CN111793171B - Platinum group element specific resin and preparation method and application thereof - Google Patents

Platinum group element specific resin and preparation method and application thereof Download PDF

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CN111793171B
CN111793171B CN202010711448.XA CN202010711448A CN111793171B CN 111793171 B CN111793171 B CN 111793171B CN 202010711448 A CN202010711448 A CN 202010711448A CN 111793171 B CN111793171 B CN 111793171B
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platinum group
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resin
specific resin
platinum
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CN111793171A (en
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薛丁帅
刘艳红
张丹萍
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Institute of Geology and Geophysics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • 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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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    • 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 provides a platinum group element special-effect resin, which is characterized in that a polydopamine coated carrier resin is connected with a polymer molecular brush, and the polymer molecular brush comprises unit structures shown in formulas (i) and (ii): wherein Q is a heterocyclic group containing N atoms and S atoms, W is an aryl or heteroaryl group, and N is an integer of 0 to 6. The polymer for modifying resin prepared by the invention has the structure of the molecular brush, and on one hand, the selective adsorption of platinum group elements in a sample can be more effectively realized through the specific chemical structure and spatial structure of the molecular brush. The platinum group specific resin modified by the polymer can selectively adsorb platinum group elements, namely iridium (Ir), ruthenium (Ru), rhodium (Rh), platinum (Pt) and palladium (Pd), and has high detection precision and recovery rate.
Figure DDA0002596682520000011

Description

Platinum group element specific resin and preparation method and application thereof
Technical Field
The invention belongs to the field of geochemistry, and particularly relates to a platinum group element specific resin, and a preparation method and application thereof.
Background
Platinum Group Elements (PGE) comprise six elements of osmium (Os), iridium (Ir), ruthenium (Ru), rhodium (Rh), Platinum (Pt) and palladium (Pd), and are extremely important strategic mineral resources and play an important role in national economy and national defense and military industries. In view of the separation of Os, the separation methods of distillation or extraction are mostly adopted in laboratories at home and abroad [1,2 ]. The present invention is mainly directed to five elements of iridium (Ir), ruthenium (Ru), rhodium (Rh), platinum (Pt), and palladium (Pd). The present invention is primarily directed to these five elements. In industry, hydrometallurgy is commonly used to refine platinum group elements. Before hydrometallurgy, the processes of concentration, extraction, separation, purification and the like are carried out. Common separation methods are: conventional methods such as coprecipitation, solution extraction, ion exchange and liquid membrane methods. However, the traditional process has the disadvantages of complex flow, low efficiency, large reagent consumption and low recovery rate. In comparison, the solid phase extraction technology has the advantages of low reagent consumption and good separation effect. However, various adsorbents or special-effect resins reported in the existing documents can only selectively adsorb part of the five elements, and then another adsorbent or special-effect resin is used for adsorbing the rest of the elements, so that the separation efficiency is seriously influenced; or the elution is not easy to occur during the elution, so that the recovery rate is low, and the detection result is influenced.
CN106568763A discloses an improved method for analyzing gold, palladium and platinum by solid phase extraction, which uses AG 1 × 8 ion exchange resin; CN106480313A discloses a method for recovering platinum from insoluble silica-alumina-based platinum-containing spent catalyst, wherein a macroporous anion exchange resin is used for enriching and recovering platinum. The traditional strong-base anion exchange resin is used for adsorbing platinum, so that the selectivity is low, and the adsorption capacity is small. CN106148689A discloses a method for efficiently enriching gold and platinum group metal concentrates by oxygen pressure acid leaching, wherein QP-TU resin is adopted to exchange and adsorb platinum and palladium in a pressurized leaching solution. Similarly, the traditional resin cannot meet the selective adsorption enrichment of trace or even trace platinum group elements in the geological sample, and further the test of the content of the platinum group elements in the geological sample is completed.
"study of platinum and rhenium adsorption Performance on D-990 ion exchange resin", Guo Yongyong et al, rare metals, "Vol.24, No. 6, separation of platinum and rhenium was accomplished using a macroporous polyamine resin which had good adsorption performance for platinum and rhenium at lower acidity but very different partition coefficients for platinum and rhenium at higher acidity. The resin can only adsorb 2 elements, and can not selectively adsorb most of platinum group elements.
