CN115404350A - Method for recovering gold by using nitrogen-containing basic group compound modified adsorption resin - Google Patents
Method for recovering gold by using nitrogen-containing basic group compound modified adsorption resin Download PDFInfo
- Publication number
- CN115404350A CN115404350A CN202210966312.2A CN202210966312A CN115404350A CN 115404350 A CN115404350 A CN 115404350A CN 202210966312 A CN202210966312 A CN 202210966312A CN 115404350 A CN115404350 A CN 115404350A
- Authority
- CN
- China
- Prior art keywords
- gold
- adsorption
- compound
- resin
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 132
- 229920005989 resin Polymers 0.000 title claims abstract description 132
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 131
- 239000010931 gold Substances 0.000 title claims abstract description 130
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 113
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 103
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 31
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims abstract description 61
- -1 nitrogen-containing basic compound Chemical class 0.000 claims abstract description 45
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 7
- OPTASPLRGRRNAP-UHFFFAOYSA-N cytosine Chemical compound NC=1C=CNC(=O)N=1 OPTASPLRGRRNAP-UHFFFAOYSA-N 0.000 claims description 40
- 238000011084 recovery Methods 0.000 claims description 24
- 229940104302 cytosine Drugs 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 239000003463 adsorbent Substances 0.000 claims description 22
- FDGQSTZJBFJUBT-UHFFFAOYSA-N hypoxanthine Chemical compound O=C1NC=NC2=C1NC=N2 FDGQSTZJBFJUBT-UHFFFAOYSA-N 0.000 claims description 22
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000004729 solvothermal method Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 claims description 12
- UGQMRVRMYYASKQ-UHFFFAOYSA-N Hypoxanthine nucleoside Natural products OC1C(O)C(CO)OC1N1C(NC=NC2=O)=C2N=C1 UGQMRVRMYYASKQ-UHFFFAOYSA-N 0.000 claims description 11
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 10
- 229930024421 Adenine Natural products 0.000 claims description 10
- 229960000643 adenine Drugs 0.000 claims description 10
- 229940075420 xanthine Drugs 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010894 electron beam technology Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000007142 ring opening reaction Methods 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 238000005658 halogenation reaction Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- GLVAUDGFNGKCSF-UHFFFAOYSA-N mercaptopurine Chemical compound S=C1NC=NC2=C1NC=N2 GLVAUDGFNGKCSF-UHFFFAOYSA-N 0.000 claims description 6
- 229940113082 thymine Drugs 0.000 claims description 6
- 229940035893 uracil Drugs 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 230000005865 ionizing radiation Effects 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 229920000307 polymer substrate Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- SMADWRYCYBUIKH-UHFFFAOYSA-N 2-methyl-7h-purin-6-amine Chemical compound CC1=NC(N)=C2NC=NC2=N1 SMADWRYCYBUIKH-UHFFFAOYSA-N 0.000 claims description 3
- LRSASMSXMSNRBT-UHFFFAOYSA-N 5-methylcytosine Chemical compound CC1=CNC(=O)N=C1N LRSASMSXMSNRBT-UHFFFAOYSA-N 0.000 claims description 3
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229960001428 mercaptopurine Drugs 0.000 claims description 3
- HPZMWTNATZPBIH-UHFFFAOYSA-N methyl adenine Natural products CN1C=NC2=NC=NC2=C1N HPZMWTNATZPBIH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims 1
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 36
- 238000002474 experimental method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003230 pyrimidines Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003212 purines Chemical class 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- LDHYTBAFXANWKM-UHFFFAOYSA-N 2-amino-3,7-dihydropurin-6-one Chemical compound O=C1NC(N)=NC2=C1NC=N2.O=C1NC(N)=NC2=C1N=CN2 LDHYTBAFXANWKM-UHFFFAOYSA-N 0.000 description 1
- DAUXLKFOFAZKPU-UHFFFAOYSA-N 3,7-dihydropurin-6-one Chemical compound OC1=NC=NC2=C1NC=N2.O=C1NC=NC2=C1NC=N2 DAUXLKFOFAZKPU-UHFFFAOYSA-N 0.000 description 1
- KJHJAABRDASKAF-UHFFFAOYSA-N 3,7-dihydropurine-2,6-dione Chemical compound OC1=NC(O)=C2N=CNC2=N1.O=C1NC(=O)NC2=C1NC=N2 KJHJAABRDASKAF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229940083251 peripheral vasodilators purine derivative Drugs 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of hydrometallurgy, and discloses a method for recovering gold by using adsorption resin modified by nitrogenous base compounds, wherein the adsorption resin has a chemical structure shown as a formula 1 or a formula 2, and R is a group corresponding to the nitrogenous base compounds; the nitrogen-containing basic compound is purine compound or pyrimidine compound. According to the invention, the detailed composition and structure of the adsorption resin are improved, so that the nitrogen-containing basic group compound modified adsorption resin is obtained, and the surface of the adsorption resin has a plurality of binding sites for acting with Au (III), so that the gold can be efficiently adsorbed.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for recovering gold by using adsorption resin modified by nitrogenous base compounds, which can recover gold from a gold-containing solution.
Background
Gold (Au) plays a key role in the fields of medical care, aerospace, electronic equipment and the like due to its unique physical and chemical properties. With the rapid development of the world's economy, large amounts of gold-containing waste are released into aquatic ecosystems through human activities. The gold-containing waste not only threatens the environment and human bodies, but also wastes gold resources. In addition, the gold content in the ore is lower than the gold content in the discharged waste. Therefore, further recovery of gold from gold-containing waste is crucial to cope with the ever-increasing gold demand.
