CN112960844A - Reactor for separating and recovering precious metals and application thereof - Google Patents
Reactor for separating and recovering precious metals and application thereof Download PDFInfo
- Publication number
- CN112960844A CN112960844A CN202110348395.4A CN202110348395A CN112960844A CN 112960844 A CN112960844 A CN 112960844A CN 202110348395 A CN202110348395 A CN 202110348395A CN 112960844 A CN112960844 A CN 112960844A
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- cylinder
- anode
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- outer cover
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- 239000010970 precious metal Substances 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 239000003463 adsorbent Substances 0.000 claims abstract description 35
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000003929 acidic solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 description 20
- 239000010931 gold Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000004070 electrodeposition Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- -1 metal complex anions Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 150000003335 secondary amines Chemical group 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SKBBQSLSGRSQAJ-UHFFFAOYSA-N 1-(4-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)=O)C=C1 SKBBQSLSGRSQAJ-UHFFFAOYSA-N 0.000 description 1
- MKVBQBLIGAFRIY-UHFFFAOYSA-N 1h-pyrrole-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)N1 MKVBQBLIGAFRIY-UHFFFAOYSA-N 0.000 description 1
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 1
- WNLWBCIUNCAMPH-UHFFFAOYSA-N 2-n,2-n-dimethylpropane-1,2-diamine Chemical compound NCC(C)N(C)C WNLWBCIUNCAMPH-UHFFFAOYSA-N 0.000 description 1
- OXEZLYIDQPBCBB-UHFFFAOYSA-N 4-(3-piperidin-4-ylpropyl)piperidine Chemical compound C1CNCCC1CCCC1CCNCC1 OXEZLYIDQPBCBB-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 229940054441 o-phthalaldehyde Drugs 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- OTMRXENQDSQACG-UHFFFAOYSA-N thiophene-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)S1 OTMRXENQDSQACG-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a reactor for separating and recovering precious metals and heavy metals and application thereof, belonging to the technical field of precious metal and heavy metal recovery. The reactor comprises: the anode comprises an anode cylinder, wherein a porous anode outer cover is arranged outside the anode cylinder, the bottom end of the porous anode outer cover is communicated with a water inlet pipe through a reducer, and a modified polymer adsorbent is arranged between the anode cylinder and the porous anode outer cover; the cathode cylinder is arranged on the outer side of the porous anode outer cover, and a cathode starting polar plate is arranged on the inner wall of the cathode cylinder; the outer frame is arranged outside the cathode cylinder, a water outlet pipe is arranged at the upper part of the outer frame and connected with a precious metal online analyzer, and the precious metal online analyzer is connected with a water outlet tank and a water inlet tank. The reactor provided by the invention is mainly used for separating and recovering the noble metal and the heavy metal in the acid solution, and has good adsorption and separation effects.
Description
Technical Field
The invention belongs to the technical field of precious metal and heavy metal recovery, and particularly relates to a reactor for precious metal separation and recovery and application thereof.
Background
Precious and heavy metals are often used in the fields of catalysis, electronic instruments and the like, the main sources of precious and heavy metal recovery are nonferrous metallurgy and secondary resources, wherein the content of the heavy metals such as copper, zinc, nickel, iron and the like is 0.1-10g/L, and the content of the precious metals cannot be ignored. For example, the content of gold and other noble metals in the nonferrous metallurgical wastewater is 0-10 mg/L; the electronic garbage in the secondary resources is more called 'sleeping mineral product', for example, the gold content of one ton of discarded mobile phones exceeds 270 g.
For noble metals, conventional recovery methods include solvent extraction, adsorption, ion exchange, etc., wherein the adsorption method has the advantages of simple operation, high speed, and high adsorption capacity.
For heavy metals, conventional recovery methods include chemical precipitation, ion exchange, adsorption, electrodeposition, and the like, and since the specificity of the metal redox ability is more significant than other physicochemical properties, the metal can be separated and efficiently recovered by adjusting parameters such as voltage or current by electrodeposition.