The prior art also has some chelating resins containing S and N by interpenetrating polymer networks, but the values have larger adsorption capacity to Fe, Cu and Al, and the effective separation of noble metals, particularly platinum group element metals and base metals cannot be completed.
CN110841607A discloses a special resin with ultra-low cost bottom gold, the chelating agent of the special resin is Fmoc-S-trityl-L-cysteine, which can effectively and selectively adsorb gold in geological samples, but has no effect on platinum group element adsorption. Therefore, it is highly desirable to develop a specific platinum group element resin which can selectively adsorb platinum group elements and complete the identification and purification of samples.
Disclosure of Invention
The invention adopts self-initiated photoinduced polymerization technology, and different types of ligands are jointly polymerized on the surface of the resin in a block mode to prepare multi-ligand block copolymer resin so as to achieve the purpose of simultaneously and selectively adsorbing multiple platinum group elements. The invention adopts dopamine to induce acrylic monomers to generate free radical polymerization, and forms a molecular brush-shaped coating on the surface of a macromolecular framework. The molecular brush refers to a special molecular chain formed by connecting one end of a polymer chain with certain length and high density and high extension to various interfaces, and is similar to a brush. The polymer molecular brush structure formed on the resin carrier can obviously improve the density of the ligand and increase the specific selectivity and adsorption capacity of the resin for platinum group element adsorption.
Specifically, the present invention provides the following technical solutions.
A platinum group element specific resin is a polydopamine coated carrier resin with a polymer molecular brush connected thereon, and the polymer molecular brush comprises unit structures shown as formulas (i) and (ii):
Figure BDA0002596682500000021
wherein Q is a heterocyclic group containing N atoms and S atoms, W is an aryl or heteroaryl group, and N is an integer of 0 to 6.
The ratio of the structural units represented by the formula (i) to the number of the structural units represented by the formula (ii) is 5-8: 1-2.
The heterocyclic group containing N atom and S atom has 2-5 carbon atoms, 1-2N atoms, 1-2S atoms and an integer of 0 to 3, for example, N is selected from 0, 1,2 and 3.
Further, the group Q is selected from thiazolyl, 1,3, 4-thiadiazolyl, 1,2, 4-thiadiazolyl; w is selected from phenyl, naphthyl, anthryl, biphenyl, pyridyl, pyrrolyl, pyrimidyl and benzoxazothyl.
Preferably, the Q group is selected from
Figure BDA0002596682500000031
The W group is selected from phenyl, naphthyl and pyridyl.
Most preferably, the structure of formula (i) is
Figure BDA0002596682500000032
The structure of the formula (ii) is
Figure BDA0002596682500000033
The weight average molecular weight of the polymer as the molecular brush is 40000-100000g/mol, preferably 50000-75000 g/mol.
The carrier resin is selected from styrene-divinylbenzene copolymer resin (such as CG161m, CG161c, CG300s, CG300m, CG300c) or methacrylate crosslinking resin (such as CG71s, CG71m, CG71 c).
The copolymer platinum group element special-effect resin is prepared by the preparation method comprising the following steps:
the poly dopamine-coated carrier resin is immersed into a mixed solution of acrylate monomers shown in formula (I) and formula (II), and is prepared by photo-initiated polymerization under the condition of illumination under the protection of inert gas,
Figure BDA0002596682500000034
wherein Q, W and n are as defined above; (I) and the acrylate monomer shown in the formula (II) is 5-8: 1-2.
