CN111057863A - Application of environment-friendly precious metal adsorption resin material - Google Patents
Application of environment-friendly precious metal adsorption resin material Download PDFInfo
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- CN111057863A CN111057863A CN201911345103.0A CN201911345103A CN111057863A CN 111057863 A CN111057863 A CN 111057863A CN 201911345103 A CN201911345103 A CN 201911345103A CN 111057863 A CN111057863 A CN 111057863A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to an application of an environment-friendly precious metal adsorption resin material. The noble metal adsorption resin material has high adsorption activity such as large adsorption capacity, high adsorption efficiency and the like on noble metals, has high adsorption selectivity on the noble metals, is not easily influenced by other metals, can flexibly adjust metal objects pointed by high adsorption activity by adjusting the pH value of a solution, does not influence the high adsorption activity of the metal objects, is suitable for adsorbing the noble metals, and is particularly suitable for adsorbing low-concentration noble metal elements in an enrichment environment; can be used for preparing materials for purification, and/or recovery, and/or separation, and/or detection, and is applied to the fields of environment, chemical industry, wet metallurgy and the like. The adsorption resin material can efficiently recover the noble metal in the aqueous solution, and the post-treatment is simple; and the preparation method is simple and convenient, low in cost, green and environment-friendly, and suitable for large-scale production and popularization.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a noble metal adsorption resin material which has the advantages of high adsorption efficiency on noble metal ions (gold, silver, platinum, palladium and the like), good adsorption selectivity, adjustable adsorption performance and the like.
Background
In recent years, noble metals have been widely used for the preparation of catalysts for chemical processing, electronic appliances, corrosion-resistant materials, and jewelry because of their unique physicochemical properties. And with the increasing development of economy, the demand for noble metals is increasing. In recent years, the increasing price of precious metals, such as gold, has highlighted their importance as strategic resources. Despite the continuous discovery of new resources, mineral products are non-renewable resources and have limited reserves. With the continuous development of gold and other precious metal minerals, the taste of the minerals is continuously reduced, and the extraction difficulty is continuously increased, so that the precious metals are urgently needed to be recovered from industrial wastewater, wastes (containing electronic devices, such as electronic mobile phones and personal computers) and the minerals.
The amino acid is a basic unit of the biological functional macromolecular protein, is simple and easy to obtain, has low cost, and is environment-friendly and safe. Currently, amino acid-based adsorbents have been reported as follows:
a spherical amino acid adsorbent (CN1269535C) is prepared by using natural polymer containing cellulose or agar as carrier, and resin with particle size of 0.45-0.9mm, activated by epichlorohydrin and fixed with effective amount of amino acid ligand, and has amino acid content of 12.5-39.7 μmol/ml; activating agar, agarose or gelatin carrier with the particle size of 0.45-0.9mm in alkaline solution by epoxy chloropropane, and fixing amino acid ligand in the alkaline solution; can be used for treating diseases such as rheumatoid arthritis and systemic lupus erythematosus.
Ni2+The preparation of the adsorbent and the adsorption method (CN104226238B) thereof disclose a method for adsorbing nickel ions in water by grafting amino acid with a silicon-based mesoporous material as a matrix and an alkyl coupling agent as a medium.
A preparation method (CN107226507A) of L-cysteine modified cellulose for removing heavy metal ions comprises the steps that under the alkaline condition, hydroxyl of carbon atom number 6 of cellulose and chlorine atom of epichlorohydrin are subjected to substitution reaction to generate epoxy cellulose; under the alkaline condition, the amino group of the cysteine supplies epoxy of the epoxy cellulose to generate L-cysteine modified cellulose which is used for heavy metal ion adsorption, has high efficiency, large adsorption capacity and stable treatment effect and is insoluble in water.
An adsorbent containing at least 1 amino acid or a salt of an amino acid among an amino acid, an acidic amino acid and a polar uncharged amino acid, wherein a solution containing an ion of a group 5 element is mixed with a solution containing at least 1 amino acid or a salt of an amino acid among an amino acid, an acidic amino acid and a polar uncharged amino acid and precipitated and separated when the group 5 element is adsorbed, and a compound recovery method (CN108138261A) using the same.
Preparation and application of cysteine modified retinervus Luffae fructus adsorbent (CN103447009B), mixing epichlorohydrin and retinervus Luffae fructus in alkaline solution to obtain epoxy retinervus Luffae fructus; fixing cysteine on the epoxy loofah sponge in an alkaline solution; the composite adsorbent is used for adsorbing heavy metal ions, and has the advantages of high efficiency, high speed, good desorption performance and strong regeneration capacity.
