CN116949305B - Method for leaching mixed rare earth compound from NdFeB waste - Google Patents
Method for leaching mixed rare earth compound from NdFeB waste Download PDFInfo
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- CN116949305B CN116949305B CN202311220140.5A CN202311220140A CN116949305B CN 116949305 B CN116949305 B CN 116949305B CN 202311220140 A CN202311220140 A CN 202311220140A CN 116949305 B CN116949305 B CN 116949305B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 83
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- -1 rare earth compound Chemical class 0.000 title claims abstract description 33
- 238000002386 leaching Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 52
- 238000005406 washing Methods 0.000 claims abstract description 31
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000002918 waste heat Substances 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- 229910052742 iron Inorganic materials 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008213 purified water Substances 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229960004887 ferric hydroxide Drugs 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 230000002269 spontaneous effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001122 Mischmetal Inorganic materials 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000003345 natural gas Substances 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003546 flue gas Substances 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000000428 dust Substances 0.000 description 14
- 239000000779 smoke Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical compound [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 description 1
- MOSURRVHVKOQHA-UHFFFAOYSA-N [Tb].[Dy] Chemical compound [Tb].[Dy] MOSURRVHVKOQHA-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- 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
-
- 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
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of rare earth recovery, in particular to a method for leaching mixed rare earth compounds from neodymium iron boron waste, which comprises the steps of wet ball grinding, natural oxidation roasting, automatic slurry mixing, rare earth leaching, solid-liquid separation and the like. The waste heat of high-temperature flue gas is adopted to enter a waste heat boiler to prepare steam for leaching rare earth and washing solid slag. The heat energy recovery is fully utilized, and a large amount of natural gas energy is saved.
Description
[ field of technology ]
The invention relates to the field of rare earth recovery, in particular to a method for leaching mixed rare earth compounds from neodymium iron boron waste.
[ background Art ]
The comprehensive utilization of waste resources in developed western countries is early, and the shortage of resources and the environmental deterioration advance the cyclic utilization of various renewable resources including renewable rare earth resources in developed western countries as early as the mid-80 s of the 20 th century. The economic laws and regulations of the circulation of the Germany and the Japanese are most perfected, and the economic circulation of the Germany and the Japanese form a complete closed loop in the implementation process, so that the main resources can be basically recycled, and the good ecological environment is maintained. In 2003, the average recycling rate of various resources in Germany and Japan reaches over 70%, for example, the recycling rate of the Germany waste batteries rises from zero in 1998 to 70% in 2003, and the utilization rate of household wastes rises from 35% in 1996 to 60% in 2003. The two countries establish the development mode of circular economy on the basis of the method, and good economic benefit, social benefit and ecological benefit are obtained.
The renewable resources in China are used in a later starting stage, the renewable resource recovery system is still imperfect, a system for centralized collection and scientific recovery is not completely formed, the resource recovery rate is low, the recycling level is low, and the scale is small. Although the renewable resources industry in China is rapidly developed in recent years, the renewable resources generation amount and the demand amount in China are greatly different from those in developed countries. There is also huge market space for the development of renewable resources in China.
In recent years, as a branch of the recycling industry, the recycling industry of rare earth waste is also in an ascending stage, and particularly, with the implementation of an instruction production plan, the production of rare earth raw ore separation enterprises is limited, and the productivity of the recycling industry of rare earth waste is in an explosive ascending. In order to promote the healthy development of the rare earth industry, the country starts to clean the unlawful and illegal and non-compliant rare earth resource recycling project, and meanwhile, the project of rare earth resource recycling, which is established with a rare earth smelting separation production line, is approved by the industry and informatization department and is listed in the limited industry. Along with the promulgation and implementation of national related laws and regulations and under the drive of rare earth permanent magnet industry, the rare earth recycling industry in China gradually starts to go on the positive rail.
