CN116334417A - A process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist - Google Patents
A process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist Download PDFInfo
- Publication number
- CN116334417A CN116334417A CN202310247364.9A CN202310247364A CN116334417A CN 116334417 A CN116334417 A CN 116334417A CN 202310247364 A CN202310247364 A CN 202310247364A CN 116334417 A CN116334417 A CN 116334417A
- Authority
- CN
- China
- Prior art keywords
- manganese
- nickel
- cobalt
- mixed solution
- coexist
- 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.)
- Pending
Links
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 126
- 239000011572 manganese Substances 0.000 title claims abstract description 126
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011259 mixed solution Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 57
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 54
- 239000010941 cobalt Substances 0.000 title claims abstract description 54
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 52
- POVGIDNLKNVCTJ-UHFFFAOYSA-J cobalt(2+);nickel(2+);disulfate Chemical compound [Co+2].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O POVGIDNLKNVCTJ-UHFFFAOYSA-J 0.000 claims abstract description 35
- 239000007800 oxidant agent Substances 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004155 Chlorine dioxide Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000001868 cobalt Chemical class 0.000 description 3
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 3
- WJNPTRISSCIBDB-UHFFFAOYSA-N cobalt(2+) nickel(2+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Co+2].[Ni+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WJNPTRISSCIBDB-UHFFFAOYSA-N 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- IITHIOWFUOHSOP-UHFFFAOYSA-L dichlorocobalt nickel Chemical compound [Co](Cl)Cl.[Ni] IITHIOWFUOHSOP-UHFFFAOYSA-L 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- LIJBHSNTSZDMFV-UHFFFAOYSA-L [OH-].[OH-].[Mn].[Ni++] Chemical compound [OH-].[OH-].[Mn].[Ni++] LIJBHSNTSZDMFV-UHFFFAOYSA-L 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940073644 nickel Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003828 vacuum filtration 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
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明公开了一种高效净化处理镍钴锰共存的混合溶液中锰的工艺方法，包括如下过程：向镍钴锰共存的混合溶液中加入氧化剂，使镍钴锰共存的混合溶液的锰以沉淀的形式析出，之后进行固液分离，将锰的沉淀物分离出来，实现了镍钴锰共存的混合溶液的净化。本发明相比于常规净化处理硫酸镍钴盐混合溶液的工艺方法具有工艺流程简单、效率高、产品纯度高、生产成本低的优点。
The invention discloses a process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist, comprising the following process: adding an oxidant to the mixed solution where nickel, cobalt and manganese coexist, so that the manganese in the mixed solution where nickel, cobalt and manganese coexist is precipitated The form of precipitation, followed by solid-liquid separation, to separate the manganese precipitate, to achieve the purification of the mixed solution of nickel, cobalt and manganese coexistence. Compared with the conventional process for purifying and treating the nickel-cobalt sulfate mixed solution, the present invention has the advantages of simple process flow, high efficiency, high product purity and low production cost.
Description
技术领域technical field
本发明属于湿法冶金的技术应用领域，涉及一种锰选择性氧化分离的技术，具体是一种高效净化处理镍钴锰共存的混合溶液中锰的工艺方法。The invention belongs to the technical application field of hydrometallurgy, and relates to a technology for selective oxidation and separation of manganese, in particular to a process for efficiently purifying manganese in a mixed solution in which nickel, cobalt and manganese coexist.
背景技术Background technique
为了有效去除废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料在浸出后形成的镍钴锰共存的硫酸盐溶液中的锰，多采用P204皂化萃取分离技术、中和沉淀技术等进行镍钴锰硫酸盐溶液体系中金属锰的去除，但是由于镍钴锰的物理和化学性质相似，所以现有的技术存在工艺流程长，操作复杂，处理成本高以及锰与镍钴难以有效分离、镍钴锰硫酸盐溶液难以被高效净化等缺点。In order to effectively remove the manganese in the nickel-cobalt-manganese coexistence sulfate solution formed after the leaching of waste lithium-ion battery positive black powder and industrial-grade nickel-cobalt hydroxide and other raw materials, P204 saponification extraction and separation technology, neutralization precipitation technology, etc. are often used. The removal of metal manganese in the nickel-cobalt-manganese sulfate solution system, but due to the similar physical and chemical properties of nickel-cobalt-manganese, the existing technology has long process flow, complicated operation, high processing cost and difficult effective separation of manganese and nickel-cobalt. Nickel-cobalt-manganese sulfate solution is difficult to be efficiently purified and other shortcomings.
