CN117305612A - Method for recovering noble metal from noble metal waste liquid - Google Patents
Method for recovering noble metal from noble metal waste liquid Download PDFInfo
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- CN117305612A CN117305612A CN202311177738.0A CN202311177738A CN117305612A CN 117305612 A CN117305612 A CN 117305612A CN 202311177738 A CN202311177738 A CN 202311177738A CN 117305612 A CN117305612 A CN 117305612A
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 124
- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 239000010814 metallic waste Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000003463 adsorbent Substances 0.000 claims abstract description 50
- 238000001914 filtration Methods 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000012265 solid product Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000004380 ashing Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 8
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- FBCHMEOPUKIZJN-UHFFFAOYSA-N dodecyl 2-aminopropanoate;sodium Chemical compound [Na].CCCCCCCCCCCCOC(=O)C(C)N FBCHMEOPUKIZJN-UHFFFAOYSA-N 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 239000010439 graphite Substances 0.000 claims description 47
- 229910002804 graphite Inorganic materials 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 235000011149 sulphuric acid Nutrition 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims description 11
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000009920 chelation Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- 239000002699 waste material Substances 0.000 description 16
- 229910052697 platinum Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 platinum ions Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering noble metals from noble metal waste liquid, which comprises the following steps: s1, filtering the noble metal waste liquid, and then adjusting the pH value to 5-6 to obtain treated noble metal waste liquid; s2, adding a modified adsorbent and an auxiliary agent into the treated noble metal waste liquid, stirring for reaction, and filtering, washing and drying after the reaction is finished to obtain an adsorbent adsorbed with noble metal; s3, ashing the adsorbent with the noble metal adsorbed in the step S2, grinding, washing with dilute hydrochloric acid, and filtering to obtain a solid product; and S4, calcining the solid product in the step S3 in a hydrogen atmosphere to obtain a noble metal mixture. The noble metal ions are adsorbed into the modified adsorbent through an adsorption method, so that the recovery time of the noble metal is shortened, and meanwhile, the added auxiliary agent consists of sodium dodecyl aminopropionate and disodium ethylenediamine tetraacetate, and the recovery rate of the noble metal is improved through chelation and the modified adsorbent together, so that the noble metal has a certain synergistic effect.
Description
Technical Field
The invention belongs to the technical field of precious metal recovery, and particularly relates to a method for recovering precious metal from precious metal waste liquid.
Background
Because noble metals have unique physical and chemical properties, the noble metals are widely applied to the modern technological and industrial fields of aerospace, electronic appliances, communication, computers, photographic equipment, automobiles, petrochemical industry and the like, and along with continuous exploitation, the resource reserves are continuously reduced. On the other hand, with the increasing emphasis of national economy and aerospace, the market demand for rare and precious rare and scattered metals is increasing, which promotes the recovery of rare and precious rare and scattered metals from waste liquid and waste residue to become a contemporary hot spot. Industrial products containing noble metals become waste products after a certain period of use, a great part of the waste products are waste liquid containing noble metals, the noble metal waste liquid is more easy to pollute the environment, and how to treat the waste liquid becomes an urgent problem to be solved.
The noble metal waste liquid is an important component of the noble metal secondary resource, can recover the noble metal in the waste liquid, can improve the economic benefit, solves the problem of rare noble metal resources in China, and is beneficial to environmental protection. Therefore, research on a new method and a new process for recovering noble metals from waste liquid will have important theoretical and practical significance.
The current methods for treating wastewater containing trace noble metals in noble metal refineries mainly comprise a metal replacement method, a precipitation method, an incineration method, an extraction method, an adsorption method, an electrolysis method, an oxidation-reduction method and the like. The metal replacement method enriches and recovers noble metals, and simultaneously causes 2-3 times longer noble metal refining process and 3-4 times more refining times because the recovery slag is polluted by various reagents. Although the ion exchange resin adsorption has the advantages of simple operation, small labor capacity and the like, the ion exchange resin has the advantages of limited loading capacity, long separation period, difficult ion resin elution, high resin price and the like, is mostly applied to the removal of heavy metal ions from industrial waste liquid, and is still remained in the research stage for the recovery of trace rare noble metals, and does not have the condition of industrial application.
