CN118028631A - Method for recovering manganese from ternary battery waste liquid - Google Patents
Method for recovering manganese from ternary battery waste liquid Download PDFInfo
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- CN118028631A CN118028631A CN202410174458.2A CN202410174458A CN118028631A CN 118028631 A CN118028631 A CN 118028631A CN 202410174458 A CN202410174458 A CN 202410174458A CN 118028631 A CN118028631 A CN 118028631A
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- acid
- treatment
- manganese
- aminosilane
- waste liquid
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- 238000000034 method Methods 0.000 title claims abstract description 77
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 51
- 239000011572 manganese Substances 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000004005 microsphere Substances 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000003480 eluent Substances 0.000 claims abstract description 56
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 53
- 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 claims abstract description 43
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 33
- -1 aminosilane modified silica Chemical class 0.000 claims abstract description 31
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 238000011049 filling Methods 0.000 claims abstract description 16
- 238000004440 column chromatography Methods 0.000 claims abstract description 15
- 238000010828 elution Methods 0.000 claims abstract description 12
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 239000003513 alkali Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims description 30
- 238000011069 regeneration method Methods 0.000 claims description 27
- 230000008929 regeneration Effects 0.000 claims description 25
- 238000004132 cross linking Methods 0.000 claims description 20
- 238000003795 desorption Methods 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 13
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 5
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 claims description 5
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- YGJHKCCQWZAUDK-UHFFFAOYSA-N 3-methyl-1-propyl-1-triethoxysilylurea Chemical compound C(CC)N(C(=O)NC)[Si](OCC)(OCC)OCC YGJHKCCQWZAUDK-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 abstract description 21
- 239000000741 silica gel Substances 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005341 cation exchange Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- 239000011148 porous material Substances 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004064 recycling Methods 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000003456 ion exchange resin Substances 0.000 description 10
- 229920003303 ion-exchange polymer Polymers 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 230000008961 swelling Effects 0.000 description 9
- 229920005990 polystyrene resin Polymers 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 230000001172 regenerating effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 229910001429 cobalt ion Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- RDNYEBBIOKDIBV-UHFFFAOYSA-N [Mn].[Co].[Ni].[Cu] Chemical compound [Mn].[Co].[Ni].[Cu] RDNYEBBIOKDIBV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for recovering manganese from ternary battery waste liquid. The method comprises the following steps: performing column chromatography on the ternary battery waste liquid, and collecting eluent; ion exchange treatment is carried out on the eluent through cation exchange resin, and manganese ions in the eluent are enriched; wherein, the chromatographic column filling adopted in the column chromatography treatment is a cross-linked aminosilane modified silica microsphere. Through the reverse adsorption and elution effects of the aminosilane modified silica microspheres, impurity ions are adsorbed by a silica gel column, and manganese ions enter eluent, so that separation of manganese ions and the impurity ions is realized, and manganese ions are adsorbed by cation exchange resin in cooperation with the subsequent cation exchange process, so that enrichment of manganese ions is realized. In addition, the method has the advantages of simple and easily-controlled process, simple and convenient operation, less equipment investment, low reagent cost, mild reaction conditions, environmental protection, controllable quality, easy industrialization, better environmental and economic effects and wide application prospect.
Description
Technical Field
The invention relates to the technical field of battery material recovery, in particular to a method for recovering manganese from ternary battery waste liquid.
Background
The industrialization rapid development of lithium batteries greatly promotes the alloy industry, and the lithium ion batteries are widely applied to the fields of medical treatment, automobiles, aviation and the like. After the battery is abandoned, heavy metal elements with high added value such as cobalt lithium and the like in the battery are required to be recycled. The ternary power battery generally refers to a power battery using a nickel cobalt lithium manganate (LiNi xCoyMnzO2) ternary material as a battery positive electrode material, and has the advantages of low cost, large discharge capacity, good cycle performance, good thermal stability, relatively stable structure and the like compared with lithium iron phosphate, lithium nickelate, lithium cobaltate and lithium manganate batteries.
Currently, according to the difference of failure modes of lithium ion batteries, two main technical routes for recycling and regenerating ternary positive electrode materials are provided: firstly, physical repair regeneration, namely directly adding a lithium source into a ternary positive electrode material which only loses active lithium element, performing in-situ reverse lithium supplementing repair regeneration by a high-temperature sintering method, and performing hydrothermal treatment and short-time high-temperature sintering regeneration on the positive electrode material with serious capacity attenuation and surface crystal structure change; secondly, metallurgical recovery is achieved, hydrometallurgical processes are widely adopted at present, and the main process flow comprises pretreatment, leaching, regeneration and other procedures. The ternary lithium battery leached by acid contains nickel ions (Ni 2+), cobalt ions (Co 2+), lithium ions and the like as main components, and the material with adsorption effect on the manganese ions often has the same adsorption effect on the cobalt ions and the nickel ions, so that the interference is large, the adsorption effect is poor, the manganese ions are difficult to separate, not to mention the enrichment of the manganese ions or the recovery of the manganese ions, and the ternary lithium battery is subsequently used for regenerating the ternary positive electrode material.
Disclosure of Invention
Based on the method, the invention provides a method for recovering manganese from the ternary battery waste liquid, which can selectively separate manganese ions and enrich manganese ions, thereby changing waste into valuables.
The technical proposal is as follows:
A method for recovering manganese from a ternary battery waste liquid, comprising the following steps:
performing column chromatography on the ternary battery waste liquid, and collecting eluent;
Ion exchange treatment is carried out on the eluent through cation exchange resin, and manganese ions in the eluent are enriched;
wherein, the chromatographic column filling adopted in the column chromatography treatment is a cross-linked aminosilane modified silica microsphere.
