon adsorption material.
The embodiment also provides a carbon adsorption material obtained by the preparation method, wherein the carbon adsorption material comprises a coconut shell activated carbon carrier and a P507 extractant loaded on the coconut shell activated carbon carrier, and the loading amount of the extractant in the carbon adsorption material is 0.34mL/g.
Example 2
The embodiment provides a preparation method of a carbon adsorption material, which comprises the following steps:
(1) Mixing 0.1mL of extractant TBP and 4mL of dichloromethane with a volume ratio of 0.1:4 to obtain extractant solution;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, wherein the BJH desorption aperture of the coconut shell activated carbon is 5.85nm, the particle size is 212-250 mu m, the solid-liquid ratio of the coconut shell activated carbon to methylene dichloride is 0.1:4g/mL, and then oscillating and impregnating for 10min at the temperature of 20 ℃ at the rotating speed of 130r/min to obtain a solid-liquid mixture;
(3) And (3) carrying out vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2) under the vacuum degree of 0.08MPa, and then drying at 60 ℃ for 12 hours to obtain the carbon adsorption material.
The embodiment also provides a carbon adsorption material obtained by the preparation method, wherein the carbon adsorption material comprises a coconut shell activated carbon carrier and TBP extractant loaded on the coconut shell activated carbon carrier, and the loading amount of the extractant in the carbon adsorption material is 0.31mL/g.
Example 3
The embodiment provides a preparation method of a carbon adsorption material, which comprises the following steps:
(1) Mixing 0.3mL of extractant P507 and 4mL of dichloromethane with a volume ratio of 0.15:4 to obtain an extractant solution;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, wherein the BJH desorption aperture of the coconut shell activated carbon is 15nm, the particle size is 212-250 mu m, the solid-liquid ratio of the coconut shell activated carbon to methylene dichloride is 0.3:4g/mL, and then oscillating and impregnating for 5min at the temperature of 25 ℃ at the rotating speed of 150r/min to obtain a solid-liquid mixture;
(3) And (3) carrying out vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2) under the vacuum degree of 0.05MPa, and then drying at 70 ℃ for 10 hours to obtain the carbon adsorption material.
The embodiment also provides a carbon adsorption material obtained by the preparation method, wherein the carbon adsorption material comprises a coconut shell activated carbon carrier and a P507 extractant loaded on the coconut shell activated carbon carrier, and the loading amount of the extractant in the carbon adsorption material is 0.47mL/g.
Example 4
This example provides a method for preparing a carbon adsorption material, which is different from example 1 only in that the BJH desorption pore diameter of the coconut shell activated carbon is 2nm.
Example 5
This example provides a method for preparing a carbon adsorption material, which is different from example 1 only in that the BJH desorption pore diameter of the coconut shell activated carbon is 30nm.
Example 6
This example provides a method for preparing a carbon adsorbing material, which differs from example 1 only in that the volume ratio of extractant P507 to ethanol is 0.04:4.
Example 7
This example provides a method for preparing a carbon adsorbing material, which differs from example 1 only in that the volume ratio of extractant P507 to ethanol is 1:4.
Example 8
This example provides a method for producing a carbon adsorbing material, which differs from example 1 only in that the vacuum degree of the vacuum rotary evaporation is 0.04MPa.
Example 9
This example provides a method for producing a carbon adsorbing material, which differs from example 1 only in that the vacuum degree of the vacuum rotary evaporation is 0.09MPa.
Comparative example 1
Comparative example an adsorbent material is provided which is coconut shell activated carbon, which is the same as in example 1.
Comparative example 2
This comparative example provides a method of preparing an adsorbent material, which differs from example 1 only in that the coconut shell activated carbon is replaced with a macroporous adsorbent resin.
Comparative example 3
This comparative example provides a method for preparing a carbon adsorbing material, which is different from example 1 only in that coconut shell activated carbon is replaced with bamboo-based activated carbon having a particle size of 212-250 μm.