发明内容Contents of the invention
为解决现有技术中存在的问题，本发明的目的在于提供一种高效净化处理镍钴锰共存的混合溶液中锰的工艺方法，本发明能够有效实现低成本、高效率分离锰与镍钴，而且工艺流程相对较短。In order to solve the problems in the prior art, the object of the present invention is to provide a process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist. The present invention can effectively separate manganese and nickel and cobalt with low cost and high efficiency. And the process flow is relatively short.
本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:
一种高效净化处理镍钴锰共存的混合溶液中锰的工艺方法，包括如下过程：A process for efficiently purifying manganese in a mixed solution in which nickel, cobalt and manganese coexist comprises the following processes:
向镍钴锰共存的混合溶液中加入氧化剂，使镍钴锰共存的混合溶液的锰以沉淀的形式析出，之后进行固液分离，将锰的沉淀物分离出来，实现了镍钴锰共存的混合溶液的净化。Add an oxidant to the mixed solution where nickel, cobalt and manganese coexist, so that the manganese in the mixed solution where nickel, cobalt and manganese coexist is precipitated, and then perform solid-liquid separation to separate the manganese precipitate, realizing the mixed solution of nickel, cobalt and manganese coexistence Solution purification.
优选的，所述镍钴锰共存的混合溶液中，金属盐以硫酸盐、氯化盐和硝酸盐中的一种或几种混合的形式存在。Preferably, in the mixed solution in which nickel, cobalt and manganese coexist, the metal salt exists in the form of one or more mixed forms of sulfate, chloride and nitrate.
优选的，所述镍钴锰共存的混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴原料的过程中产出的含锰的硫酸镍钴盐混合溶液。Preferably, the nickel-cobalt-manganese coexisting mixed solution is a manganese-containing nickel-cobalt sulfate mixed solution produced during the process of treating waste lithium-ion battery positive electrode black powder and industrial-grade nickel-cobalt hydroxide raw materials.
优选的，所述氧化剂采用能够氧化二价锰离子并生成二氧化锰沉淀的氧化物。Preferably, the oxidant is an oxide capable of oxidizing divalent manganese ions and generating manganese dioxide precipitates.
优选的，所述氧化剂采用高锰酸钾、锰酸钾、氯酸钠、臭氧、二氧化氯、过硫酸盐或者二氧化硫与氧气混合气体。Preferably, the oxidizing agent is potassium permanganate, potassium manganate, sodium chlorate, ozone, chlorine dioxide, persulfate or a mixed gas of sulfur dioxide and oxygen.
优选的，二氧化硫与氧气混合气体中，二氧化硫体积含量为2％-20％。Preferably, in the mixed gas of sulfur dioxide and oxygen, the volume content of sulfur dioxide is 2%-20%.
优选的，向镍钴锰共存的混合溶液中加入氧化剂，使镍钴锰共存的混合溶液的锰以沉淀的形式析出时：Preferably, an oxidizing agent is added to the mixed solution in which nickel, cobalt and manganese coexist, and when the manganese in the mixed solution in which nickel, cobalt and manganese coexist is separated out in the form of precipitation:
反应温度为40℃～100℃，pH值为2.5～7，反应时间为30min～120min。The reaction temperature is 40°C-100°C, the pH value is 2.5-7, and the reaction time is 30min-120min.
优选的，分离出的锰的沉淀物作为锰精矿或者干电池的去极化剂。Preferably, the separated manganese precipitate is used as a manganese concentrate or a depolarizer for dry batteries.
优选的，固液分离后，将分离得到的液体浓缩结晶，将所得物用作电池的正极原材料或生产硫酸盐产品。Preferably, after solid-liquid separation, the separated liquid is concentrated and crystallized, and the resultant is used as a positive electrode raw material for a battery or to produce sulfate products.
优选的，本发明高效净化处理镍钴锰共存的混合溶液中锰的工艺方法的脱锰率为99.5％以上，镍钴损失量低于1％。Preferably, the manganese removal rate of the process for efficiently purifying and treating manganese in a mixed solution in which nickel, cobalt and manganese coexist is above 99.5%, and the loss of nickel and cobalt is less than 1%.
