CN110975826B - Adsorbing material based on crosslinked protein and application thereof in precious metal recovery - Google Patents

Adsorbing material based on crosslinked protein and application thereof in precious metal recovery Download PDF

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CN110975826B
CN110975826B CN201910460157.5A CN201910460157A CN110975826B CN 110975826 B CN110975826 B CN 110975826B CN 201910460157 A CN201910460157 A CN 201910460157A CN 110975826 B CN110975826 B CN 110975826B
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CN110975826A (en
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杨鹏
杨发翠
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Shaanxi Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid 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 form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/04Obtaining noble metals by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24Treatment 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4856Proteins, DNA
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a cross-linked protein-based adsorption material and application thereof in precious metal recovery. The preparation method of the adsorbing material is simple, and the adsorbing material has the characteristics of low cost, low energy consumption, environmental protection and the like, and when the adsorbing material is used for treating ore leaching solution containing precious metals and leaching solution of precious metals in electronic garbage, the adsorbing effect on the precious metals is good, the adsorbing material can be repeatedly used, the operation method is simple and convenient, the cost is low, and the adsorbing material is easy to popularize and apply.

Description

Adsorbing material based on crosslinked protein and application thereof in precious metal recovery
Technical Field
The invention relates to a cross-linked protein-based adsorption material and a method for selectively extracting gold and other precious metals from ore leaching liquor or other metal ion waste liquor by using the adsorption material.
Background
The noble metal ion separation and recovery method includes adsorption method, membrane filtration method, wet metallurgy method, etc. Among them, the adsorption method is the most economical and efficient method for recovering noble metal ions. Commonly used adsorbent materials are activated carbon and ion exchange resins. The activated carbon contains rich mesoporous and microporous structures, has a large specific surface area and becomes an effective gold-absorbing material, but the pore structure of the activated carbon slows down the adsorption of gold, and meanwhile, the recycling of the activated carbon requires high energy consumption. Ion exchange resins are highly selective but costly. Therefore, it is necessary to find an adsorbing material which can adsorb gold rapidly and efficiently and can be reused.
The biological adsorption method is considered to be a promising waste water noble metal recovery technology in recent years due to the advantages of low cost, high efficiency, environmental friendliness and the like. In bioadsorption, precious metals in solution are mainly recovered by microorganisms (such as bacteria, fungi, algae, etc.). However, the microbial bio-adsorbent has the disadvantages of small particle size, poor mechanical strength, difficult solid-liquid separation, immature technology for recovering noble metals by a microbiological method, inability of large-scale application, and the like.
Disclosure of Invention
The invention aims to provide an adsorbing material based on cross-linked protein and provides a new application for the adsorbing material.
Aiming at the purposes, the adsorbing material is a microparticle formed by crosslinking phase-transition protein by a crosslinking agent or a double-layer film with a lower layer being a compact nano film and an upper layer being a dense accumulation layer of the microparticle, wherein the protein is lysozyme or bovine serum albumin.
The adsorbing material is prepared by the following method: adjusting a pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 15-100 mmol/L tris (2-carboxyethyl) phosphine hydrochloride to 4.0-11.0 by using NaOH, mixing the buffer solution with a 1-50 mg/mL protein 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution in the same volume, incubating at room temperature for 1-12 hours, centrifuging and cleaning the obtained phase-transition protein microparticles, then crosslinking in a 0.2-5% crosslinking agent aqueous solution at room temperature for 0.5-6 hours, and finally cleaning and freeze-drying the crosslinked microparticles to obtain the crosslinked protein adsorbing material; or adjusting the pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 15-100 mmol/L tris (2-carboxyethyl) phosphine hydrochloride to 4.0-11.0 by using NaOH, mixing the buffer solution with the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 1-50 mg/mL protein in equal volume, directly paving the obtained mixed solution on the surface of a glass sheet, and incubating at room temperature for 1-12 hours to deposit a layer of phase-transition protein film on the glass sheet; and then placing the glass sheet deposited with the layer of the phase transition protein film in a cross-linking agent aqueous solution with the mass fraction of 0.2-5%, cross-linking for 0.5-6 hours at room temperature, then placing the glass sheet in a sodium hydroxide aqueous solution with the mass fraction of 0.5-3 mol/L, soaking for 0.5-2 hours, and finally stripping the film from the glass sheet to obtain a double-layer protein film with a compact nano film at the lower layer and a micro-particle dense accumulation layer at the upper layer, namely the cross-linked protein adsorbing material.