Neodymium iron boron alloy is a rare earth permanent magnet material with excellent performance, and about 30% of waste materials can be generated in the using process due to the production process and the using factors. The NdFeB waste is basically consistent with the components of NdFeB magnetic materials, and consists of rare earth (mainly neodymium, praseodymium and dysprosium in balance), iron and boron, wherein the rare earth content is about 30%, the boron is 1%, and the balance is pure iron. Of the 30% rare earths, praseodymium neodymium is about 87%, gadolinium is about 4%, dysprosium is about 3%, and terbium is about 0.5%. Along with the development of the neodymium iron boron preparation technology, the rare earth component has the trend of cerium increase and dysprosium terbium decrease. The components of the NdFeB waste material can be seen to be full utilization value of rare earth or pure iron.
In the aspect of the supply of the NdFeB waste, the upstream of the NdFeB waste is the manufacturing enterprise of the NdFeB permanent magnet material. The capacity of the NdFeB manufacturing enterprises determines the supply of NdFeB waste materials. With the rapid development of IT industry, automobiles and machinery manufacturing industry, there is an increasing market demand for neodymium-iron-boron magnets. A batch of 'NdFeB heat' appears in China, and a lot of large NdFeB enterprises increase energy and expand production, and a batch of new NdFeB enterprises also grow. One notable feature of the new round of "NdFeB heat" is that the NdFeB magnet industry is accelerating the transfer to the source. Since 1990, three major neodymium iron boron magnet production bases of Zhejiang, shanxi and Jingjin have been developed in China. Subsequently, sintered nd-fe-b magnet industries in the toe cap and smoke counter areas have also been rapidly developed. Currently, third-generation rare earth permanent magnet materials, namely neodymium iron boron, are fully dominant in the market. Along with the continuous expansion of the application field of the neodymium iron boron permanent magnet material, the demand of the market for neodymium iron boron is greatly increased for a long time, and meanwhile, the neodymium iron boron waste recycling industry related to the production and processing of neodymium iron boron is also in a new development period.
Rare earth elements can be recovered for processing neodymium iron boron waste materials as required. Therefore, the downstream application of neodymium iron boron waste recycling is mainly distributed in the fields of permanent magnets, batteries, metallurgy, automobile catalysts, FCC catalysts, polishing powder, ceramics, fluorescent powder and the like, and the application is wide. In China, the national institute of health is discharged from the national institute of health on 5 months and 10 days 2011, and the national exploitation of the raw rare earth mine realizes the instruction production plan management and the strict total rare earth exploitation amount management. Under the condition that the rare earth resource market is limited in supply, the secondary utilization of the rare earth resource is beneficial to saving resources, avoiding the waste of the rare earth resource, reducing industrial garbage and protecting the environment. The recovery of rare earth elements in the NdFeB waste is beneficial to relieving the high-speed increase demand of the domestic market on rare earth resources.
The existing rare earth recovery is carried out on the rare earth by the heat generated by natural gas combustion, such as patent application number: CN202021395004.1 discloses a comprehensive utilization system of heat energy of rare earth firing rotary kiln, air heated in an air heat exchanger is sent into the kiln body through a combustion-supporting fan to mix natural gas for combustion, and rare earth is recovered by burning natural gas, so that the energy consumption is high and the cost is high.
The invention is researched and proposed for overcoming the defects of the prior art.
[ invention ]
The invention aims to overcome the defects of the prior art and provides a method for leaching mixed rare earth compounds from neodymium iron boron waste.