本发明具有如下有益效果：The present invention has following beneficial effect:
本发明采用氧化沉淀法单独将镍钴锰共存的混合溶液中的锰转变成锰沉淀从溶液中分离出来，而金属镍和钴依旧留在溶液中。该氧化沉淀分离技术不仅能有效进行硫酸镍钴盐溶液中金属锰的选择性分离，高效脱除硫酸镍钴盐溶液中的锰，得到的二氧化锰沉淀渣的纯度高，可以作为锰精矿或干电池的去极化剂进行出售，而且最后溶液中有价金属镍和钴的损失率低，脱锰后液的纯度高，浓缩结晶后可以作为电池的正极原材料出售或生产相应的硫酸盐产品。本发明方法工艺过程简单可靠、高效无污染，在高效去除硫酸镍钴盐混合溶液中锰的同时混合溶液中镍和钴的损失小，产出的二氧化锰沉淀渣可实现资源重新分配利用；简化了工艺流程，降低了生产成本，紧贴工业实际，具有良好的应用背景。The invention adopts an oxidation precipitation method to separately convert the manganese in the mixed solution where nickel, cobalt and manganese coexist into manganese precipitates and separate them from the solution, while metal nickel and cobalt remain in the solution. This oxidation precipitation separation technology can not only effectively carry out the selective separation of metal manganese in the nickel cobalt sulfate solution, but also efficiently remove the manganese in the nickel cobalt sulfate solution, and the obtained manganese dioxide precipitate has high purity and can be used as manganese concentrate Or dry battery depolarizer for sale, and the loss rate of valuable metals nickel and cobalt in the final solution is low, the purity of the solution after demanganization is high, after concentration and crystallization, it can be sold as the positive electrode raw material of the battery or produce corresponding sulfate products . The process of the method of the present invention is simple, reliable, efficient and pollution-free, and the loss of nickel and cobalt in the mixed solution is small while efficiently removing manganese in the nickel sulfate-cobalt salt mixed solution, and the produced manganese dioxide precipitated slag can realize resource redistribution and utilization; The technological process is simplified, the production cost is reduced, it is close to the industrial reality and has a good application background.
附图说明Description of drawings
图1为本发明高效净化处理镍钴锰共存的混合溶液中锰的工艺方法的工艺流程图。Fig. 1 is the process flow diagram of the process method of the present invention for efficiently purifying manganese in a mixed solution in which nickel, cobalt and manganese coexist.
具体实施方式Detailed ways
下面结合附图和实例对本发明作进一步说明。The present invention will be further described below in conjunction with accompanying drawing and example.
如图1所示，本发明高效净化处理镍钴锰共存的混合溶液中锰的工艺方法的核心是选择性氧化分离脱除镍钴锰共存的混合溶液(如硫酸镍钴盐混合溶液)中的锰离子；向镍钴锰共存的混合溶液中加入氧化剂，氧化剂与镍钴锰共存的混合溶液中的锰发生反应，使锰从硫酸镍钴盐混合溶液中以二氧化锰沉淀的形式析出，而金属镍和钴依旧留在溶液中，进而实现镍钴锰共存的混合溶液中锰的高效脱除，解决现有技术方法中锰与镍钴难以有效分离、镍钴锰硫酸盐溶液难以高效净化的问题。脱锰后液在进行简单的固液分离后，得到高纯度的二氧化锰沉淀渣，可作为锰精矿或者作为干电池的去极化剂出售，从而实现硫酸镍钴盐混合溶液中锰的综合利用。As shown in Figure 1, the core of the process method of the present invention to efficiently purify and treat manganese in a mixed solution where nickel, cobalt and manganese coexist is to selectively oxidize and separate and remove Manganese ion; add oxidizing agent in the mixed solution that nickel cobalt manganese coexists, the manganese in the mixed solution that oxidant and nickel cobalt manganese coexist reacts, and manganese is separated out with the form of manganese dioxide precipitation from nickel sulfate cobalt salt mixed solution, and The metal nickel and cobalt still remain in the solution, thereby realizing the efficient removal of manganese in the mixed solution where nickel, cobalt and manganese coexist, and solving the problem that manganese and nickel and cobalt are difficult to effectively separate and nickel, cobalt and manganese sulfate solution are difficult to efficiently purify in the prior art methods question. After simple solid-liquid separation of the demanganized solution, high-purity manganese dioxide precipitated slag can be obtained, which can be sold as manganese concentrate or as a depolarizer for dry batteries, so as to realize the synthesis of manganese in the mixed solution of nickel sulfate and cobalt salt use.