Chinese patent application No. 201110389890.6 discloses a hydrazine hydrate system which is a strong reducing agent under the strong alkaline condition, platinum ions in organic alcohol waste liquid containing platinum are reduced into simple substance platinum, however, the platinum leaching efficiency of the system is low, the reducing agent is too strong, the selectivity to platinum metals is poor, and metal impurities such as copper, nickel and the like are often mixed in the reduced metals. Chinese patent application No. 202211125555.X discloses a method for recovering platinum and palladium from waste liquid containing trace noble metals, comprising the steps of: regulating the potential of the waste liquid, determining the acidity of the solution by a NaOH titration method, and obtaining the solution to be extracted; extracting the adjusted waste liquid by using a mixed solution of an extracting agent LIX84-I and Solveso150 to obtain an organic phase carrying palladium and iron; washing the organic phase with dilute hydrochloric acid to obtain a palladium-loaded organic phase; back-extracting the palladium-carrying organic phase by using concentrated hydrochloric acid to obtain a palladium-containing solution; extracting the raffinate by using the mixture of tri-n-octylamine and tributyl phosphate to obtain an organic phase carrying platinum and iron; washing the loaded organic phase with dilute hydrochloric acid to obtain a platinum-loaded organic phase; and back-extracting the platinum-carrying organic phase by using thiourea to obtain a platinum-containing solution. The method has simple process, the extractant has higher selectivity on platinum and palladium, and the treated waste liquid can be directly combined into the treatment of a conventional sewage treatment plant, so that the recycling of waste water is realized, and the problem of environmental protection is effectively solved. However, a large amount of solvents and small molecular organic matters are added in the recovery process of the patent, so that the pollution to the environment is easy to cause, the treatment process is complex, and the cost is high.
Therefore, the research and development of the noble metal recovery method with high recovery rate, short recovery flow and simple operation has great significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for recovering noble metals from noble metal waste liquid, which has the advantages of simple operation, high recovery rate, high purity of the recovered noble metals, low residual rate of the noble metals in the noble metal waste liquid and wide application prospect.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for recovering noble metals from noble metal waste liquid, comprising the steps of:
s1, filtering the noble metal waste liquid, and then adjusting the pH value to 5-6 to obtain treated noble metal waste liquid;
s2, adding a modified adsorbent and an auxiliary agent into the treated noble metal waste liquid, stirring for reaction, and filtering, washing and drying after the reaction is finished to obtain an adsorbent adsorbed with noble metal;
s3, ashing the adsorbent with the noble metal adsorbed in the step S2, grinding, washing with dilute hydrochloric acid, and filtering to obtain a solid product;
s4, calcining the solid product in the step S3 in a hydrogen atmosphere to obtain a noble metal mixture;
the preparation method of the modified adsorbent comprises the following steps:
s21, adding the flake graphite into H2O2/H2SO4 solution, stirring and impregnating, and filtering, washing and drying after the impregnation is finished to obtain pretreated flake graphite;
s22, adding the pretreated crystalline flake graphite obtained in the step S21 into an ethanol water solution, carrying out ultrasonic treatment for 8-12 hours, then adding gamma-aminopropyl triethoxysilane and succinic anhydride, carrying out heating reaction, and filtering, washing and drying after the reaction is finished to obtain modified crystalline flake graphite;
s23, adding 2-mercaptopyridine and 1, 5-hexadiene-3, 4-diol into deionized water, and carrying out mercapto-alkene reaction in nitrogen atmosphere to obtain a mixed solution after the reaction is completed; and adding the modified crystalline flake graphite and the phosphoric acid solution in the step S22 into the mixed solution, performing constant-temperature reaction, and filtering, washing and drying after the reaction is finished to obtain the modified adsorbent.
Preferably, the H2O2/H2SO4 solution in the step is formed by mixing 30% of H2O2 and 98% of H2SO4 in mass fraction, the mass ratio of the H2O2 to the H2SO4 is 1:3, and the soaking temperature is 50-60 ℃ for 1-2H.
Preferably, in the step S22, the volume ratio of ethanol to water in the ethanol aqueous solution is 1:1, the mass ratio of the pretreated crystalline flake graphite to the ethanol aqueous solution to the gamma-aminopropyl triethoxysilane to the succinic anhydride is 10-20:500:4-8:3-6, the temperature of the heating reaction is 60-70 ℃, and the reaction time is 3-5h.