In order to overcome the above problems, many techniques have been developed for removing and recovering gold from wastes, such as membrane separation, precipitation, adsorption, ion exchange, and solvent extraction. In these methods, solvent extraction has a low extraction rate, and stripping is difficult. The two recovery methods of ion exchange and membrane separation are complex, high in cost and limited in application range. The recovery process of the coprecipitation technology is relatively complex and can bring secondary pollution to the environment. In contrast to these methods, the adsorption method is considered to be a preferred method for recovering gold because of its advantages such as excellent adsorption efficiency, environmental efficiency, easy operation, and high practicability. The most critical of the adsorption process is the adsorbent. To date, a number of adsorbents have been developed for the recovery of gold in solution, such as: graphene, natural polymers, two-dimensional layered transition metal carbides or carbonitrides (MXene), metal-organic frameworks, and the like. However, these adsorbents have problems of high cost, environmental hazard, poor selectivity, difficult column experimental packing and weak acting force on metal ions, which limits their practical application. Therefore, the development of a novel adsorbent with good reusability, strong adsorption capacity and high stability is imperative to the recycling of gold in secondary resources.
The inventor of the invention researches earlier to obtain a method for recovering gold by using adsorption resin (see Chinese patent application CN 113278815A), and prepares high-density sulfur-containing nitrogen-containing adsorption resin aiming at gold recovery. But the method has higher preparation cost and is not beneficial to commercial popularization and application. The research and development of a new process with low cost has practical significance.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention provides a method for recovering gold by using an adsorption resin modified by a nitrogenous base compound, wherein the adsorption resin modified by a nitrogenous base compound is obtained by improving the detailed composition and structure of the adsorption resin, and the surface of the adsorption resin modified by a nitrogenous base compound has a plurality of binding sites (for example, a plurality of nitrogen-containing functional groups such as-NH, C-N and C = N) for acting with Au (III), and on the one hand, the adsorption resin can be subjected to ion exchange with metal ions; on the other hand, the metal ions can be coordinated through the synergistic effect of the functional groups, so that the high-efficiency adsorption of gold is realized. In addition, the invention can selectively adsorb gold, has low cost and is very favorable for the popularization and application of the adsorption resin.
In order to achieve the above object, according to one aspect of the present invention, there is provided a nitrogen-containing basic group compound-modified adsorbent resin for gold recovery, wherein the adsorbent resin has a chemical structure represented by formula 1 or formula 2 below:
wherein, the R group is a group corresponding to a nitrogenous basic compound; the nitrogenous basic compound is a purine compound or a pyrimidine compound;
As a further preferred aspect of the present invention, the polymer substrate is selected from: cellulose and its derivatives, chitosan and its derivatives, polyethylene, polypropylene, polystyrene-divinylbenzene type copolymer, ethylene-vinyl alcohol copolymer;
the purine compound is any one of guanine, xanthine, hypoxanthine, adenine, 2,6,8-trioxypurine, methyladenine, 6-mercaptopurine and derivatives thereof;
the pyrimidine compound is any one of cytosine, uracil, thymine, 5-methyl-cytosine, 5-cytosine formyl and derivatives thereof.
In a further preferred embodiment of the present invention, the nitrogen-containing basic compound is any one of guanine, xanthine, hypoxanthine, adenine, cytosine, uracil and thymine.
In a further preferred embodiment of the present invention, the adsorbent resin is in the form of a sphere, a fiber or a film; preferably, the adsorbent resin is spherical, and the spherical resin has an average particle diameter of 100 to 1500 μm.
According to another aspect of the present invention, there is provided the above-mentioned method for producing an adsorption resin modified with a nitrogen-containing basic group compound for gold recovery, which comprises grafting an unsaturated monomer containing an epoxy group or a halogen onto the surface of a polymer base, and introducing the nitrogen-containing basic group compound further onto the surface of the polymer base by an epoxy ring-opening or halogenation reaction, thereby obtaining the adsorption resin modified with a nitrogen-containing basic group compound for gold recovery.
As a further preferred aspect of the present invention, the unsaturated monomer containing an epoxy group or a halogen is specifically Glycidyl Methacrylate (GMA), allyl alcohol glycidyl ether or chlorostyrene;
the grafting is specifically ionizing radiation grafting or chemical grafting;
preferably, the ionizing radiation grafting is electron beam pre-irradiation grafting; the irradiation dose adopted by the electron beam pre-irradiation grafting is more preferably 10-100 kGy;
the chemical grafting is performed by using an initiator; the initiator is preferably an organic peroxide or an azo initiator, wherein the organic peroxide is preferably cyclohexanone peroxide, dibenzoyl peroxide or tert-butyl hydroperoxide; the azo initiator is preferably azobisisobutyronitrile or azobisisoheptonitrile.
In a further preferred embodiment of the present invention, the polymer base material is in a spherical shape, a fibrous shape, or a film shape; correspondingly, the obtained adsorbent resin is also spherical, fibrous or film-shaped.