本发明以下实施例中，镍钴锰共存的混合溶液以硫酸镍钴盐混合溶液为例进行说明，其中，所述的硫酸镍钴盐混合溶液是在处理NCM正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液。氧化剂是能够氧化二价锰离子的氧化剂，如氧化剂是能够氧化二价锰离子的高锰酸钾(KMnO4)、锰酸钾(K2MnO4)、氯酸钠(NaClO3)、臭氧(O3)、二氧化氯(ClO2)、过硫酸盐或者二氧化硫与氧气混合气体(SO2/O2)。In the following examples of the present invention, the mixed solution of nickel, cobalt and manganese coexistence is illustrated by taking the mixed solution of nickel sulfate and cobalt salt as an example, wherein, the mixed solution of nickel sulfate and cobalt salt is used to process NCM positive electrode black powder and industrial grade nickel hydroxide Manganese-containing nickel sulfate cobalt salt mixed solution produced during the process of cobalt and other raw materials. The oxidizing agent is an oxidizing agent capable of oxidizing divalent manganese ions, such as potassium permanganate (KMnO 4 ), potassium manganate (K 2 MnO 4 ), sodium chlorate (NaClO 3 ), ozone ( O 3 ), chlorine dioxide (ClO 2 ), persulfate or a mixed gas of sulfur dioxide and oxygen (SO 2 /O 2 ).
实施例1：Example 1:
如图1所示，本实施例硫酸镍钴盐混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液，其中镍含量104.5g/L，钴含量25.9g/L，锰含量3.8g/L，取硫酸镍钴盐混合溶液250mL，向其中加入氧化剂进行锰的选择性沉淀分离。采用1mol/L的锰酸钾(K2MnO4)水溶液作为氧化剂，加入18mL，在pH值为2.5、反应温度为90℃、反应时间为120min并不断搅拌的条件下，反应后对浆液进行真空抽滤，最后滤液中残余锰量为2.8mg/L，脱锰率为99.68％，镍钴损失率分别为0.36％、0.55％。As shown in Figure 1, the nickel-cobalt sulfate mixed solution of the present embodiment is the manganese-containing nickel-cobalt sulfate mixed solution produced in the process of processing waste lithium-ion battery positive electrode black powder and industrial grade nickel-cobalt hydroxide and other raw materials. Wherein nickel content is 104.5g/L, cobalt content is 25.9g/L, manganese content is 3.8g/L, takes nickel sulfate cobalt salt mixed solution 250mL, adds oxidizing agent wherein to carry out the selective precipitation separation of manganese. Use 1mol/L potassium manganate (K 2 MnO 4 ) aqueous solution as the oxidant, add 18mL, under the conditions of pH value 2.5, reaction temperature 90°C, reaction time 120min and constant stirring, vacuum the slurry after reaction After suction filtration, the residual manganese content in the final filtrate was 2.8mg/L, the manganese removal rate was 99.68%, and the nickel and cobalt loss rates were 0.36% and 0.55%, respectively.
实施例2：Example 2:
如图1所示，本实施例硫酸镍钴盐混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液，其中镍含量70g/L，钴含量51.6g/L，锰含量10.9g/L，取硫酸镍钴盐混合溶液250mL，向其中加入氧化剂进行锰的选择性沉淀分离。采用1mol/L的高锰酸钾(KMnO4)水溶液作为氧化剂，加入12mL，在pH值为4.7、反应温度为100℃、反应时间为60min并不断搅拌的条件下，反应后对浆液进行真空抽滤，最后滤液中残余锰量为0.13mg/L，脱锰率为99.99％，镍钴损失率分别为0.33％、0.28％。As shown in Figure 1, the nickel-cobalt sulfate mixed solution of the present embodiment is the manganese-containing nickel-cobalt sulfate mixed solution produced in the process of processing waste lithium-ion battery positive electrode black powder and industrial grade nickel-cobalt hydroxide and other raw materials. Wherein the nickel content is 70g/L, the cobalt content is 51.6g/L, and the manganese content is 10.9g/L. Take nickel sulfate cobalt salt mixed solution 250mL, add oxidant thereinto and carry out the selective precipitation separation of manganese. Use 1mol/L potassium permanganate (KMnO 4 ) aqueous solution as the oxidant, add 12mL, under the conditions of pH value 4.7, reaction temperature 100°C, reaction time 60min and constant stirring, vacuum pump the slurry after reaction After filtration, the residual manganese content in the final filtrate was 0.13mg/L, the manganese removal rate was 99.99%, and the nickel and cobalt loss rates were 0.33% and 0.28%, respectively.