Preferably, in step S23, the mass ratio of the 2-mercaptopyridine, the 1, 5-hexadiene-3, 4-diol and the deionized water is 20-40:10-20:320-400; the temperature of the mercapto-alkene reaction is 60-80 ℃ and the reaction time is 2-3h.
Preferably, in the step S23, the mass ratio of the mixed solution to the modified crystalline flake graphite to the phosphoric acid solution is 350-460:10-20:40-70, the mass concentration of the phosphoric acid solution is 20-30%, the temperature of the constant temperature reaction is 70-80 ℃, and the reaction time is 2-3 hours.
Preferably, the auxiliary agent in the step S2 is formed by mixing sodium dodecyl amino propionate and disodium ethylenediamine tetraacetate in a mass ratio of 1:1-2.
Preferably, the volume mass ratio of the noble metal waste liquid, the modified adsorbent and the auxiliary agent after the treatment in the step S2 is 1L:5-10g:1-2g.
Preferably, the temperature of the stirring reaction in the step S2 is 45-60 ℃ and the time is 20-30min.
Preferably, the ashing temperature in step S3 is 600-800 ℃ for 1-2 hours.
Preferably, the calcination temperature in step S4 is 380-420 ℃ and the time is 0.5-1h.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method for recovering noble metals from the noble metal waste liquid, the modified adsorbent and the auxiliary agent are added into the noble metal waste liquid, noble metal ions are adsorbed into the modified adsorbent by utilizing an adsorption method, so that the noble metal recovery time is shortened, the adsorption rate and selectivity of the noble metals are improved, the added auxiliary agent consists of sodium dodecyl amino propionate and disodium ethylenediamine tetraacetate, and the recovery rate of the noble metals is improved together with the modified adsorbent through chelation, so that the method has a certain synergistic effect.
(2) According to the method for recovering noble metals from the noble metal waste liquid, the added modified adsorbent is prepared by acidizing and oxidizing flake graphite serving as a base material, so that the number of oxygen-containing functional groups in the graphite is increased, and then the pretreated flake graphite is subjected to ultrasonic treatment, so that the flake graphite has larger specific surface area and high diffusivity, is beneficial to subsequent reaction, and then reacts with gamma-aminopropyl triethoxysilane and succinic anhydride to obtain carboxylated flake graphite; then, 2-mercaptopyridine and 1, 5-hexadiene-3, 4-diol are subjected to mercapto-ene reaction to obtain an intermediate product containing two pyridine groups, the pyridine groups in the intermediate product are increased by introducing the 2-mercaptopyridine into the 1, 5-hexadiene-3, 4-diol, so that the intermediate product has better selectivity and adsorption rate on noble metals, then, the intermediate product is reacted with modified crystalline flake graphite, and the pyridine groups are introduced into the surface of the crystalline flake graphite through the action of carboxyl and hydroxyl, so that on one hand, a large amount of oxygen-containing groups in the modified crystalline flake graphite promote the combination with noble metal ions through the action of ion exchange, coordination, physical adsorption, electrostatic attraction and the like, the adsorption amount of the adsorbent is improved, and on the other hand, sulfur-containing functional groups in the introduced pyridine groups are good gold chelating ligands, can have strong chemical interactions with Ag (I), pd (II) and Au (III), so that the selective adsorption of the noble metals is improved, and the adsorbent has good acid resistance and interference resistance.
(3) The method for recovering the noble metal from the noble metal waste liquid is simple, and the mixture with higher noble metal content can be obtained by simple ashing, impurity dissolution and reduction treatment of the adsorbent with the noble metal.
Drawings
FIG. 1 is a schematic illustration of the preparation of a modified flake graphite of the present invention;
FIG. 2 is a schematic representation of the preparation of a modified adsorbent of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The noble metal-containing waste liquid refers to waste liquid containing gold, platinum, palladium, rhodium, iridium and other noble metals, which is generated by metal replacement, chemical precipitation, ion exchange, adsorption or electrolysis methods in the noble metal refining process; the flake graphite is purchased from tourmaline mineral products limited company of Shijia, and is aimed at 325 meshes.