Comparative example 4
This comparative example provides a method for producing a carbon adsorbing material, comprising the steps of:
(1) Mixing 0.12mL of extractant P507 and 4mL of ethanol with a volume ratio of 0.12:4 to obtain an extractant solution;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, wherein the BJH desorption aperture of the coconut shell activated carbon is 9.44nm, the particle size is 212-250 mu m, the solid-liquid ratio of the coconut shell activated carbon to ethanol is 0.2:4g/mL, and stirring and soaking for 7min at the temperature of 22 ℃ at the rotating speed of 140r/min to obtain a solid-liquid mixture;
(3) Filtering the solid-liquid mixture obtained in the step (2), washing the solid phase with distilled water with the mass of 10 times of that of the solid phase, and then drying the solid phase in vacuum at 65 ℃ for 11 hours to obtain the carbon adsorption material.
Comparative example 5
The comparative example provides an extractant, which is P507.
Application example 1
The present application example provides a use of the carbon adsorbing material of example 1, as shown in fig. 3, comprising the steps of:
(a) Acid leaching is carried out on the waste copper indium gallium selenide photovoltaic module by adopting nitric acid to obtain acid leaching liquid; the pickle liquor contains ：Zn2+53.7％wt.％,In3+17.5％,Cu2+15.5％,Ga3+7.5％,Cd2+1.9％,Mg2+1.5％,Ni2+1.5％ and 0.9 percent of Al 3+ by mass percent.
(B) Mixing the pickle liquor obtained in the step (a) with a carbon adsorption material under the condition of pH of 1, performing primary adsorption (the solid-to-liquid ratio of the carbon adsorption material to the pickle liquor is 0.6 g/L.), filtering to obtain a first filtrate and a first filter residue, mixing the first filtrate and the carbon adsorption material again, performing secondary adsorption while keeping the solid-to-liquid ratio unchanged, and filtering to obtain a second filtrate and a second filter residue;
(c) Mixing the second filtrate obtained in the step (b) with a carbon adsorption material under the condition of pH of 2, performing three-time adsorption (the solid-to-liquid ratio of the carbon adsorption material to the second filtrate is 0.6 g/L.), filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate and the carbon adsorption material again, performing four-time adsorption while keeping the solid-to-liquid ratio unchanged, and filtering to obtain a separated solution and a fourth filter residue;
(d) Immersing the first filter residue and the second filter residue obtained in the step (b) and the third filter residue and the fourth filter residue obtained in the step (c) into a nitric acid solution of 0.1mol/L for primary desorption, filtering to obtain a first desorption material, immersing the first desorption material into the nitric acid solution of 0.1mol/L for secondary desorption, and filtering to obtain a second desorption material; the filtrate obtained by filtering after the primary desorption and the secondary desorption is gallium nitrate solution;
(e) Immersing the second desorption material obtained in the step (d) into 4mol/L nitric acid solution for three times of desorption, filtering to obtain a third desorption material, immersing the third desorption material into 4mol/L nitric acid solution for four times of desorption, and filtering to obtain a completely desorbed carbon adsorption material; the filtrate obtained by filtering after the three-time desorption and the four-time desorption is an indium nitrate solution;
The fully desorbed carbon adsorbent material may be reused in step (b) and step (c).