In one embodiment, the aminosilane-modified silica gel microsphere has a particle size of 0.1mm to 0.8mm and a pore size of 10nm to 1000nm.
In one embodiment, the chromatographic column is further subjected to elution and regeneration treatment after column chromatography, wherein the elution procedure adopted is acid washing, water washing and alkali treatment, and the acid washing liquid is nickel cobalt copper ion enrichment liquid.
In one embodiment, the column temperature is 20-50 ℃.
In one embodiment, the desorption agent used in the acid washing step is one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1-15%.
In one embodiment, in the pickling treatment step, the flow rate of the eluent is 0.5BV/h to 5BV/h, and the treatment time is 1h to 10h.
In one embodiment, the water washing step is to wash the packed column with pure water at a flow rate of 0.5BV/h to 5BV/h for a treatment time of 1h to 10h.
In one embodiment, the alkali solution used in the alkali treatment step is a mixed solution of one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the mass concentration of the alkali in the alkali solution is 1% -15%.
In one embodiment, in the alkaline treatment step, the flow rate of the eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-4 h.
In one embodiment, the surface of the aminosilane-modified silica microsphere contains 14 to 35 mass percent of amino groups.
In one embodiment, the crosslinked aminosilane-modified silica microspheres are prepared as follows:
Mixing silica microspheres and an aminosilane coupling agent in a first solvent, and preparing aminosilane modified silica microspheres through a grafting reaction;
mixing the aminosilane-modified silica microspheres with a crosslinking agent, and preparing the crosslinked aminosilane-modified silica microspheres through a crosslinking reaction.
In one embodiment, the method further comprises the step of mixing the crude silica microsphere with an acid to perform an impurity removal reaction prior to the step of mixing the silica microsphere with the aminosilane coupling agent in the first solvent.
In one embodiment, the mass ratio of the crude silica microsphere to the acid is 1 (0.1-0.75).
In one embodiment, the acid comprises one or more of hydrochloric acid, sulfuric acid, and nitric acid.
In one embodiment, the impurity removal reaction is carried out at a temperature of 30-60 ℃ for 4-8 hours.
In one embodiment, the aminosilane coupling agent comprises one or more of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, 1-propyl-1- (triethoxysilyl) methylurea, gamma-aminopropyl methyldiethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropyl methyl-dimethoxysilane.
In one embodiment, the first solvent comprises one or more of methanol, ethanol, methylene chloride, isopropanol, and 1, 2-dichloroethane.
In one embodiment, the mass ratio of the silica microsphere to the aminosilane coupling agent is 1 (0.05-0.3).
In one embodiment, the grafting reaction is carried out at a temperature of 40℃to 80℃for a period of 8 hours to 16 hours.
In one embodiment, the mixing mass ratio of the aminosilane-modified silica microspheres to the crosslinking agent is 1 (0.05-0.3).
In one embodiment, the cross-linking agent comprises one or more of epichlorohydrin, tetraethyl silicate, and tetrabutyl titanate.
In one embodiment, the temperature of the crosslinking reaction is 40-80 ℃ and the time is 8-16 h.
In one embodiment, after the step of preparing the crosslinked aminosilane-modified silica microspheres by a crosslinking reaction, a step of purifying the product of the crosslinking reaction is further included.
In one embodiment, the purification process comprises the steps of:
And (3) carrying out alcohol washing treatment and water washing treatment on the cross-linked reaction product.
In one embodiment, the cation exchange resin comprises one or more of a sulfonic acid resin, an iminodiacetic acid resin, a phosphoric acid resin, and an phosphoramidate resin.
In one embodiment, the cation exchange resin has a particle size of 0.1mm to 0.5mm and a pore size of 10mm to 1000nm.
In one embodiment, after the step of ion exchange treatment, a step of desorbing and regenerating the cation exchange resin enriched with manganese ions is further included.
In one embodiment, the elution procedure adopted by desorption regeneration is acid washing, water washing and alkali treatment, wherein the acid washing liquid is manganese ion enrichment liquid obtained after the ion exchange treatment.
In one embodiment, the column temperature is 20-50 ℃ during the desorption regeneration step of the cation exchange resin.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the desorption agent used for acid washing is one or more mixed liquid of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1-15%.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the pickling eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-10 h.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the water washing is to wash the packed column with pure water, the flow rate of the water is 0.5BV/h to 5BV/h, and the treatment time is 1h to 10h.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the alkali solution used in the alkali treatment comprises a mixed solution of one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and the mass concentration of the alkali in the alkali solution is 1-15%.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the alkali treatment eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-4 h.
The invention has at least the following beneficial effects:
The method for recovering manganese from the ternary battery waste liquid comprises the steps of performing column chromatography treatment on the ternary battery waste liquid and collecting eluent; and a step of enriching manganese ions in the eluent by ion exchange treatment of the eluent by cation exchange resin; the chromatographic column filler adopted in column chromatography treatment is a cross-linked aminosilane modified silica microsphere, an amino functional group of the chromatographic column filler can selectively adsorb impurity ions (cobalt ions, nickel ions and copper ions) by utilizing the chelation of N coordination atoms of the chromatographic column filler, and manganese ions are not adsorbed or are slightly adsorbed, and the impurity ions are adsorbed by the silica gel column and the manganese ions enter eluent through the reverse adsorption elution effect of the microsphere, so that the separation of the manganese ions and the impurity ions is realized, and the manganese ions are adsorbed by cation exchange resin in cooperation with the subsequent cation exchange process, so that the enrichment of the manganese ions is realized.