Example 1
A method for recovering noble metals from a noble metal waste stream, comprising the steps of:
s1, filtering the noble metal waste liquid, and then adjusting the pH value to 6 by using hydrochloric acid with the mass fraction of 5% to obtain treated noble metal waste liquid;
s2, adding 80g of modified adsorbent and 15g of auxiliary agent into 10L of treated noble metal waste liquid, stirring and reacting for 25min at 50 ℃, and filtering, washing and drying after the reaction is finished to obtain the adsorbent adsorbed with noble metal;
s3, ashing the adsorbent with the noble metal adsorbed in the step S2 at 700 ℃ for 1.5 hours, washing with 5% of dilute hydrochloric acid by mass fraction after grinding, and filtering to obtain a solid product;
s4, calcining the solid product in the step S3 in a hydrogen atmosphere at the temperature of 400 ℃ for 1h to obtain a noble metal mixture;
the preparation method of the modified adsorbent comprises the following steps:
s21, adding 50g of flake graphite into 800mL of H2O2/H2SO4 solution (30 wt% H2O2 and 98wt% H2SO4 with the mass ratio of 1:3), stirring and soaking at 55 ℃ for 1.5H, and filtering, washing and drying after soaking to obtain pretreated flake graphite;
s22, adding 15g of the pretreated crystalline flake graphite in the step S21 into 500mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), carrying out ultrasonic treatment for 10h, then adding 6g of gamma-aminopropyl triethoxysilane and 5g of succinic anhydride, heating and reacting in a nitrogen atmosphere at the temperature of 65 ℃ for 4h, and filtering, washing and drying after the reaction is completed to obtain the modified crystalline flake graphite;
s23, adding 30g of 2-mercaptopyridine and 15g of 1, 5-hexadiene-3, 4-diol into 360g of deionized water, and carrying out mercapto-alkene reaction under the atmosphere of nitrogen at the temperature of 70 ℃ for 2.5h to obtain a mixed solution after the reaction is completed; and then adding 15g of modified crystalline flake graphite and 60g of phosphoric acid solution with mass concentration of 25% in the step S22 into 400g of mixed solution, carrying out constant-temperature reaction at 75 ℃ for 2.5h, and filtering, washing and drying after the reaction is completed to obtain the modified adsorbent.
Wherein, the auxiliary agent in the step S2 is formed by mixing sodium dodecyl amino propionate and disodium ethylenediamine tetraacetate with the mass ratio of 1:1.5.
Example 2
A method for recovering noble metals from a noble metal waste stream, comprising the steps of:
s1, filtering the noble metal waste liquid, and then adjusting the pH value to 5 by using hydrochloric acid with the mass fraction of 5% to obtain treated noble metal waste liquid;
s2, adding 80g of modified adsorbent and 15g of auxiliary agent into 10L of treated noble metal waste liquid, stirring at 60 ℃ for reaction for 20min, and filtering, washing and drying after the reaction is finished to obtain the adsorbent adsorbed with noble metal;
s3, ashing the adsorbent with the noble metal adsorbed in the step S2 at 600 ℃ for 2 hours, washing with 5% of dilute hydrochloric acid by mass fraction after grinding, and filtering to obtain a solid product;
s4, calcining the solid product in the step S3 in a hydrogen atmosphere at 380 ℃ for 1h to obtain a noble metal mixture;
the preparation method of the modified adsorbent comprises the following steps:
s21, adding 50g of flake graphite into 800mL of H2O2/H2SO4 solution (30 wt% H2O2 and 98wt% H2SO4 with the mass ratio of 1:3), stirring and soaking at 50 ℃ for 2 hours, and filtering, washing and drying after soaking to obtain pretreated flake graphite;
s22, adding 10g of the pretreated crystalline flake graphite in the step S21 into 500mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), carrying out ultrasonic treatment for 8h, then adding 4g of gamma-aminopropyl triethoxysilane and 3g of succinic anhydride, heating and reacting in a nitrogen atmosphere at the temperature of 60 ℃ for 5h, and filtering, washing and drying after the reaction is completed to obtain the modified crystalline flake graphite;
s23, adding 20g of 2-mercaptopyridine and 10g of 1, 5-hexadiene-3, 4-diol into 320g of deionized water, and carrying out mercapto-alkene reaction at a temperature of 60 ℃ for 3 hours under a nitrogen atmosphere to obtain a mixed solution after the reaction is completed; and then adding 10g of modified crystalline flake graphite in the step S22 and 40g of phosphoric acid solution with the mass concentration of 30% into 350g of mixed solution, carrying out constant-temperature reaction at 70 ℃ for 3 hours, and filtering, washing and drying after the reaction is completed to obtain the modified adsorbent.
