CN114870818A - Method for adsorbing and separating gold, platinum and palladium by utilizing polyion liquid gel adsorbent - Google Patents
Method for adsorbing and separating gold, platinum and palladium by utilizing polyion liquid gel adsorbent Download PDFInfo
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- CN114870818A CN114870818A CN202210525430.XA CN202210525430A CN114870818A CN 114870818 A CN114870818 A CN 114870818A CN 202210525430 A CN202210525430 A CN 202210525430A CN 114870818 A CN114870818 A CN 114870818A
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- imidazole
- platinum
- palladium
- gold
- vinyl
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 158
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 79
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 78
- 239000010931 gold Substances 0.000 title claims abstract description 78
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 73
- 239000007788 liquid Substances 0.000 title claims abstract description 72
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003463 adsorbent Substances 0.000 title claims abstract description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 125
- -1 alkenyl imidazole Chemical compound 0.000 claims abstract description 95
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 150000002500 ions Chemical group 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 61
- 239000002608 ionic liquid Substances 0.000 claims description 22
- 238000004132 cross linking Methods 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000010894 electron beam technology Methods 0.000 claims description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 5
- ZOAUWMFMEPRJAG-UHFFFAOYSA-N [Br].C(C)N1CN(C=C1)C=C Chemical compound [Br].C(C)N1CN(C=C1)C=C ZOAUWMFMEPRJAG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- DFOYUMQLIPAYTQ-UHFFFAOYSA-N C=CN1C=C[N+](CCCCCC[N+]2=CN(C=C)C=C2)=C1 Chemical class C=CN1C=C[N+](CCCCCC[N+]2=CN(C=C)C=C2)=C1 DFOYUMQLIPAYTQ-UHFFFAOYSA-N 0.000 claims description 3
- ZEELLPKEWSINEL-UHFFFAOYSA-N CCCN(C1)C=CN1C=C.Br Chemical compound CCCN(C1)C=CN1C=C.Br ZEELLPKEWSINEL-UHFFFAOYSA-N 0.000 claims description 3
- CHKXIPXVBKADAA-UHFFFAOYSA-N [Br].C(=C)N1CN(C=C1)C Chemical compound [Br].C(=C)N1CN(C=C1)C CHKXIPXVBKADAA-UHFFFAOYSA-N 0.000 claims description 3
- UQHLSCXJMYBEGM-UHFFFAOYSA-N [Cl].C(=C)N1CN(C=C1)C Chemical compound [Cl].C(=C)N1CN(C=C1)C UQHLSCXJMYBEGM-UHFFFAOYSA-N 0.000 claims description 3
- GBJRHAIMSUEFEA-UHFFFAOYSA-N [Cl].C(C)N1CN(C=C1)C=C Chemical compound [Cl].C(C)N1CN(C=C1)C=C GBJRHAIMSUEFEA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 238000010382 chemical cross-linking Methods 0.000 claims description 3
- 230000005251 gamma ray Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 60
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GELXFVQAWNTGPQ-UHFFFAOYSA-N [N].C1=CNC=N1 Chemical compound [N].C1=CNC=N1 GELXFVQAWNTGPQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- 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
-
- 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
-
- 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 relates to a method for adsorbing and separating gold, platinum and palladium by utilizing a polyion liquid gel adsorbent, belonging to a method for adsorbing and separating gold, platinum and palladium. The alkenyl imidazole type polyion liquid gel is added into a gold solution, a platinum solution and a palladium solution containing gold, platinum or palladium, and the selective adsorption of the gold, the platinum or the palladium in the solution is realized by utilizing different ion forms of the gold, the platinum or the palladium and other coexisting ions in the solution. The imidazole polyion liquid gel provided by the invention can achieve adsorption efficiency of more than 99% on gold, platinum and palladium, and the three-dimensional network porous structure of the gel enables the adsorption of gold, platinum and palladium to be balanced very quickly. In addition, the adsorbent can selectively separate gold, platinum or palladium from a solution containing a large amount of coexisting ions of copper, iron, zinc and nickel. The method has the advantages of simple operation, resource saving, no secondary pollution to the environment, economy and environmental protection.