In addition, the method for recycling manganese from the ternary battery waste liquid has the advantages of simple and easily controlled process, simple and convenient operation, less equipment investment, low reagent cost, mild reaction conditions, environment friendliness, controllable quality, easy industrialization, good environmental and economic effects, wide application range, suitability for recycling manganese from the ternary battery recycling liquid in industrial production, stable structure of the crosslinked aminosilane modified silicon dioxide microsphere, stable column bed and difficult collapse in the use process, recycling and reuse of the microsphere and wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of the crosslinked aminosilane-modified silica microspheres prepared in example 1;
FIG. 2 is an adsorption experimental diagram of the cross-linked aminosilane modified silica microspheres prepared in example 1 to enrich copper cobalt nickel and macroporous cation exchange resin to enrich manganese;
Fig. 3 is a schematic view of an apparatus for recovering manganese from a ternary battery waste liquid in examples 1 to 4.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and figures. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, another element may be added, unless a specifically defined term is used, such as "consisting of … …," etc.
The words "preferably," "more preferably," "more preferably," and the like, refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. That is, in the present invention, "preferable", "more preferable", etc. are merely description of embodiments or examples that are more effective, but do not limit the scope of the present invention.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, "at least one" means one or more, such as one, two or more. The meaning of "plural" or "several" means at least two, for example, two, three, etc., and the meaning of "multiple" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
All steps of the present invention may be performed sequentially or randomly unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further comprise step (c), meaning that step (c) may be added to the method in any order, e.g., the method may comprise steps (a), (b) and (c), steps (a), (c) and (b), steps (c), (a) and (b), etc.
In the present invention, "above" or "below" includes the present number. E.g., 1 or less, including 1.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
The raw materials, reagent materials, and the like used in the following embodiments are commercially available products unless otherwise specified.
Currently, according to the difference of failure modes of lithium ion batteries, two main technical routes for recycling and regenerating ternary positive electrode materials are provided: firstly, physical repair regeneration, namely directly adding a lithium source into a ternary positive electrode material which only loses active lithium element, performing in-situ reverse lithium supplementing repair regeneration by a high-temperature sintering method, and performing hydrothermal treatment and short-time high-temperature sintering regeneration on the positive electrode material with serious capacity attenuation and surface crystal structure change; secondly, metallurgical recovery is carried out, hydrometallurgical processes are widely adopted at present, the main process flow comprises pretreatment, leaching, regeneration and other working procedures, and the ternary lithium battery leached by acid contains nickel ions (Ni 2+) as main components besides manganese: how to effectively separate these valuable ions, such as cobalt ions (Co 2+) and lithium ions, has been a matter of routine skill in the industry.
There are few reports on manganese adsorbents on the market, mainly because manganese ions have a positive divalent charge, and electrons are arranged in a half-full structure [ Ar ]3d 5. Five unpaired 3d electrons in the manganese ion electron arrangement give them a higher electron density, which may lead to electron exclusion effects when forming covalent bonds with other ligands. Such electron repulsion may increase the energy barrier of the coordination reaction, thereby making coordination adsorption of manganese ions more difficult. However, the material having adsorption effect on manganese ions often has the same adsorption effect on cobalt ions and nickel ions, so that the interference is large and the selective adsorption effect is poor.
The technical proposal is as follows:
A method for recovering manganese from a ternary battery waste liquid, comprising the following steps:
performing column chromatography on the ternary battery waste liquid, and collecting eluent;
Ion exchange treatment is carried out on the eluent through cation exchange resin, and manganese ions in the eluent are enriched;
wherein, the chromatographic column filling adopted in the column chromatography treatment is a cross-linked aminosilane modified silica microsphere.
The method for recovering manganese from the ternary battery waste liquid according to the present invention will be described in detail by way of a stepwise description.
S100: and (3) carrying out column chromatography treatment on the ternary battery waste liquid, and collecting eluent, wherein chromatographic column filling adopted in the column chromatography treatment is cross-linked aminosilane modified silica microspheres.
In one embodiment, the surface of the aminosilane-modified silica microsphere contains 14 to 35 mass percent of amino groups.
In one embodiment, the aminosilane-modified silica gel microsphere has a particle size of 0.1mm to 0.8mm and a pore size of 10nm to 1000nm.
In one embodiment, the crosslinked aminosilane-modified silica microspheres are prepared as follows:
Mixing silica microspheres and an aminosilane coupling agent in a first solvent, and preparing aminosilane modified silica microspheres (formula I) through a grafting reaction;
Mixing the aminosilane modified silica microspheres with a crosslinking agent, and preparing the crosslinked aminosilane modified silica microspheres through a crosslinking reaction, wherein the chemical formula is (SiO 2)n(SiC3O3NH8)m, n is (0.1-10), and m is (0.1-10);
in one embodiment, the method further comprises the step of mixing the crude silica microsphere with an acid to perform an impurity removal reaction prior to the step of mixing the silica microsphere with the aminosilane coupling agent in the first solvent. Mixing the crude silica microsphere with acid liquor to wash out excessive impurities on the surface of the microsphere.
It will be appreciated that in the present invention, the crude silica microspheres may be commercially available or not, and that no particular requirement is imposed on this, and in a specific example, the crude silica microspheres are purchased from Qingdao Xin Yong silica gel Co.
In one embodiment, the mass ratio of the crude silica microsphere to the acid is 1 (0.1-0.75), including but not limited to 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, or 1:0.75.