Wherein, the auxiliary agent in the step S2 is formed by mixing sodium dodecyl amino propionate and disodium ethylenediamine tetraacetate with the mass ratio of 1:1.
Example 3
A method for recovering noble metals from a noble metal waste stream, comprising the steps of:
s1, filtering the noble metal waste liquid, and then adjusting the pH value to 5 by using hydrochloric acid with the mass fraction of 5% to obtain treated noble metal waste liquid;
s2, adding 80g of modified adsorbent and 15g of auxiliary agent into 10L of treated noble metal waste liquid, stirring at 45 ℃ for reaction for 30min, and filtering, washing and drying after the reaction is finished to obtain the adsorbent adsorbed with noble metal;
s3, ashing the adsorbent with the noble metal adsorbed in the step S2 at 800 ℃ for 1h, washing with 5% of dilute hydrochloric acid by mass fraction after grinding, and filtering to obtain a solid product;
s4, calcining the solid product in the step S3 in a hydrogen atmosphere at the temperature of 420 ℃ for 0.5h to obtain a noble metal mixture;
the preparation method of the modified adsorbent comprises the following steps:
s21, adding 50g of flake graphite into 800mL of H2O2/H2SO4 solution (30 wt% H2O2 and 98wt% H2SO4 with the mass ratio of 1:3), stirring and soaking at 60 ℃ for 1H, and filtering, washing and drying after soaking to obtain pretreated flake graphite;
s22, adding 20g of the pretreated crystalline flake graphite in the step S21 into 500mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), carrying out ultrasonic treatment for 12h, then adding 8g of gamma-aminopropyl triethoxysilane and 6g of succinic anhydride, heating and reacting in a nitrogen atmosphere at the temperature of 70 ℃ for 3h, and filtering, washing and drying after the reaction is completed to obtain the modified crystalline flake graphite;
s23, adding 40g of 2-mercaptopyridine and 20g of 1, 5-hexadiene-3, 4-diol into 400g of deionized water, and carrying out mercapto-alkene reaction under the nitrogen atmosphere at the temperature of 60-80 ℃ for 2-3 hours to obtain a mixed solution after the reaction is completed; and then adding 20g of modified crystalline flake graphite in the step S22 and 70g of phosphoric acid solution with the mass concentration of 20% into 460g of mixed solution, carrying out constant-temperature reaction at 80 ℃ for 2 hours, and filtering, washing and drying after the reaction is completed to obtain the modified adsorbent.
Wherein, the auxiliary agent in the step S2 is formed by mixing sodium dodecyl amino propionate and disodium ethylenediamine tetraacetate with the mass ratio of 1:2.
Comparative example 1
A method for recovering noble metals from a noble metal waste stream, comprising the steps of:
s1, filtering the noble metal waste liquid, and then adjusting the pH value to 6 by using hydrochloric acid with the mass fraction of 5% to obtain treated noble metal waste liquid;
s2, adding 80g of modified adsorbent and 15g of auxiliary agent into 10L of treated noble metal waste liquid, stirring and reacting for 25min at 50 ℃, and filtering, washing and drying after the reaction is finished to obtain the adsorbent adsorbed with noble metal;
s3, ashing the adsorbent with the noble metal adsorbed in the step S2 at 700 ℃ for 1.5 hours, washing with 5% of dilute hydrochloric acid by mass fraction after grinding, and filtering to obtain a solid product;
s4, calcining the solid product in the step S3 in a hydrogen atmosphere at the temperature of 400 ℃ for 1h to obtain a noble metal mixture;
the preparation method of the modified adsorbent comprises the following steps:
s21, adding 50g of flake graphite into 800mL of H2O2/H2SO4 solution (30 wt% H2O2 and 98wt% H2SO4 with the mass ratio of 1:3), stirring and soaking at 55 ℃ for 1.5H, and filtering, washing and drying after soaking to obtain pretreated flake graphite;
s22, adding 30g of 2-mercaptopyridine into 360g of deionized water, then adding 15g of pretreated crystalline flake graphite and 60g of phosphoric acid solution with mass concentration of 25% in the step S21, carrying out constant-temperature reaction at 75 ℃ for 2.5h, and filtering, washing and drying after the reaction is completed to obtain the modified adsorbent.