The conventional equipment for recovering noble and heavy metals through electrodeposition is mainly a cyclone electrodeposition tank, and the working principle of the equipment is that high-speed water flow pumped by a lifting pump forms cyclone in the electrodeposition tank, so that concentration polarization of a cathode region is reduced, and the high-efficiency separation and recovery of heavy metals are realized by adjusting power supply parameters. However, since in acidic solutions, the noble metal is often present in the form of a complex ion with the anion in the solution, such as AuCl4 -，PtCl4 -And the like, the complex anions are difficult to migrate to the surface of the cathode due to the opposite charge characteristics to generate corresponding noble metal deposition, so that the cathode is causedIts severe precious metal loss.
Disclosure of Invention
The invention provides a reactor for realizing the high-efficiency separation and recovery of noble and heavy metals by combining selective adsorption and deposition technologies, which realizes the separation and high-efficiency recovery of metal resources in a multi-element noble and heavy metal solution by utilizing the difference of occurrence forms of noble and heavy metals in an acid solution and combining an adsorption technology for selectively adsorbing noble metal ions in an anode region and an electrodeposition technology for reducing heavy metals by a cathode.
The invention provides a reactor for separating and recovering precious metals, which comprises:
the anode comprises an anode cylinder, wherein a porous anode outer cover is arranged outside the anode cylinder, the bottom end of the porous anode outer cover is communicated with a water inlet pipe through a reducer, and a modified polymer adsorbent is arranged between the anode cylinder and the porous anode outer cover;
the cathode cylinder is arranged on the outer side of the porous anode outer cover, and a cathode starting polar plate is arranged on the inner wall of the cathode cylinder;
the outer frame is arranged outside the cathode cylinder, a water outlet pipe is arranged at the upper part of the outer frame and connected with a precious metal online analyzer, and the precious metal online analyzer is connected with a water outlet tank and a water inlet tank.
Furthermore, the device is provided with a direct current power supply, the anode cylinder is connected with the anode of the direct current power supply,
the cathode cylinder is connected with the negative pole of the direct current power supply.
Further, the anode cylinder is a titanium mesh cylinder loaded with noble metals, and the noble metals are ruthenium and iridium;
the outer cover of the porous anode is a titanium cylinder; the bottom of the porous anode outer cover is of a net structure; the opening on the porous anode outer cover is round or square.
Further, the cathode cylinder is a titanium cylinder or a stainless steel cylinder;
the cathode starting plate is a copper plate, a titanium plate or a stainless steel plate.
Furthermore, a lifting pump is arranged between the water inlet pipe and the water inlet tank.
Further, the preparation method of the modified polymer adsorbent comprises the following steps:
(1) mixing elemental sulfur, a multi-amino compound, a multi-carbonyl compound and a load substrate, and adding an organic solvent to obtain a solid-liquid mixed solution;
(2) heating the solid-liquid mixed solution to react under the atmosphere of protective gas to obtain a modified polymer mixed solution;
(3) cooling the modified polymer mixed solution to room temperature, washing, centrifuging and drying to obtain a modified polymer adsorbent;
wherein the loading substrate is a large-particle porous adsorption material, and the particle size of the large-particle porous adsorption material is between 1cm and 5 cm.
Further, in the step (1), the molar number of carbonyl groups in the polybasic carbonyl compound: the molar number of amine groups in the polyamine compound is as follows: the molar ratio of sulfur atoms in the elemental sulfur is (1-6) to 1 (1-6);
in the step (1), the mass ratio of the load substrate to the elemental sulfur is (0.5-10): 1.
Further, in the step (1), the elemental sulfur is sublimed sulfur;
in the step (1), the polyamine-based compound contains primary amine groups or secondary amine groups;
in the step (1), the polybasic carbonyl compound contains aldehyde group or carboxyl;
in the step (1), the large-particle porous adsorption material comprises at least one of columnar activated carbon, carbon nanotubes, a carbon felt, activated carbon fibers and a carbon-based composite material.