Preparation and application (CN103447009B) of cysteine modified palm bark adsorbent, mixing epichlorohydrin and palm bark in alkaline solution to generate epoxy group palm bark; fixing cysteine on the epoxy palm bark in an alkaline solution; the composite adsorbent is used for adsorbing heavy metal ions, and has the advantages of high efficiency, high speed, good desorption performance and strong regeneration capacity.
L-cysteine-modified fiber, a preparation method and application thereof (CN104624164B) disclose that swelling cellulose reacts with L-cysteine under the action of inert gas and inorganic catalyst to generate L-cysteine-modified cellulose which is used for the selective separation of Se (IV) in food.
However, the existing amino acid-based adsorbents are mainly focused on the adsorption application of heavy metal ions, and the adsorption and separation of noble metal ions are only reported, and the adsorption and separation application of noble metal ions is still yet to be researched.
Disclosure of Invention
The invention aims to provide application of an environment-friendly precious metal adsorption resin material. The noble metal adsorption resin material has the advantages of high adsorption activity, high adsorption selectivity, flexible regulation of adsorption objects and the like on noble metals (gold, silver, platinum, palladium and the like), can be recycled, can directly recover the noble metals in one step through high-temperature calcination, has small environmental pollution and high reusability, saves capital, is suitable for recovering the noble metals in all noble metal-containing solutions, and is particularly suitable for recovering the noble metals with low-concentration noble metal elements in adsorption enrichment environments, such as electroplating wastewater, tailings waste liquid containing the noble metals and the like.
The noble metal adsorption resin material has high adsorption activity such as large adsorption capacity, high adsorption efficiency and the like on noble metals such as gold, silver, platinum, palladium and the like, when various metals exist, the selective high adsorption of the noble metal adsorption resin material on the noble metals is not influenced by other metals, a metal object pointed by the high adsorption activity of the noble metal adsorption resin material can be flexibly adjusted by adjusting the pH value of a solution, the high adsorption activity of the noble metal adsorption resin material is not influenced, and the noble metal adsorption resin material is suitable for adsorbing the noble metals, particularly the adsorption enrichment of low-concentration noble metal elements in the environment; therefore, the noble metal adsorption resin material has high adsorption performance such as high selectivity of an adsorption object, flexible regulation of the adsorption object, high efficiency, high capacity adsorption and the like, can be used for preparing materials for purification, and/or recovery, and/or separation, and/or detection, particularly for high-efficiency purification, and/or recovery, and/or separation, and/or detection of noble metal elements in water, has the noble metal adsorption activity of adjustability, high selectivity and high adsorption, and is applied to the technical fields of environment, chemical industry, hydrometallurgy and the like, such as the recovery of noble metals in copper-nickel ores and electroplating wastewater.
The invention provides a material for purification, and/or recovery, and/or separation, and/or detection, which contains an environment-friendly precious metal adsorption resin material with adjustable, and/or high-selectivity, and/or high-adsorption precious metal adsorption activity.
The invention also provides a material for separating the noble metal in the water liquid, which contains an adjustable and/or high-selectivity and/or high-adsorption noble metal adsorption active environment-friendly noble metal adsorption resin material and can efficiently recover the noble metal in the water liquid.
The noble metal adsorption resin material is prepared by adopting radiation technologies such as gamma-ray or electron beam and the like to initiate epoxy-containing monomers to be grafted and polymerized on the surface of a natural polymer substrate, and then carrying out epoxy ring opening reaction on the natural polymer substrate with the grafted and polymerized epoxy groups and amino acid-like substances. The method comprises the following specific steps:
1) in an inert environment, high molecular base material free radicals generated under the action of radiation or a free radical initiator are mixed in emulsion containing epoxy group-containing monomers, and the epoxy group-containing monomers are graft-polymerized on the surface of the high molecular base material to prepare a precursor of the noble metal adsorption resin material;
2) and carrying out epoxy ring-opening reaction on the precursor of the noble metal adsorption resin material and the amino acid sample substance to prepare the noble metal adsorption resin material.