实施例3：Example 3:
如图1所示，本实施例硫酸镍钴盐混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液，其中镍含量74.3g/L，钴含量69.9g/L，锰含量5.1g/L，取硫酸镍钴盐混合溶液250mL，向其中加入氧化剂进行锰的选择性沉淀分离。采用臭氧(O3)作为氧化剂，通气速度为0.2L/min，在pH值为3.2、反应温度为85℃、反应时间为90min并不断搅拌的条件下，反应后对浆液进行真空抽滤，最后滤液中残余锰量为0.08mg/L，脱锰率为99.99％，镍钴损失率分别为0.38％、0.22％。As shown in Figure 1, the nickel-cobalt sulfate mixed solution of the present embodiment is the manganese-containing nickel-cobalt sulfate mixed solution produced in the process of processing raw materials such as waste lithium-ion battery positive electrode black powder and industrial grade nickel-cobalt hydroxide. Wherein nickel content is 74.3g/L, cobalt content is 69.9g/L, manganese content is 5.1g/L, takes nickel sulfate cobalt salt mixed solution 250mL, adds oxidant thereinto and carries out the selective precipitation separation of manganese. Ozone (O 3 ) was used as the oxidant, the ventilation rate was 0.2L/min, the pH value was 3.2, the reaction temperature was 85°C, the reaction time was 90min and the conditions were constant stirring. After the reaction, the slurry was vacuum filtered, and finally The residual manganese content in the filtrate was 0.08mg/L, the manganese removal rate was 99.99%, and the nickel and cobalt loss rates were 0.38% and 0.22%, respectively.
实施例4：Example 4:
如图1所示，本实施例硫酸镍钴盐混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液，其中镍含量81.6g/L，钴含量77.8g/L，锰含量9.4g/L，取硫酸镍钴盐混合溶液250mL，向其中加入氧化剂进行锰的选择性沉淀分离。采用为2.5mol/L的氯酸钠(NaClO3)水溶液作为氧化剂，加入21mL，在pH值为6.4、反应温度为70℃、反应时间为90min并不断搅拌的条件下，反应后对浆液进行真空抽滤，最后滤液中残余锰量为2.3mg/L，脱锰率为99.73％，镍钴损失率分别为0.2％、0.16％。As shown in Figure 1, the nickel-cobalt sulfate mixed solution of the present embodiment is the manganese-containing nickel-cobalt sulfate mixed solution produced in the process of processing waste lithium-ion battery positive electrode black powder and industrial grade nickel-cobalt hydroxide and other raw materials. Wherein nickel content is 81.6g/L, cobalt content is 77.8g/L, manganese content is 9.4g/L, takes nickel sulfate cobalt salt mixed solution 250mL, adds oxidizing agent to it and carries out the selective precipitation separation of manganese. Use 2.5mol/L sodium chlorate (NaClO 3 ) aqueous solution as the oxidant, add 21mL, under the condition that the pH value is 6.4, the reaction temperature is 70°C, the reaction time is 90min and the stirring is constant, the slurry is vacuumed after the reaction. After suction filtration, the residual manganese content in the final filtrate was 2.3mg/L, the manganese removal rate was 99.73%, and the nickel and cobalt loss rates were 0.2% and 0.16%, respectively.