Further, in the step (2), the temperature of the heating reaction is 60-120 ℃; the heating reaction time is 4-24 h.
In the step (3), the rotation speed of the centrifugation is 5000-13000 rpm; the centrifugation time is 5-10 minutes;
in the step (3), the drying temperature is 20-50 ℃;
in the step (3), the drying is carried out for more than 12 hours in vacuum.
The invention also provides the application of any one of the reactors in separating and recovering the noble metal and the heavy metal in the acidic solution, wherein the pH value of the acidic solution is less than or equal to 4.
The invention has the following advantages:
according to the reactor for separating and recycling precious metals, a specific modified polymer adsorbent is adopted, a selective adsorption and deposition technology is combined to realize the efficient separation and recycling of precious metals and heavy metals, the opposite migration effect of the precious metals and the heavy metals under the action of an electric field is realized by utilizing the difference of physicochemical properties of the precious metals and the heavy metals in an acidic solution, finally, the precious metals are recycled by specific adsorption particles nearby at an anode, and the heavy metals are subjected to electrodeposition in a cathode region, so that the precious metals and the heavy metals are effectively separated and recycled.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of a reactor according to the present invention; wherein,
1-an anode cylinder; 1 a-a porous anode housing; 1 b-a reducer;
2-a cathode cylinder; 2 a-a cathode starting plate; 2 b-a modified polymeric adsorbent;
3-an outer frame; 4-a direct current power supply; 5-noble metal on-line analyzer; 6-water outlet groove; 7-a water inlet tank; 8-water inlet pipe; 9-water outlet pipe.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
As shown in fig. 1, an embodiment of the present invention provides a reactor for separating and recovering precious metals, the reactor including:
the device comprises an anode cylinder 1, wherein a porous anode outer cover 1a is arranged outside the anode cylinder 1, the bottom end of the porous anode outer cover 1a is communicated with a water inlet pipe 8 through a reducer 1b, and a modified polymer adsorbent 2b is arranged between the anode cylinder 1 and the porous anode outer cover 1 a;
the cathode cylinder 2 is arranged on the outer side of the porous anode outer cover 1a, and a cathode starting plate 2a is arranged on the inner wall of the cathode cylinder 2;
the outer frame 3 is arranged outside the cathode cylinder 2, the upper part of the outer frame 3 is provided with a water outlet pipe 9, the water outlet pipe 9 is connected with the precious metal on-line analyzer 5, and the precious metal on-line analyzer 5 is connected with the water outlet tank 6 and the water inlet tank 7.
According to the reactor for separating and recycling precious metals, a specific modified polymer adsorbent is adopted, a selective adsorption and deposition technology is combined to realize the efficient separation and recycling of precious metals and heavy metals, the opposite migration effect of the precious metals and the heavy metals under the action of an electric field is realized by utilizing the difference of physicochemical properties of the precious metals and the heavy metals in an acidic solution, precious metal complex anions are selectively adsorbed by the modified polymer adsorbent at an anode, heavy metal cations can migrate to a cathode through openings in a porous anode housing to generate the deposition effect, finally, the precious metals are recycled by specific adsorption particles nearby the anode at the anode, and the heavy metals are subjected to the electrodeposition effect at a cathode area, so that the effective separation of the precious metals and the heavy metals is realized.
It is noted that the precious metals described herein include precious metals and heavy metals. The noble metal comprises at least one of gold, platinum, rhodium and iridium. The heavy metal comprises at least one of copper, nickel, zinc and iron.
Further, the device is provided with a direct current power supply 4, the anode cylinder 1 is connected with the positive pole of the direct current power supply 4, and the cathode cylinder 2 is connected with the negative pole of the direct current power supply 4.