Description
Technical Field
The invention belongs to a method for adsorbing and separating gold, platinum and palladium. In particular to a method for adsorbing and separating gold, platinum and palladium by utilizing a polyion liquid gel adsorbent.
Background
In recent years, precious metals such as gold, platinum, palladium, etc. have been widely used in various industrial fields including jewelry, corrosion-resistant materials, electronic technology, chemical catalysts, etc. due to their characteristics such as luster, ductility, non-corrosiveness and high stability, and the application rate in electronic and catalytic processes exceeds 90.0%. Currently, the global demand for gold, platinum, palladium in the electronics field is still rapidly increasing. Due to the limited resources and inexhaustible demand of precious metals such as gold, platinum, palladium and the like, it is urgently needed to recover these precious metals from secondary resources such as waste water, electronic waste and the like containing these precious metals.
At present, a plurality of methods for recovering and separating gold, platinum and palladium comprise a precipitation method, a solvent extraction method, an adsorption method and the like. The chemical precipitation method has complex treatment process, can generate toxic sludge and has poor selectivity, and gold, platinum and palladium commonly coexist with other metal ions and are easy to generate coprecipitation; the solvent extraction method has a complex operation flow, needs a large amount of dangerous, toxic and volatile organic solvent and extractant which is difficult to recycle, has a large potential safety hazard, and is easy to cause secondary pollution to the environment; the adsorption method seems to be a method more suitable for precious metal recovery due to the advantages of high efficiency, low cost, simple and convenient operation, less use of organic solvents, simple equipment requirements, suitability for low-concentration adsorption and the like, and thus the adsorption method is widely concerned in the field of hydrometallurgy. For the adsorption technique, the separation effect depends mainly on the choice of the adsorbent material. Ionic liquids are a class of organic salts that consist entirely of anions and cations, are normally liquid at room temperature, and are commonly used as green solvents. It has also been extensively studied in the field of metal separation due to its higher stability, programmable structure and functional groups. Many reports have been made on the preparation of adsorbents for gold, platinum and palladium recovery by immobilizing ionic liquids on substrates such as cellulose, graphene and silica, but the adsorption capacities and/or adsorption rates of these materials are generally limited by nonfunctional substrates, and most of these studies are limited to the adsorption of single metals. The polyion liquid gel is a material which can combine the self functional advantages of the ionic liquid and a three-dimensional network structure of the gel, and can realize rapid adsorption kinetics while achieving high adsorption capacity. At present, the polyion liquid gel is not reported to be used for separating gold, platinum and palladium noble metals in a solution.
Disclosure of Invention
The invention provides a method for adsorbing and separating gold, platinum and palladium by utilizing a polyion liquid gel adsorbent, and aims to find a more efficient, economic and environment-friendly method for recovering gold, platinum or palladium from a separation waste liquid.
The technical scheme adopted by the invention is as follows: adding alkenyl imidazole type polyion liquid gel into a gold solution, a platinum solution and a palladium solution containing gold, platinum or palladium, and realizing selective adsorption of the gold, the platinum or the palladium in the solution by utilizing different ion forms of the gold, the platinum or the palladium and other coexisting ions in the solution;
in which gold, platinum and platinum are respectively mixed with AuCl in the solution 4 - 、PtCl 6 2- 、PdCl 4 2- The form exists;
the pH value of the solution containing gold or platinum is adjusted to be 1-6, and the pH value of the solution containing palladium is adjusted to be 1-5;
the structure of the alkenyl imidazole type polyion liquid gel is as follows:
m and n are integers between 1 and 12, X is Cl, Br and NO 3 ,BF 4 ,NTf 2 ,PF 6 。
The solution containing gold, platinum or palladium also comprises an ore solution, a catalyst waste liquid and a metallurgical waste liquid.
The alkenyl imidazole polyion liquid gel is obtained by polymerization and crosslinking reaction of an alkenyl imidazole ionic liquid monomer and a crosslinking agent; the preparation method is radiation polymerization crosslinking, firstly induces the C ═ C bond to generate free radical, and further initiates the polymerization and crosslinking between the ionic liquid monomer and the molecular chain of the crosslinking agent, thereby forming the alkenyl imidazole type polyion liquid gel.