In one embodiment, the acid comprises one or more of hydrochloric acid, sulfuric acid, and nitric acid. It is understood that when in use, the concentrated acid is diluted into a dilute acid aqueous solution for use, and the mass concentration of the acid in the dilute acid aqueous solution is 5-15%.
In one embodiment, the temperature of the impurity removal reaction is from 30℃to 60℃including, but not limited to, 30℃40 ℃, 50℃or 60 ℃.
In one embodiment, the time for the impurity removal reaction is 4h to 8h, including but not limited to 4h, 5h, 6h, 7h, or 8h.
In one embodiment, the aminosilane coupling agent comprises one or more of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, 1-propyl-1- (triethoxysilyl) methylurea, gamma-aminopropyl methyldiethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropyl methyl-dimethoxysilane.
In one embodiment, the first solvent comprises one or more of methanol, ethanol, methylene chloride, isopropanol, and 1, 2-dichloroethane.
In one embodiment, the mass ratio of the silica microsphere to the aminosilane coupling agent is 1 (0.05-0.3), including but not limited to 1:0.05, 1:0.1, 1:0.2 or 1:0.3.
In one embodiment, the grafting reaction is at a temperature of 40℃to 80℃including, but not limited to, 40℃50℃60℃70℃or 80 ℃.
In one embodiment, the grafting reaction is for a period of time ranging from 8 hours to 16 hours, including but not limited to 8 hours, 10 hours, 12 hours, 14 hours, or 16 hours.
In one embodiment, swelling the silica microspheres subjected to impurity removal treatment in a first solvent for 0.5-4 hours, adding an aminosilane coupling agent, and heating to perform grafting reaction.
In one embodiment, the aminosilane-modified silica microspheres are mixed with the cross-linking agent in a mass ratio of 1 (0.05-0.3), including but not limited to 1:0.05, 1:0.1, 1:0.2 or 1:0.3.
In one embodiment, the cross-linking agent comprises one or more of epichlorohydrin, tetraethyl silicate, and tetrabutyl titanate.
In one embodiment, the temperature of the crosslinking reaction is 40℃to 80℃including, but not limited to, 40℃50℃60℃70℃or 80 ℃.
In one embodiment, the time for the crosslinking reaction is 8h to 16h, including but not limited to 8h, 10h, 12h, 14h, or 16h.
In one embodiment, after the step of preparing the crosslinked aminosilane-modified silica microspheres by a crosslinking reaction, a step of purifying the product of the crosslinking reaction is further included.
In one embodiment, the purification process comprises the steps of:
And (3) carrying out alcohol washing treatment and water washing treatment on the cross-linked reaction product.
The organic matter remaining on the surface of the material after the synthesis is removed by the alcohol washing treatment, and the alcohol on the surface of the material is removed by the water washing treatment.
In one embodiment, the alcohol used in the alcohol wash treatment is a mixture of one or more of methanol, ethanol, and isopropanol.
In one embodiment, the column (or packed column) is also subjected to an elution regeneration process after the column chromatography step. Further, the elution procedure adopted is acid washing, water washing and alkali treatment, wherein the acid washing liquid is nickel cobalt copper ion enrichment liquid.
In one embodiment, the column temperature is 20-50 ℃.
In one embodiment, the desorption agent used in the acid washing step is one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1-15%.
In one embodiment, in the pickling treatment step, the flow rate of the eluent is 0.5BV/h to 5BV/h, and the treatment time is 1h to 10h.
In one embodiment, the water washing step is to wash the packed column with pure water at a flow rate of 0.5BV/h to 5BV/h for a treatment time of 1h to 10h.
In one embodiment, the alkali solution used in the alkali treatment step is a mixed solution of one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the mass concentration of the alkali in the alkali solution is 1% -15%.
In one embodiment, in the alkaline treatment step, the flow rate of the eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-4 h.
S200: and (3) carrying out ion exchange treatment on the eluent by using cation exchange resin to enrich manganese ions in the eluent.
In one embodiment, the cation exchange resin comprises one or more of a sulfonic acid resin, an iminodiacetic acid resin, a phosphoric acid resin, and an phosphoramidate resin. Further, the matrix of the ion exchange resin is polystyrene.
In one embodiment, the cation exchange resin has a particle size of 0.1mm to 0.5mm and a pore size of 10mm to 1000nm.
S300: and (5) post-treatment.
In one embodiment, the step of ion exchange treatment is followed by a step of desorbing the cation exchange resin enriched in manganese ions.
In one embodiment, the elution procedure adopted by the macroporous cation exchange resin column is acid washing, water washing and alkali treatment, wherein the acid washing liquid is manganese ion enrichment liquid obtained after the ion exchange treatment;
in one embodiment, in the step of desorbing and regenerating the cation exchange resin, the column temperature is 20-50 ℃;
In one embodiment, in the step of desorbing and regenerating the cation exchange resin, the desorbing agent used for pickling is a mixed solution of one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration is 1% -15%. It is understood that the acids are formulated for use as aqueous dilute acid solutions in which the mass concentration of the acid is 1% to 15%.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the pickling eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-10 h.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the water washing is to wash the packed column with pure water, the flow rate of the water is 0.5BV/h to 5BV/h, and the treatment time is 1h to 10h.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the alkali solution used in the alkali treatment comprises a mixed solution of one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and the mass concentration of the alkali in the alkali solution is 1-15%. It is understood that the alkali is prepared into a diluted alkali aqueous solution for use, and the mass concentration of the alkali in the diluted alkali aqueous solution is 1-15%.
