CN110042252B - A kind of method for recycling valuable metal elements of scrapped nickel-hydrogen battery - Google Patents
A kind of method for recycling valuable metal elements of scrapped nickel-hydrogen battery Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 87
- 239000001257 hydrogen Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 196
- -1 cobalt-nickel rare earth Chemical class 0.000 claims abstract description 136
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000002699 waste material Substances 0.000 claims abstract description 109
- 239000000843 powder Substances 0.000 claims abstract description 88
- 239000007788 liquid Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 49
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 45
- 238000001556 precipitation Methods 0.000 claims abstract description 32
- 238000011084 recovery Methods 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 162
- 238000000605 extraction Methods 0.000 claims description 154
- 238000006243 chemical reaction Methods 0.000 claims description 75
- 235000006408 oxalic acid Nutrition 0.000 claims description 54
- 239000000706 filtrate Substances 0.000 claims description 39
- 238000001914 filtration Methods 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 29
- 239000012074 organic phase Substances 0.000 claims description 27
- 229910000831 Steel Inorganic materials 0.000 claims description 26
- 239000010959 steel Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 25
- 238000007599 discharging Methods 0.000 claims description 20
- 230000019635 sulfation Effects 0.000 claims description 10
- 238000005670 sulfation reaction Methods 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000003916 acid precipitation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 49
- 239000002184 metal Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 2
- 230000001180 sulfating effect Effects 0.000 abstract 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 61
- 239000003795 chemical substances by application Substances 0.000 description 48
- 229910001429 cobalt ion Inorganic materials 0.000 description 23
- 238000007873 sieving Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910018661 Ni(OH) Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 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 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
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- 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
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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- 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
- C22B23/00—Obtaining nickel or cobalt
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
技术领域technical field
本发明属于固废综合利用领域，具体涉及一种报废镍氢电池有价金属元素回收的方法。The invention belongs to the field of comprehensive utilization of solid waste, and in particular relates to a method for recovering valuable metal elements of scrapped nickel-hydrogen batteries.
背景技术Background technique
镍氢电池是20世纪90年代发展起来的一种新型化学电池，其正极材料为氢氧化镍，负极材料含有Co、Ni、稀土等元素，具有高能量、长寿命、无污染等特点，被广泛地应用于电子及汽车产业，其消耗量逐年增加，同时产生的报废镍氢电池也在逐渐增多，如对其处理不当，将造成环境污染严重，Co、Ni及稀土等有价金属大量损失，因此回收报废镍氢电池，不仅具有显著的环境效益，还具有一定的经济效益和社会效益。Nickel-metal hydride battery is a new type of chemical battery developed in the 1990s. Its positive electrode material is nickel hydroxide, and its negative electrode material contains Co, Ni, rare earth and other elements. It has the characteristics of high energy, long life and no pollution. It is widely used. It is widely used in the electronics and automobile industries, and its consumption is increasing year by year. At the same time, the number of scrapped nickel-metal hydride batteries is also increasing. If it is not handled properly, it will cause serious environmental pollution and a large amount of loss of valuable metals such as Co, Ni and rare earth. Therefore, recycling scrapped nickel-metal hydride batteries not only has significant environmental benefits, but also has certain economic and social benefits.