The invention can be realized by the following technical scheme:
the invention discloses a method for leaching mixed rare earth compounds from neodymium iron boron waste, which comprises the following steps:
s1: wet ball milling, namely putting neodymium iron boron waste materials into a ball mill, adding water for wet ball milling, milling to more than 200 meshes, and then transferring to the next working procedure;
s2: natural oxidation roasting, namely discharging the ground rare earth waste into a roasting furnace, blowing air, generating heat of oxidation reaction between iron, rare earth elements and the blown air, wherein oil is contained on the surface of the neodymium iron boron waste, the oxidation reaction of Fe generates heat, and rare earth metal simple substance can generate spontaneous combustion at the temperature of more than 280 ℃, the roasting temperature is controlled to be 600-900 ℃ and the roasting time is 2-3 h, and Fe and rare earth metal in the waste are oxidized into Fe 2 O 3 And rare earth oxide, control reaction temperature and roasting time with the feed rate, smoke and dust exhaust gas produced by roasting is discharged into the exhaust-heat boiler, heat and recovered smoke and dust powder of smoke and dust exhaust gas produced by roasting are recovered through the exhaust-heat boiler;
s3: automatic size mixing, wherein the oxidized and roasted material automatically enters a feed liquid size mixing barrel through a closed material conveying system, and smoke dust powder recovered by a waste heat boiler is also discharged into the size mixing barrel, so that the method comprises the following steps of 1:3, adding washing purified water into the solid-liquid ratio for size mixing;
s4: leaching rare earth, pumping the slurry into an acid dissolving tank, adding washing purified water and inorganic acid according to a certain proportion, controlling the liquid-solid ratio at 3-4:1, controlling the pH value at 1-2, mechanically stirring uniformly, and introducing steam generated by a waste heat boiler to keep the solution temperature in the dissolving tank at 80-90 ℃ for 3-4 hours, so that rare earth oxide is dissolved out preferentially;
s5: solid-liquid separation, namely pumping the mixed solution in the dissolving tank into a filter press under certain pressure and flow rate to realize solid-liquid separation, so as to obtain mixed solution of high-abundance iron slag and various rare earth compounds;
s6: the second stage of washing of the solid slag, because the high-abundance iron slag also contains 1-3% of mixed rare earth compound liquid, after the filter pressing is finished, the steam generated by the waste heat boiler is used for heating washing purified water to 70-80 ℃, the high-abundance iron slag is washed in two stages, and the first stage takes 2 hours, and the mixed rare earth compound is washed out by 98%; the second stage takes 4.5 hours to obtain clean high-abundance iron slag, and the washing purified water formed after the washing liquid is purified and regenerated completely enters three working procedures of automatic size mixing, rare earth leaching and slag fixing two-stage washing for recycling.
Preferably, after the rare earth oxide is leached in the step S4, a certain amount of oxidant is added into a dissolution tank to oxidize ferrous ions into 3-valent iron ions, and then alkali liquor is added to adjust the pH value back to 3.5-4, so that 3-valent iron ions are hydrolyzed to form ferric hydroxide, thereby realizing iron removal and achieving the purpose of leaching mixed rare earth compounds.
Preferably, the inorganic acid in step S4 is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the oxidant is one or a mixture of more of hydrogen peroxide, sodium hypochlorite, potassium hypochlorite and sodium chlorate.
Preferably, the alkali liquor is one or a mixture of more of sodium hydroxide, calcium hydroxide and ammonia water.
Compared with the prior art, the invention has the following advantages:
1. the traditional technology is that high-temperature flue gas after oxidizing roasting of neodymium iron boron waste is emptied after surface cooling, cyclone dust collection, cloth bag dust collection and spray washing, and the project adopts the waste heat of the high-temperature flue gas to enter a waste heat boiler to prepare steam for leaching rare earth and washing solid slag. The heat energy recovery is fully utilized, a large amount of natural gas energy is saved, and positive contribution is made to 'double carbon' emission reduction.
2. After the tap water enters the deionization equipment, the soft water enters the waste heat boiler to generate steam, and the concentrated water enters the wet ball grinding process. The abandoned water after washing the high-abundance iron slag is purified and regenerated and then enters into three working procedures of automatic size mixing, rare earth leaching and slag fixing two-stage washing for recycling, the water resource is recycled by 100%, and the highly clean production without process wastewater discharge is achieved.