The vinyl ionic liquid comprises 1-allyl-3-vinyl imidazolium salt and 3,3 '-divinyl-1, 1' (1, 6-hexanediyl) diimidazolium salt.
The alkene chemical cross-linking agent comprises divinyl alkyl and divinyl benzene.
The structure of the alkenyl imidazole type ionic liquid monomer is as follows:
n is an integer of 1 to 12, X ═ Cl, Br, NO 3 ,BF 4 ,NTf 2 ,PF 6 。
The alkenyl-containing imidazole type ionic liquid monomer comprises 1-vinyl-3-methyl-imidazole bromine salt, 1-vinyl-3-methyl-imidazole chlorine salt, 1-vinyl-3-methyl-imidazole nitrate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole hexafluorophosphate, 1-vinyl-3-methyl-imidazole bistrifluoromethylsulfinate, 1-vinyl-3-ethyl-imidazole bromine salt, 1-vinyl-3-ethyl-imidazole chlorine salt, 1-vinyl-3-ethyl-imidazole nitrate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-imidazole tetrafluoroborate, 1-vinyl-imidazole tetrafluoroborate, 1-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-imidazole tetrafluoroborate, 1-ethyl-imidazole tetrafluoroborate, 1-vinyl-imidazole salts, 1-vinyl-3-ethyl-imidazole hexafluorophosphate, 1-vinyl-3-ethyl-imidazole bistrifluoromethylsulfinate, and 1-vinyl-3-propyl-imidazole bromide.
The radiation polymerization crosslinking of the invention adopts 60 Co gamma-ray, electronBeam or X-ray with an irradiation dose of 10-300 kGy; the gel fraction is 50% or more.
The polymerization crosslinking reaction is carried out in 5-80 wt% concentration imidazole type ionic liquid water solution, ethanol or DMSO solution, and the reaction temperature is controlled at 25-85 deg.C.
The pore diameter of the alkenyl imidazole type polyion liquid gel is 50-1500 mu m.
The alkenyl imidazole polyion liquid gel synthesized by the invention is different from most reported gels, and is mainly characterized in that alkenyl imidazole ionic liquid containing double C ═ C bonds is used as a functional cross-linking agent, no chemical initiator, catalyst and the like are needed to be added, the polyion liquid gel is synthesized in one step through electron beam irradiation, the density of adsorption functional groups is effectively increased, so that the gel has high adsorption efficiency and high adsorption speed on gold, platinum or palladium, and the alkenyl imidazole polyion liquid gel has high adsorption speed on gold, platinum and palladium, and reaches balance within 4 min. In addition, the gel provided by the invention only uses imidazole nitrogen with positive charges as an adsorption group, but cannot adsorb metal ions with positive charges, so that gold can be adsorbed and separated from a solution containing a large amount of coexisting ions of copper, iron, zinc and nickel in a high selectivity manner, the gel is more suitable for high-selectivity adsorption of gold in a leachate with higher impurity ions, and the gel has a better application prospect and a market prospect.
The invention has the following beneficial effects:
the alkenyl imidazole type polyion liquid gel provided by the invention can comprehensively recover gold, platinum and palladium, has the adsorption efficiency of more than 99%, is high in adsorption speed, and can be used in a wider pH range.
The alkenyl imidazole type polyion liquid gel provided by the invention can be used for high-selectivity recovery of gold, platinum or palladium in a solution containing a large amount of copper, iron, zinc and nickel.
The preparation method of the alkenyl imidazole type polyion liquid gel is simple, easy to control conditions, low in energy consumption, safe and environment-friendly, and suitable for mass production.
The alkenyl imidazole type polyion liquid gel obtained by the invention has the advantages of easily available raw materials, low cost, environmental protection and no secondary pollution to the environment.
Drawings
FIG. 1 is a graph showing the experimental analysis of the adsorption of gold, platinum and palladium on the alkenyl imidazole type polyion liquid gel prepared in Experimental example 1 at different acidity levels.