目前报废镍氢电池的回收方法主要有火法和湿法。湿法多为酸性介质浸出，经过滤分离提取不同金属。火法即将报废电池碎片经焙烧，从排出的气体、烟气、熔炼渣中分离提纯金属。中国发明专利（申请号201110173754.3）公开了一种从废旧镍氢电池中回收金属的方法，将镍氢电池经放电、破碎、筛分、磁选、热处理和熔炼工序，从而获得铁镍基合金、镍基合金和高品位稀土氧化物，该方法处理量大，但是其对焙烧气氛要求严格，并且设备能耗较高。中国发明专利（申请号201110304896.9）公开了一种废旧镍氢电池中金属元素回收方法，将废旧镍氢电池还原焙烧后，在酸性介质中氧化浸出，萃取，回收金属。该方法镍钴回收率高，但稀土提取过程繁琐且回收率低，耗酸量大、废水量大，环境污染严重。中国发明专利（申请号 201610708390.7）公开了一种从废旧镍氢电池中回收稀土并转型的方法，将废旧镍氢电池破碎后进行硫酸浸出、固液分离、硫酸钠沉淀、二次固液分离、再经硫酸稀土复盐处理后得到碳酸稀土沉淀，该方法采用硫酸与双氧水协同浸出、回收稀土元素，每kg报废镍氢电池粉需要12-18 mol硫酸溶解，耗酸量大，废水量大。中国发明专利（申请号201710097235.0）公开了一种从废旧镍氢电池中回收有价金属的方法，将镍氢电池、还原剂、硫化剂与造渣剂混匀进行焙烧，使镍、钴、铁形成硫化物，稀土元素形成化合物，该方法无需对镍氢电池进行粉碎处理，但后续提取金属硫化物分离提取产生硫氧化物污染，钴、镍、稀土等分离提取困难。At present, the recycling methods of scrapped Ni-MH batteries mainly include fire method and wet method. The wet method is mostly acid medium leaching, and different metals are extracted by filtration separation. The fire method is to roast the scrapped battery fragments to separate and purify the metal from the exhaust gas, flue gas and smelting slag. Chinese invention patent (application number 201110173754.3) discloses a method for recovering metals from waste nickel-metal hydride batteries. The nickel-metal hydride batteries are subjected to the processes of discharge, crushing, screening, magnetic separation, heat treatment and smelting to obtain iron-nickel-based alloys, For nickel-based alloys and high-grade rare earth oxides, this method has a large processing capacity, but it has strict requirements on the baking atmosphere, and the equipment energy consumption is high. Chinese invention patent (application number 201110304896.9) discloses a method for recovering metal elements in waste nickel-hydrogen batteries. After reducing and roasting waste nickel-hydrogen batteries, oxidative leaching, extraction and recovery of metals are carried out in an acidic medium. The method has a high recovery rate of nickel and cobalt, but the extraction process of rare earth is cumbersome and the recovery rate is low, the acid consumption is large, the amount of waste water is large, and the environmental pollution is serious. The Chinese invention patent (application number 201610708390.7) discloses a method for recovering rare earths from waste nickel-hydrogen batteries and transforming them. After crushing the waste nickel-hydrogen batteries, sulfuric acid leaching, solid-liquid separation, sodium sulfate precipitation, secondary solid-liquid separation, Rare earth carbonate precipitation is obtained after the double salt treatment of rare earth sulfate. This method uses sulfuric acid and hydrogen peroxide to synergize leaching and recovery of rare earth elements. Each kg of scrapped nickel-hydrogen battery powder needs 12-18 mol of sulfuric acid to dissolve, which consumes a large amount of acid and a large amount of waste water. The Chinese invention patent (application number 201710097235.0) discloses a method for recovering valuable metals from waste nickel-hydrogen batteries. The nickel-hydrogen batteries, reducing agent, vulcanizing agent and slag-forming agent are mixed and roasted to make nickel, cobalt, iron and Sulfide is formed, and rare earth elements form compounds. This method does not need to pulverize the nickel-hydrogen battery, but the subsequent extraction of metal sulfides produces sulfur oxide pollution, and it is difficult to separate and extract cobalt, nickel, and rare earth.
综上，现有的从废旧镍氢电池中回收有价金属的技术，工序复杂，物耗能耗高，环境污染严重。因此，亟需研发绿色高效回收报废镍氢电池中有价金属元素的方法。To sum up, the existing technology for recovering valuable metals from waste nickel-hydrogen batteries has complicated procedures, high material consumption and energy consumption, and serious environmental pollution. Therefore, there is an urgent need to develop a green and efficient method for recovering valuable metal elements in end-of-life nickel-metal hydride batteries.