In a further preferred aspect of the present invention, the introduction of the nitrogen-containing basic group-containing compound onto the surface of the polymer base material by an epoxy ring-opening or halogenation reaction is specifically carried out by a solvothermal reaction; the solvent adopted by the solvothermal reaction is dimethyl sulfoxide, toluene, ethylene glycol or N, N-dimethylformamide, and the reaction temperature of the solvothermal reaction is 80-140 ℃; preferably, the mass fraction of the nitrogen-containing basic compound in the reaction precursor liquid is 0.1 to 5wt%.
According to still another aspect of the present invention, there is provided a method for gold recovery using an adsorption resin modified with a nitrogenous basic group-based compound for gold recovery, the method comprising the steps of:
(1) Adding the adsorption resin modified by the nitrogenous base compound for recovering gold into a solution containing gold ions, and adsorbing the gold ions in the adsorption resin; or flowing a solution containing gold ions into an adsorption column loaded with the adsorption resin modified by the nitrogenous base compound for recovering gold through a peristaltic pump so as to adsorb the gold ions in the solution;
(2) After adsorption, eluting, concentrating, separating and regenerating gold loaded on the adsorption resin obtained by the treatment in the step (1) by using an eluent, and recovering the gold; or, after adsorption, calcining the adsorption resin obtained by the treatment in the step (1), and recovering to obtain the gold simple substance.
In a further preferred aspect of the present invention, in the step (2), the eluting solution is a hydrochloric acid solution of 0.05 to 5mol/L, or a mixture of hydrochloric acid and thiourea of which final concentration of hydrochloric acid is 0.05 to 3mol/L and final concentration of thiourea is 0.05 to 0.5 mol/L.
Compared with the prior art, the technical scheme provided by the invention has the advantages that the nitrogen-containing basic compound modified group (namely, purine compound group or pyrimidine compound group) is introduced into the surface of the high polymer base material, so that the obtained adsorption resin has stronger acting force on hardware as a whole, and has excellent gold selectivity and reusability. Based on the soft and hard acid-base rules, the nitrogen-containing functional monomer can form a stable complex with Au (III). Purines such as guanine, xanthine, hypoxanthine and adenine and derivatives thereof, pyrimidines such as cytosine, uracil and thymine and derivatives thereof, which contain a pyridine ring and an azole ring and have multiple binding sites for Au (III), for example: -NH, C-N and C = N. Therefore, the purine and pyrimidine functionalized adsorbent is expected to realize high selectivity and high adsorption capacity adsorption of Au (III). In addition, purine, pyrimidine and derivatives thereof only contain C, H, N and O element, are environment-friendly, and can be recycled to obtain simple substance gold by means of calcination. However, purine and pyrimidine and their derivatives have low solubility in various solvents, which limits their applications. The novel technology for immobilizing the purine, the pyrimidine and the derivatives thereof is developed, the purine, the pyrimidine and the derivatives thereof are immobilized on a base material, and the adsorption resin modified by the nitrogenous base compound with a plurality of N active sites on the surface is designed and has important significance for recovering gold.
On one hand, purine, pyrimidine and derivatives thereof have low solubility and are difficult to immobilize, and on the other hand, cellulose derivatives, polystyrene and other high polymer base materials lack active sites; the invention comprehensively utilizes the 2 materials, makes good use of the advantages and avoids the disadvantages, prepares the nitrogen-containing basic group compound modified adsorption resin with a plurality of N active sites on the surface, and can be particularly used for recovering gold. According to the invention, the nitrogenous base compounds are immobilized on the base material by a solvothermal method, so that the adsorption performance of the material is improved, and the application range of the nitrogenous base compounds is widened. The invention has simple operation and low cost; the adsorbent is not only suitable for enriching low-concentration gold in the environment, but also has strong regenerability, can be filled in an adsorption column for use, and is suitable for large-scale gold recovery in industry.
The invention has the characteristic of low cost, and takes the previous research of the inventor of the invention to obtain a high-density sulfur-containing nitrogen-containing adsorption resin aiming at the recovery of gold as a reference object for comparison (the previous research can be specifically seen in Chinese patent application CN113278815A, the name of the invention is a method for recovering gold by utilizing the adsorption resin), and the invention can use a solvothermal method to immobilize purine, purine derivatives, pyrimidine and derivatives thereof which can be extracted from organisms onto a base material. Compared with the traditional chemical reagent, the compound is more environment-friendly. The prepared adsorption resin has lower cost (Table 1), and simple substance gold can be directly obtained by calcination.
TABLE 1 comparison of the cost of nitrogen-containing base-based adsorption resin with high-density sulfur-containing nitrogen-containing gold-adsorbing resin
Note: N-CM in the table represents a pentaethylenehexamine modified cellulose-based adsorbent material; NS-CM is the adsorbing material obtained by further modifying N-CM with ethylene sulfide.
Specifically, the present invention can achieve the following advantageous effects:
(1) The material of the invention has simple preparation, cheap and easily obtained raw materials and environment-friendly preparation process.
(2) The adsorption resin modified by the nitrogenous base compound provided by the invention has stronger acting force on hardware.
(3) The adsorption resin modified by the nitrogenous base compound provided by the invention has excellent selectivity and reusability on hardware.
(4) The particle size of the adsorption resin provided by the invention can be especially 100-1500 mu m, and the industrial adsorption column filling use requirement is met.
(5) The adsorption resin modified by the nitrogenous base compounds has simple and convenient operation on the recovery process of gold, can efficiently and selectively recover gold, and is suitable for industrial popularization.