The adsorbing material is preferably prepared by the following method: adjusting the pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 40-60 mmol/L tris (2-carboxyethyl) phosphine hydrochloride to 5.0-8.0 by using NaOH, mixing the buffer solution with the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 20-40 mg/mL protein in the same volume, incubating at room temperature for 2-12 hours, centrifuging and cleaning the obtained phase-transition protein microparticles, then crosslinking in a 1-2% crosslinking agent aqueous solution at room temperature for 1-3 hours, and finally cleaning and freeze-drying the crosslinked microparticles to obtain the crosslinked protein adsorption material; or adjusting the pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 40-60 mmol/L tris (2-carboxyethyl) phosphine hydrochloride to 5.0-8.0 by using NaOH, mixing the buffer solution with the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 20-40 mg/mL protein in equal volume, directly paving the obtained mixed solution on the surface of a glass sheet, and incubating at room temperature for 2-12 hours to deposit a layer of phase-transition protein film on the glass sheet; and then placing the glass sheet deposited with the phase transition protein film in a cross-linking agent aqueous solution with the mass fraction of 1-2%, cross-linking for 1-3 hours at room temperature, then placing the glass sheet in a sodium hydroxide aqueous solution with the mass fraction of 1-2 mol/L, soaking for 1-2 hours, and finally stripping the film from the glass sheet to obtain a double-layer protein film with a compact nano film at the lower layer and a micro-particle dense accumulation layer at the upper layer, namely the cross-linked protein adsorption material.
The cross-linking agent is any one of glutaraldehyde, genipin, glutamine transaminase and carbodiimide.
The adsorption material based on the cross-linked protein is applied to the recovery of precious metals, and can be particularly used for the recovery of precious metals in an ore leaching solution and the recovery of precious metals in an electronic garbage leaching solution, preferably, the pH of the ore leaching solution or the electronic garbage leaching solution is 2-5, and the precious metals are any one or more of gold, silver, platinum, palladium, ruthenium, rhodium, osmium and iridium.
The invention has the following beneficial effects:
the preparation method of the adsorbing material is simple, the cost is low, the adsorbing effect on the noble metal is good, the gold and other noble metals can be quickly and selectively extracted from the ore leaching liquor or other metal ion waste liquor, and the adsorbing material is economical and practical, is simple and convenient to operate, and has better popularization and application prospects.
Drawings
FIG. 1 is a scanning electron micrograph of an adsorbent material of cross-linked lysozyme.
FIG. 2 is a graph showing the influence of gold ion adsorption amounts of gold ion adsorbing materials of cross-linked lysozyme by gold ion solutions of different temperatures and different concentrations.
FIG. 3 shows the adsorption time of gold ions in gold ion solutions of different concentrations by the adsorption material of cross-linked lysozyme.
FIG. 4 shows the adsorption rate of the adsorption material of cross-linked lysozyme in the mixed noble metal ion solution.
FIG. 5 is a graph showing the selective adsorption of gold by an adsorbing material of cross-linked lysozyme in a 40-fold diluted ore leaching solution.
FIG. 6 is a graph of the selective extraction of gold from an adsorbent material of cross-linked lysozyme in a 50-fold diluted electronic garbage leachate.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Adjusting the pH value of a 50 mmol/L4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of tris (2-carboxyethyl) phosphine hydrochloride to 7.0 by NaOH, mixing the pH value with the equal volume of the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 30mg/mL lysozyme, incubating at room temperature for 4 hours, centrifuging and cleaning the obtained phase-transition lysozyme microparticles, then crosslinking in a 1% glutaraldehyde aqueous solution at room temperature for 1 hour, and finally cleaning and freeze-drying the crosslinked microparticles to obtain the adsorbing material of the crosslinked lysozyme.