发明内容SUMMARY OF THE INVENTION
针对上述技术问题，本发明公开了一种报废镍氢电池有价金属元素回收的方法，该方法将报废镍氢电池经预处理（放电、破碎）、硫酸化焙烧、水溶解等工艺解决现有技术中金属回收率低，处理过程污染严重，硫酸消耗量大，能耗较高等问题。In view of the above technical problems, the present invention discloses a method for recovering valuable metal elements of scrapped nickel-metal hydride batteries, which solves the problem of existing In the technology, the metal recovery rate is low, the treatment process is seriously polluted, the consumption of sulfuric acid is large, and the energy consumption is high.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种报废镍氢电池有价金属元素回收的方法，所述方法包括：A method for recovering valuable metal elements of scrapped nickel-metal hydride batteries, the method comprising:
报废镍氢电池预处理：将报废镍氢电池余电放电后，经拆解、破碎后获得废镍氢电池粉和钢壳；Pretreatment of scrapped nickel-metal hydride batteries: after discharging the residual power of scrapped nickel-metal hydride batteries, after dismantling and crushing, waste nickel-hydrogen battery powder and steel shell are obtained;
硫酸化焙烧：将所述废镍氢电池粉和硫酸按照比例混合后，进行硫酸化焙烧；Sulfation roasting: after the waste nickel-hydrogen battery powder and sulfuric acid are mixed in proportion, sulfation roasting is carried out;
水溶解：对硫酸化焙烧后的产物进行水溶解、过滤，获得浸出渣和浸出液；Water dissolving: water dissolving and filtering the product after sulfation roasting to obtain leaching residue and leachate;
萃取与反萃取：利用萃取剂对所述浸出液进行萃取，使镍元素和钴元素富集在有机相中，稀土元素富集在萃取余液中；然后用酸液反萃取有机相获得含镍钴元素的富集液，萃取剂回用于镍钴萃取；Extraction and back-extraction: extract the leaching liquid with an extractant, so that nickel and cobalt elements are enriched in the organic phase, and rare earth elements are enriched in the extraction residue; Elemental enrichment solution, the extractant is reused for nickel and cobalt extraction;
稀土元素沉淀：向所述萃取余液中加入草酸沉淀、过滤后得到草酸稀土沉淀和滤液；滤液回用于水溶解。Rare earth element precipitation: adding oxalic acid precipitation to the extraction residual liquid, and filtering to obtain rare earth oxalate precipitation and filtrate; the filtrate is reused for water dissolution.
进一步地，所述硫酸化焙烧为：将干燥的废镍氢电池粉和浓度为98wt%的浓硫酸在150℃~800℃下焙烧10~120min，浓硫酸加入量为化学反应计量数的1.0-1.1倍。Further, the sulfation roasting is as follows: roasting the dried waste nickel-hydrogen battery powder and the concentrated sulfuric acid with a concentration of 98wt% at 150 ℃ ~ 800 ℃ for 10 ~ 120min, and the addition amount of the concentrated sulfuric acid is 1.0-1. 1.1 times.
进一步地，所述水溶解的条件控制为：采用水溶解硫酸化焙烧产物，水和所述硫酸化焙烧产物的液固比为5~20(L/kg)，在20~100℃下水溶15~180min。Further, the condition control of described water dissolving is: adopt water dissolving sulfated roasting product, the liquid-solid ratio of water and described sulfated roasting product is 5～20 (L/kg), at 20～100 ℃, water-soluble 15 ~180min.
进一步地，在所述稀土元素沉淀的步骤中，向萃取余液中加入草酸沉淀稀土，草酸加入量为化学反应计量数的1.1-1.5倍，反应时间为5~90min，过滤后获得草酸稀土沉淀，稀土元素回收率为99%以上。Further, in the step of precipitation of rare earth elements, oxalic acid is added to the extraction residual liquid to precipitate rare earths, and the amount of oxalic acid added is 1.1-1.5 times of the chemical reaction stoichiometric number, and the reaction time is 5 to 90 minutes, and the rare earth oxalate precipitate is obtained after filtration. , the recovery rate of rare earth elements is more than 99%.