In one embodiment, in the desorption regeneration step of the cation exchange resin, the flow rate of the alkali treatment eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-4 h.
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention.
It will be appreciated that the ternary battery waste liquid may be slightly different in terms of element composition, but the method of recovering manganese from ternary battery waste liquid provided by the present invention is applicable to various ternary battery waste liquids, and for convenience of description of the present invention, the element contents in ternary battery waste liquids used in the following examples and comparative examples are analyzed as in table 1 below.
TABLE 1
The balance is basically carbon element and oxygen element, except for the above elements.
Example 1
The embodiment provides a method for recycling manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in methanol for 2 hours according to the silica microspheres: the mass ratio of the gamma-aminopropyl triethoxysilane is 1:0.2 adding gamma-aminopropyl triethoxysilane KH550, heating to 60 ℃ and reacting and refluxing for 12 hours;
(c) Crosslinking reaction: mixing the aminosilane modified silicon dioxide microspheres prepared in the step (b) with tetraethyl silicate according to a mass ratio of 1:0.1, uniformly mixing and stirring, and heating to 60 ℃ for reaction for 4 hours to improve the stability of the modified microspheres;
(d) Purifying: the modified microsphere prepared in the step (c) is washed by ethanol and water to obtain a reaction product, wherein the reaction product is a crosslinked aminosilane modified silicon dioxide microsphere, the particle size of the reaction product is 0.1-0.8 mm, the pore diameter of the reaction product is 10-1000 nm, the reaction product is subjected to Fourier infrared analysis, and as shown in a result of FIG. 1, absorption peaks at 3500cm -1 and 1590cm -1 represent that a composite material with amino functional groups on the surface is successfully synthesized.
(E) The method of connecting a silica gel material filling column and a large Kong Yangli ion exchange resin filling column in series is used for distributing and separating nickel, cobalt and copper and manganese ions so as to achieve the purpose of recovering manganese ions, as shown in fig. 2, the silica gel material filling column can obviously observe the phenomenon of nickel, cobalt and copper layering, which shows that nickel, cobalt and copper are adsorbed on the silica gel material, and then manganese ions are adsorbed through iminodiacetic acid resin shown in fig. two, wherein the desorption regeneration method of the silica gel column is to treat 2 hours at the flow rate of 2BV/h by using 5% HCl solution, then treat 1 hour at the flow rate of 5BV/h by using pure water, then regenerate by using 15% sodium carbonate solution, treat 1 hour at the flow rate of 2BV/h, and the pickling solution is nickel, cobalt and copper enrichment liquid at the temperature of Quan Chengzhu ℃ at 45 ℃. The desorption regeneration method of the macroporous cation exchange resin comprises the steps of treating for 2 hours at a flow rate of 2BV/h by using 15% HCl solution, treating for 1 hour at a flow rate of 5BV/h by using pure water, regenerating by using 5% sodium hydroxide solution, treating for 1 hour at a flow rate of 2BV/h, wherein the temperature of Quan Chengzhu is 45 ℃, and the pickling solution is the manganese enrichment solution, and the specific process flow is shown in figure 3.
The results of each metal ion in the eluate were tested as shown in table 2 below;
The manganese ions in the eluent were adsorbed by using iminodiacetic acid type polystyrene resin (particle size 0.1 mm-0.5 mm, pore size 10 nm-1000 nm), and manganese was enriched, and the results of manganese ions contained in the eluent flowing out of the ion exchange resin were shown in Table 3 below.
Example 2
The embodiment provides a method for recycling manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in methanol for 2 hours according to the silica microspheres: the mass ratio of the N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:0.2 adding N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, heating to 60 ℃ and reacting and refluxing for 12 hours;
(c) Crosslinking reaction: mixing the aminosilane modified silicon dioxide microspheres prepared in the step (b) with tetraethyl silicate according to a mass ratio of 1:0.1, uniformly mixing and stirring, and heating to 60 ℃ for reaction for 4 hours to improve the stability of the modified microspheres;
(d) Purifying: washing the modified microsphere prepared in the step (c) with ethanol and water to obtain a reaction product, wherein the reaction product is a crosslinked aminosilane modified silica microsphere, the particle size of the reaction product is 0.1-0.8 mm, and the pore diameter of the reaction product is 10-1000 nm;
(e) Separating nickel, cobalt, copper and manganese in the ternary battery waste liquid by using the silica gel material prepared in the step d through a method of filling a column, collecting eluent, and testing, wherein the technological process parameters are the same as those of the embodiment 1, and the results of each metal ion in the eluent are shown in the table 2 below;
The manganese ions in the eluent were adsorbed by using iminodiacetic acid type polystyrene resin (particle size 0.1 mm-0.5 mm, pore size 10 nm-1000 nm), and manganese was enriched, and the results of manganese ions contained in the eluent flowing out of the ion exchange resin were shown in Table 3 below.