Application example 2
The present application example provides a use of the carbon adsorbing material, the carbon adsorbing material adopting the carbon adsorbing material in example 2, the use comprising the steps of:
(a) Acid leaching is carried out on the waste copper indium gallium selenide photovoltaic module by adopting nitric acid to obtain acid leaching liquid; the pickle liquor was the same as in example 1;
(b) Mixing the pickle liquor obtained in the step (a) with a carbon adsorption material under the condition of pH of 0.9, performing primary adsorption (the solid-to-liquid ratio of the carbon adsorption material to the pickle liquor is 0.5 g/L.), filtering to obtain a first filtrate and a first filter residue, mixing the first filtrate and the carbon adsorption material again, performing secondary adsorption while keeping the solid-to-liquid ratio unchanged, and filtering to obtain a second filtrate and a second filter residue;
(c) Mixing the second filtrate obtained in the step (b) with a carbon adsorption material under the condition of a pH of 1.9, performing three-time adsorption (the solid-to-liquid ratio of the carbon adsorption material to the second filtrate is 0.5 g/L.), filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate and the carbon adsorption material again, performing four-time adsorption while keeping the solid-to-liquid ratio unchanged, and filtering to obtain a separated solution and a fourth filter residue;
(d) Immersing the first filter residue and the second filter residue obtained in the step (b) and the third filter residue and the fourth filter residue obtained in the step (c) into a nitric acid solution of 0.12mol/L for primary desorption, filtering to obtain a first desorption material, immersing the first desorption material into a nitric acid solution of 0.12mol/L for secondary desorption, and filtering to obtain a second desorption material; the filtrate obtained by filtering after the primary desorption and the secondary desorption is gallium nitrate solution;
(e) Immersing the second desorption material obtained in the step (d) into 4.05mol/L nitric acid solution for three times of desorption, filtering to obtain a third desorption material, immersing the third desorption material into 4.05mol/L nitric acid solution for four times of desorption, and filtering to obtain a completely desorbed carbon adsorption material; the filtrate obtained by filtering after the three-time desorption and the four-time desorption is an indium nitrate solution;
The fully desorbed carbon adsorbent material may be reused in step (b) and step (c).
Application example 3
The present application example provides a use of the carbon adsorbing material of example 3, comprising the steps of:
(a) Acid leaching is carried out on the waste copper indium gallium selenide photovoltaic module by adopting nitric acid to obtain acid leaching liquid; the pickle liquor was the same as in example 1;
(b) Mixing the pickle liquor obtained in the step (a) with a carbon adsorption material under the condition of pH of 1.1, performing primary adsorption (the solid-to-liquid ratio of the carbon adsorption material to the pickle liquor is 0.7 g/L.), filtering to obtain a first filtrate and a first filter residue, mixing the first filtrate and the carbon adsorption material again, performing secondary adsorption while keeping the solid-to-liquid ratio unchanged, and filtering to obtain a second filtrate and a second filter residue;
(c) Mixing the second filtrate obtained in the step (b) with a carbon adsorption material under the condition of a pH of 2.1, performing three-time adsorption (the solid-to-liquid ratio of the carbon adsorption material to the second filtrate is 0.7 g/L.), filtering to obtain a third filtrate and a third filter residue, mixing the third filtrate and the carbon adsorption material again, performing four-time adsorption while keeping the solid-to-liquid ratio unchanged, and filtering to obtain a separated solution and a fourth filter residue;
(d) Immersing the first filter residue and the second filter residue obtained in the step (b) and the third filter residue and the fourth filter residue obtained in the step (c) into a nitric acid solution of 0.15mol/L for primary desorption, filtering to obtain a first desorption material, immersing the first desorption material into the nitric acid solution of 0.15mol/L for secondary desorption, and filtering to obtain a second desorption material; the filtrate obtained by filtering after the primary desorption and the secondary desorption is gallium nitrate solution;
(e) Immersing the second desorption material obtained in the step (d) into 4.1mol/L nitric acid solution for three times of desorption, filtering to obtain a third desorption material, immersing the third desorption material into 4.1mol/L nitric acid solution for four times of desorption, and filtering to obtain a completely desorbed carbon adsorption material; the filtrate obtained by filtering after the three-time desorption and the four-time desorption is an indium nitrate solution;
The fully desorbed carbon adsorbent material may be reused in step (b) and step (c).
Comparative example 1 was used
The present application example comparative example provides a use of a carbon adsorbing material, which differs from application example 1 only in that the carbon adsorbing material is replaced with coconut shell activated carbon in comparative example 1.