Usually, the chemical synthesis is carried out under heating reflux, and most of the conventional modifications are carried out under such conditions. The purine and pyrimidine compounds are insoluble or have extremely low solubility (such as dimethyl sulfoxide, toluene, ethylene glycol or N, N-dimethylformamide) in most solvents, the invention utilizes a solvothermal method, the properties of the solvents can be greatly modified under the solvothermal condition, the solubility, the dispersion and the reaction activity of reactants can be improved, the solubility of purine and pyrimidine can be effectively changed, the functional modification of the purine and pyrimidine compounds to a base material can be successfully realized, and the adsorption performance of metal ions can be further improved.
Drawings
FIG. 1 is a scheme showing the synthesis of guanine-functionalized resins.
FIG. 2 is a scheme showing the synthesis of a xanthine functionalized resin.
FIG. 3 is a scheme showing the synthesis of hypoxanthine functionalized resins.
FIG. 4 is a scheme showing the synthesis of adenine functionalized resins.
FIG. 5 is a scheme showing the synthesis of cytosine functionalized resins.
FIG. 6 is a graph showing the results of experiments on gold adsorption pH by purine resins.
FIG. 7 is a graph showing the results of experiments on the recycling of gold by purine resins.
FIG. 8 is a graph showing the results of a dynamic adsorption experiment of gold to a purine resin (the abscissa BV in the figure, which represents the ratio of the amount of sample to the volume of the adsorption column).
FIG. 9 is a graph showing the adsorption result of purine resin to low-concentration gold in slag.
FIG. 10 is a graph showing the results of pH adsorption experiments on gold with cytosine functionalized resin.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
According to the present invention, purine and derivatives thereof, pyrimidine and derivatives thereof can be used as nitrogen-containing basic compounds to modify the surface of a polymer substrate, thereby obtaining an adsorption resin (i.e., nitrogen-containing basic compound-modified adsorption resin) that can be used for gold recovery; the purine and its derivatives may be, for example, guanine, xanthine, hypoxanthine, adenine, 2,6,8-trioxypurine, methyladenine, 6-mercaptopurine, and other purines and their derivatives; pyrimidines and derivatives thereof, such as cytosine, uracil, thymine, 5-methyl-cytosine, and 5-cytosine formyl. For example:
in the specific preparation, an unsaturated monomer containing an epoxy group or halogen is grafted to the surface of the polymer base material, and then a nitrogenous base compound is further introduced to the surface of the polymer base material through an epoxy ring-opening or halogenation reaction, so as to obtain the nitrogenous base compound modified adsorption resin. Ring opening by an epoxy group (e.g., GMA) corresponds to the formation of a compound of formula 1:
by halogenation, the corresponding compound of formula 2 is obtained:
such as
(of course, in addition to the benzene ring structure, a non-benzene ring structure is also possible);
in the formulas 1 and 2, the R group is a group corresponding to a nitrogenous base compound; the nitrogenous basic compound is a purine compound or a pyrimidine compound;
Wherein, the grafting can adopt ionizing radiation grafting (such as electron beam pre-irradiation grafting method) or chemical grafting. Taking an electron beam pre-irradiation grafting method as an example, glycidyl Methacrylate (GMA) is grafted on the surface of a polymer substrate by using the electron beam pre-irradiation grafting method to introduce an epoxy group, and then a nitrogenous base compound monomer is introduced through a ring-opening reaction to prepare the nitrogen base compound monomer modified adsorption resin.
The nitrogen-containing basic compound is further introduced to the surface of the polymer base material by an epoxy ring-opening or halogenation reaction, and for example, an epoxy intermediate and nitrogen-containing basic compounds having different mass fractions are subjected to a solvothermal reaction at a certain temperature. Solvents for the nitrogenous base-based compounds of different mass fractions may be, for example, dimethyl sulfoxide, toluene, ethylene glycol and N, N-dimethylformamide; the mass fraction of the nitrogen-containing basic compound may be, for example, 0.1 to 5wt%; the temperature of the solvothermal reaction may be, for example, 80 to 140 ℃.
In addition, the polymer base material can adopt raw materials with different shapes according to actual requirements, such as a spherical shape, a fibrous shape or a film shape; the finally obtained nitrogenous base group compound monomer modified adsorption resin will also have a corresponding shape (e.g., spherical, fibrous or film-like). For example, the adsorbent resin may be a spherical material having an average particle size of 100 to 1500 μm so as to fill the column during application.
When the adsorption resin is used, for example, the following steps can be included:
(1) Adding nitrogen-containing basic compound modified adsorption resin into the solution containing the gold ions to adsorb gold; or, the gold-containing solution flows into an adsorption column loaded with nitrogen-containing base compound modified adsorption resin (the adsorption column can be filled with spherical adsorption resin) through a peristaltic pump;
(2) After adsorption, eluting, concentrating, separating and regenerating the gold adsorbed on the resin by using eluent, or calcining the adsorption resin modified by the nitrogenous base compound for adsorbing the gold, and directly recovering the gold simple substance.
The adsorption resin can adsorb gold ions, and in the adsorption process, functional groups on the adsorption resin can reduce gold into Cheng Jin simple substance; therefore, through the final calcination treatment, the adsorption material can be carbonized, only the gold simple substance is reserved, and the recovery of the gold simple substance is realized.