Example 3
The embodiment provides a method for recycling manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in methanol for 2 hours according to the silica microspheres: the mass ratio of the gamma-aminopropyl methyl diethoxy silane is 1:0.2 adding gamma-aminopropyl methyl diethoxy silane, heating to 60 ℃ and reacting and refluxing for 12 hours;
(c) Crosslinking reaction: mixing the aminosilane modified silicon dioxide microspheres prepared in the step (b) with tetraethyl silicate according to a mass ratio of 1:0.1, uniformly mixing and stirring, and heating to 60 ℃ for reaction for 4 hours to improve the stability of the modified microspheres;
(d) Purifying: washing the two modified microspheres prepared in the step (c) with ethanol and water to obtain a reaction product, wherein the reaction product is a crosslinked aminosilane modified silica microsphere, the particle size of the reaction product is 0.1-0.8 mm, and the pore diameter of the reaction product is 10-1000 nm;
(e) Separating nickel, cobalt, copper and manganese in the ternary battery waste liquid by using the silica gel material prepared in the step d through a method of filling a column, collecting eluent, and testing, wherein the technological process parameters are the same as those of the embodiment 1, and the results of each metal ion in the eluent are shown in the table 2 below;
The manganese ions in the eluent were adsorbed by using iminodiacetic acid type polystyrene resin (particle size 0.1 mm-0.5 mm, pore size 10 nm-1000 nm), and manganese was enriched, and the results of manganese ions contained in the eluent flowing out of the ion exchange resin were shown in Table 3 below.
Example 4
The embodiment provides a method for recycling manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in methanol for 2 hours according to the silica microspheres: the mass ratio of the gamma-aminopropyl triethoxysilane is 1:0.3 adding gamma-aminopropyl triethoxysilane, heating to 60 ℃ and reacting and refluxing for 12 hours;
(c) Crosslinking reaction: mixing the aminosilane modified silicon dioxide microspheres prepared in the step (b) with tetraethyl silicate according to a mass ratio of 1:0.1, uniformly mixing and stirring, and heating to 60 ℃ for reaction for 4 hours to improve the stability of the modified microspheres;
(d) Purifying: washing the modified microsphere prepared in the step (c) with ethanol and water to obtain a reaction product, wherein the reaction product is a crosslinked aminosilane modified silica microsphere, the particle size of the reaction product is 0.1-0.8 mm, and the pore diameter of the reaction product is 10-1000 nm;
(e) Separating nickel, cobalt, copper and manganese in the ternary battery waste liquid by using the silica gel material prepared in the step d through a method of filling a column, collecting eluent, and testing, wherein the technological process parameters are the same as those of the embodiment 1, and the results of each metal ion in the eluent are shown in the table 2 below;
The manganese ions in the eluent were adsorbed by using iminodiacetic acid type polystyrene resin (particle size 0.1 mm-0.5 mm, pore size 10 nm-1000 nm), and manganese was enriched, and the results of manganese ions contained in the eluent flowing out of the ion exchange resin were shown in Table 3 below.
Example 5
The embodiment provides a method for recycling manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in methanol for 2 hours according to the silica microspheres: the mass ratio of the gamma-aminopropyl triethoxysilane is 1:0.2 adding gamma-aminopropyl triethoxysilane, heating to 60 ℃ and reacting and refluxing for 12 hours;
(c) Crosslinking reaction: mixing the aminosilane modified silicon dioxide microspheres prepared in the step (b) with tetraethyl silicate according to a mass ratio of 1:0.2, uniformly mixing and stirring, and heating to 60 ℃ for reaction for 4 hours to improve the stability of the modified microspheres;
(d) Purifying: washing the modified microsphere prepared in the step (c) with ethanol and water to obtain a reaction product, wherein the reaction product is a crosslinked aminosilane modified silica microsphere, the particle size of the reaction product is 0.1-0.8 mm, and the pore diameter of the reaction product is 10-1000 nm;
(e) Separating nickel, cobalt, copper and manganese in the ternary battery waste liquid by using the silica gel material prepared in the step d through a method of filling a column, collecting eluent, and testing, wherein the technological process parameters are the same as those of the embodiment 1, and the results of each metal ion in the eluent are shown in the table 2 below;
The manganese ions in the eluent were adsorbed by using iminodiacetic acid type polystyrene resin (particle size 0.1 mm-0.5 mm, pore size 10 nm-1000 nm), and manganese was enriched, and the results of manganese ions contained in the eluent flowing out of the ion exchange resin were shown in Table 3 below.
Example 6
The embodiment provides a method for recycling manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in methanol for 2 hours according to the silica microspheres: the mass ratio of the gamma-aminopropyl triethoxysilane is 1:0.2 adding gamma-aminopropyl triethoxysilane, heating to 40 ℃ and reacting and refluxing for 12 hours;
(c) Crosslinking reaction: mixing the aminosilane modified silicon dioxide microspheres prepared in the step (b) with tetraethyl silicate according to a mass ratio of 1:0.1, uniformly mixing and stirring, and heating to 40 ℃ for reaction for 4 hours to improve the stability of the modified microspheres;
(d) Purifying: washing the modified microsphere prepared in the step (c) with ethanol and water to obtain a reaction product, wherein the reaction product is a crosslinked aminosilane modified silica microsphere, the particle size of the reaction product is 0.1-0.8 mm, and the pore diameter of the reaction product is 10-1000 nm;
(e) Separating nickel, cobalt, copper and manganese in the ternary battery waste liquid by using the silica gel material prepared in the step d through a method of filling a column, collecting eluent, and testing, wherein the technological process parameters are the same as those of the embodiment 1, and the results of each metal ion in the eluent are shown in the table 2 below;
The manganese ions in the eluent were adsorbed by using iminodiacetic acid type polystyrene resin (particle size 0.1 mm-0.5 mm, pore size 10 nm-1000 nm), and manganese was enriched, and the results of manganese ions contained in the eluent flowing out of the ion exchange resin were shown in Table 3 below.