Wherein, the auxiliary agent in the step S2 is formed by mixing sodium dodecyl amino propionate and disodium ethylenediamine tetraacetate with the mass ratio of 1:1.5.
Comparative example 2
A method for recovering noble metals from a noble metal waste stream, comprising the steps of:
s1, filtering the noble metal waste liquid, and then adjusting the pH value to 6 by using hydrochloric acid with the mass fraction of 5% to obtain treated noble metal waste liquid;
s2, adding 80g of modified adsorbent into 10L of treated noble metal waste liquid, stirring and reacting for 25min at 50 ℃, and filtering, washing and drying after the reaction is finished to obtain the adsorbent adsorbed with noble metal;
s3, ashing the adsorbent with the noble metal adsorbed in the step S2 at 700 ℃ for 1.5 hours, washing with 5% of dilute hydrochloric acid by mass fraction after grinding, and filtering to obtain a solid product;
s4, calcining the solid product in the step S3 in a hydrogen atmosphere at the temperature of 400 ℃ for 1h to obtain a noble metal mixture;
the preparation method of the modified adsorbent comprises the following steps:
s21, adding 50g of flake graphite into 800mL of H2O2/H2SO4 solution (30 wt% H2O2 and 98wt% H2SO4 with the mass ratio of 1:3), stirring and soaking at 55 ℃ for 1.5H, and filtering, washing and drying after soaking to obtain pretreated flake graphite;
s22, adding 15g of the pretreated crystalline flake graphite in the step S21 into 500mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), carrying out ultrasonic treatment for 10h, then adding 6g of gamma-aminopropyl triethoxysilane and 5g of succinic anhydride, heating and reacting in a nitrogen atmosphere at the temperature of 65 ℃ for 4h, and filtering, washing and drying after the reaction is completed to obtain the modified crystalline flake graphite;
s23, adding 30g of 2-mercaptopyridine and 15g of 1, 5-hexadiene-3, 4-diol into 360g of deionized water, and carrying out mercapto-alkene reaction under the atmosphere of nitrogen at the temperature of 70 ℃ for 2.5h to obtain a mixed solution after the reaction is completed; and then adding 15g of modified crystalline flake graphite and 60g of phosphoric acid solution with mass concentration of 25% in the step S22 into 400g of mixed solution, carrying out constant-temperature reaction at 75 ℃ for 2.5h, and filtering, washing and drying after the reaction is completed to obtain the modified adsorbent.
The concentrations of Pd (II), au (III) and Ag (I) in the noble metal waste solutions after the adsorption in examples 1-3 and comparative examples 1-2 were measured, respectively, and the recovery rate of each noble metal ion was calculated by measuring the concentration of Pd (II) in the noble metal waste solution before the treatment to be 5.8mg/L, au (III) and the concentration of Pd (I) to be 10.7mg/L, ag (I) to be 15.3 mg/L. The test results are shown in Table 1 below:
TABLE 1
As can be seen from the above Table 1, the recovery method of the invention has good recovery effect on the noble metal waste liquid with extremely low noble metal content, has high recovery rate, has good application prospect on the recovery rate of Pd (II), au (III) and Ag (I) which are all above 97%.
The noble metal mixtures obtained in example 1 and comparative examples 1 to 2 were weighed and content-tested, and the data obtained are shown in Table 2 below:
TABLE 2
As can be seen from Table 2, the noble metal mixture obtained by the method has high purity and high recovery rate of noble metal, fully recovers the resources in the noble metal waste liquid, and has wide prospect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for recovering noble metals from a noble metal waste stream, comprising the steps of:
s1, filtering the noble metal waste liquid, and then adjusting the pH value to 5-6 to obtain treated noble metal waste liquid;
s2, adding a modified adsorbent and an auxiliary agent into the treated noble metal waste liquid, stirring for reaction, and filtering, washing and drying after the reaction is finished to obtain an adsorbent adsorbed with noble metal;
s3, ashing the adsorbent with the noble metal adsorbed in the step S2, grinding, washing with dilute hydrochloric acid, and filtering to obtain a solid product;
s4, calcining the solid product in the step S3 in a hydrogen atmosphere to obtain a noble metal mixture;
the preparation method of the modified adsorbent comprises the following steps:
s21, adding the flake graphite into H2O2/H2SO4 solution, stirring and impregnating, and filtering, washing and drying after the impregnation is finished to obtain pretreated flake graphite;
s22, adding the pretreated crystalline flake graphite obtained in the step S21 into an ethanol water solution, carrying out ultrasonic treatment for 8-12 hours, then adding gamma-aminopropyl triethoxysilane and succinic anhydride, carrying out heating reaction, and filtering, washing and drying after the reaction is finished to obtain modified crystalline flake graphite;
s23, adding 2-mercaptopyridine and 1, 5-hexadiene-3, 4-diol into deionized water, and carrying out mercapto-alkene reaction in nitrogen atmosphere to obtain a mixed solution after the reaction is completed; and adding the modified crystalline flake graphite and the phosphoric acid solution in the step S22 into the mixed solution, performing constant-temperature reaction, and filtering, washing and drying after the reaction is finished to obtain the modified adsorbent.