In the emulsion system of the step 1), the concentration of the epoxy group-containing monomer is 5 to 50 wt%, preferably 20 to 35 wt%, and more preferably 30 wt%; the emulsion system is prepared by fully mixing water solution and surfactant; the concentration of the surfactant is 1 to 20 wt%, preferably 1 to 10 wt%, more preferably 3 wt%; the surfactant comprises a cationic, anionic, zwitterionic or nonionic surfactant, preferably a nonionic surfactant, more preferably tween.
In the step 1), the inert gas comprises any one or combination of nitrogen, helium or argon, preferably nitrogen; the graft polymerization temperature is 40 to 60 ℃, preferably 45 to 55 ℃, more preferably 50 ℃.
In the step 1), the radiation action conditions are that the radiation rays are gamma-rays, α -rays, electron beams or X-rays, preferably electron beams, the irradiation voltage is 0.5-5MeV, preferably 1MeV, the irradiation dose is 10-250kGy, preferably 30-50kGy, and the dose rate is 5-100kGy/pass, preferably 10 kGy/pass.
Under the radiation irradiation, free radicals are generated on the polymer substrate, so that the epoxy group-containing monomer is grafted and polymerized on the surface of the polymer substrate. The graft polymerization rate of the epoxy group-containing monomer on the surface of the polymer base material is 50%, preferably 100%. From this, it is understood that the radical-formed polymer substrate contributes to the surface graft polymerization of the epoxy group-containing monomer.
In the step 1), the free radical initiator is organic peroxide or azo initiator, the organic peroxide comprises cyclohexanone peroxide, dibenzoyl peroxide or tert-butyl hydroperoxide and the like, and the azo initiator comprises azobisisobutyronitrile or azobisisoheptonitrile and the like.
In step 1), the polymer substrate is cellulose with a certain crystallinity, and comprises any one or combination of polysaccharides such as chitin, chitin and the like and respective derivatives thereof, wherein the crystallinity of a single polysaccharide polymer material is more than 30%.
Preferably, the polymer base material is spherical or fibrous, and when being spherical, the polymer base material can be regular spherical or irregular spherical, and the particle size is 30-800 micrometers, preferably 150-300 micrometers, and more preferably 200 micrometers; in the form of fibers, the diameter is 5 to 200. mu.m, preferably 50 to 130. mu.m, more preferably 80 μm; the length is 100-1000 microns, preferably 400-600 microns, and more preferably 500 microns.
In step 1), the epoxy group-containing monomer is preferably an epoxy group-containing unsaturated monomer, such as glycidyl methacrylate or hydroxybutyl glycidyl acrylate.
In the step 1), the amino acid-like substance refers to a substance which has the same or similar physicochemical properties as amino acid, and/or has the same or similar amino and/or carboxyl functional groups, and/or has other functional groups with the same or similar physicochemical properties as amino and/or carboxyl. Preferably any one or a combination of amino acids and their respective derivatives. The amino acid is any one or combination (amino acid salt, amino acid hydrate or polycondensate) of cysteine, lysine, histidine, arginine, ornithine, citrulline, glutamic acid and respective derivatives, and in the step 2), the concentration of the amino acid-like substance in the epoxy group ring-opening reaction system is 5-40 wt%, preferably 15-30 wt%, and more preferably 20 wt%; the reaction solvent is water, ethanol, DMF or DMSO, preferably DMF. The reaction temperature is 50 to 85 ℃, preferably 70 to 80 ℃, more preferably 80 ℃. The reaction time is 10-36h, preferably 24 h.
After the epoxy group ring-opening reaction in the step 2), the mass percentage of the amino acid introduced into the noble metal adsorption resin material is 20-80%, preferably 20-45%.
The preparation method of the invention also comprises the following steps: the noble metal adsorption resin material is washed and dried. The solvent used for washing is any one of deionized water or ethanol or the combination of the deionized water and the ethanol in any proportion. The drying treatment is carried out for 12-24 h under vacuum at the temperature of 30-80 ℃, the drying temperature is preferably 45-60 ℃, and the drying time is preferably 15-20 h.
The mass percent of amino acid in the noble metal resin adsorption material prepared by the preparation method is 20-80%, preferably 15-30 wt%, and more preferably 20 wt%; can be microspheres with the particle size of 30-800 microns, preferably 150-300 microns, more preferably 200 microns; or the fiber with the diameter of 5-200 microns and the length of 100-1000 microns; preferably 50-130 microns in diameter and 400-600 microns in length; more preferred are fibers having a diameter of 80 microns and a length of 500 microns.