Metal ion adsorption effect test:
The adsorbents of examples 1 to 9 and comparative examples 1 to 4 and the extractant of comparative example 5 (In the test, the amount of the extractant of comparative example 5 was controlled to be equal to the amount of the extractant contained In the carbon adsorbent of example 1) were placed In 250mL conical flasks, each of the metal source solutions containing In 3+、Ga3+、Al3+、Zn2+、Cd2+、Cu2+、Mg2+ and Ni + (the concentration of each metal ion was 0.1 mmol/L) were added to the examples 1 to 9 and comparative examples 1 to 4 at a solid-to-liquid ratio of 0.6g/L, the same metal source solutions were added to the comparative example 5 In equal volumes to obtain mixed solutions, the pH was adjusted to 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5.5 and 6, respectively, and the concentration of each metal ion In the mixed solutions after the reaction was measured at each pH at a temperature of 25℃and an oscillation speed of 140r/min was reacted for 3 hours, and the adsorption rate of each metal ion was calculated. The adsorption rate of indium at pH 1 is shown in Table 1. The adsorption rate of gallium at pH 2 is shown in Table 1.
Taking example 1 and comparative example 1 as examples, the adsorption rate of each metal ion in example 1 is shown in fig. 1, and the adsorption rate of each metal ion in comparative example 1 is shown in fig. 2. As can be seen from fig. 1, the carbon adsorption material has selective adsorption capacity for indium and gallium. As can be seen from fig. 2, the coconut shell activated carbon, which is a raw material of the carbon adsorbent, has no selective adsorption capacity for indium and gallium, and the adsorption rate is only 15% or less.
Calculating a separation coefficient:
the calculation formula of the separation coefficient SF A B is:
Wherein:
C A,0 -initial concentration of metal ion A in the mixed solution (mg/L);
C A,e -equilibrium concentration of metal ion A in the mixed solution (mg/L);
C B,0 -initial concentration of metal ion B in the mixed solution (mg/L);
c B,e -equilibrium concentration of metal ion B in the mixed solution (mg/L).
Taking example 1 as an example, in the above metal ion adsorption effect test, the carbon adsorption material provided in example 1 has a separation coefficient of separating indium ions from gallium ions at pH 1 ofThe separation coefficient of the carbon adsorption material provided in example 1 for separating gallium ions from other ions at pH 2 was
Calculation of adsorption quantity:
The calculation formula of the adsorption quantity q i is as follows:
Wherein:
c i,0 -initial concentration of metal ions in the mixed solution (mg/L);
C i,e -initial concentration of metal ions in the mixed solution (mg/L);
v-volume of mixed solution (L);
w is the addition amount (g) of the adsorption material.
Taking example 1 as an example, in the above metal ion adsorption effect test, the adsorption amount of the carbon adsorption material provided in example 1 to indium ions under the condition that the pH is 1 is 53.85mg/g; the carbon adsorbing material provided in example 1 had an adsorption amount of gallium ions at pH 2 of 50.66mg/g.
The extraction rate of the samples of examples 1 to 9 and comparative examples 2 to 4 was measured by the following method: the results of the titration are shown in Table 1.
The contents of gallium ions and indium ions in the gallium nitrate solution and the indium nitrate solution obtained in application examples 1 to 3 and application comparative example 1 were measured, and the recovery rates of gallium and indium were calculated, respectively, and the results are shown in table 2. The calculation formula of the recovery rate is as follows:
TABLE 1
In table 1 "-" indicates that there is no such data.