Preferably, the voltage provided by the DC power supply 4 is 1-10V. More preferably, the voltage provided by the DC power supply 4 is 3-6V. Different kinds of heavy metals can be recovered by adjusting different voltages.
Specifically, the anode cylinder 1 is a columnar anode cylinder. The anode cylinder is a titanium mesh cylinder loaded with noble metals, and the noble metals are ruthenium, iridium and the like.
The porous anode outer cover 1a is a titanium cylinder.
The bottom of the porous anode outer cover 1a is of a net structure. The setting of network structure is used for loading modified polymer adsorbent 2b on the one hand, and the waste liquid of being convenient for on the other hand gets into porous anode housing from the bottom to make waste liquid and modified polymer adsorbent 2b carry out the full action.
The openings in the porous anode casing may be circular or square. When the opening is circular, the diameter thereof may be 0.3 to 1 cm. The pore diameter of the open pore on the outer cover of the porous anode is smaller than the particle diameter of the large-particle porous adsorption material.
Specifically, the cathode cylinder 2 is a columnar cathode cylinder. The cathode cylinder is a titanium cylinder or a stainless steel cylinder. The cathode starting plate is a copper plate, a titanium plate or a stainless steel plate.
As shown in FIG. 1, the bottom end of the porous anode housing 1a is communicated with the water inlet pipe 9a through the bottom of the cathode cylinder 2 via a reducer 1 b.
And a lifting pump is arranged between the water inlet pipe 8 and the water inlet tank 7. The water inlet tank is used for rapidly conveying waste liquid to be treated in the water inlet tank 7 to a position between the porous anode outer cover 1a and the anode cylinder 1 for treatment through the action of the lifting pump and the water inlet pipe.
The precious metal on-line analyzer 5 is respectively connected with a reactor water outlet tank 6 and a reactor water inlet tank 7 through a three-way valve. So that the water sample analyzed by the precious metal on-line analyzer 5 is distributed into the water outlet tank 6 and the water inlet tank 7 through the three-way valve respectively. Wherein, if the detection reaches the standard, the water is directly delivered to the water outlet groove 6. If the detection is not up to the standard, the water enters the water inlet tank 7 again for recycling and separating treatment.
In an embodiment of the present invention, a method for preparing the modified polymer adsorbent includes the following steps:
(1) mixing elemental sulfur, a multi-amino compound, a multi-carbonyl compound and a load substrate, and adding an organic solvent to obtain a solid-liquid mixed solution;
(2) heating the solid-liquid mixed solution to react under the atmosphere of protective gas to obtain a modified polymer mixed solution;
(3) cooling the modified polymer mixed solution to room temperature, washing, centrifuging and drying to obtain a modified polymer adsorbent;
wherein the loading substrate is a large-particle porous adsorption material, and the particle size of the large-particle porous adsorption material is between 1cm and 5 cm.
According to the invention, the modified polymer adsorbent is added with a large-particle porous adsorption material as a load substrate, and the sulfur simple substance, the multi-amino compound and the multi-carbonyl compound are subjected to in-situ polymerization on the surface of the load substrate.
In one embodiment of the present invention, in step (1), the molar number of carbonyl groups in the polyvalent carbonyl compound is: the molar number of amine groups in the polyamine compound is as follows: the molar ratio of sulfur atoms in the elemental sulfur is (1-6) to 1 (1-6).
In the step (1), the mass ratio of the load substrate to the elemental sulfur is (0.5-10): 1.
In an embodiment of the present invention, in the step (1), the elemental sulfur is sublimed sulfur;
in the step (1), the polyamine-based compound contains primary amine groups or secondary amine groups;
in the step (1), the polyvalent carbonyl compound contains an aldehyde group or a carboxyl group.