Preferably, the monomer structures of formula (I) and formula (II) are represented by the following formulas (I-1) and (II-1), respectively:
Figure BDA0002596682500000041
methods for coating carrier resins with polydopamine are well known in the art and are specifically achieved by immersing the carrier resin in a buffered dopamine solution and reacting overnight. Preferably, the mass-to-volume ratio of the carrier resin to the dopamine buffer solution is 1:5-10g/mL, the pH of the dopamine buffer solution is weakly alkaline, generally 8-9, and the concentration of dopamine in the dopamine buffer solution is 1-2mg/mL (prepared by dissolving dopamine in 10mmol/mL Tris-HCl at pH 8.5). Dopamine is a biological neurotransmitter, and can undergo oxidative polymerization reaction under a wet environment, and a polymerization product of the dopamine can be fixed on the surface of a substrate and shows super-strong adhesive properties. The polydopamine can generate free radicals with polymerization activity under the condition of illumination to initiate polymerization reaction, and the characteristic of the dopamine makes the polydopamine a hot door for surface modification of solid materials. The invention uses dopamine to coat the resin, and then carries out photopolymerization in the monomer solution.
In the acrylate monomer mixed solution, the concentration of the monomer shown in the formula (I) is 0.1-0.2 mol/L, the concentration of the monomer shown in the formula (II) is 0.015-0.04 mol/L, and the condition is that the ratio of the amount of the monomer shown in the formula (I) to the amount of the monomer shown in the formula (II) is 5-8: 1-2.
The solvent is not particularly limited, and may be one capable of dissolving the acrylate derivative monomers represented by the formulae (I) and (II), such as acetonitrile, acetone, methanol, N-dimethylformamide, and the like.
The illumination condition is that the light-initiated polymerization is carried out under the irradiation of a xenon lamp light source, and the power of the xenon lamp is 200-300W; the photo-initiated polymerization is carried out at the room temperature of 20-30 ℃ and the reaction is carried out for 4-16 hours.
The polymer for modifying the resin prepared by the invention has the structure of the molecular brush, and on one hand, the polymer can more effectively anchor and adsorb platinum group elements in a sample through the specific chemical structure and spatial structure of the molecular brush. The platinum group specific resin modified by the polymer can selectively adsorb platinum group elements, namely iridium (Ir), ruthenium (Ru), rhodium (Rh), platinum (Pt) and palladium (Pd), and improve the detection precision and recovery rate.
The invention also provides application of the platinum group element specific resin in selective adsorption recovery of platinum group elements, which comprises the following steps:
(1) column assembling: filling the platinum group element specific resin into a solid phase extraction column;
(2) loading: loading a solution containing platinum group metal ions, wherein the medium of the loading solution is 3-5mol/L HCl, preferably 3.5-4 mol/L;
(3) and (3) elution: the platinum group element is HNO with the concentration of 8-12mol/L3And (4) eluting under the condition.
Preferably, HNO is used in step (3)3Before elution, the alkali metal is eluted with 3-5mol/L HCl.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a platinum group specific resin with a molecular brush polymer attached to a resin carrier according to the present invention.
FIG. 2 is an electron micrograph of the platinum group specific resin obtained in example 1, wherein the left image is a carrier resin and the right image is a carrier resin to which a polymer molecular brush is bonded.
FIG. 3 shows the maximum adsorption capacity of the platinum group specific resin obtained in example 1 for each metal in a 4mol/L HCl medium.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs.
The metal solution used in the present invention is a chloride solution of a metal, and the standard solution is purchased from steel Yannak detection technology, Inc.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
A polydopamine-coated resin was prepared by immersing 10g of the resin styrene-divinylbenzene copolymer resin (Amberchrom: CG161m) in 100mL of a dopamine pH 8.5 buffer solution (dopamine 2.0 mg/mL; buffer: 10mmol/L Tris-HCl) for 24 hours. The coated resin is washed with water and ethanol for three times respectively and dried for standby. The poly dopamine coated resin is immersed into an acrylate acetone solution consisting of 0.15mol/L of a monomer of formula (I-1) and 0.030mol/L of a monomer of formula (II-1), a reaction bottle is repeatedly vacuumized by adopting a Schlenk technology (anaerobic synthesis technology), argon is introduced for 20 minutes, and the whole reaction is carried out under the protection of nitrogen gas. Then, the reaction flask was moved to a 300W xenon lamp (CEL-S500, Beijing Zhongzhijin science and technology Co., Ltd.) and reacted at room temperature for 12 hours. The synthesized resin was washed three times with water and ethanol, respectively, and stored in a 95% ethanol solution.