[ description of the drawings ]
The invention is described in further detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a junction process flow diagram of the present invention;
[ detailed description ] of the invention
Embodiments of the present invention will be described in detail below with reference to the attached drawings:
example 1
The invention discloses a method for leaching mixed rare earth compounds from neodymium iron boron waste, which comprises the following steps:
s1: wet ball milling, namely putting neodymium iron boron waste materials into a ball mill, adding water for wet ball milling, milling to 300 meshes, and then transferring to the next working procedure;
s2: natural oxidation roasting, namely discharging the ground rare earth waste into a roasting furnace, and blowing air, wherein iron, rare earth elements and the blown air generate heat for oxidation reaction, oil is contained on the surface of the neodymium iron boron waste, the oxidation reaction of Fe generates heat, and rare earth metal simple substances can generate spontaneous combustion at the temperature of more than 280 ℃, the roasting temperature is controlled to 800 ℃, the roasting time is 2 hours, and Fe and rare earth metals in the waste are oxidized into Fe 2 O 3 And rare earth oxide, control reaction temperature and roasting time with the feed rate, smoke and dust exhaust gas produced by roasting is discharged into the exhaust-heat boiler, heat and recovered smoke and dust powder of smoke and dust exhaust gas produced by roasting are recovered through the exhaust-heat boiler;
s3: automatic size mixing, wherein the oxidized and roasted material automatically enters a feed liquid size mixing barrel through a closed material conveying system, and smoke dust powder recovered by a waste heat boiler is also discharged into the size mixing barrel, so that the method comprises the following steps of 1:3, adding washing purified water into the solid-liquid ratio for size mixing;
s4: leaching rare earth, pumping the slurry into an acid dissolving tank, adding washing purified water and hydrochloric acid according to a certain proportion, controlling the liquid-solid ratio to be 3:1, controlling the pH value to be 1, mechanically stirring uniformly, and introducing steam generated by a waste heat boiler to keep the solution temperature in the dissolving tank at the constant temperature of 80 ℃ for 4 hours, so that rare earth oxide is dissolved out preferentially;
s5: solid-liquid separation, namely pumping the mixed solution in the dissolving tank into a filter press under certain pressure and flow rate to realize solid-liquid separation, so as to obtain mixed solution of high-abundance iron slag and various rare earth compounds;
s6: because the high-abundance iron slag also contains 1-3% of mixed rare earth compound liquid, after the filter pressing is finished, steam generated by a waste heat boiler is used for heating washing purified water to 70 ℃, the high-abundance iron slag is washed in two stages, the first stage takes 2 hours, and the mixed rare earth compound is washed out by 98%; the second stage takes 4.5 hours to obtain clean high-abundance iron slag, and the washing purified water formed after the washing liquid is purified and regenerated completely enters three working procedures of automatic size mixing, rare earth leaching and slag fixing two-stage washing for recycling.
And after leaching the rare earth oxide in S4, adding a certain amount of sodium chlorate into a dissolution tank to oxidize ferrous ions into 3-valent iron ions, adding ammonia water to adjust the pH value to 3.5, and hydrolyzing the 3-valent iron ions to form ferric hydroxide so as to realize iron removal and achieve the purpose of leaching the mixed rare earth compound.