In one embodiment of the present invention, in step (1), the polyamine-based compound contains primary or secondary amine groups;
preferably, the polyamine-based compound includes at least one of hexamethylenediamine, piperazine, p-phenylenediamine, ethylenediamine, 1, 4-cyclohexanediamine, dimethylpropylenediamine, N N '-diethylethylenediamine, 1, 8-diamino-3, 6-dioxaoctane, 4' -diaminodiphenyl ether, N N '-diethylethylenediamine, N N' -diethylethylenediamine, p-xylylenediamine, 1, 3-bis (4-piperidyl) propane, and o-phenylenediamine;
in the step (1), the polybasic carbonyl compound contains aldehyde group or carboxyl;
preferably, the polybasic carbonyl compound comprises at least one of polyurethane, terephthalaldehyde, p-toluenesulfonic acid, isophthalic acid, 2, 5-thiophenedicarboxaldehyde, 1H-pyrrole-2, 5-dicarbaldehyde, o-phthalaldehyde, pyridine-2, 6-dicarbaldehyde and 1, 4-diacetylbenzene.
In an embodiment of the present invention, in step (1), the large-particle porous adsorption material includes at least one of columnar activated carbon, carbon nanotube, carbon felt, activated carbon fiber, and carbon-based composite material.
In one embodiment of the invention, in the step (2), the temperature of the heating reaction is 60-120 ℃; the heating reaction time is 4-24 h.
In an embodiment of the present invention, in the step (3), the number of washing is 4 to 6.
The rotating speed of the centrifugation is 5000-; the centrifugation time is 5-10 minutes.
The drying temperature is 20-50 ℃.
The drying adopts vacuum drying for more than 12 hours.
An embodiment of the invention also provides application of any one of the reactors in separation and recovery of precious metals and heavy metals in an acidic solution. Preferably, the pH of the acidic solution is 4 or less.
Further, the noble metal comprises at least one of gold, platinum, rhodium and iridium; the heavy metal comprises at least one of copper, nickel, zinc and iron. In addition, the reactor provided by the invention can also be used for reducing metal arsenic in an acid solution into pentavalent arsenic at the anode, thereby reducing the toxicity of the wastewater.
An embodiment of the present invention further provides a method for separating and recovering precious metals and heavy metals in an acidic solution by using the reactor, including the following steps:
the wastewater containing precious metals in the water inlet tank 7 enters between the porous anode outer cover 1a and the cathode cylinder 2 through the lift pump, the modified polymer adsorbent 2b moves in a fluidized bed mode under the driving of high-speed water flow, so that the modified polymer adsorbent 2b is fully contacted with precious metals and heavy metals in the wastewater, and the heavy metals flow to the cathode cylinder 2 along with the opening of the porous anode outer cover 1a and are deposited on the cathode starting plate 2 a.
The present invention will be described in detail with reference to examples.
Example 1A method for preparing a modified polymeric adsorbent, comprising the steps of:
(1) weighing 48.1mg of elemental sulfur, 145.6mg of p-phenylenediacetic acid, 58.1mg of hexamethylenediamine and 24mg of columnar activated carbon (the diameter is 5mm) in a 20mL pressure-resistant tube, adding 2mLN, N-dimethylacetamide, adding a magnetic rotor, stirring for 12 minutes, putting the mixture into an ultrasonic instrument, and performing ultrasonic treatment for 12 minutes to obtain a solid-liquid mixed solution;
(2) vacuumizing the solid-liquid mixed solution obtained in the step (1) until no bubbles exist, filling nitrogen, heating to 100 ℃, and reacting for 15 hours to obtain a modified polymer mixed solution;
(3) adding the modified polymer mixed solution obtained in the step (2) into 4mL of N, N-dimethylformamide, stirring for 10 minutes, slowly dripping into 100mL of methanol, centrifuging for 5 minutes, removing supernate and collecting precipitate; and then washing the precipitate with methanol, centrifuging for 5 minutes again after washing, removing the supernatant, repeating the process for 5 times, finally placing the centrifuged precipitate in a vacuum drying oven, and drying at 40 ℃ for 12 hours to obtain the modified polymer adsorbent for selectively adsorbing and recovering the noble metal ions.