FIG. 2 is an electron micrograph of a platinum group specific tree obtained in example 1, wherein the left image is a carrier resin and the right image is a carrier resin to which a polymer molecular brush is bonded. As can be seen from the figure, after the resin carrier is coated with polydopamine and reacts with the acrylate monomer on the surface of the resin carrier under the illumination condition, the smooth surface of the carrier is coated with a polymer coating. The coating is a polymer of the molecular brush, and the polymerization degree of the coating can be conveniently adjusted by the using amount of a polymerization monomer and the polymerization time.
Since the polymer is linked to the polymeric resin carrier, it is not easy to test the molecular weight, and the molecular weight is tested by polymerizing the same amount of monomer and dopamine under the same illumination condition. The weight average molecular weight (Mw) and the molecular weight distribution (PDI) were determined by PL-GPC120 gel permeation chromatography using an HTRI refractometer with a column PL gel 5 μm mixed-D300X 7.5 mm. The mobile phase adopts DMF (containing 0.01mol/L LiBr), the flow rate is 1.0mL/min, the test temperature is 60 ℃, narrow-distribution polystyrene standard substances are used as standard samples, and a standard curve is established. The weight average molecular weight was determined to be about 63800 with a molecular weight distribution of 2.6. Because the brush for preparing molecules is used for selectively adsorbing various platinum group target elements, the molecular weight distribution does not need to be controlled deliberately, and the selective adsorption of the specific resin to the platinum group is not influenced by the wider molecular weight distribution.
Example 2
The other conditions and procedure were the same as in example 1 except that the resin was replaced with a methacrylate crosslinking resin CG71 m.
Example 3
The other conditions and procedure were the same as in example 1 except that the concentration of the monomer of the formula (I-1) was 0.2mol/L and the concentration of the monomer of the formula (II-1) was 0.025 mol/L. The polymerization was carried out under otherwise identical polymerization conditions without the addition of a resin carrier, and the resulting polymer was found to have a weight average molecular weight of about 74200 and a molecular weight distribution of 2.8.
Example 4
The other conditions and procedure were the same as in example 1 except that the concentration of the monomer of the formula (I-1) was 0.1mol/L and the concentration of the monomer of the formula (II-1) was 0.02 mol/L. The polymerization was carried out under otherwise identical polymerization conditions without the addition of the resin carrier, and the resulting polymer was found to have a weight average molecular weight of about 57100 and a molecular weight distribution of 2.5.
Example 5
The other conditions and procedure were the same as in example 1 except that the concentration of the monomer of the formula (I-1) was 0.1mol/L and the concentration of the monomer of the formula (II-1) was 0.1 mol/L. The polymerization reaction was carried out without adding a resin carrier under the same other polymerization conditions, and the obtained polymer was found to have a weight average molecular weight of about 61400 and a molecular weight distribution of 2.9 by test.
Example 6
The other conditions and procedure were the same as in example 1 except that the concentration of the monomer of the formula (I-1) was 0.2mol/L and the concentration of the monomer of the formula (II-1) was 0.01 mol/L. The polymerization was carried out under otherwise identical polymerization conditions without the addition of the resin carrier, and the resulting polymer was found to have a weight average molecular weight of about 68300 and a molecular weight distribution of 2.7.
Example 7
The other conditions and procedure were the same as in example 1 except that the reaction time at room temperature was changed to 4 hours under a 300W xenon lamp light source. The polymerization was carried out under otherwise identical polymerization conditions without the addition of the resin carrier, and the resulting polymer was found to have a weight average molecular weight of about 38500 and a molecular weight distribution of 2.5.
Comparative example 1
The adsorption resin was a commercially available strong basic anion resin 201X 7(717 #).
Comparative example 2
With graphene polyurethane molecular brushes, the reference inventor's previous patent literature was prepared: xue D, Selective acquisition and recovery of statistical measures from water and statistical slice by polymer branched polyethylene-polyurethane composite, reactive and Functional Polymers,2019,136, 138-.