The invention also provides a method for separating noble metals from water, which comprises the following steps: adding a noble metal separation material containing an environment-friendly noble metal adsorption resin material into water liquid containing noble metals, adjusting the pH value of the water liquid, and selectively adsorbing the noble metals by the noble metal separation material in the water liquid to realize the separation of the noble metals in the water liquid.
Eluting the noble metal separation material in the water solution adsorbing the noble metal by using eluent to regenerate the noble metal separation material in the water solution; or calcining the noble metal separation material in the water solution for adsorbing the noble metal at high temperature to directly recover the noble metal simple substance.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention adopts radiation technology or free radical initiator to prepare amino acid modified resin for noble metal adsorption separation, the ionizing radiation grafting technology has no limitation on the shape or variety of the polymer substrate and the monomer containing epoxy group, can be selected randomly, has the advantages of no catalyst residue in the grafting product, and the like, and particularly adopts an electron beam initiated pre-radiation grafting method, which can separate the radiation process of the polymer substrate from the grafting reaction process of the monomer containing epoxy group, does not easily generate homopolymer in the reaction process, has high reaction efficiency and strong controllability, and is suitable for introducing specific functional groups on the surface of the material at high density. The preparation method is simple, the conditions are easy to control, the energy consumption is low, the method is safe, green and environment-friendly, the cost is reduced, and the method is more suitable for industrial production.
2) The invention selects the common microspheric and fibrous natural polysaccharide high polymer material which is easy to obtain and has low cost as the base material, and the amino acid as the ligand with low price, thereby not only having good adsorption performance to noble metal, but also having high biological safety. The adsorbent prepared by the invention has low production cost, has specific selectivity on noble metals, and can obtain higher economic benefit and social benefit.
3) Different from the traditional noble metal adsorption material, the invention realizes the introduction of amino acid and derivatives thereof into the surface of a polymer substrate, so that the particle size of the noble metal adsorption resin material can reach 300-400 microns, the swelling rate is low (20 percent), the hydrophilicity is good, the requirement of filling and using an adsorption column in the industry is met, and the invention has great industrial application prospect.
4) Different from the traditional noble metal adsorbing material, the noble metal adsorbing material can be recycled, has simple post-treatment, is easy to recover noble metals, and has wide popularization and application prospects. According to actual needs, the noble metal can be directly recovered in one step by high-temperature calcination. The environment-friendly precious metal adsorption resin material provided by the invention takes natural polymers as a base material, takes amino acid as a functional component, takes CHON as a main constituent element, does not contain halogen components such as Cl and the like, has a high combustion value, is environment-friendly, and is very suitable for recovering precious metal simple substances by directly burning after precious metal saturation adsorption.
Drawings
FIG. 1 is a schematic diagram of the epoxy ring-opening reaction of epoxy group and amino acid according to the present invention.
FIG. 2 is a graph showing the selective adsorption tendency of the noble metal adsorption material of example 5 on Au, Pt, Pd, Fe, Co, Ni, Cu metals in a metal blend solution at different acidity and pH values.
Fig. 3 is a statistical graph of selective adsorption activity of the noble metal adsorbent of example 5 on Mg, Ca, Ni, Zn, and Ag metals in a blended solution at different concentrations of coexisting metals, which shows that the noble metal adsorbent always maintains high selective adsorption activity on noble metals such as Ag, and is not affected by external factors such as changes in the concentration of coexisting metals.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
1) Crystalline cellulose microspheres (average diameter of about 200 microns, crystallinity 76%) as a polymeric substrate were placed 10 grams of the above material in a PE bag containing nitrogen and electron beam irradiation was performed using an electron accelerator to generate active free radicals for the grafting reaction. Irradiation conditions: the irradiation voltage is 1MeV, the irradiation dose is 30kGy, and the dose rate is 10 kGy/pass.
2) Immediately after irradiation, the microparticles were put into an emulsion reaction system composed of 30 wt% of GMA, 3 wt% of polyoxyethylene sorbitan monolaurate (Tween20) and 67 wt% of water to carry out graft polymerization. The emulsion reaction system of GMA monomer was continuously purged with nitrogen gas for 30 minutes before use to remove oxygen from water. The graft polymerization was carried out at 50 ℃ and the reaction was terminated after about 2 hours (the graft ratio of the substrate reached about 250%).
3) Washing and drying the GMA monomer graft product, adding 20 wt% L-cysteine in DMF solution to perform epoxy ring opening reaction (figure 1), oscillating and reacting at 80 ℃ for 24 hours, taking out, washing with ethanol and water, and drying to obtain the noble metal adsorption resin.