TABLE 2
Recovery/% Recovery/%
Application example 1 99.9 99.9
Application example 2 90.3 89.5
Application example 3 94.5 85.3
Comparative example 1 was used 1.2 1.5
From tables 1 and 2, the following points can be seen:
(1) As can be seen from the data of examples 1-9, the extractant loading of the carbon adsorption material provided by the invention can reach more than 0.08mL/g, and can reach more than 0.31mL/g under the optimal condition; when the pH is 1, the indium adsorption rate can reach more than 52.9 percent, and can reach more than 87.9 percent under the better condition; when the pH is 2, the adsorption rate of gallium can reach more than 50.1 percent, and under the optimal condition, the adsorption rate of gallium can reach more than 84.9 percent.
As can be seen from the data of application examples 1-3, the carbon adsorption material provided by the invention is used for treating the waste copper-indium-gallium-selenium photovoltaic module pickle liquor, the recovery rate of indium can reach more than 90.3%, and the recovery rate of gallium can reach more than 85.3%.
(2) As can be seen from a combination of the data of examples 1 and examples 4-5, the BJH desorption pore diameter of the coconut shell activated carbon of example 1 was 9.44nm, and the loading of the extractant in example 1 was significantly higher than that of example 4, compared to 2nm and 30nm in examples 4-5, respectively, and the agglomeration of the carbon adsorbent material easily occurred although the loading of the extractant in example 5 was large. Therefore, the indium adsorption rate and the gallium adsorption rate in the embodiment 1 are obviously higher than those in the embodiments 4-5, so that the BJH desorption pore diameter of the coconut shell activated carbon is preferably controlled, and the adsorption capacity of the carbon adsorption material to indium and gallium can be further improved.
(3) As can be seen from a combination of the data of examples 1 and examples 6-7, the extractant loading in example 1 was significantly higher than that in example 6, as compared to the extractant loading in examples 6-7, which was 0.04:4 and 1:4, respectively, with the volume ratio of extractant P507 to ethanol in example 1 being 0.12:4, and the carbon adsorbing material agglomeration was likely to occur, although the extractant loading in example 7 was greater. Therefore, the indium adsorption rate and the gallium adsorption rate in the embodiment 1 are obviously higher than those in the embodiments 6-7, so that the invention can preferably control the volume ratio of the extractant P507 to the ethanol, and further improve the adsorption capacity of the carbon adsorption material to indium and gallium.
(4) As can be seen from the data of comparative examples 1 and examples 8 to 9, the vacuum degree of the vacuum rotary evaporation in example 1 is 0.06MPa, and the loading amount of the extractant, the indium adsorption rate and the gallium adsorption rate in example 1 are all higher than those in examples 8 to 9 compared with 0.04MPa and 0.09MPa in examples 8 to 9, respectively, so that the adsorption capacity of the carbon adsorption material to indium and gallium can be further improved by preferably controlling the vacuum degree of the vacuum rotary evaporation.
(5) As can be seen from the data of comparative examples 1 and 1 to 5, the extractant loading, indium adsorption rate and gallium adsorption rate in example 1 are far higher than those in comparative examples 1 to 5, so that the carbon adsorption material and the preparation method thereof provided by the invention greatly improve the selective separation capacity and adsorption capacity for the dispersed metallic indium and gallium.
(6) As can be seen from the data of the application example 1 and the application comparative example 1, the recovery rate of indium and gallium in the application example 1 is far higher than that of the application comparative example 1, so that the carbon adsorption material provided by the invention is used for treating the waste copper indium gallium selenide photovoltaic module pickle liquor, and can realize the high-efficiency separation and high-purity recovery of indium and gallium.
In conclusion, the carbon adsorption material provided by the invention has high loading capacity and excellent selective separation capability on scattered metal indium and gallium through interaction of coconut shell activated carbon and an extractant, can be used for treating the acid leaching liquid of the waste copper indium gallium selenium photovoltaic module, can realize high-efficiency separation and high-purity recovery of indium and gallium, and can be recycled.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (25)

1. A method for preparing a carbon adsorbing material, comprising the steps of:
(1) Mixing an extractant and a solvent to obtain an extractant solution;
The extractant comprises a phosphine-based extractant;
The phosphine extractant comprises any one or a combination of at least two of P204, P507 or TBP;
the volume ratio of the extractant to the solvent is (0.1-0.15): 4;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, and carrying out oscillation impregnation to obtain a solid-liquid mixture;
(3) Performing vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2), and then drying to obtain the carbon adsorption material;
the vacuum degree of the vacuum rotary steaming is 0.05-0.08MPa;
the BJH desorption aperture of the coconut shell activated carbon is 5-15nm.