实施例5：Example 5:
如图1所示，本实施例硫酸镍钴盐混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液，其中镍含量93.2g/L，钴含量44.9g/L，锰含量8.3g/L，取硫酸镍钴盐混合溶液250mL，向其中加入氧化剂进行锰的选择性沉淀分离。采用二氧化硫与氧气混合气体(SO2/O2)作为氧化剂，其中二氧化硫体积含量为10％，通气速度为0.3L/min，在pH值为7.0、反应温度为60℃、反应时间为60min并不断搅拌的条件下，反应后对浆液进行真空抽滤，最后滤液中残余锰量为1.42mg/L，脱锰率为99.85％，镍钴损失率分别为0.13％、0.11％。As shown in Figure 1, the nickel-cobalt sulfate mixed solution of the present embodiment is the manganese-containing nickel-cobalt sulfate mixed solution produced in the process of processing waste lithium-ion battery positive electrode black powder and industrial grade nickel-cobalt hydroxide and other raw materials. Wherein nickel content is 93.2g/L, cobalt content is 44.9g/L, manganese content is 8.3g/L, takes nickel sulfate cobalt salt mixed solution 250mL, adds oxidant thereinto and carries out the selective precipitation separation of manganese. Use sulfur dioxide and oxygen mixed gas (SO 2 /O 2 ) as the oxidant, wherein the volume content of sulfur dioxide is 10%, the ventilation rate is 0.3L/min, the pH value is 7.0, the reaction temperature is 60°C, and the reaction time is 60min. Under the condition of stirring, the slurry was subjected to vacuum filtration after the reaction, the residual manganese content in the filtrate was 1.42mg/L, the manganese removal rate was 99.85%, and the nickel and cobalt loss rates were 0.13% and 0.11%, respectively.
实施例6：Embodiment 6:
如图1所示，本实施例硫酸镍钴盐混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液，其中镍含量98.9g/L，钴含量25.5g/L，锰含量6.8g/L，取硫酸镍钴盐混合溶液250mL，向其中加入氧化剂进行锰的选择性沉淀分离。采用二氧化氯(ClO2)作为氧化剂，通气速度为0.2L/min，在pH值为2.5、反应温度为40℃、反应时间为35min并不断搅拌的条件下，反应后对浆液进行真空抽滤，最后滤液中残余锰量为2.33mg/L，脱锰率为99.72％，镍钴损失率分别为0.43％、0.24％。As shown in Figure 1, the nickel-cobalt sulfate mixed solution of the present embodiment is the manganese-containing nickel-cobalt sulfate mixed solution produced in the process of processing waste lithium-ion battery positive electrode black powder and industrial grade nickel-cobalt hydroxide and other raw materials. Wherein nickel content is 98.9g/L, cobalt content is 25.5g/L, manganese content is 6.8g/L, takes nickel sulfate cobalt salt mixed solution 250mL, adds oxidizing agent to it and carries out the selective precipitation separation of manganese. Chlorine dioxide (ClO 2 ) was used as the oxidant, the ventilation rate was 0.2L/min, and the pH value was 2.5, the reaction temperature was 40°C, the reaction time was 35min, and the slurry was continuously stirred, and the slurry was vacuum filtered after the reaction. , the residual manganese content in the final filtrate was 2.33mg/L, the manganese removal rate was 99.72%, and the nickel and cobalt loss rates were 0.43% and 0.24%, respectively.
实施例7：Embodiment 7:
如图1所示，本实施例硫酸镍钴盐混合溶液是在处理废旧锂离子电池正极黑粉和工业级氢氧化镍钴等原料的过程中产出的含锰的硫酸镍钴盐混合溶液，其中镍含量117.4g/L，钴含量34.8g/L，锰含量14.8g/L，取硫酸镍钴盐混合溶液250mL，向其中加入氧化剂进行锰的选择性沉淀分离。采用1.5mol/L的过硫酸胺水溶液作为氧化剂，加入12mL，在pH值为4.7、反应温度为50℃、反应时间为120min并不断搅拌的条件下，反应后对浆液进行真空抽滤，最后滤液中残余锰量为1.19mg/L，脱锰率为99.93％，镍钴损失率分别为0.86％、0.42％。As shown in Figure 1, the nickel-cobalt sulfate mixed solution of the present embodiment is the manganese-containing nickel-cobalt sulfate mixed solution produced in the process of processing waste lithium-ion battery positive electrode black powder and industrial grade nickel-cobalt hydroxide and other raw materials. Wherein nickel content is 117.4g/L, cobalt content is 34.8g/L, manganese content is 14.8g/L, takes nickel sulfate cobalt salt mixed solution 250mL, adds oxidizing agent wherein to carry out the selective precipitation separation of manganese. Use 1.5mol/L ammonium persulfate aqueous solution as oxidant, add 12mL, under the conditions of pH value 4.7, reaction temperature 50°C, reaction time 120min and constant stirring, vacuum filter the slurry after reaction, and finally filtrate The residual manganese content in the medium is 1.19mg/L, the manganese removal rate is 99.93%, and the nickel and cobalt loss rates are 0.86% and 0.42%, respectively.