Example 2
This example was synthesized in the same manner as example 1, except that lysine was used in place of L-cysteine as a reactive monomer to obtain a noble metal-adsorbing resin.
Example 3
This example was synthesized in the same manner as example 1, except that histidine was used in place of L-cysteine as a reactive monomer to obtain a noble metal-adsorbing resin.
Example 4 static adsorption testing of noble Metal adsorbent resin Material
0.05g of the noble metal-adsorbing resin material prepared in example 1 was weighed and put into 50mL of an aqueous solution containing Au (III) at room temperature to perform a static Batch adsorption test. Au (III) solution for adsorption test prepared from HAuCl4H2O, pH 2.4. In the adsorption test, the resin was adsorbed for a certain period of time while stirring at room temperature, and the supernatant was collected and the residual concentration of Au (III) in the solution was measured by ICP to calculate the amount of adsorption of the resin. The maximum adsorption of the noble metal adsorption resin material on gold reaches 714 mg/g.
0.05g of the noble metal-adsorbing resin material prepared in example 1 was weighed and charged into 50mL of an aqueous solution containing Ag (I) at room temperature to conduct a static Batch adsorption test. Ag (I) solution for adsorption test prepared from AgNO3Adjusted to pH 4. In the adsorption test, the resin was adsorbed for a certain period of time while stirring at room temperature, and the supernatant was collected and the residual concentration of Ag (I) in the solution was measured by ICP to calculate the amount of adsorption of the resin. The maximum adsorption of the noble metal adsorption resin material on Ag reaches 66 mg/g.
Example 5 selective adsorption testing of noble Metal-resin coated materials
0.05g of the noble metal-adsorbing resin material prepared in example 1 was weighed, and 50mL of a mixed solution containing 0.1mmol/L of Fe (III), Cu (II), Ni (II), Au (III), Pd (II), and Pt (IV) was added thereto at room temperature to prepare solutions having different acidity and pH. After a certain period of adsorption, the supernatant was recovered, and the concentrations of various metal ions before and after adsorption of the test solution in the solution were measured by ICP. As shown in FIG. 2, the adsorption rates of various metals under different acidity and pH values are shown, and as a result, the adsorption resin has good selectivity on noble metals (Au (III), Pd (II), Pt (IV)) between pH 0 and pH 3, and particularly can adsorb Pd from a blending system with high selectivity under the strongly acidic condition. Therefore, it is considered that the adsorption resin of the present invention can be suitably used for the recovery of noble metals, particularly palladium, from electroplating wastewater. The object pointed by the high adsorption activity of the noble metal adsorption resin material is adjusted by adjusting PH, and the high selective high adsorption activity of the noble metal adsorption resin material can be flexibly adjusted.
Preparing metal blend liquid with different concentration ratios, such as Ag (I), Mg (II), Ca (II), Ni (II), Zn (II), 1:1:1: 1; 1:5:5:5: 5; 1:10:10:10, 0.05g of the noble metal adsorption resin material prepared in example 1 was weighed and added to the above-mentioned blended solution containing 50mL, after shaking and adsorbing for a certain time, the concentration of the blending ion in the solution before and after adsorption was measured by ICP. The adsorption amounts of the respective metal ions were calculated, and the experimental results are shown in fig. 3. When the concentration of the coexisting metal ions is ten times that of silver, the adsorption resin can still recover silver with high selectivity. Therefore, it is considered that the adsorbent resin of the present invention can be suitably used for recovering noble metals from electroplating wastewater. The high selective activity and the high adsorption activity of the adsorption resin of the invention on noble metals are demonstrated.
Example 6 calcination experiment after gold saturation adsorption of noble metal-resin material
2g of the adsorption resin prepared under the conditions of example 1 was subjected to saturation adsorption of Au (III) under the same adsorption experiment conditions such as the solid-to-liquid ratio as in example 4, and then washed repeatedly with clean water, the resin was placed in a muffle furnace at 1000 ℃ or higher for 4 hours and sufficiently calcined, all organic components were burned off, the remaining components were elemental gold, and the purity of gold was analyzed to be 99% or higher.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The application of an environment-friendly precious metal adsorption resin material in preparing materials for purification, and/or recovery, and/or separation, and/or detection, wherein the environment-friendly precious metal adsorption resin material has adjustable, and/or high-selectivity, and/or high-adsorption precious metal adsorption activity.