The following are specific examples:
example 1 Synthesis of guanine-functionalized resin
The scheme for the synthesis of guanine-functionalized resins is shown in FIG. 1. 5.00g of microcrystalline cellulose Microspheres (MCC) were vacuum-sealed and passed through a 1MeV electron beam accelerator (irradiation dose rate 10kGy/pass, irradiation dose 10 kGy) with dry ice cooling. Then, the irradiated MCC was put into GMA emulsion (30wt% GMA,3wt% surfactant Tween 20, solvent is water) and reacted in a water bath at 50 ℃ for 2 hours. The product was washed with ethanol and dried under vacuum at 60 ℃ to yield MCC-g-GMA.
35mL of DMSO and 5mL of Triethylamine (TEA) were added to a stainless steel reaction vessel, and 1g of Guanine (Guanine) was added thereto. Then, 1g of MCC-g-GMA was added to the above mixture and placed in an oven at 120 ℃ for reaction for 24 hours. After the reaction is completed, washing with dilute alkali solution (such as sodium hydroxide aqueous solution), ethanol and deionized water in sequence, and vacuum drying at 50 ℃ to obtain the guanine functionalized resin as MCC-G-GMA-G.
Example 2 Synthesis of xanthine functionalized resins
The synthetic scheme of the xanthine functionalized resin is shown in FIG. 2. Following the synthesis procedure of example 1, 1g of MCC-g-GMA was subjected to solvothermal reaction with 35mL of 2.85wt% Xanthine (Xanthine) in DMSO to obtain a Xanthine functionalized resin (MCC-g-GMA-X).
Example 3 Synthesis of hypoxanthine functionalized resins
The synthetic scheme of the hypoxanthine functionalized resin is shown in FIG. 3. Following the synthetic procedure of example 2, 1g of MCC-g-GMA was subjected to solvothermal reaction with 35mL of 2.29wt% Hypoxanthine (Hypoxanthine) in DMSO to give Hypoxanthine functionalized resin (MCC-g-GMA-H).
EXAMPLE 4 Synthesis of adenine-functionalized resin
FIG. 4 shows a scheme for synthesis of adenine-functionalized resins. In accordance with the synthesis method in example 2, 1g of MCC-g-GMA and 35mL of 1.71wt% Adenine (Adenine) in DMSO solution are subjected to solvothermal reaction to obtain Adenine functionalized resin (MCC-g-GMA-A).
Example 5 Synthesis of cytosine functionalized resins
The synthetic scheme for cytosine functionalized resins is shown in FIG. 5. In accordance with the synthetic method of example 2, 1g of MCC-g-GMA was subjected to solvothermal reaction with 35mL of 2.85wt% Cytosine (Cytosine) in DMF to give a Cytosine functionalized resin (MCC-g-GMA-C).
Example 6 adsorption pH test of purine resin on gold
0.01g of an adsorbent resin was weighed and put into 10mL of an aqueous solution containing 100mg/L of gold at 35 ℃ to perform a static adsorption experiment. The gold solution for the adsorption experiment was prepared using chloroauric acid. The pH of the solution was adjusted to 1, 2, 3, 4, 5, 6, respectively, for adsorption experiments. After adsorbing for 24h, the supernatant was filtered off with a filter head, and the residual concentration of gold was measured by ICP-OES, and the adsorption efficiency was calculated.
The pH test of the purine-functionalized resin for gold adsorption is shown in FIG. 6. As can be seen from the figure, at pH 1.0-2.0 or 3.0, the adsorption efficiency of the four purine-functionalized resin to Au (III) increases with the increase of pH. However, the pH was in the range of 2.0 to 6.0, and the adsorption efficiency of guanine-functionalized resin, hypoxanthine-functionalized resin, and adenine-functionalized resin on Au (III) was not affected by the pH. At a pH of 2.0 to 6.0, the efficiency of adsorption of Au (III) by the xanthine-functionalized resin is reduced due to the appearance of chlorohydroxy complexes of gold and the reduction of protonated N. Comparing the adsorption results of the four purine-based adsorption resins on Au (III) at different pH values, it was found that the guanine-functionalized resin, hypoxanthine and adenine-functionalized resins can adsorb Au (III) in a wide pH range, and the optimum pH for adsorbing Au (III) by the xanthine-functionalized resin was 3.
Example 7 experiment for gold reuse by purine resin
0.01g of the adsorbent resin was weighed and charged into 10mL of an aqueous solution containing gold at 35 ℃. After a certain period of adsorption at pH =3, the supernatant was filtered off with a filter head, and the remaining gold concentration was detected with ICP-OES and the recovery rate was calculated. The resin loaded with gold was washed three times with deionized water, and 0.5mol/L of a mixture of HCl and thiourea was added thereto as an eluent to elute. The resin for each adsorption experiment is washed three times by deionized water and then circulated for the next time. This was repeated five times.
The results of the experiment for recycling gold by purine resin are shown in fig. 7. It can be seen from the figure that after five cycles, the adsorption efficiency of MCC-g-GMA-G, MCC-g-GMA-X, MCC-g-GMA-H and MCC-g-GMA-A to Au (III) is not changed basically, which indicates that the four adsorbents have better cyclic regeneration.