FIG. 2 is a graph showing the experimental analysis of the saturation adsorption of gold, platinum and palladium on the alkenyl imidazole type polyion liquid gel prepared in Experimental example 1.
FIG. 3 is a graph showing the experimental analysis of the adsorption kinetics of the alkenyl imidazole type polyion liquid gel prepared in Experimental example 1 for gold, platinum and palladium, respectively.
FIG. 4 is a diagram showing experimental analysis of the alkenyl imidazole type polyion liquid gel prepared in Experimental example 1 for adsorbing and separating gold, platinum or palladium in a solution containing coexisting ions of copper, iron, zinc and nickel.
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.
Adding alkenyl imidazole type polyion liquid gel into a gold solution, a platinum solution and a palladium solution containing gold, platinum or palladium, and realizing selective adsorption of the gold, the platinum or the palladium in the solution by utilizing different ion forms of the gold, the platinum or the palladium and other coexisting ions in the solution;
in which gold, platinum and platinum are respectively mixed with AuCl in the solution 4 - 、PtCl 6 2- 、PdCl 4 2- The form exists;
the pH value of the solution containing gold or platinum is adjusted to be 1-6, and the pH value of the solution containing palladium is adjusted to be 1-5;
the alkenyl imidazole type polyion liquid gel has the following structure:
m and n are integers between 1 and 12, X is Cl, Br and NO 3 ,BF 4 ,NTf 2 ,PF 6 。
The solution containing gold, platinum or palladium also comprises an ore solution, a catalyst waste liquid and a metallurgical waste liquid.
The alkenyl imidazole polyion liquid gel is obtained by polymerization and crosslinking reaction of an alkenyl imidazole ionic liquid monomer and a crosslinking agent; the preparation method is radiation polymerization crosslinking, firstly induces the C ═ C bond to generate free radicals, and further initiates the polymerization and crosslinking between the ionic liquid monomer and the molecular chain of the crosslinking agent, thereby forming the alkenyl imidazole polyion liquid gel.
The vinyl ionic liquid comprises 1-allyl-3-vinyl imidazolium salt and 3,3 '-divinyl-1, 1' (1, 6-hexanediyl) diimidazolium salt.
The alkene chemical cross-linking agent comprises divinyl alkyl and divinyl benzene.
The structure of the alkenyl imidazole type ionic liquid monomer is as follows:
n is an integer of 1 to 12, X ═ Cl, Br, NO 3 ,BF 4 ,NTf 2 ,PF 6 。
The alkenyl-containing imidazole type ionic liquid monomer comprises 1-vinyl-3-methyl-imidazole bromine salt, 1-vinyl-3-methyl-imidazole chlorine salt, 1-vinyl-3-methyl-imidazole nitrate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole hexafluorophosphate, 1-vinyl-3-methyl-imidazole bistrifluoromethylsulfinate, 1-vinyl-3-ethyl-imidazole bromine salt, 1-vinyl-3-ethyl-imidazole chlorine salt, 1-vinyl-3-ethyl-imidazole nitrate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-imidazole tetrafluoroborate, 1-vinyl-imidazole tetrafluoroborate, 1-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-imidazole tetrafluoroborate, 1-ethyl-imidazole tetrafluoroborate, 1-vinyl-imidazole salts, 1-vinyl-3-ethyl-imidazole hexafluorophosphate, 1-vinyl-3-ethyl-imidazole bistrifluoromethylsulfinate, and 1-vinyl-3-propyl-imidazole bromide.
The radiation polymerization crosslinking of the invention adopts 60 Co gamma-ray, electron beam or X-ray with the irradiation dose of 10-300 kGy; the gel fraction is 50% or more.
The polymerization crosslinking reaction is carried out in 5-80 wt% concentration imidazole type ionic liquid water solution, ethanol or DMSO solution, and the reaction temperature is controlled at 25-85 deg.C.
The pore diameter of the alkenyl imidazole type polyion liquid gel is 50-1500 mu m.
The invention is further illustrated by the following experimental examples.