Example 2
The invention discloses a method for leaching mixed rare earth compounds from neodymium iron boron waste, which comprises the following steps:
s1: wet ball milling, namely putting neodymium iron boron waste materials into a ball mill, adding water for wet ball milling, milling to 250 meshes, and then transferring to the next working procedure;
s2: natural oxidation roasting, namely, the ground rare earth waste is discharged into a roasting furnace, air is blown in, the iron, the rare earth elements and the blown air generate heat for oxidation reaction, oil is contained on the surface of the neodymium iron boron waste, the oxidation reaction of Fe generates heat, and the rare earth metal simple substance can generate spontaneous combustion at the temperature of more than 280 ℃, and the roasting temperature is highThe temperature is controlled at 600 ℃, the roasting time is 3 hours, and Fe and rare earth metal in the waste material are oxidized into Fe 2 O 3 And rare earth oxide, control reaction temperature and roasting time with the feed rate, smoke and dust exhaust gas produced by roasting is discharged into the exhaust-heat boiler, heat and recovered smoke and dust powder of smoke and dust exhaust gas produced by roasting are recovered through the exhaust-heat boiler;
s3: automatic size mixing, wherein the oxidized and roasted material automatically enters a feed liquid size mixing barrel through a closed material conveying system, and smoke dust powder recovered by a waste heat boiler is also discharged into the size mixing barrel, so that the method comprises the following steps of 1:3, adding washing purified water into the solid-liquid ratio for size mixing;
s4: leaching rare earth, pumping the slurry into an acid dissolving tank, adding washing purified water and hydrochloric acid according to a certain proportion, controlling the liquid-solid ratio to be 4:1, controlling the pH value to be 2, mechanically stirring uniformly, and introducing steam generated by a waste heat boiler to keep the solution temperature in the dissolving tank at the constant temperature of 80 ℃ for 4 hours, so that rare earth oxide is dissolved out preferentially;
s5: solid-liquid separation, namely pumping the mixed solution in the dissolving tank into a filter press under certain pressure and flow rate to realize solid-liquid separation, so as to obtain mixed solution of high-abundance iron slag and various rare earth compounds;
s6: because the high-abundance iron slag also contains 1-3% of mixed rare earth compound liquid, after the filter pressing is finished, steam generated by a waste heat boiler is used for heating washing purified water to 70 ℃, the high-abundance iron slag is washed in two stages, the first stage takes 2 hours, and the mixed rare earth compound is washed out by 98%; the second stage takes 4.5 hours to obtain clean high-abundance iron slag, and the washing purified water formed after the washing liquid is purified and regenerated completely enters three working procedures of automatic size mixing, rare earth leaching and slag fixing two-stage washing for recycling.
After the rare earth oxide is leached in S4, a certain amount of hydrogen peroxide is added into a dissolution tank to oxidize ferrous ions into 3-valent iron ions, and then sodium hydroxide is added to adjust the pH value back to 4, so that 3-valent iron ions are hydrolyzed to form ferric hydroxide, iron removal is realized, and the purpose of leaching the mixed rare earth compound is achieved.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that various changes, modifications, substitutions and alterations can be made herein by those skilled in the art without departing from the technical principles of the present invention, and such changes, modifications, substitutions and alterations are also to be regarded as the scope of the invention.
Claims (2)
1. A method for leaching mixed rare earth compounds from neodymium iron boron waste materials, which is characterized by comprising the following steps:
s1: wet ball milling, namely putting neodymium iron boron waste materials into a ball mill, adding water for wet ball milling, milling to more than 200 meshes, and then transferring to the next working procedure;
s2: natural oxidation roasting, namely discharging the ground rare earth waste into a roasting furnace, blowing air, generating heat of oxidation reaction between iron, rare earth elements and the blown air, wherein oil is contained on the surface of the neodymium iron boron waste, the oxidation reaction of Fe generates heat, and rare earth metal simple substance can generate spontaneous combustion at the temperature of more than 280 ℃, the roasting temperature is controlled to be 600-900 ℃ and the roasting time is 2-3 h, and Fe and rare earth metal in the waste are oxidized into Fe 2 O 3 And rare earth oxide, controlling the reaction temperature and the roasting time at the feeding speed;