Test example 1A method for wastewater treatment (gold, copper, nickel, zinc) using a modified polymeric adsorbent comprising the steps of:
the selected reactor: the cathode starting plate is a titanium plate, the anode is a titanium mesh ruthenium plating, the aperture of the porous anode outer cover is 5mm, the modified polymer adsorbent 1 (obtained in example 1) is filled in the porous anode outer cover, and the columnar modified polymer adsorbent 1 accounts for 50% of the total volume of the anode outer cover.
The operation of the reactor: 1L of acidic multi-heavy and noble metal solution (pH 3) containing gold ions (concentration of 0.1g/L), copper ions (concentration of 10g/L), nickel ions (concentration of 0.5g/L) and zinc ions (concentration of 1g/L) as heavy metals and metalloid arsenic (concentration of 0.1g/L) was placed in a water storage tank.
The pumping flow of the lift pump is adjusted to be 0.4L/h, the direct current power supply is started, the voltage is set to be 1.5-3V, and after circulating flow is carried out for 90min, the recovery rate of gold ions is 99.6% and the recovery rate of copper ions is 90%.
After the copper sheet deposited at the cathode is recovered, a region of 0.4cm multiplied by 0.4cm is cut off, and the copper sheet is put into concentrated nitric acid for digestion to test the contents of gold, copper, nickel and zinc ions in the copper sheet, wherein the contents of the gold, nickel and zinc ions are respectively less than 3%, 5% and 5% (mass concentration). In addition, the voltage is adjusted to be 2.8-4V, and copper and nickel can be deposited on the cathode. The voltage is adjusted to be 5-6V, and copper, zinc and nickel can be deposited on the cathode.
The purity of the granular gold reaches more than 90% after the absorbent for recovering gold at the anode is burned for 2 hours at 1000 ℃, which shows that the reactor can realize the purpose of high-efficiency separation and recovery of noble and heavy metals. Meanwhile, metalloid arsenic in the wastewater is reduced to pentavalent arsenic at the anode, the toxicity of the wastewater is reduced, and the metalloid arsenic is removed by further subsequent treatment of the effluent.
Example 2A method for preparing a modified polymeric adsorbent, comprising the steps of:
(1) weighing 481mg of sulfur simple substance, 1750mg of piperazine, 1660mg of terephthalaldehyde and 200mg of polyurethane (cube small block of 1cm x 1 cm) in a pressure resistant tube, adding 20mLN, N-dimethylacetamide, adding a magnetic rotor, stirring for 12 minutes, putting into an ultrasonic instrument, and ultrasonically treating for 12 minutes to obtain a solid-liquid mixed solution;
(2) vacuumizing the solid-liquid mixed solution obtained in the step (1) until no bubbles exist, filling nitrogen, heating to 100 ℃, and reacting for 15 hours to obtain a modified polymer mixed solution;
(3) slowly dropping the modified polymer mixed solution obtained in the step (2) into 200mL of methanol, centrifuging for 5 minutes, removing supernatant, and collecting precipitate; and then washing the precipitate with methanol, centrifuging for 5 minutes again after washing, removing supernatant, repeating the steps for 5 times, finally placing the centrifuged precipitate in a vacuum drying oven, and drying at 50 ℃ for 12 hours to obtain the modified polymer adsorbent for selectively adsorbing and recovering the noble metal ions.
Test example 2Method for wastewater treatment (platinum, zinc) using modified polymeric adsorbentsThe method comprises the following steps:
1L of acidic multi-heavy and noble metal solution (pH 4) is placed in a water storage tank, wherein the noble metal in the solution is platinum ion with the concentration of 0.05g/L, and the heavy metal is zinc ion with the concentration of 10 g/L.