2. The method of claim 1, wherein the solvent comprises any one or a combination of at least two of ethanol, dichloromethane, or diethyl ether.
3. The method of claim 1, wherein the coconut shell activated carbon has a particle size of 212-550 μm.
4. The method according to claim 3, wherein the coconut shell activated carbon has a particle size of 250 to 270. Mu.m.
5. The method according to claim 1, wherein the solid-to-liquid ratio of the coconut shell activated carbon to the solvent is (0.1-0.3) 4g/mL.
6. The method according to claim 1, wherein the rotational speed of the oscillating impregnation is 130-150r/min.
7. The method of claim 1, wherein the temperature of the oscillating impregnation is 5-35 ℃.
8. The method of claim 7, wherein the temperature of the oscillating impregnation is 20-25 ℃.
9. The method of claim 1, wherein the time of the shaking impregnation is 30s to 48h.
10. The method of claim 9, wherein the time of the shaking impregnation is 1-10min.
11. The method of claim 10, wherein the time of the shaking impregnation is 5-10min.
12. The process according to claim 1, wherein the drying temperature in step (3) is not less than 40 ℃.
13. The method according to claim 12, wherein the drying temperature in step (3) is not less than 50 ℃.
14. The method of claim 13, wherein the drying in step (3) is performed at a temperature of 60-70 ℃.
15. The method according to claim 1, wherein the drying time in the step (3) is not less than 8 hours.
16. The method of claim 15, wherein the drying in step (3) is performed for a period of 8 to 24 hours.
17. The method of claim 16, wherein the drying in step (3) is performed for a period of 10 to 12 hours.
18. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) 4, mixing the phosphine extractant and the solvent according to the volume ratio of (0.1-0.15) to obtain an extractant solution;
(2) Mixing the extractant solution obtained in the step (1) with coconut shell activated carbon, wherein the BJH desorption aperture of the coconut shell activated carbon is 5-15nm, the particle size is 212-550 mu m, the solid-liquid ratio of the coconut shell activated carbon to the solvent is (0.1-0.3): 4g/mL, and then oscillating and impregnating for 5-10min at the rotating speed of 130-150r/min at the temperature of 20-25 ℃ to obtain a solid-liquid mixture;
(3) And (3) performing vacuum rotary evaporation on the solid-liquid mixture obtained in the step (2) under the vacuum degree of 0.05-0.08MPa, and then drying at the temperature of 60-70 ℃ for 10-12h to obtain the carbon adsorption material.
19. A carbon adsorbing material, characterized in that the carbon adsorbing material is obtained by the method for producing a carbon adsorbing material according to any one of claims 1 to 18.
20. The carbon adsorbing material according to claim 19, wherein the carbon adsorbing material comprises a coconut activated carbon support and an extractant supported on the coconut activated carbon support.
21. The carbon adsorbent material of claim 19, wherein the loading of extractant in the carbon adsorbent material is (0.3-0.35) mL/g.
22. Use of a carbon adsorbing material according to any one of claims 19 to 21 for selectively separating and recovering a dispersed metal element in a solution.
23. Use according to claim 22, characterized in that the rare earth metal element comprises indium and/or gallium.
24. The use according to claim 22, wherein the solution comprises an pickle liquor of a copper indium gallium diselenide photovoltaic module.