2. A material for purification, and/or recovery, and/or separation, and/or detection, characterized by comprising an environmentally friendly noble metal adsorption resin material having an adjustable, and/or highly selective, and/or highly adsorptive noble metal adsorption activity.
3. The application of an environment-friendly precious metal adsorption resin material in preparing a material for separating precious metals in water liquid is disclosed, wherein the environment-friendly precious metal adsorption resin material has adjustable and/or high-selectivity and/or high-adsorption precious metal adsorption activity.
4. The material for separating noble metal in water liquid features that it contains environment friendly noble metal adsorbing resin material with adjustable and/or high selectivity and/or high adsorbing noble metal adsorbing activity.
5. A method for separating noble metals from water solution, which is characterized in that the pH value of the water solution is adjusted, the environment-friendly noble metal adsorption resin material of claims 1 to 4 is added into the water solution containing noble metals, and the noble metal separation material selectively adsorbs the noble metals in the water solution, thereby realizing the separation of the noble metals in the water solution.
6. The method according to claim 3, further comprising subjecting the noble metal-separating material after adsorbing the noble metal to an elution treatment using an eluent to regenerate the noble metal-separating material in the aqueous liquid; or calcining the noble metal separation material in the water solution for adsorbing the noble metal at high temperature to directly recover the noble metal simple substance.
7. The material according to claim 2 or 4, wherein the preparation of the environment-friendly noble metal adsorption resin material comprises:
1) in an inert environment, high molecular base material free radicals generated under the action of radiation or a free radical initiator are mixed in emulsion containing epoxy group-containing monomers, and the epoxy group-containing monomers are graft-polymerized on the surface of the high molecular base material to prepare a precursor of the noble metal adsorption resin material;
2) and carrying out epoxy ring-opening reaction on the precursor of the noble metal adsorption resin material and the amino acid sample substance to prepare the noble metal adsorption resin material.
8. The preparation method according to claim 7, wherein in the emulsion system of step 1), the concentration of the epoxy group-containing monomer is 5 to 50 wt%, the concentration of the surfactant is 1 to 20 wt%, and the surfactant comprises a cationic type, an anionic type, a zwitterionic type or a nonionic type;
in the step 1), inert gas comprises any one or combination of nitrogen, helium or argon, and the temperature of the graft polymerization reaction is 40-60 ℃;
in the step 1), the radiation action condition is that the radiation ray is gamma-ray, α -ray, electron beam or X-ray, and the radiation dose is 10-250 kGy.
In the step 1), the free radical initiator is organic peroxide or azo initiator, the organic peroxide comprises cyclohexanone peroxide, dibenzoyl peroxide or tert-butyl hydroperoxide, and the azo initiator comprises azobisisobutyronitrile or azobisisoheptonitrile.
In step 1), the polymer substrate is cellulose with a certain crystallinity, and comprises any one or combination of chitin, chitin polysaccharide and their respective derivatives, and the crystallinity of the single polysaccharide polymer material is more than 30%.
In the step 1), the amino acid-like substance refers to a substance which has the same or similar physicochemical properties as amino acid, and/or has the same or similar amino and/or carboxyl functional groups, and/or has other functional groups with the same or similar physicochemical properties as amino and/or carboxyl.
9. The preparation method according to claim 7, wherein in the step 2), the concentration of the amino acid-like substance in the epoxy group ring-opening reaction system is 5-40 wt%, the reaction solvent is water, ethanol, DMF or DMSO, the reaction temperature is 50-85 ℃, and the reaction time is 10-36 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114225924A (en) * | 2021-12-23 | 2022-03-25 | 华中科技大学 | Method for recovering bismuth by using plant polyphenol modified adsorption resin |
| CN114574709A (en) * | 2022-03-02 | 2022-06-03 | 北京工业大学 | Method for recovering precious metal based on floating covalent organic polymer material |
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| CN114225924B (en) * | 2021-12-23 | 2024-03-19 | 华中科技大学 | Method for recycling bismuth by using plant polyphenol modified adsorption resin |
| CN114574709A (en) * | 2022-03-02 | 2022-06-03 | 北京工业大学 | Method for recovering precious metal based on floating covalent organic polymer material |
| CN114574709B (en) * | 2022-03-02 | 2023-11-24 | 北京工业大学 | Method for recycling noble metal based on floating covalent organic polymer material |
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