The cathode starting plate of the reactor is a titanium plate, the anode is titanium mesh ruthenium plating, the modified polymer adsorbent 2 is filled in the porous anode outer cover, and the modified polymer adsorbent 2 (obtained in example 2) accounts for 50% of the total volume of the anode outer cover. The pumping flow of the pump is adjusted to be 0.2L/min, the direct current power supply is started, the voltage is set to be 5-6V, and after circulating flow is carried out for 120min, the recovery rate of platinum ions is 99.5% and the recovery rate of zinc ions is 90% through detection.
After the zinc deposited at the cathode is recovered, a region of 0.4cm multiplied by 0.4cm is cut off, and the zinc deposited at the cathode is put into concentrated nitric acid for digestion to test the content of platinum and zinc ions, wherein the content of the platinum ions is less than 3 percent (mass concentration).
The purity of the granular platinum reaches above 90% after the adsorbent for recovering platinum at the anode is burned for 4 hours at 1000 ℃, which shows that the reactor can realize the purpose of high-efficiency separation and recovery of noble and heavy metals.
Example 3A method for preparing a modified polymeric adsorbent, comprising the steps of:
(1) weighing 240mg of sulfur simple substance, 581mg of hexamethylenediamine, 830mg of terephthalaldehyde and 200mg of carbon felt (a cuboid small block of 0.5cm x 2cm x 1 cm) in a pressure-resistant tube, adding 30mL of p-toluenesulfonic acid, adding a magnetic rotor, stirring for 12 minutes, putting into an ultrasonic instrument, and ultrasonically treating for 12 minutes to obtain a solid-liquid mixed solution;
(2) vacuumizing the solid-liquid mixed solution obtained in the step (1) until no bubbles exist, filling nitrogen, heating to 100 ℃, and reacting for 15 hours to obtain a modified polymer mixed solution;
(3) slowly dropping the modified polymer mixed solution obtained in the step (2) into 250mL of methanol, centrifuging for 5 minutes, removing supernatant, and collecting precipitate; and then washing the precipitate with methanol, centrifuging for 5 minutes again after washing, removing supernatant, repeating the steps for 5 times, finally placing the centrifuged precipitate in a vacuum drying oven, and drying at 50 ℃ for 12 hours to obtain the modified polymer adsorbent for selectively adsorbing and recovering the noble metal ions.
Test example 3A method for wastewater treatment (gold, zinc, copper) by using a modified polymer adsorbent comprises the following steps:
1L of acidic multi-heavy and noble metal solution (pH 4) is placed in a water storage tank, wherein the noble metal in the solution is gold ions with the concentration of 0.2g/L, and the heavy metals are copper ions and zinc ions with the concentration of 10 g/L.
The cathode starting plate of the reactor is a titanium plate, the anode is titanium mesh ruthenium plating, the modified polymer adsorbent 3 is filled in the porous anode outer cover, and the modified polymer adsorbent 3 (obtained in example 3) accounts for 50% of the total volume of the anode outer cover. The pumping flow of the adjusting pump is 0.4L/h, the voltage of the direct current power supply is 2V, and the deposited copper sheets are taken out after the solution circularly flows for 120 min. And (3) replacing the titanium plate, adjusting the pumping flow of the pump to be 0.2L/h, setting the direct-current voltage to be 6V, and taking out the deposited zinc sheet after the solution circularly flows for 120 min. The adsorbent for recovering gold is burned for 2 hours at 1000 ℃ to obtain granular gold, the concentration of the treated solution is detected, the recovery rate of gold is 99 percent, and the recovery rates of copper and zinc are 90 percent.