Comparative example 1
The comparative example provides a method for recovering manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in ethylenediamine for 4 hours according to the silica microspheres: the mass ratio of the ethylenediamine is 1:0.2, mixing, and heating to 110 ℃ for reaction reflux for 12 hours;
(c) Crosslinking reaction: mixing the ethylenediamine modified silicon dioxide microspheres prepared in the step (b) with tetraethyl silicate according to a mass ratio of 1:0.1, uniformly mixing and stirring, and heating to 60 ℃ for reaction for 4 hours to improve the stability of the modified microspheres;
(d) Purifying: washing the sexual microsphere prepared in the step (c) with ethanol and water to obtain a silica gel reaction product;
(e) Separating nickel, cobalt, copper and manganese in the ternary battery waste liquid by using the silica gel material prepared in the step d through a method of filling a column, collecting eluent, and testing, wherein the specific process parameters are the same as those in the embodiment 1, and the results of each metal ion in the eluent are shown in the table 2 below;
the results of the manganese ions contained in the eluate, which was eluted through the ion exchange resin, were shown in Table 3 below, by adsorbing manganese ions in the eluate using an aminocarboxylic acid type polystyrene resin (particle diameter: 0.1mm to 0.5mm, pore diameter: 10nm to 1000 nm), and enriching manganese.
Comparative example 2
The comparative example provides a method for recovering manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Purifying: washing the silica microspheres obtained in the step (a) with water to obtain a product;
The rest of the procedure is the same as in example 1.
Comparative example 3
The comparative example provides a method for recovering manganese from ternary battery waste liquid, which comprises the following steps:
(a) Pretreatment of silica microspheres: mixing the purchased silica microspheres with 15wt% hydrochloric acid solution, heating to 70 ℃ and refluxing for 12 hours to wash out redundant impurities on the surfaces of the microspheres;
(b) Grafting reaction: swelling the pretreated silica microspheres in methanol for 2 hours according to the silica microspheres: the mass ratio of the gamma-aminopropyl triethoxysilane is 1:0.2 adding gamma-aminopropyl triethoxysilane KH550, heating to 60 ℃ and reacting and refluxing for 12 hours;
(c) Purifying: washing the modified microsphere prepared in the step (b) with ethanol and water to obtain a reaction product, and carrying out the rest steps in the same manner as in example 1.
Comparative example 4
Carboxylate cationic silica gel was purchased as a product, and this comparative example was prepared by connecting 5 packed columns filled with carboxylate cationic silica gel material (10 mL each, about 8.1 g) end to end, with the remaining process parameters being the same as in example 1.
The products obtained in examples 1 to 6 and comparative examples 1 to 4 were subjected to performance tests, specifically as follows:
(1) Taking 10mL of amino silica gel adsorption materials synthesized in the examples 1-6 (named products A-F respectively), respectively marking the materials obtained in the comparative examples 1-4 as products G-J, loading the materials into columns, and adding 100mL of ternary battery waste liquid respectively containing 200ppm of cobalt, nickel, copper and manganese for adsorption experiments, wherein the products J are 5 columns connected in series;
(2) The effluent from step (1) was passed through a 0.45 μm membrane and the content of cobalt nickel copper manganese ions was measured, and the results are shown in Table 2.
TABLE 2 adsorption effects of different silica gel adsorption materials on Co-Ni-Cu-Mn
| Sample name | Co2+(ppm) | Ni+(ppm) | Cu2+(ppm) | Mn2+(ppm) |
| Raw water | 200 | 200 | 200 | 200 |
| Product A | 0 | 0 | 0 | 163 |
| Product B | 0 | 0 | 0 | 146 |
| Product C | 0 | 0 | 0 | 133 |
| Product D | 0 | 0 | 0 | 131 |
| Product E | 23.4 | 31.9 | 13.6 | 186 |
| Product F | 9.33 | 7.62 | 0.560 | 183 |
| Product G | 3.30 | 4.10 | 2.90 | 13.2 |
| Product H | 178 | 184 | 169 | 194 |
| Product I | 4.76 | 5.12 | 0.780 | 177 |
| Product J | 0 | 0 | 0 | 0 |
As is clear from table 2 above, the amino silica gel adsorption materials synthesized in examples 1 to 6 of the present invention are more excellent in the performance of adsorbing nickel cobalt copper ions than comparative examples 1 to 4, in which the actual measurement effect of the sample described in example 1 is better.
The effluent obtained after adsorption of the silica gel columns of examples 1 to 6 and comparative examples 1 to 4 were collected, respectively, and the effluent was enriched for manganese ions using commercially available cationic exchange resin iminodiacetic acid type polystyrene resin, as follows:
TABLE 3 results of manganese ions contained in the eluate from ion exchange resin flow
| Sample name | Mn2+(ppm) |
| Product A | 0 |
| Product B | 0 |
| Product C | 0 |
| Product D | 0 |
| Product E | 0 |
| Product F | 0 |
| Product G | 0 |
| Product H | 0 |
| Product I | 0 |
| Product J | 0 |
As can be seen from the above Table 3, the manganese ions in the effluent of the silica gel column are completely adsorbed by the cation exchange resin, which demonstrates that the method has a good effect for enriching manganese ions.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logic analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (11)
1. A method for recovering manganese from a ternary battery waste liquid, comprising the steps of:
performing column chromatography on the ternary battery waste liquid, and collecting eluent;
Ion exchange treatment is carried out on the eluent through cation exchange resin, and manganese ions in the eluent are enriched;
wherein, the chromatographic column filling adopted in the column chromatography treatment is a cross-linked aminosilane modified silica microsphere.