Example 2
Adjusting the pH value of a 50 mmol/L4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of tris (2-carboxyethyl) phosphine hydrochloride to 7.0 by using NaOH, then mixing the pH value with the equal volume of the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 30mg/mL lysozyme, directly spreading the obtained mixed solution on the surface of a glass sheet, culturing at room temperature for 3 hours, depositing a film on the glass sheet, and cleaning by using clear water. And then soaking the glass sheet on which the membrane is deposited in 1% glutaraldehyde water solution by mass fraction, crosslinking for 1 hour at room temperature, cleaning with clear water, soaking the glass sheet in 1mol/L sodium hydroxide water solution for 1 hour, and finally stripping the membrane from the glass sheet to obtain the adsorption material of the crosslinked lysozyme. As can be seen from figure 1, the adsorbing material has a thickness of 23 μm and consists of an upper layer and a lower layer, wherein the lower layer is a dense nano-film, and the upper layer is a dense microparticle accumulation layer assembled by phase-transition lysozyme aggregates deposited on the nano-film.
Example 3
Adjusting the pH value of a 50 mmol/L4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of tris (2-carboxyethyl) phosphine hydrochloride to 5.0 by using NaOH, then mixing the pH value with a 40mg/mL 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of bovine serum albumin in an equal volume, directly spreading the obtained mixed solution on the surface of a glass sheet, culturing at room temperature for 12 hours, depositing a film on the glass sheet, and cleaning by using clear water. And then soaking the glass sheet on which the membrane is deposited in a glutaraldehyde aqueous solution with the mass fraction of 2%, crosslinking for 2 hours at room temperature, cleaning with clear water, soaking the glass sheet in a sodium hydroxide aqueous solution with the concentration of 1mol/L for 1 hour, and finally stripping the membrane from the glass sheet to obtain the adsorbing material of the crosslinked bovine serum albumin.
Example 4
Application of adsorption material of cross-linked lysozyme to adsorption of gold ions
1. Influence of pH on adsorption Properties of adsorbent Material
Respectively adding 2mmol/L HAuCl4Adjusting the pH value of the aqueous solution to 1-11, adding the adsorbing material of the cross-linked lysozyme in the embodiment 2, wherein the adding amount of the adsorbing material is 0.4g/L, placing the solution in an oscillator, oscillating for 12 hours, and measuring the content of gold ions in the solution by using ICP-MS. The result shows that the adsorption rate of the adsorption material to gold in the pH range of 2-5 reaches more than 90%.
2. Influence of gold ion concentration and temperature on adsorption performance of adsorption material
Respectively adding 1, 2, 3, 4 and 5mmol/L HAuCl4The pH of the aqueous solution was adjusted to 3, and then the adsorbing material of the crosslinked lysozyme of example 2 was added in an amount of 0.4g/L, and the adsorption of gold ions at different temperatures (10, 37 and 60 ℃) was examined, and after shaking for 24 hours in an oscillator, the content of gold ions contained in the solution was measured by ICP-MS. The results show that the gold adsorption increases with increasing temperature (see fig. 2), with the adsorption material having a maximum saturation of gold at 60 c (see fig. 2)The adsorption amount was 1034.4 mg/g.
3. Influence of adsorption time on adsorption performance of adsorption material at different gold ion concentrations
Respectively adding 0.5, 1, 1.5, 2, 2.5 and 3mmol/L HAuCl4The pH value of the aqueous solution was adjusted to 3, and then the adsorbing material of the crosslinked lysozyme in example 2 was added in an amount of 0.4g/L, and the gold ion adsorption of the adsorbing material at different times was examined, and the gold ion content in the solution was measured by ICP-MS. The results show that when HAuCl is used4Initial concentration of<At 1.5mmol/L, the adsorption rate of the adsorbent to gold ions rapidly increased to 80% in the first 3 hours, and slowly increased to reach equilibrium in 5.0 hours. When HAuCl is present4Initial concentration of>At 1.5mmol/L, the adsorption time was extended to 24 hours to reach equilibrium. Indicating that at low concentrations, the adsorbent material had a faster adsorption rate for gold ions (see fig. 3).