Experimental example 1 preparation of alkenyl imidazole type polyion liquid gel
1) Adding 1-vinyl-3-ethylimidazole bromine salt and 1-allyl-3-vinylimidazole bromine salt into 1mL of deionized water, wherein the concentrations of the two are 80% and 4.9%, respectively, after ultrasonic dissolution, pouring the uniform solution into a polyethylene bag, and using N to dissolve the uniform solution 2 Degassing and sealing;
2) and (3) carrying out electron beam radiation by using an electron accelerator, so that the vinyl generates active free radicals for polymerization crosslinking reaction, and the molecular chains of reactants are induced to be polymerized and crosslinked to form the polyion liquid gel. Irradiation conditions: the irradiation voltage is 10MeV, the irradiation dose is 80kGy, and the dose rate is 10 kGy/pass. Drying the obtained gel at 50 ℃ to constant weight, soaking the gel in deionized water to remove sol part, and drying the gel at 50 ℃ to constant weight to obtain the polyion liquid gel with the gel fraction of 78%.
Experimental example 2 pH adsorption Effect experiment of alkenyl imidazole type polyion liquid gel
Weighing 10mg of the prepared alkenyl imidazole type polyion liquid gel, and adding 10mL of AuCl-containing solution at room temperature 4 - Or PtCl 6 2- Or PdCl 4 2- In waterIn the solution, dilute acid diluted alkali is used for regulating the content of AuCl 4 - Or PtCl 6 2- The pH variation range of the solution is 1-6, and the PdCl content is adjusted 4 2- And (5) carrying out a static adsorption test when the pH variation range of the solution is 1-5. The adsorption test was carried out in a 25 ℃ water bath shaker, and after 24 hours of adsorption, the supernatant was collected and the gold, platinum or palladium concentration in the solution was measured by ICP-OES to calculate the amount of adsorption of the gel (Q) e )。
The pH-dependent effect on the adsorption of gold, platinum and palladium on the alkenyl imidazole polyionic liquid gel of Experimental example 1 is shown in FIG. 1. The alkenyl imidazole type polyion liquid gel can efficiently adsorb gold and platinum at the pH of 1-6, and can efficiently adsorb palladium at the pH of 1-5.
Experimental example 3 saturated adsorption experiment of alkenyl imidazole type polyion liquid gel
Adding 10mg of alkenyl imidazole type polyion liquid gel into 10mL of a series of gold solution (20-2000ppm) or platinum solution (20-800ppm) or palladium solution (20-500ppm) with different concentrations, respectively, adsorbing in a water bath oscillator at 25 deg.C for 48h, collecting clear solution, and detecting the concentration of gold, platinum or palladium in the solution by ICP-OES to calculate gel adsorption amount (Q) e )。
The saturated adsorption curves of the alkenyl imidazole type polyionic liquid gel of experimental example 1 on gold, platinum and palladium are respectively shown in FIG. 2, and the saturated adsorption capacities of the alkenyl imidazole type polyionic liquid gel on gold, platinum and palladium are respectively 879mg/g, 420mg/g and 278 mg/g.
Experimental example 4 kinetic adsorption experiment of alkenyl imidazole type polyion liquid gel
Adding 10mg of alkenyl imidazole type polyion liquid gel into 10mL of gold or platinum or palladium solution with concentration of 100ppm, reacting for 1-120min, collecting clear solution, and detecting the concentration of gold or platinum or palladium in the solution by ICP-OES to calculate gel adsorption amount (Q) e )。
The kinetic adsorption curves of the alkenyl imidazole type polyion liquid gel of the experimental example 1 on gold, platinum and palladium are respectively shown in fig. 3, and it can be seen that the adsorption on gold, platinum and palladium reaches equilibrium within 4 min.
Experimental example 5 alkenyl imidazole type polyion liquid gel gold, platinum and palladium were adsorbed and separated from various coexisting ionic solutions, respectively
The waste liquid of gold, platinum and palladium often contains other metal ions, so a series of blending solutions containing gold or platinum or palladium and copper, iron, zinc and nickel in different concentration ratios are prepared. Adding 10mg alkenyl imidazole type polyion liquid gel into 10mL solution, adsorbing for 24 hr, collecting clear solution, detecting the concentration of each metal ion in the solution with ICP-OES to calculate gel adsorption amount (Q) e )。
The adsorption results of the alkenyl imidazole type polyionic liquid gel of experimental example 1 on each metal ion in the blend solution are respectively shown in fig. 4, and it can be seen that the alkenyl imidazole type polyionic liquid gel has excellent adsorption selectivity on gold, platinum or palladium, and does not substantially adsorb the rest of the coexisting metal ions.