本发明上述的技术方法不仅适用于硫酸镍钴盐混合溶液体系，还适用于含锰的氯化镍钴盐混合溶液、含锰的硝酸镍钴盐混合溶液或者他们的混合体系，或者含锰的硫酸镍钴盐混合溶液与含锰的氯化镍钴盐混合溶液的混合体系、含锰的硫酸镍钴盐混合溶液与含锰的硝酸镍钴盐混合溶液的混合体系，或者含锰的氯化镍钴盐混合溶液、含锰的硝酸镍钴盐混合溶液与含锰的硫酸镍钴盐混合溶液三者的混合体系。在氧化沉淀的过程中，水溶液中的锰离子较二价镍离子和二价钴优先被氧化剂氧化。The above-mentioned technical method of the present invention is not only applicable to nickel sulfate cobalt salt mixed solution system, also is suitable for manganese-containing nickel-cobalt chloride salt mixed solution, manganese-containing nickel-cobalt nitrate salt mixed solution or their mixed systems, or manganese-containing A mixed system of nickel sulfate cobalt salt mixed solution and manganese-containing nickel cobalt chloride salt mixed solution, a mixed system of manganese-containing nickel cobalt sulfate salt mixed solution and manganese-containing nickel cobalt nitrate salt mixed solution, or a manganese-containing chloride A mixed system of nickel-cobalt salt mixed solution, manganese-containing nickel-cobalt nitrate mixed solution and manganese-containing nickel-cobalt sulfate mixed solution. During the oxidation precipitation process, the manganese ions in the aqueous solution are oxidized by the oxidant preferentially compared with the divalent nickel ions and divalent cobalt.
通过本发明上述技术方案可以看出，本发明具有以下特点：Can find out by above-mentioned technical scheme of the present invention, the present invention has the following characteristics:
(1)本发明使硫酸镍钴盐混合溶液中的金属锰得到了有效脱除，实现了金属锰的高效率分离和资源可持续利用。(1) The present invention effectively removes the metal manganese in the nickel sulfate cobalt salt mixed solution, realizes the high-efficiency separation of the metal manganese and the sustainable utilization of resources.
(2)本发明方法采用氧化沉淀法进行镍钴锰硫酸盐混合溶液中二价锰离子的单独沉淀分离，锰的去除率高，得到的二氧化锰沉淀纯度高。(2) The method of the present invention adopts the oxidation precipitation method to carry out the separate precipitation and separation of divalent manganese ions in the nickel-cobalt-manganese sulfate mixed solution, the removal rate of manganese is high, and the precipitated manganese dioxide obtained has high purity.
(3)本发明方法工艺过程简单可靠，高效无污染，在高效去除硫酸镍钴盐混合溶液中锰的同时混合溶液中镍和钴的损失小，产出的二氧化锰沉淀渣可实现资源重新分配利用；简化了工艺流程，降低了生产成本，紧贴工业实际，具有良好的应用背景。(3) The technological process of the inventive method is simple and reliable, highly efficient and pollution-free, while efficiently removing manganese in the nickel sulfate cobalt salt mixed solution, the loss of nickel and cobalt in the mixed solution is small, and the manganese dioxide precipitated slag of output can realize resource recovery Distribution and utilization; the technological process is simplified, the production cost is reduced, it is close to the industrial reality, and has a good application background.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310247364.9A CN116334417A (en) | 2023-03-14 | 2023-03-14 | A process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310247364.9A CN116334417A (en) | 2023-03-14 | 2023-03-14 | A process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116334417A true CN116334417A (en) | 2023-06-27 |
Family
ID=86881659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310247364.9A Pending CN116334417A (en) | 2023-03-14 | 2023-03-14 | A process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116334417A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117083248A (en) * | 2023-06-30 | 2023-11-17 | 青美邦新能源材料有限公司 | Cobalt nickel hydroxide quality improving method |
| CN117120641A (en) * | 2023-07-07 | 2023-11-24 | 广东邦普循环科技有限公司 | Method for removing manganese element in nickel-cobalt-manganese-containing solution and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088215A (en) * | 2012-10-16 | 2013-05-08 | 赣州市豪鹏科技有限公司 | Method for separating nickel-cobalt and manganese in nickel-cobalt-manganese material with high manganese-cobalt ratio |
| CN109868373A (en) * | 2019-02-02 | 2019-06-11 | 广东芳源环保股份有限公司 | A method of substep leaching nickel, cobalt from nickel, cobalt, manganese mixture |
| CN113584309A (en) * | 2021-07-05 | 2021-11-02 | 广东佳纳能源科技有限公司 | Method for separating manganese in ternary lithium ion battery anode leachate |