本发明的原理如下：The principle of the present invention is as follows:
（1）报废镍氢电池硫酸化焙烧使电池粉中的Ni(OH)2、Co3O4、稀土元素（RE）等转化为相应的硫酸盐，利于后续浸出反应；反应如下：(1) Sulfation roasting of scrapped nickel-hydrogen batteries converts Ni(OH) 2 , Co 3 O 4 , rare earth elements (RE), etc. in the battery powder into corresponding sulfates, which is beneficial to the subsequent leaching reaction; the reaction is as follows:
Ni(OH)2+H2SO4=NiSO4+2H2O （1）Ni(OH) 2 +H 2 SO 4 =NiSO 4 +2H 2 O (1)
2Co3O4+6H2SO4=6CoSO4+O2↑+6H2O （2）2Co 3 O 4 +6H 2 SO 4 =6CoSO 4 +O 2 ↑+6H 2 O (2)
2RE(OH)3+3H2SO4=RE2(SO4)3+6H2O （3）2RE(OH) 3 +3H 2 SO 4 =RE 2 (SO 4 ) 3 +6H 2 O (3)
（2）用水溶解镍钴稀土的硫酸盐；(2) Dissolve the sulfate of nickel-cobalt rare earth with water;
（3）用萃取剂将镍钴硫酸盐富集在有机相中，稀土硫酸盐进入水相萃取余液；有机相经反萃得到镍钴富集液； 本发明所述方法采用萃取浸出液实现了镍钴与稀土的精准分离，反萃取富集了镍钴元素 。(3) The nickel-cobalt sulfate is enriched in the organic phase with an extractant, and the rare earth sulfate enters the water-phase extraction residue; the organic phase is back-extracted to obtain a nickel-cobalt enriched solution; the method of the present invention adopts the extraction leachate to achieve Precise separation of nickel-cobalt and rare earth, and back-extraction to enrich nickel-cobalt elements.
（4）向萃取余液中加入草酸，沉淀稀土，其反应式如下：(4) Add oxalic acid to the extraction residue to precipitate rare earth, and the reaction formula is as follows:
2RE3++3H2C2O4+xH2O=RE2(C2O4)3·xH2O↓+6H+ （4）2RE 3+ +3H 2 C 2 O 4 +xH 2 O=RE 2 (C 2 O 4 ) 3 xH 2 O↓+6H + (4)
其中，本发明采用草酸沉淀稀土，稀土回收率高，达99%以上。Among them, the present invention adopts oxalic acid to precipitate rare earth, and the recovery rate of rare earth is high, reaching more than 99%.
本发明的有益技术效果：Beneficial technical effects of the present invention:
（1）本发明所述方法采用硫酸化焙烧废镍氢电池粉，然后水溶解钴镍稀土的硫酸盐；与直接用硫酸浸出废镍氢电池粉相比，减少了水和酸的消耗量；(1) The method of the present invention adopts sulfation roasting waste nickel-hydrogen battery powder, and then water dissolves the sulfate of cobalt-nickel rare earth; compared with directly leaching the waste nickel-hydrogen battery powder with sulfuric acid, the consumption of water and acid is reduced;
（2）本发明所述方法实现了报废镍氢电池有价金属全组分绿色高效提取，尾液实现了循环利用，无排放；(2) The method of the present invention realizes the green and efficient extraction of the whole valuable metal components of the scrap nickel-hydrogen battery, and the tail liquid realizes the recycling without discharge;
（3）本发明具有工艺简单、成本低、无污染、适用性广的优点，易于工业化。(3) The present invention has the advantages of simple process, low cost, no pollution, wide applicability and easy industrialization.