While the invention has been described with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for adsorbing and separating gold, platinum and palladium by utilizing polyion liquid gel adsorbent is characterized by comprising the following steps: adding alkenyl imidazole type polyion liquid gel into a gold solution, a platinum solution and a palladium solution containing gold, platinum or palladium, and realizing selective adsorption of the gold, the platinum or the palladium in the solution by utilizing different ion forms of the gold, the platinum or the palladium and other coexisting ions in the solution;
in which gold, platinum and platinum are respectively mixed with AuCl in the solution 4 - 、PtCl 6 2- 、PdCl 4 2- The form exists;
the pH value of the solution containing gold or platinum is adjusted to be 1-6, and the pH value of the solution containing palladium is adjusted to be 1-5;
the structure of the alkenyl imidazole type polyion liquid gel is as follows:
m and n are integers between 1 and 12, X is Cl, Br and NO 3 ,BF 4 ,NTf 2 ,PF 6 。
2. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 1, wherein: the solution containing gold or platinum or palladium also comprises an ore solution, a catalyst waste liquid and a metallurgical waste liquid.
3. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 1, wherein: the alkenyl imidazole polyion liquid gel is obtained by polymerization and crosslinking reaction of an alkenyl imidazole ionic liquid monomer and a crosslinking agent; the preparation method is radiation polymerization crosslinking, firstly induces the C ═ C bond to generate free radicals, and further initiates the polymerization and crosslinking between the ionic liquid monomer and the molecular chain of the crosslinking agent, thereby forming the alkenyl imidazole polyion liquid gel.
4. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 3, wherein: the vinyl ionic liquid comprises 1-allyl-3-vinyl imidazolium salt and 3,3 '-divinyl-1, 1' (1, 6-hexanediyl) diimidazolium salt.
5. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 3, wherein: the alkene chemical cross-linking agent comprises divinyl alkyl and divinyl benzene.
6. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 3, wherein: the structure of the alkenyl imidazole type ionic liquid monomer is as follows:
n is an integer of 1 to 12, X ═ Cl, Br, NO 3 ,BF 4 ,NTf 2 ,PF 6 。
7. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 6, wherein: the imidazole type ionic liquid monomer containing alkenyl comprises 1-vinyl-3-methyl-imidazole bromine salt, 1-vinyl-3-methyl-imidazole chlorine salt, 1-vinyl-3-methyl-imidazole nitrate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole hexafluorophosphate, 1-vinyl-3-methyl-imidazole bistrifluoromethylsulfinate, 1-vinyl-3-ethyl-imidazole bromine salt, 1-vinyl-3-ethyl-imidazole chlorine salt, 1-vinyl-3-ethyl-imidazole nitrate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-methyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-imidazole tetrafluoroborate, 1-ethyl-imidazole tetrafluoroborate, 1-vinyl-imidazole tetrafluoroborate, 1-3-imidazole, 1-vinyl-3-ethyl-imidazole hexafluorophosphate, 1-vinyl-3-ethyl-imidazole bistrifluoromethylsulfinate, and 1-vinyl-3-propyl-imidazole bromide.
8. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent according to claim 3, wherein the method comprises the following steps: the radiation polymerization crosslinking adopts 60 Co gamma-ray, electron beam or X-ray with the irradiation dose of 10-300 kGy; the gel fraction is 50% or more.
9. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 3, wherein: the polymerization crosslinking reaction is carried out in 5-80 wt% imidazole ionic liquid water solution, ethanol or DMSO solution, and the reaction temperature is controlled at 25-85 deg.C.
10. The method for adsorbing and separating gold, platinum and palladium by using the polyion liquid gel adsorbent as claimed in claim 3, wherein: the pore diameter of the alkenyl imidazole type polyion liquid gel is 50-1500 mu m.
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