Application example 1Testing of maximum adsorption Capacity at different pH
20 mg of the specific resin synthesized in example 1 was added to 10 ml of a mixed solution containing a noble metal and a base metal. The concentrations of the noble metals (platinum, palladium, iridium, ruthenium, rhodium) were all 5mg/mL, and the concentrations of the base metals (magnesium, calcium, nickel, chromium, iron, zinc) were all 100 mg/mL. The maximum adsorption capacity of the resin for each metal ion was tested at different hydrochloric acid concentrations. The results are shown in table 1 and fig. 3. The adsorption capacity is calculated by the following formula:
Figure BDA0002596682500000071
in the formula: qe-adsorption capacity at equilibrium concentration of Co, mg/g;
v-volume of adsorbate solution, mL;
co-the initial mass concentration of adsorbate in solution, mg/mL;
ce-the residual mass concentration of adsorbate in the adsorption equilibrium of the special-effect resin, mg/L;
m is the amount of the special-effect resin and g.
TABLE 1
Figure BDA0002596682500000072
As can be seen from the data in Table 1, the platinum group specific resin provided by the invention has the selective adsorption capacity for the noble metals in the platinum group, and the higher the concentration of hydrochloric acid is, the higher the maximum adsorption capacity is. When the concentration of hydrochloric acid of base metal is increased, the adsorption amount of the base metal is reduced. However, the adsorption capacity for platinum group element ions started to decrease after the hydrochloric acid concentration was 4mol/L, probably because the acidity was too strong and chloride ions were competing with functional groups on the resin, resulting in a decrease in the maximum adsorption capacity. Therefore, the acidity of hydrochloric acid of 4mol/L is taken as the acidity of the sample solution.
FIG. 3 is the maximum adsorption capacity of the platinum group specific resin of example 1 for each metal element at 4mol/L HCl concentration, and it can be seen that the present invention provides a platinum group specific resin having a large adsorption capacity and little adsorption of base metals. Can complete the adsorption with high adsorption quantity and high specific selectivity.
Application example 2
Comparing the platinum group specific resin prepared in example 1 with the 201 × 7(717#) resin of comparative example 1 and the graphene polyurethane brush composite of comparative example 2 at a hydrochloric acid concentration of 4mol/L, the maximum adsorption capacities for each of the precious metal and the base metal are shown in table 2 below:
TABLE 2
Figure BDA0002596682500000081
As can be seen, the adsorption capacity of the general commercial adsorption resin for platinum group elements is very low, especially for ruthenium and rhodium, and the maximum adsorption capacity is only 3-4mg/g, which is far from meeting the practical requirement.
The graphene polyurethane molecular brush compound as a resin has a remarkably improved maximum adsorption amount for platinum group elements, but has substantially no adsorption for iridium and rhodium, and has a large adsorption amount for base metals, so that the aim of selectively adsorbing platinum group elements cannot be fulfilled.
Application example 3
The specific resin synthesized in example 1 was loaded on a solid phase extraction cartridge (Berlod resin column Cat. #731-1550, type S, inner diameter 0.5mm, column length 42mm, bed volume corresponding to the loaded resin 1mL), and 5mL of 4.0mol L of the specific resin was used first- 1The resin was prewashed with HCl and ultrapure water and then 5mL of 4.0mol L-1The HCl solution was column equilibrated.