附图说明Description of drawings
图1为本发明实施例中一种报废镍氢电池有价金属元素回收的方法的流程示意图。FIG. 1 is a schematic flow diagram of a method for recovering valuable metal elements of a scrapped nickel-metal hydride battery according to an embodiment of the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细描述。应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
相反，本发明涵盖任何由权利要求定义的在本发明的精髓和范围上做的替代、修改、等效方法以及方案。进一步，为了使公众对本发明有更好的了解，在下文对本发明的细节描述中，详尽描述了一些特定的细节部分。对本领域技术人员来说没有这些细节部分的描述也可以完全理解本发明。On the contrary, the present invention covers any alternatives, modifications, equivalents and arrangements within the spirit and scope of the present invention as defined by the appended claims. Further, in order to give the public a better understanding of the present invention, some specific details are described in detail in the following detailed description of the present invention. The present invention can be fully understood by those skilled in the art without the description of these detailed parts.
实施例1Example 1
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行350℃焙烧98min，硫酸用量为废镍氢电池粉化学反应计量数的1.1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为8（L/kg）于100℃水溶解18min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.1倍，反应90min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 350°C for 98min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.1 times of the chemical reaction count; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 8 (L/kg), dissolve it in water at 100 ° C for 18 minutes to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.1 times of the chemical reaction of rare earth sulfate. The reaction is 90 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例2Example 2
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行800℃焙烧10min，硫酸用量为废镍氢电池粉化学反应计量数的1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为5（L/kg）于98℃水溶解30min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.12倍，反应85min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-metal hydride battery was discharged, disassembled, crushed and sieved to obtain waste nickel-metal hydride battery powder and steel shell; 98wt% concentrated sulfuric acid and waste nickel-metal hydride battery powder were mixed uniformly, and then roasted at 800 °C for 10 minutes, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1 times the number of chemical reaction measurements; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving it in water at 98°C for 30 minutes according to the liquid-solid ratio of 5 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.12 times of the chemical reaction of rare earth sulfate. The reaction is 85 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolution process.
实施例3Example 3
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行750℃焙烧15min，硫酸用量为废镍氢电池粉化学反应计量数的1.02倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为6（L/kg）于95℃水溶解40min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.16倍，反应70min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。Discharge, disassemble, crush and sieve the waste nickel-metal hydride battery to obtain waste nickel-hydrogen battery powder and steel shell; mix 98wt% concentrated sulfuric acid and waste nickel-metal hydride battery powder, and then roast at 750 °C for 15min, and the amount of sulfuric acid is waste. Nickel-metal hydride battery powder is 1.02 times the number of chemical reactions of the powder; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving in water at 95 °C for 40 minutes according to the liquid-solid ratio of 6 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.16 times of the chemical reaction of rare earth sulfate. The reaction is 70 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolving process.
实施例4Example 4
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行700℃焙烧20min，硫酸用量为废镍氢电池粉化学反应计量数的1.03倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为7（L/kg）于90℃水溶解50min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.2倍，反应60min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained after discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 700°C for 20min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.03 times the number of chemical reactions of the powder; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving it in water at 90°C for 50 min according to the liquid-solid ratio of 7 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.2 times of the chemical reaction of rare earth sulfate. The reaction is 60 minutes. After filtration, rare earth oxalate and filtrate are obtained. The recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolution process.
实施例5Example 5
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行650℃焙烧25min，硫酸用量为废镍氢电池粉化学反应计量数的1.04倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为9（L/kg）于50℃水溶解120min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.22倍，反应55min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 650 ℃ for 25min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.04 times the number of chemical reaction measurements; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving it in water at 50 ° C for 120 minutes according to the liquid-solid ratio of 9 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.22 times of the chemical reaction of rare earth sulfate. The reaction is performed for 55 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例6Example 6
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行600℃焙烧35min，硫酸用量为废镍氢电池粉化学反应计量数的1.05倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为12（L/kg）于85℃水溶解20min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.24倍，反应48min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 600 °C for 35min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.05 times the number of chemical reaction counts; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving it in water at 85 °C for 20 minutes according to the liquid-solid ratio of 12 (L/kg). The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.24 times the chemical reaction of rare earth sulfate. The reaction is 48 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolution process.