Example 8 experiment of dynamic adsorption of purine resin to gold
0.4562G of MCC-G-GMA-G, 0.3525G of MCC-G-GMA-X, 0.3608G of MCC-G-GMA-H and 0.3724G of MCC-G-GMA were weighed, and each was independently packed inbase:Sub>A 1mL glass adsorption column (Φ 5 mm. Times.60 mm) inbase:Sub>A wet state. Preparing simulation liquid of a five-element system, and adjusting the pH to 3 by using 0.1mol/L HCl and NaOH; wherein the concentration of Au (III) in the simulated solution is 20mg/L solution, and the molar ratio of the concentration of coexisting ions of Cu (II), fe (III), zn (II) and Ni (II) to the concentration of Au (III) is 1:1. Peristaltic pump at 0.33mL/min (SV 20 h) -1 ) The simulated liquid is pumped into the adsorption column at a flow rate of (2). And measuring the concentration of each metal ion in the solution at the sample inlet and the sample outlet by utilizing ICP-OES.
The dynamic adsorption test evaluation was performed according to the above test conditions, and the penetration curve of fig. 8 was obtained by sampling analysis. The results show that the purine resin can selectively recover gold. At the beginning of the experiment, several coexisting ions of Cu (II), fe (III), zn (II) and Ni (II) immediately come out of the adsorption column, which shows that the resin has no acting force on the ions. Leakage points of the MCC-g-GMA-G, MCC-g-GMA-X, MCC-g-GMA-H and the MCC-g-GMA-A for adsorbing Au (III) (corresponding to the Au (III) coming out from the adsorption column) respectively occur at 5760BV, 2400BV, 2460BV and 4990BV; when the adsorption saturation is achieved, the adsorption capacity is 292.59mg/g, 169.49mg/g, 160.75mg/g and 303.11mg/g respectively, the adsorption capacity is 57.35%, 55.08%, 45.65% and 65.78% of the static saturation adsorption capacity for 24 hours, and the dynamic adsorption capacity reaches more than 50% of the static adsorption capacity (the adsorption material in the prior art is usually in the order of 20% -30%), which indicates that the functionalized resin has the potential for large-scale industrial gold recovery.
Example 9 static adsorption test of purine resin on low-concentration gold in practical slag leachate
0.01g of the adsorption resin was weighed and placed in 10mL of the slag leachate (pH = 2) at 35 ℃ to perform a static Batch adsorption experiment. After adsorbing for 24h, filtering the supernatant by using a filter head, detecting the concentration of metal ions in the leachate by using ICP-MS and ICP-OES, and calculating the adsorption efficiency.
The above experimental results are shown in fig. 9 and table 2, and the purine resin does not substantially adsorb coexisting ions, and can selectively adsorb 0.39mg/L of gold in the practical leachate, indicating that the purine adsorbent material has potential for industrial practical application.
TABLE 2 concentrations of respective metal ions before and after adsorption by the nitrogen-containing basic adsorption resin
Example 10 adsorption of cytosine functionalized resin to gold pH experiment
In accordance with the adsorption method in example 6, 0.01g of cytosine functionalized resin was weighed and put into 10mL of an aqueous solution containing 100mg/L of gold at 35 ℃ to perform a static adsorption experiment. The pH of the solution was adjusted to 2, 3, 4, 5, respectively, and adsorption experiments were performed. After adsorbing for 24h, the supernatant was filtered off with a filter head, and the residual concentration of gold was measured by ICP-OES, and the adsorption efficiency was calculated.
The pH adsorption experiment of cytosine functionalized resin on gold is shown in FIG. 10. It can be obtained from the figure that the adsorption efficiency of cytosine to gold is above 90% in the studied pH range, which indicates that the functional group of the cytosine functional resin has stronger acting force on gold, and can effectively capture gold.
Example 11 gold reuse experiments with cytosine functionalized resins
In accordance with the adsorption method in example 7, 0.01g of cytosine-functionalized adsorption resin was weighed and charged into 10mL of 10mg/L gold solution containing gold aqueous solution at 35 ℃. After 24h of adsorption, the supernatant was filtered off with a filter head and the remaining gold concentration was determined by ICP-OES. The resin loaded with gold was washed three times with deionized water, and 0.5mol/L of a mixture of HCl and thiourea was added thereto as an eluent to elute. The resin for each adsorption experiment is washed three times by deionized water and then circulated for the next time. This was repeated five times.
Experimental research shows that the adsorption efficiency of the cytosine functionalized resin on gold is kept unchanged after five times of adsorption-desorption cycles, which indicates that the adsorption resin has good recycling performance.
The above examples are only examples, and the purine resin obtained by the method of the invention using other purine raw materials has a comparable gold selective adsorption effect. In addition, the raw materials used in the above examples were all commercially available.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.
Claims (10)
1. An adsorption resin modified by a nitrogenous base compound for gold recovery, the adsorption resin having a chemical structure represented by the following formula 1 or formula 2:
wherein, the R group is a group corresponding to a nitrogenous basic compound; the nitrogenous basic compound is a purine compound or a pyrimidine compound;
2. The nitrogen-containing basic group compound-modified adsorbent resin for gold recovery according to claim 1, wherein the polymeric base material is selected from the group consisting of: cellulose and its derivatives, chitosan and its derivatives, polyethylene, polypropylene, polystyrene-divinylbenzene type copolymer, ethylene-vinyl alcohol copolymer;
the purine compound is any one of guanine, xanthine, hypoxanthine, adenine, 2,6,8-trioxypurine, methyladenine, 6-mercaptopurine and derivatives thereof;
the pyrimidine compound is any one of cytosine, uracil, thymine, 5-methyl-cytosine, 5-cytosine formyl and derivatives thereof.