As can be seen from the above, in the range of pH 2-5, the higher the temperature is, the lower the concentration of the noble metal ions is, and the adsorption of the noble metal ions by the adsorbing material of the invention is facilitated.
Example 5
Adsorption of adsorption material of cross-linked lysozyme in mixed noble metal ion solution
Preparing a noble metal ion mixed solution containing gold, platinum, palladium, ruthenium, rhodium, osmium and iridium, wherein the concentration of each noble metal ion is 0.5, 1, 10 or 50ppm, adjusting the pH value to 3, adding an adsorbing material of the cross-linked lysozyme in the embodiment 2, wherein the adding amount of the adsorbing material is 0.4g/L, placing the adsorbing material in an oscillator, oscillating for 24 hours, and measuring the content of each noble metal ion in the solution by using ICP-MS. The results showed that the adsorbent had a good adsorption property to the mixed noble metal ion at a concentration of less than 1ppm, and the adsorption rate was 90% or more (see FIG. 4).
Example 6
Selective extraction of gold in ore leaching liquor by adsorption material of cross-linked lysozyme
1g of gold raw ore powder (China, Jiangxi) was added to a 100mL round-bottomed flask, then 20mL of prepared aqua regia (concentrated hydrochloric acid: concentrated nitric acid ═ 3:1) was slowly added, magnetons were added and the round-bottomed flask was covered with a three-way valve with a balloon, the balloon was kept in communication with the round-bottomed flask, and the reaction was carried out at 300rpm for 24 hours. After the reaction is finished, filtering the filtrate by using a filter element with the diameter of 0.22 mu m to obtain an ore leaching liquor. Diluting 1mL of the obtained ore leaching solution to 40mL by using distilled water, adding the adsorption material of the cross-linked lysozyme in the example 2, placing the solution in an oscillator, oscillating the solution for 12 hours, and measuring the content of gold ions in the solution by using ICP-MS. As can be seen from figure 5, the adsorbing material can better selectively adsorb gold after the ore leaching solution is diluted to 40 times, and the adsorption rate reaches over 90 percent after 2 hours.
Example 7
Selective extraction of gold in waste electronic products by adsorption material of cross-linked lysozyme
In a 100mL beaker, 80g of the cell phone chip was added, then 100mL of prepared aqua regia (concentrated hydrochloric acid: concentrated nitric acid: 3:1) was slowly added, magnetons were added and the round-bottom flask was capped with a three-way valve with a balloon, the balloon was kept in communication with the round-bottom flask, and the reaction was carried out at 300rpm for 24 hours. And after the reaction is finished, filtering the filtrate by using a filter element with the diameter of 0.22 mu m to obtain the electronic garbage leaching solution. Diluting 1mL of the obtained electronic garbage leaching solution to 50mL by using distilled water, adding the adsorbing material of the cross-linked lysozyme in the embodiment 2, placing the electronic garbage leaching solution in an oscillator, oscillating the electronic garbage leaching solution for 12 hours, and measuring the content of gold ions in the solution by using ICP-MS. As can be seen from the graph 6, the adsorbing material can better selectively adsorb gold after the electronic garbage leaching solution is diluted to 50 times, and the adsorption rate reaches over 90% after 2 hours.
Example 8
Desorption-adsorption experiment of adsorption material of cross-linked lysozyme on gold
And adding the adsorbing material after adsorbing the gold into an aqueous solution containing 130mmol/L thiourea, 780mmol/L ammonium thiocyanate and 28mmol/L ferric sulfate, slowly shaking for 12 hours, and measuring the concentration of the gold ions contained in the solution by using ICP-MS. And performing adsorption experiments again on the resolved adsorption material, and repeating desorption-adsorption for three times. The results show that after three times of adsorption-desorption, the gold adsorption still reaches 90%.
Example 9
Application of cross-linked bovine serum albumin adsorbing material in adsorbing gold ions
Respectively adding 1, 2, 3, 4 and 5mmol/L HAuCl4The pH value of the aqueous solution is adjusted to 3, then the adsorbing material of the cross-linked bovine serum albumin in the example 3 is added, the adding amount of the adsorbing material is 0.4g/L, the adsorption of the adsorbing material on gold ions at room temperature is inspected, the gold ions are placed in an oscillator to be vibrated for 24 hours, and the content of the gold ions in the solution is measured by ICP-MS. The result showed that the maximum saturated adsorption amount of the adsorbing material to gold at room temperature was 713.2 mg/g.