实施例7Example 7
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行550℃焙烧40min，硫酸用量为废镍氢电池粉化学反应计量数的1.06倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为13（L/kg）于80℃水溶解25min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.18倍，反应75min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。After discharging, disassembling, crushing and sieving the waste nickel-hydrogen battery, the waste nickel-hydrogen battery powder and steel shell were obtained; 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder were mixed uniformly and then roasted at 550°C for 40min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.06 times the number of chemical reaction measurements; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving in water at 80 °C for 25 minutes according to the liquid-solid ratio of 13 (L/kg); The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.18 times the chemical reaction of rare earth sulfate. The reaction is 75 minutes. After filtration, rare earth oxalate and filtrate are obtained. The recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolving process.
实施例8Example 8
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行150℃焙烧120min，硫酸用量为废镍氢电池粉化学反应计量数的1.1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为14（L/kg）于20℃水溶解180min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.28倍，反应45min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 150°C for 120min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.1 times of the chemical reaction count; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 14 (L/kg), dissolve it in water at 20 ° C for 180min to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.28 times of the chemical reaction of rare earth sulfate. The reaction is 45 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例9Example 9
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行200℃焙烧115min，硫酸用量为废镍氢电池粉化学反应计量数的1.08倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为20（L/kg）于25℃水溶解170min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.3倍，反应43min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 200°C for 115min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.08 times of the chemical reaction count; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 20 (L/kg), dissolve in water at 25 ° C for 170 minutes to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.3 times the chemical reaction of rare earth sulfate. The reaction is 43 minutes. After filtration, rare earth oxalate and filtrate are obtained. The recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolving process.
实施例10Example 10
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行250℃焙烧110min，硫酸用量为废镍氢电池粉化学反应计量数的1.09倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为15（L/kg）于30℃水溶解160min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.35倍，反应40min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。After discharging, disassembling, crushing and sieving the waste nickel-hydrogen battery, the waste nickel-hydrogen battery powder and steel shell were obtained; 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder were mixed, and then roasted at 250 °C for 110min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.09 times the number of chemical reactions of the powder; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare-earth sulfate is obtained by dissolving in water at 30 ° C for 160min according to the liquid-solid ratio of 15 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.35 times of the chemical reaction of rare earth sulfate. The reaction is performed for 40 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例11Example 11
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行300℃焙烧105min，硫酸用量为废镍氢电池粉化学反应计量数的1.07倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为19（L/kg）于99℃水溶解15min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.38倍，反应37min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 300°C for 105min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.07 times the number of chemical reaction measurements; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving it in water at 99 °C for 15 minutes according to the liquid-solid ratio of 19 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.38 times of the chemical reaction of rare earth sulfate. The reaction is 37 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例12Example 12
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行350℃焙烧100min，硫酸用量为废镍氢电池粉化学反应计量数的1.06倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为16（L/kg）于40℃水溶解150min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.4倍，反应34min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-metal hydride battery was discharged, disassembled, crushed and sieved to obtain waste nickel-metal hydride battery powder and steel shell; 98wt% concentrated sulfuric acid and waste nickel-metal hydride battery powder were mixed, and then roasted at 350 °C for 100 minutes, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.06 times of the chemical reaction count; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 16 (L/kg), dissolve it in water at 40 ° C for 150 minutes to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.4 times the chemical reaction of rare earth sulfate. The reaction is 34 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例13Example 13
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行400℃焙烧96min，硫酸用量为废镍氢电池粉化学反应计量数的1.05倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为17（L/kg）于35℃水溶解175min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.41倍，反应30min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 400°C for 96min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.05 times of the chemical reaction count; obtain the sulfate roasting product of nickel-cobalt rare earth, and dissolve it in water at 35 ° C for 175 minutes according to the liquid-solid ratio of 17 (L/kg) to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.41 times of the chemical reaction of rare earth sulfate. The reaction is carried out for 30 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例14Example 14
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行450℃焙烧95min，硫酸用量为废镍氢电池粉化学反应计量数的1.1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为18（L/kg）于45℃水溶解140min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.42倍，反应24min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-metal hydride battery was discharged, disassembled, crushed and sieved to obtain waste nickel-hydrogen battery powder and steel shell; 98wt% concentrated sulfuric acid and waste nickel-hydrogen battery powder were mixed, and then roasted at 450°C for 95min, and the amount of sulfuric acid was waste. 1.1 times the number of chemical reactions of nickel-hydrogen battery powder; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 18 (L/kg), dissolve it in water at 45 ° C for 140min to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.42 times of the chemical reaction of rare earth sulfate. The reaction is 24 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolving process.