3. The adsorption resin modified with a nitrogenous base compound for gold recovery according to claim 1, wherein the nitrogenous base compound is any one of guanine, xanthine, hypoxanthine, adenine, cytosine, uracil and thymine.
4. The nitrogen-containing basic group compound-modified adsorbent resin for gold recovery according to claim 1, wherein the adsorbent resin is spherical, fibrous or film-like; preferably, the adsorbent resin is spherical, and the spherical resin has an average particle diameter of 100 to 1500 μm.
5. The method for producing the adsorption resin modified with a nitrogen-containing basic group compound for gold recovery according to any one of claims 1 to 4, wherein the adsorption resin modified with a nitrogen-containing basic group compound for gold recovery is obtained by grafting an unsaturated monomer containing an epoxy group or halogen onto the surface of a polymer base and then introducing a nitrogen-containing basic group compound further onto the surface of the polymer base by an epoxy ring-opening or halogenation reaction.
6. The process according to claim 5, wherein the unsaturated monomer containing an epoxy group or a halogen is Glycidyl Methacrylate (GMA), allyl alcohol glycidyl ether or chlorostyrene;
the grafting is specifically ionizing radiation grafting or chemical grafting;
preferably, the ionizing radiation grafting is electron beam pre-irradiation grafting; the irradiation dose adopted by the electron beam pre-irradiation grafting is more preferably 10-100 kGy;
the chemical grafting is performed by using an initiator; the initiator is preferably an organic peroxide or an azo initiator, wherein the organic peroxide is preferably cyclohexanone peroxide, dibenzoyl peroxide or tert-butyl hydroperoxide; the azo initiator is preferably azobisisobutyronitrile or azobisisoheptonitrile.
7. The production method according to claim 5, wherein the polymer base material is in a spherical shape, a fibrous shape or a film shape; correspondingly, the obtained adsorbent resin is also spherical, fibrous or film-shaped.
8. The method according to claim 5, wherein the introduction of the nitrogen-containing basic group compound is further carried out on the surface of the polymer substrate by an epoxy ring-opening or halogenation reaction, specifically by a solvothermal reaction; the solvent adopted by the solvothermal reaction is dimethyl sulfoxide, toluene, ethylene glycol or N, N-dimethylformamide, and the reaction temperature of the solvothermal reaction is 80-140 ℃; preferably, the mass fraction of the nitrogen-containing basic compound in the reaction precursor liquid is 0.1 to 5wt%.
9. The method for recovering gold according to any one of claims 1 to 4, comprising the steps of:
(1) Adding the adsorption resin modified by the nitrogenous basic group compound for recovering gold according to any one of claims 1 to 4 into a solution containing gold ions, and adsorbing the gold ions; or, the solution containing gold ions is flowed into an adsorption column loaded with the nitrogen-containing basic group compound modified adsorption resin for gold recovery according to any one of claims 1 to 4 through a peristaltic pump, so as to adsorb the gold ions in the solution;
(2) After adsorption, eluting, concentrating, separating and regenerating the gold loaded on the adsorption resin obtained by the treatment in the step (1) by using eluent, and recovering the gold; or, after adsorption, calcining the adsorption resin obtained by the treatment in the step (1), and recovering to obtain the gold simple substance.
10. The method for recovering gold according to claim 9, wherein in the step (2), the leaching solution is a hydrochloric acid solution of 0.05mol/L to 5mol/L, or a mixture of hydrochloric acid and thiourea having a final hydrochloric acid concentration of 0.05mol/L to 3mol/L and a final thiourea concentration of 0.05mol/L to 0.5 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210966312.2A CN115404350B (en) | 2022-08-12 | 2022-08-12 | Method for recovering gold by utilizing adsorption resin modified by nitrogenous base compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210966312.2A CN115404350B (en) | 2022-08-12 | 2022-08-12 | Method for recovering gold by utilizing adsorption resin modified by nitrogenous base compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115404350A true CN115404350A (en) | 2022-11-29 |
| CN115404350B CN115404350B (en) | 2024-06-04 |
Family
ID=84158724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210966312.2A Active CN115404350B (en) | 2022-08-12 | 2022-08-12 | Method for recovering gold by utilizing adsorption resin modified by nitrogenous base compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115404350B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116037076A (en) * | 2022-12-07 | 2023-05-02 | 东华大学 | Efficient selective gold adsorption 1,2, 4-triazole polyelectrolyte adsorbent and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306350A (en) * | 2008-07-10 | 2008-11-19 | 中国科学院化学研究所 | Use of thymine as special mercury ion absorbent |
| CN103804694A (en) * | 2014-01-26 | 2014-05-21 | 华东师范大学 | Polymer gene transfection vector based on nucleic acid base derivative and preparation method and application thereof |
| CN104689802A (en) * | 2015-02-11 | 2015-06-10 | 上海交通大学 | High-selectivity gold adsorption resin material as well as preparation method and application thereof |
| CN104755543A (en) * | 2012-10-30 | 2015-07-01 | 可乐丽股份有限公司 | Porous graft copolymer particles, method for producing same, and adsorbent material using same |