Example 10
Application of adsorption material of cross-linked lysozyme to adsorption of gold ions
2mmol/L HAuCl4The pH value of the aqueous solution is adjusted to 3, then the adsorbing material of the cross-linked lysozyme in the example 1 is added, the adding amount of the adsorbing material is 0.4g/L, the adsorption of the adsorbing material on gold ions at room temperature is inspected, the gold ions are placed in an oscillator to vibrate for 24 hours, and the content of the gold ions in the solution is measured by ICP-MS. The result shows that the adsorption rate of the adsorption material to gold at room temperature reaches 99.2%.

Claims (6)

1. A cross-linked protein based adsorbent material, characterized by: the adsorption material is a double-layer protein film which is formed by crosslinking phase-change protein by a crosslinking agent, has a compact nano film as a lower layer and a micro-particle dense accumulation layer as an upper layer, and is used for recovering noble metals in an ore leaching solution or an electronic garbage leaching solution, wherein the protein is lysozyme or bovine serum albumin;
the adsorbing material is prepared by the following method: adjusting the pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 15-100 mmol/L tris (2-carboxyethyl) phosphine hydrochloride to 4.0-11.0 by using NaOH, mixing the buffer solution with the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 1-50 mg/mL protein in equal volume, directly paving the obtained mixed solution on the surface of a glass sheet, and incubating at room temperature for 1-12 hours to deposit a layer of phase-transition protein film on the glass sheet; and then placing the glass sheet deposited with the layer of the phase transition protein film in a cross-linking agent aqueous solution with the mass fraction of 0.2-5%, cross-linking for 0.5-6 hours at room temperature, then placing the glass sheet in a sodium hydroxide aqueous solution with the mass fraction of 0.5-3 mol/L, soaking for 0.5-2 hours, and finally stripping the film from the glass sheet to obtain a double-layer protein film with a compact nano film at the lower layer and a micro-particle dense accumulation layer at the upper layer, namely the cross-linked protein adsorbing material.
2. The crosslinked protein based adsorbent material according to claim 1, wherein said adsorbent material is prepared by the following method: adjusting the pH value of a 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 40-60 mmol/L tris (2-carboxyethyl) phosphine hydrochloride to 5.0-8.0 by using NaOH, mixing the buffer solution with the 4-hydroxyethyl piperazine ethanesulfonic acid buffer solution of 20-40 mg/mL protein in equal volume, directly paving the obtained mixed solution on the surface of a glass sheet, and culturing at room temperature for 2-12 hours to deposit a layer of phase transition protein film on the glass sheet; and then placing the glass sheet deposited with the phase transition protein film in a cross-linking agent aqueous solution with the mass fraction of 1-2%, cross-linking for 1-3 hours at room temperature, then placing the glass sheet in a sodium hydroxide aqueous solution with the mass fraction of 1-2 mol/L, soaking for 1-2 hours, and finally stripping the film from the glass sheet to obtain a double-layer protein film with a compact nano film at the lower layer and a micro-particle dense accumulation layer at the upper layer, namely the cross-linked protein adsorption material.
3. The crosslinked protein-based adsorbent according to any one of claims 1 to 2, characterized in that: the cross-linking agent is any one of glutaraldehyde, genipin, glutamine transaminase and carbodiimide.
4. Use of a cross-linked protein based adsorption material according to claim 1 for the recovery of precious metals from ore leaching or electronic waste leaching.
5. Use of a cross-linked protein based adsorption material for the recovery of precious metals according to claim 4, characterized in that: the pH value of the ore leaching solution or the electronic garbage leaching solution is 2-5.
6. Use of a cross-linked protein based adsorption material for the recovery of precious metals according to claim 4, characterized in that: the noble metal is any one or more of gold, silver, platinum, palladium, ruthenium, rhodium, osmium and iridium.
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