实施例15Example 15
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行500℃焙烧44min，硫酸用量为废镍氢电池粉化学反应计量数的1.04倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为20（L/kg）于48℃水溶解80min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.43倍，反应20min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。Waste nickel-hydrogen battery powder and steel shell are obtained after discharging, disassembling, crushing and sieving the residual power of waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and waste nickel-hydrogen battery powder, calcining at 500℃ for 44min, the amount of sulfuric acid is waste Nickel-metal hydride battery powder is 1.04 times the number of chemical reaction measurements; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving in water at 48°C for 80 minutes according to the liquid-solid ratio of 20 (L/kg); extracting The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.43 times of the chemical reaction of rare earth sulfate. The reaction is performed for 20 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例16Example 16
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行480℃焙烧50min，硫酸用量为废镍氢电池粉化学反应计量数的1.06倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为11（L/kg）于70℃水溶解60min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.44倍，反应18min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained after discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 480°C for 50min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.06 times of the chemical reaction count; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 11 (L/kg), dissolve it in water at 70 ° C for 60 minutes to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.44 times the chemical reaction of rare earth sulfate. The reaction is performed for 18 minutes. After filtration, rare earth oxalate and filtrate are obtained. The recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolving process.
实施例17Example 17
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行420℃焙烧90min，硫酸用量为废镍氢电池粉化学反应计量数的1.1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为17（L/kg）于55℃水溶解160min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.45倍，反应14min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-metal hydride battery was discharged, disassembled, crushed and sieved to obtain waste nickel-hydrogen battery powder and steel shell; 98wt% concentrated sulfuric acid and waste nickel-hydrogen battery powder were mixed, and then roasted at 420 °C for 90min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.1 times of the chemical reaction count; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 17 (L/kg), dissolve it in water at 55 ° C for 160min to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.45 times of the chemical reaction of rare earth sulfate. The reaction is performed for 14 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolution process.
实施例18Example 18
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行470℃焙烧80min，硫酸用量为废镍氢电池粉化学反应计量数的1.06倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为13（L/kg）于60℃水溶解70min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.46倍，反应13min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained after discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 470°C for 80min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.06 times the number of chemical reactions of the powder; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving it in water at 60 °C for 70 minutes according to the liquid-solid ratio of 13 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.46 times the chemical reaction of rare earth sulfate. The reaction is performed for 13 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例19Example 19
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行475℃焙烧70min，硫酸用量为废镍氢电池粉化学反应计量数的1.07倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为20（L/kg）于47℃水溶解90min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.47倍，反应10min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained after discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 475°C for 70min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1.07 times the number of chemical reactions of the powder; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare earth sulfate is obtained by dissolving it in water at 47°C for 90 minutes according to the liquid-solid ratio of 20 (L/kg); using extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.47 times the chemical reaction of rare earth sulfate. The reaction is performed for 10 minutes. After filtration, rare earth oxalate and filtrate are obtained. The recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolving process.