s3: automatic size mixing, wherein the oxidized and roasted material automatically enters a feed liquid size mixing barrel through a closed material conveying system, and the mixing ratio is 1:3, adding washing purified water into the solid-liquid ratio for size mixing;
s4: leaching rare earth, pumping the slurry into an acid dissolving tank, adding washing purified water and inorganic acid according to a certain proportion, controlling the liquid-solid ratio to be 3-4:1, controlling the pH value to be 1-2, mechanically stirring uniformly, introducing steam generated by a waste heat boiler to keep the solution temperature in the dissolving tank at the constant temperature of 80-90 ℃ for 3-4 hours, leading rare earth oxide to be preferentially dissolved out, adding a certain amount of oxidant into the dissolving tank to fully oxidize ferrous ions into 3-valent iron ions after leaching the rare earth oxide, and then adding alkali liquor to adjust the pH value back to 3.5-4, so that 3-valent iron ions are hydrolyzed to form ferric hydroxide to realize iron removal, thereby achieving the purpose of leaching mixed rare earth compounds; the oxidant is one or a mixture of more of hydrogen peroxide, sodium hypochlorite, potassium hypochlorite and sodium chlorate; the alkali liquor is one or a mixture of more of sodium hydroxide, calcium hydroxide and ammonia water;
s5: solid-liquid separation, namely pumping the mixed solution in the dissolving tank into a filter press under certain pressure and flow rate to realize solid-liquid separation, so as to obtain mixed solution of high-abundance iron slag and various rare earth compounds;
s6: the second stage of washing of the solid slag, because the high-abundance iron slag also contains 1-3% of mixed rare earth compound liquid, after the filter pressing is finished, the steam generated by the waste heat boiler is used for heating washing purified water to 70-80 ℃, the high-abundance iron slag is washed in two stages, and the first stage takes 2 hours, and the mixed rare earth compound is washed out by 98%; the second stage takes 4.5 hours to obtain clean high-abundance iron slag, and the washing purified water formed after the washing liquid is purified and regenerated completely enters three working procedures of automatic size mixing, rare earth leaching and slag fixing two-stage washing for recycling.
2. The method of leaching misch metal compounds from neodymium iron boron waste according to claim 1, wherein: the inorganic acid in the step S4 is one or a mixture of more of hydrochloric acid, sulfuric acid and nitric acid.
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| CN104446427A (en) * | 2014-11-18 | 2015-03-25 | 连云港市兆昱新材料实业有限公司 | Rare-earth doped spinel type ferrite magnetic powder prepared based on NdFeB wastes and preparation method thereof |
| CN106282553A (en) * | 2015-05-26 | 2017-01-04 | 有研稀土新材料股份有限公司 | The smelting separation method of Rare Earth Mine |
| CN113652550A (en) * | 2021-07-15 | 2021-11-16 | 江西理工大学 | Method for comprehensively recovering rare earth and iron from neodymium iron boron oil sludge |
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| US20160068929A1 (en) * | 2014-09-08 | 2016-03-10 | Patrick R. Taylor | EXTRACTION OF RARE EARTH METALS FROM NdFeB USING SELECTIVE SULFATION ROASTING |
| EP3715482A1 (en) * | 2019-03-29 | 2020-09-30 | Tata Consultancy Services Limited | Method and system for separation of rare earth elements from secondary sources |
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| CN104446427A (en) * | 2014-11-18 | 2015-03-25 | 连云港市兆昱新材料实业有限公司 | Rare-earth doped spinel type ferrite magnetic powder prepared based on NdFeB wastes and preparation method thereof |
| CN106282553A (en) * | 2015-05-26 | 2017-01-04 | 有研稀土新材料股份有限公司 | The smelting separation method of Rare Earth Mine |
| CN113652550A (en) * | 2021-07-15 | 2021-11-16 | 江西理工大学 | Method for comprehensively recovering rare earth and iron from neodymium iron boron oil sludge |
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Application publication date: 20231027 Assignee: Xinfeng Yili Renewable Resources Recycling Co.,Ltd. Assignor: XINFENG BAOGANG XINLI RARE EARTH Co.,Ltd. Contract record no.: X2024980005495 Denomination of invention: A method for leaching mixed rare earth compounds from neodymium iron boron waste Granted publication date: 20231205 License type: Common License Record date: 20240509 |