2. The method for recovering manganese from a ternary battery waste liquid according to claim 1, wherein the preparation method of the crosslinked aminosilane-modified silica microspheres is as follows:
Mixing silica microspheres and an aminosilane coupling agent in a first solvent, and preparing aminosilane modified silica microspheres through a grafting reaction;
mixing the aminosilane-modified silica microspheres with a crosslinking agent, and preparing the crosslinked aminosilane-modified silica microspheres through a crosslinking reaction.
3. The method for recovering manganese from a ternary battery waste liquid according to claim 2, wherein the grafting reaction satisfies at least one of the following (1) to (4):
(1) The mass ratio of the silicon dioxide microspheres to the aminosilane coupling agent is 1 (0.05-0.3);
(2) The grafting reaction temperature is 40-80 ℃ and the grafting reaction time is 8-16 h;
(3) The aminosilane coupling agent comprises one or more of gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, 1-propyl-1- (triethoxysilyl) methylurea, gamma-aminopropyl methyldiethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl methyl-dimethoxysilane;
(4) The first solvent includes one or more of methanol, ethanol, methylene chloride, isopropanol, and 1, 2-dichloroethane.
4. The method for recovering manganese from a ternary battery waste liquid according to claim 2, wherein the crosslinking reaction satisfies at least one of the following (1) to (3):
(1) The mixing mass ratio of the aminosilane modified silicon dioxide microsphere to the cross-linking agent is 1 (0.05-0.3);
(2) The cross-linking agent comprises one or more of epichlorohydrin, tetraethyl silicate and tetrabutyl titanate;
(3) The temperature of the crosslinking reaction is 40-80 ℃ and the time is 8-16 h.
5. The method for recovering manganese from a waste ternary battery solution according to claim 2, further comprising the step of mixing the crude silica microspheres with an acid to perform a removal reaction, before the step of mixing the silica microspheres and the aminosilane coupling agent in the first solvent.
6. The method for recovering manganese from a ternary battery waste liquid according to claim 5, wherein the impurity removal reaction satisfies at least one of the following (1) to (3):
(1) The mass ratio of the silica microsphere crude product to the acid is 1: (0.1 to 0.75);
(2) The acid comprises one or more of hydrochloric acid, sulfuric acid and nitric acid;
(3) The temperature of the impurity removal reaction is 30-60 ℃ and the time is 4-8 h.
7. The method for recovering manganese from a ternary battery waste liquid according to claim 2, further comprising the step of subjecting the crosslinked aminosilane-modified silica microspheres to a purification treatment after the step of producing the crosslinked aminosilane-modified silica microspheres by a crosslinking reaction.
8. The method for recovering manganese from a ternary battery waste liquid according to claim 7, wherein the purification treatment comprises the steps of:
And (3) carrying out alcohol washing treatment and water washing treatment on the cross-linked reaction product.
9. The method for recovering manganese from a ternary battery waste liquid according to any one of claims 1 to 8, wherein the column is further subjected to an elution regeneration treatment after column chromatography, satisfying at least one of the following (1) to (7):
(1) The elution procedure adopted by the elution regeneration is acid washing, wherein the acid washing liquid is nickel cobalt copper ion enrichment liquid;
(2) The column temperature is 20-50 ℃;
(3) The desorption agent used in the pickling step is one or more mixed liquid of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1% -15%;
(4) The flow rate of the eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-10 h;
(5) The water washing step is to wash the filling column by pure water, the flow rate of the water is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-10 h;
(6) The alkali solution used in the alkali treatment step is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and the mass concentration of alkali in the alkali solution is 1-15%;
(7) In the alkali treatment step, the flow rate of the eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-4 h.
10. The method for recovering manganese from a ternary battery waste liquid according to any one of claims 1 to 8, wherein at least one of the following (1) to (3) is satisfied:
(1) The grain diameter of the aminosilane modified silica gel microsphere is 0.1 mm-0.8 mm, and the aperture is 10 nm-1000 nm;
(2) The cation exchange resin comprises one or more of sulfonic acid resin, iminodiacetic acid resin, phosphoric acid resin and phosphoramidate resin;
(3) The particle size of the cation exchange resin is 0.1-0.5 mm, and the aperture is 10-1000 nm.
11. The method for recovering manganese from a ternary battery waste liquid according to any one of claims 1 to 8, further comprising, after the step of ion exchange treatment, a step of subjecting the cation exchange resin enriched with manganese ions to desorption regeneration, wherein the step satisfies at least one of the following (1) to (7):
(1) The elution procedure adopted by desorption regeneration comprises acid washing, water washing and alkali treatment, wherein the acid washing liquid is manganese ion enrichment liquid obtained after the ion exchange treatment;
(2) The column temperature is 20-50 ℃;
(3) The desorption agent used in the pickling step is one or more mixed liquid of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1% -15%;
(4) In the pickling treatment step, the flow rate of the eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-10 h;
(5) The water washing step is to wash the filling column by pure water, the flow rate of the water is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-10 h;
(6) The alkali solution used in the alkali treatment step comprises a mixed solution of one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and the mass concentration of alkali in the alkali solution is 1-15%;
(7) In the alkali treatment step, the flow rate of the eluent is 0.5 BV/h-5 BV/h, and the treatment time is 1 h-4 h.
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| WO1985000758A1 (en) * | 1983-08-17 | 1985-02-28 | Litovitz, Theodore, Aaron | Improved silica-based chromatographic supports containing additives |
| WO2000053820A1 (en) * | 1999-03-09 | 2000-09-14 | Bhp Minerals International, Inc. | Recovery of nickel and cobalt from ore |
| WO2001002600A2 (en) * | 1999-07-06 | 2001-01-11 | General Atomics | Detection of analytes using attenuated enzymes |
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