实施例20Example 20
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行510℃焙烧60min，硫酸用量为废镍氢电池粉化学反应计量数的1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为20（L/kg）于55℃水溶解110min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.48倍，反应8min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained after discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 510 °C for 60min, and the amount of sulfuric acid was waste Nickel-metal hydride battery powder is 1 times the number of chemical reaction measurements; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 20 (L/kg), dissolve it in water at 55 ° C for 110 minutes to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.48 times of the chemical reaction of rare earth sulfate. The reaction is performed for 8 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%;
实施例21Example 21
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行530℃焙烧55min，硫酸用量为废镍氢电池粉化学反应计量数的1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为8（L/kg）于50℃水溶解130min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.49倍，反应6min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。After discharging, disassembling, crushing and sieving the waste nickel-hydrogen battery, the waste nickel-hydrogen battery powder and steel shell were obtained; 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder were mixed, and then roasted at 530 °C for 55 minutes, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1 times the number of chemical reactions; the sulfate roasting product of nickel-cobalt rare earth is obtained, and the solution of nickel-cobalt rare-earth sulfate is obtained by dissolving in water at 50 °C for 130 min according to the liquid-solid ratio of 8 (L/kg); extracting The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.49 times the chemical reaction of rare earth sulfate. The reaction is performed for 6 minutes. After filtration, rare earth oxalate and filtrate are obtained. The recovery rate of rare earth is over 99%;
实施例22Example 22
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行600℃焙烧45min，硫酸用量为废镍氢电池粉化学反应计量数的1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为6（L/kg）于60℃水溶解100min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.5倍，反应5min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained after discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 600 °C for 45min, and the amount of sulfuric acid was waste Nickel-metal hydride battery powder is 1 times the number of chemical reaction counts; obtain the sulfate roasting product of nickel-cobalt rare earth, according to the liquid-solid ratio of 6 (L/kg), dissolve it in water at 60 ° C for 100min to obtain the sulfate solution of nickel-cobalt rare earth; use extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.5 times of the chemical reaction of rare earth sulfate. The reaction is performed for 5 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolution process.
实施例23Example 23
将废旧镍氢电池余电放电、拆解、粉碎过筛后得到废镍氢电池粉和钢壳；将98wt%浓硫酸和废镍氢电池粉混匀后进行650℃焙烧30min，硫酸用量为废镍氢电池粉化学反应计量数的1倍；得到镍钴稀土的硫酸盐焙烧产物，按液固比为11（L/kg）于75℃水溶解58min得镍钴稀土的硫酸盐溶液；采用萃取剂将镍钴离子富集在有机相中，硫酸稀土富集于萃取余液中；然后采用硫酸反萃得到镍钴富集液和萃取剂，萃取剂回用于萃取工序；向萃取余液中加入草酸得到草酸稀土沉淀，草酸用量为硫酸稀土化学反应计量数的1.32倍，反应41min，经过滤得到草酸稀土和滤液，稀土回收率达99%以上；滤液回用于水溶解工序。The waste nickel-hydrogen battery powder and steel shell were obtained by discharging, disassembling, crushing and sieving the residual power of the waste nickel-hydrogen battery; after mixing 98wt% concentrated sulfuric acid and the waste nickel-hydrogen battery powder, calcined at 650 °C for 30min, and the amount of sulfuric acid was waste. Nickel-metal hydride battery powder is 1 times the number of chemical reaction counts; the sulfate roasting product of nickel-cobalt rare earth is obtained. According to the liquid-solid ratio of 11 (L/kg), it is dissolved in water at 75 ° C for 58 minutes to obtain the sulfate solution of nickel-cobalt rare earth; extraction The nickel-cobalt ions are enriched in the organic phase, and the rare earth sulfate is enriched in the extraction residual liquid; then the nickel-cobalt enriched liquid and the extraction agent are obtained by back-extraction with sulfuric acid, and the extraction agent is reused in the extraction process; Add oxalic acid to obtain rare earth oxalate precipitation. The amount of oxalic acid is 1.32 times of the chemical reaction of rare earth sulfate. The reaction is 41 minutes. After filtration, rare earth oxalate and filtrate are obtained, and the recovery rate of rare earth is over 99%; the filtrate is reused in the water dissolution process.
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