A mixed solution containing iridium (Ir), ruthenium (Ru), rhodium (Rh), platinum (Pt) and palladium (Pd) as well as copper, nickel, chromium, iron, zinc, magnesium and calcium was used as a simulated sample for separation by column chromatography. Wherein the concentration of the noble metal is 200 mug/mL, and the concentration of the base metal is 10 mg/mL. The solution system is 4.0mol/L HCl medium. 1.0ml of the mixed solution was pipetted onto the column. The base metal retention on the column is very limited and can be eluted with 2mL of 4.0mol/L HCl. The noble metal is eluted by using 5mL of 12.0mol/L nitric acid solution. The recovery of each element was tested. The tests were carried out according to the same procedure and conditions, except that the specific resins were replaced with the resins of examples 2 to 6 and comparative example, and the test results were as follows, with the results shown in Table 3 below:
TABLE 3
Figure BDA0002596682500000091
As can be seen from the data in Table 3, the platinum group specific resin provided by the invention has large adsorption amount of platinum group elements in the solution, so that the recovery rate is high and is basically over 90 percent, and particularly the recovery rate of platinum and palladium in the preferred embodiment is over 99 percent. Among the catalytic reactions, especially commercial catalysts that have been marketed, platinum-based and palladium-based catalysts are most common. Therefore, the platinum group special-effect resin provided by the invention can not adsorb base metals and has good specific adsorption for recovering the catalyst in the reaction, thereby having high popularization value and commercial potential. The data in table 3 also show that for the recovery of the platinum group specific resin, the ratio, amount and molecular weight of the two monomers are controlled in the proper range to achieve the optimal adsorption of the platinum group elements. It is demonstrated that the number of repeating structural units of the two monomers and the length of the molecular brush all affect the adsorption on the polymer structure of the molecular brush. For example, the recovery rate of the platinum group specific resin of example 7 is not high because the polymerization reaction time is short, the molecular weight of the polymer is low, the length of the molecular brush is short, and the platinum group elements cannot be sufficiently adsorbed.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A platinum group element specific resin is a polydopamine coated carrier resin with a polymer molecular brush connected thereon, and the polymer molecular brush comprises unit structures shown as formulas (i) and (ii):
Figure FDA0002928289110000011
the number ratio of the structural units shown in the formula (i) to the structural units shown in the formula (ii) is 5-8: 1-2; n is an integer of 0 to 6;
the group Q is selected from thiazolyl, 1,3, 4-thiadiazolyl, 1,2, 4-thiadiazolyl; w is selected from pyridyl and pyrrolyl.
2. The platinum group specific resin of claim 1 wherein the group Q is selected from the group consisting of
Figure FDA0002928289110000012
Figure FDA0002928289110000013
The W group is selected from pyridyl.
3. The platinum group specific resin according to claim 1, wherein the structure of formula (i) is
Figure FDA0002928289110000014
The structure of the formula (ii) is
Figure FDA0002928289110000021
4. The platinum group element specific resin according to claim 1, wherein the weight average molecular weight of the polymer molecular brush is 40000-100000 g/mol.
5. The platinum group specific resin according to claim 4, wherein the weight average molecular weight of the polymer molecular brush is 50000-75000 g/mol.
6. The method for preparing the platinum group element specific resin according to any one of claims 1 to 5, comprising the steps of:
the preparation method comprises the following steps of immersing polydopamine-coated carrier resin into a mixed solution containing acrylate monomers shown in formula (I) and formula (II), and carrying out photoinitiated polymerization under the condition of illumination under the protection of inert gas to prepare the polydopamine-coated carrier resin:
Figure FDA0002928289110000022
7. the method according to claim 6, wherein the monomer structures of formula (I) and formula (II) are represented by the following formulae (I-1) and formula (II-1), respectively:
Figure FDA0002928289110000031
8. the method according to claim 6, wherein the acrylic ester monomer mixed solution has a concentration of the monomer represented by formula (I) of 0.1 to 0.2mol/L and a concentration of the monomer represented by formula (II) of 0.015 to 0.04mol/L, provided that the ratio of the amounts of the monomer represented by formula (I) and the monomer represented by formula (II) is 5-8: 1-2; and/or the illumination condition is that the light-initiated polymerization is carried out under the irradiation of a xenon lamp light source, and the power of the xenon lamp is 200-300W; the photo-initiated polymerization is carried out at the room temperature of 20-30 ℃ and the reaction is carried out for 4-16 hours.
9. Use of the platinum group element specific resin of any one of claims 1 to 5 for selective adsorptive recovery of platinum group elements, comprising the steps of:
(1) column assembling: filling the platinum group element specific resin into a solid phase extraction column;
(2) loading: loading a solution containing platinum group metal ions, wherein the medium of the loading solution is 3-5mol/L HCl;
(3) and (3) elution: the platinum group element is HNO with the concentration of 8-12mol/L3And (4) eluting under the condition.
10. Use according to claim 9, characterized in that HNO is used in step (3)3Before elution, the alkali metal is eluted with 3-5mol/L HCl.
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