-
2023
- 2023-03-14 CN CN202310247364.9A patent/CN116334417A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088215A (en) * | 2012-10-16 | 2013-05-08 | 赣州市豪鹏科技有限公司 | Method for separating nickel-cobalt and manganese in nickel-cobalt-manganese material with high manganese-cobalt ratio |
| CN109868373A (en) * | 2019-02-02 | 2019-06-11 | 广东芳源环保股份有限公司 | A method of substep leaching nickel, cobalt from nickel, cobalt, manganese mixture |
| CN113584309A (en) * | 2021-07-05 | 2021-11-02 | 广东佳纳能源科技有限公司 | Method for separating manganese in ternary lithium ion battery anode leachate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117083248A (en) * | 2023-06-30 | 2023-11-17 | 青美邦新能源材料有限公司 | Cobalt nickel hydroxide quality improving method |
| WO2025000491A1 (en) * | 2023-06-30 | 2025-01-02 | 青美邦新能源材料有限公司 | Method for improving quality of nickel-cobalt hydroxide |
| CN117120641A (en) * | 2023-07-07 | 2023-11-24 | 广东邦普循环科技有限公司 | Method for removing manganese element in nickel-cobalt-manganese-containing solution and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104911358B (en) | A kind of method that arsenic and selenium are separated in the alkaline leaching liquid from copper anode mud | |
| CN111471864A (en) | Method for recovering copper, aluminum and iron from waste lithium ion battery leachate | |
| CN116334417A (en) | A process for efficiently purifying manganese in a mixed solution where nickel, cobalt and manganese coexist | |
| JP7283720B2 (en) | Method for preparing battery grade Ni-Co-Mn mixture and battery grade Mn solution | |
| CN109022793B (en) | Method for selectively leaching lithium from waste powder of cathode material containing at least one of cobalt, nickel and manganese | |
| CN110983045A (en) | Method for removing iron and aluminum from nickel-cobalt-manganese solution | |
| CN108456788A (en) | A kind of method of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode | |
| CN115747521A (en) | Method for recovering and preparing lithium carbonate from waste lithium ion battery positive electrode material | |
| CN114291854A (en) | A kind of treatment method of waste battery cathode material recycling | |
| CN115535987B (en) | Method for recycling valuable elements from lithium iron manganese phosphate positive electrode waste | |
| CN115627346B (en) | A method for recycling waste lithium battery positive electrode material | |
| CN103055834A (en) | Regeneration method for spent ferric oxide desulfurizer | |
| US12062765B2 (en) | Method for extracting lithium from waste lithium battery | |
| CN116409769B (en) | A method for preparing battery-grade iron phosphate and lithium carbonate using crude lithium phosphate | |
| CN114606398B (en) | Method for recycling lithium from waste lithium ion battery anode material leaching waste liquid | |
| CN115216649B (en) | Method for preparing vanadium dioxide battery material by using waste vanadium-titanium-based SCR catalyst | |
| CN106395910A (en) | Method for preparation of battery grade high-purity manganese sulfate from industrial grade manganese sulfate | |
| CN114959306A (en) | Method for recovering lithium from lithium precipitation mother liquor by closed cycle method | |
| CN115927856B (en) | Slag-making agent and its application, recycling process of retired ternary lithium-ion batteries | |
| CN119571061B (en) | Precipitation method of heavy metal solution | |
| CN114212806B (en) | Recovery method of nickel-cobalt-manganese sulfide slag | |
| CN108754179A (en) | A kind of method of oxidation pre-treatment secondary material containing zinc | |
| CN119614872A (en) | Method for recovering lithium from NMP cleaning waste liquid in lithium battery industry | |
| CN118621153A (en) | A method for selectively recovering lithium from lithium iron manganese phosphate cathode waste powder | |
| CN119284862A (en) | A method for recycling lithium iron manganese phosphate waste |
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 |