And (3) shearing a recovered sheet with the thickness of 0.4cm multiplied by 0.4cm, digesting by concentrated nitric acid, and testing the concentrations of copper, zinc and gold, wherein the contents of gold and zinc in the recovered copper sheet are less than 3% and 5% (mass concentration), and the contents of gold and copper in the recovered zinc sheet are less than 3% and 1% (mass concentration). The purity of the recovered granular gold is more than 90%, which shows that the reactor can realize the purposes of high-efficiency separation and recovery of noble metals and heavy metals.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A reactor for the separation and recovery of precious metals, characterized in that it comprises:
the device comprises an anode cylinder (1), wherein a porous anode cover (1a) is arranged outside the anode cylinder (1), the bottom end of the porous anode cover (1a) is communicated with a water inlet pipe (8) through a reducing pipe (1b), and a modified polymer adsorbent (2b) is arranged between the anode cylinder (1) and the porous anode cover (1 a);
the cathode cylinder (2) is arranged on the outer side of the porous anode outer cover (1a), and a cathode starting polar plate (2a) is arranged on the inner wall of the cathode cylinder (2);
the outer frame (3) is arranged outside the cathode cylinder (2), a water outlet pipe (9) is arranged at the upper part of the outer frame (3), the water outlet pipe (9) is connected with the precious metal online analyzer (5), and the precious metal online analyzer (5) is connected with a water outlet groove (6) and a water inlet groove (7).
2. The reactor of claim 1, wherein:
the device is provided with a direct current power supply (4), the anode cylinder (1) is connected with the anode of the direct current power supply (4), and the cathode cylinder (2) is connected with the cathode of the direct current power supply (4).
3. The reactor of claim 1, wherein:
the anode cylinder (1) is a titanium mesh cylinder loaded with noble metals, and the noble metals are ruthenium and iridium;
the porous anode outer cover (1a) is a titanium cylinder; the bottom of the porous anode outer cover (1a) is of a net structure; the opening on the porous anode outer cover is round or square.
4. The reactor of claim 1, wherein:
the cathode cylinder (2) is a titanium cylinder or a stainless steel cylinder;
the cathode starting plate (2a) is a copper plate, a titanium plate or a stainless steel plate.
5. The reactor of claim 1, wherein:
and a lifting pump is arranged between the water inlet pipe (8) and the water inlet tank (7).
6. The reactor of claim 1, wherein:
the preparation method of the modified polymer adsorbent comprises the following steps:
(1) mixing elemental sulfur, a multi-amino compound, a multi-carbonyl compound and a load substrate, and adding an organic solvent to obtain a solid-liquid mixed solution;
(2) heating the solid-liquid mixed solution to react under the atmosphere of protective gas to obtain a modified polymer mixed solution;
(3) cooling the modified polymer mixed solution to room temperature, washing, centrifuging and drying to obtain a modified polymer adsorbent;
wherein the loading substrate is a large-particle porous adsorption material, and the particle size of the large-particle porous adsorption material is between 1cm and 5 cm.
7. The reactor of claim 6, wherein:
in the step (1), the molar number of carbonyl groups in the polybasic carbonyl compound is as follows: the molar number of amine groups in the polyamine compound is as follows: the molar ratio of sulfur atoms in the elemental sulfur is (1-6) to 1 (1-6);
in the step (1), the mass ratio of the load substrate to the elemental sulfur is (0.5-10): 1.
8. The reactor of claim 6, wherein:
in the step (1), the elemental sulfur is sublimed sulfur;
in the step (1), the polyamine-based compound contains primary amine groups or secondary amine groups;
in the step (1), the polybasic carbonyl compound contains aldehyde group or carboxyl;
in the step (1), the large-particle porous adsorption material comprises at least one of columnar activated carbon, carbon nanotubes, a carbon felt, activated carbon fibers and a carbon-based composite material.
9. The reactor of claim 6, wherein:
in the step (2), the temperature of the heating reaction is 60-120 ℃; the heating reaction time is 4-24 h.
In the step (3), the rotation speed of the centrifugation is 5000-13000 rpm; the centrifugation time is 5-10 minutes;
in the step (3), the drying temperature is 20-50 ℃;
in the step (3), the drying is carried out for more than 12 hours in vacuum.
10. Use of a reactor according to any one of claims 1 to 9 for separating and recovering precious and heavy metals from an acidic solution, wherein the acidic solution has a pH of 4 or less.
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