2. The method according to claim 1, wherein the H2O2/H2SO4 solution is prepared by mixing 30% by mass of H2O2 and 98% by mass of H2SO4, the mass ratio of the H2O2 to the H2SO4 is 1:3, and the soaking temperature is 50-60 ℃ for 1-2H.
3. The method according to claim 1, wherein the volume ratio of ethanol to water in the aqueous ethanol solution in step S22 is 1:1, the mass ratio of the pretreated crystalline flake graphite, the aqueous ethanol solution, the gamma-aminopropyl triethoxysilane and the succinic anhydride is 10-20:500:4-8:3-6, the temperature of the heating reaction is 60-70 ℃, and the reaction time is 3-5h.
4. The method according to claim 1, wherein the mass ratio of the 2-mercaptopyridine, the 1, 5-hexadiene-3, 4-diol, and the deionized water in the step S23 is 20-40:10-20:320-400; the temperature of the mercapto-alkene reaction is 60-80 ℃ and the reaction time is 2-3h.
5. The method according to claim 1, wherein the mass ratio of the mixed solution, the modified crystalline flake graphite and the phosphoric acid solution in the step S23 is 350-460:10-20:40-70, the mass concentration of the phosphoric acid solution is 20-30%, the temperature of the constant temperature reaction is 70-80 ℃, and the reaction time is 2-3 hours.
6. The method according to claim 1, wherein the auxiliary agent in the step S2 is formed by mixing sodium dodecyl aminopropionate and disodium ethylenediamine tetraacetate in a mass ratio of 1:1-2.
7. The method according to claim 1, wherein the volume-to-mass ratio of the treated noble metal waste liquid, the modified adsorbent and the auxiliary agent in the step S2 is 1l:5-10g:1-2g.
8. The method according to claim 1, wherein the temperature of the stirring reaction in step S2 is 45-60 ℃ for 20-30min.
9. The method according to claim 1, wherein the ashing temperature in step S3 is 600 to 800 ℃ for 1 to 2 hours.
10. The method according to claim 1, wherein the calcination temperature in step S4 is 380-420 ℃ for 0.5-1h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107583627A (en) * | 2017-08-31 | 2018-01-16 | 同济大学 | A kind of Au nano particles/graphene oxide composite material and its preparation method and application |
| US20190099737A1 (en) * | 2016-03-28 | 2019-04-04 | Tda Research, Inc. | Carbon sorbent for removal of metal catalysts from pharmaceuticals |
| CN111910082A (en) * | 2020-08-31 | 2020-11-10 | 武汉北湖云峰环保科技有限公司 | Method for recovering noble metal from strong acid waste liquid |
| CN116179864A (en) * | 2022-09-18 | 2023-05-30 | 浙江遂昌汇金有色金属有限公司 | Method for sectionally recovering noble metal from noble metal-containing waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20190099737A1 (en) * | 2016-03-28 | 2019-04-04 | Tda Research, Inc. | Carbon sorbent for removal of metal catalysts from pharmaceuticals |
| CN107583627A (en) * | 2017-08-31 | 2018-01-16 | 同济大学 | A kind of Au nano particles/graphene oxide composite material and its preparation method and application |
| CN111910082A (en) * | 2020-08-31 | 2020-11-10 | 武汉北湖云峰环保科技有限公司 | Method for recovering noble metal from strong acid waste liquid |
| CN116179864A (en) * | 2022-09-18 | 2023-05-30 | 浙江遂昌汇金有色金属有限公司 | Method for sectionally recovering noble metal from noble metal-containing waste liquid |
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