25. Use according to claim 24, characterized in that it comprises the following steps:
(a) Acid leaching is carried out on the copper indium gallium selenide photovoltaic module by adopting nitric acid to obtain acid leaching liquid;
(b) Mixing the pickle liquor obtained in the step (a) with a carbon adsorption material under the condition that the pH value is 0.9-1.1, performing primary adsorption, performing solid-liquid separation to obtain a first filtrate and a first filter residue, mixing the first filtrate with the carbon adsorption material again, performing secondary adsorption, and performing solid-liquid separation to obtain a second filtrate and a second filter residue;
(c) Mixing the second filtrate obtained in the step (b) with a carbon adsorption material under the condition that the pH is 1.9-2.1, performing three-time adsorption, performing solid-liquid separation to obtain a third filtrate and a third filter residue, mixing the third filtrate with the carbon adsorption material again, performing four-time adsorption, and performing solid-liquid separation to obtain a separated solution and a fourth filter residue;
(d) Immersing the first filter residue and the second filter residue obtained in the step (b) and the third filter residue and the fourth filter residue obtained in the step (c) into 0.05-0.15mol/L nitric acid solution for primary desorption, then performing solid-liquid separation to obtain a first desorption material, immersing the first desorption material into 0.05-0.15mol/L nitric acid solution for secondary desorption, and then performing solid-liquid separation to obtain a second desorption material; the filtrate obtained by solid-liquid separation after the primary desorption and the secondary desorption is gallium nitrate solution;
(e) Immersing the second desorption material obtained in the step (d) into 3.9-4.1mol/L nitric acid solution for three times of desorption, then performing solid-liquid separation to obtain a third desorption material, immersing the third desorption material into 3.9-4.1mol/L nitric acid solution for four times of desorption, and then performing solid-liquid separation to obtain a completely desorbed carbon adsorption material; and the filtrate obtained by solid-liquid separation after the three desorption and four desorption is an indium nitrate solution.
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Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2616157A1 (en) * 1987-06-02 1988-12-09 Pechiney Aluminium PROCESS FOR EXTRACTING AND PURIFYING GALLIUM FROM BAYER LIQUEURS
JPH0762600A (en) * 1993-07-22 1995-03-07 Shin Etsu Chem Co Ltd Method for continuously removing impurity metallic ion in plating bath and device therefor
CN102140580B (en) * 2011-03-17 2012-07-18 刘辉 Multi-metal recycling method of electric furnace tin-smelting dust
CN102275911B (en) * 2011-06-03 2013-06-19 中国林业科学研究院林产化学工业研究所 Microporous active carbon and preparation method by chemical agent aperture regulation and control
CA2790558A1 (en) * 2012-09-19 2014-03-19 Orbite Aluminae Inc. Processes for recovering rare earth elements and rare metals
CN103320611B (en) * 2013-06-09 2014-09-17 中南大学 Method for selectively extracting gallium and germanium from peracid lixivium containing gallium and germanium
CN108300877A (en) * 2017-12-29 2018-07-20 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 The method of gallium germanium indium in extraction and recovery zinc replacement slag leachate
CN109576510B (en) * 2019-01-02 2021-03-30 建水正业矿冶有限公司 Method for recovering gallium from zinc replacement slag
CN110184483A (en) * 2019-06-25 2019-08-30 广西大学 A method of enrichment and gallium-purifying from alkaline solution
CN112938971A (en) * 2021-04-26 2021-06-11 中国科学院城市环境研究所 Coconut shell based mesoporous activated carbon and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Evaluation of Several Biochar Types as Inoculant Carrier for Indigenous Phosphate Solubilizing Microoorganism from Acid Sulphate Soil;Nurul Husna等;Journal of Ecological Engineering;20190520;第20卷(第6期);1-8 *
High-yield recycling and recovery of copper, indium, and gallium from waste copper indium gallium selenide thin-film solar panels;Fan-Wei Liu等;Solar Energy Materials and Solar Cells;20220401;第241卷;111691 *

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