| CN104861130A (en) * | 2015-05-07 | 2015-08-26 | 西北大学 | Polymer brush graft boracic acid affinity separation material and preparation method and application |
| CN106824112A (en) * | 2017-03-06 | 2017-06-13 | 济南大学 | A kind of preparation of 2 mercaptopyrimidine modified magnetic cotton stalk skins adsorbent |
| CN108586648A (en) * | 2018-03-30 | 2018-09-28 | 浙江工商大学 | A kind of chelating resin and its preparation method and application |
| CN111393546A (en) * | 2020-03-31 | 2020-07-10 | 浙江康特生物科技有限公司 | Preparation of chelate resin and application of chelate resin in removing cobalt ions in kit purified water |
| CN113278815A (en) * | 2021-05-26 | 2021-08-20 | 华中科技大学 | Method for recovering gold by using adsorption resin |
| CN113429523A (en) * | 2021-07-09 | 2021-09-24 | 西南石油大学 | Core-shell polymer microsphere and preparation method thereof |
-
2022
- 2022-08-12 CN CN202210966312.2A patent/CN115404350B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306350A (en) * | 2008-07-10 | 2008-11-19 | 中国科学院化学研究所 | Use of thymine as special mercury ion absorbent |
| CN104755543A (en) * | 2012-10-30 | 2015-07-01 | 可乐丽股份有限公司 | Porous graft copolymer particles, method for producing same, and adsorbent material using same |
| CN103804694A (en) * | 2014-01-26 | 2014-05-21 | 华东师范大学 | Polymer gene transfection vector based on nucleic acid base derivative and preparation method and application thereof |
| CN104689802A (en) * | 2015-02-11 | 2015-06-10 | 上海交通大学 | High-selectivity gold adsorption resin material as well as preparation method and application thereof |
| CN104861130A (en) * | 2015-05-07 | 2015-08-26 | 西北大学 | Polymer brush graft boracic acid affinity separation material and preparation method and application |
| CN106824112A (en) * | 2017-03-06 | 2017-06-13 | 济南大学 | A kind of preparation of 2 mercaptopyrimidine modified magnetic cotton stalk skins adsorbent |
| CN108586648A (en) * | 2018-03-30 | 2018-09-28 | 浙江工商大学 | A kind of chelating resin and its preparation method and application |
| CN111393546A (en) * | 2020-03-31 | 2020-07-10 | 浙江康特生物科技有限公司 | Preparation of chelate resin and application of chelate resin in removing cobalt ions in kit purified water |
| CN113278815A (en) * | 2021-05-26 | 2021-08-20 | 华中科技大学 | Method for recovering gold by using adsorption resin |
| CN113429523A (en) * | 2021-07-09 | 2021-09-24 | 西南石油大学 | Core-shell polymer microsphere and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116037076A (en) * | 2022-12-07 | 2023-05-02 | 东华大学 | Efficient selective gold adsorption 1,2, 4-triazole polyelectrolyte adsorbent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115404350B (en) | 2024-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102294231B (en) | Molecularly imprinted fiber material and preparation method thereof | |
| JP5045269B2 (en) | Particulate cellulose-based adsorbent and method for producing the same | |
| CN107469653B (en) | Synthesis method of molecular imprinting composite membrane for enriching and separating norfloxacin | |
| Liao et al. | Comparison of Co2+ adsorption by chitosan and its triethylene-tetramine derivative: performance and mechanism | |
| Sahiner et al. | Highly porous acrylonitrile-based submicron particles for UO22+ absorption in an immunosensor assay | |
| CN101905151A (en) | Preparation method and applications of magnetic metal ion surface imprinted polymer | |
| CN115404350B (en) | Method for recovering gold by utilizing adsorption resin modified by nitrogenous base compounds | |
| CN110923480B (en) | Application of aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium | |
| Kavakli et al. | A highly efficient chelating polymer for the adsorption of uranyl and vanadyl ions at low concentrations | |
| CN102863579B (en) | Barbituric acid chelating resin and preparation method and application thereof | |
| Pengfei et al. | Synthesis of PGMA microspheres with amino groups for high-capacity adsorption of Cr (VI) by cerium initiated graft polymerization | |
| CN113061215B (en) | MOFs-based cobalt ion imprinted polymer and preparation method and application thereof | |
| CN113278815B (en) | Method for recovering gold by using adsorption resin | |
| CN106824124A (en) | A kind of method of nitrogenous porous polymer chelating resin and preparation and treatment uranium-containing waste water | |
| JP2010504377A (en) | Ion exchange resins and methods for their use | |
| Dolak | Ion imprinted affinity Cryogels for the selective adsorption uranium in real samples | |
| CN109319891B (en) | Magnetic nano material, preparation method thereof and application thereof in radioactive element treatment | |
| CN111019147A (en) | Metal organic framework adsorbent, one-step preparation method and application thereof | |
| CN101130171B (en) | Polyalcohol integral separation medium and preparation process thereof | |
| CN108976361B (en) | Preparation method and application of single-hole hollow boron affinity imprinted polymer | |
| CN105854844B (en) | Arteannuic acid magnetic blotting microballoon and its preparation method and application | |
| CN111057863A (en) | Application of environment-friendly precious metal adsorption resin material | |
| CN114225924B (en) | Method for recycling bismuth by using plant polyphenol modified adsorption resin | |
| CN101824117A (en) | Chelate resin immobilized with dendrimer and preparation method thereof | |
| CN108854154B (en) | Peanut shell polyphenol selective enrichment method using magnetic microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |