CN111349798B - Neodymium iron boron waste recycling system and method - Google Patents
Neodymium iron boron waste recycling system and method Download PDFInfo
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- CN111349798B CN111349798B CN202010186548.5A CN202010186548A CN111349798B CN 111349798 B CN111349798 B CN 111349798B CN 202010186548 A CN202010186548 A CN 202010186548A CN 111349798 B CN111349798 B CN 111349798B
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- 239000002699 waste material Substances 0.000 title claims abstract description 164
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 118
- 238000004064 recycling Methods 0.000 title claims abstract description 50
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims description 151
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 344
- 238000002386 leaching Methods 0.000 claims abstract description 183
- 239000007788 liquid Substances 0.000 claims abstract description 176
- 239000002253 acid Substances 0.000 claims abstract description 161
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 130
- 238000000926 separation method Methods 0.000 claims abstract description 121
- 238000011084 recovery Methods 0.000 claims abstract description 116
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 91
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 80
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims description 90
- 235000021110 pickles Nutrition 0.000 claims description 63
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000012065 filter cake Substances 0.000 claims description 57
- -1 rare earth metal chloride Chemical class 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 45
- 238000000746 purification Methods 0.000 claims description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 41
- 239000003546 flue gas Substances 0.000 claims description 41
- 239000011343 solid material Substances 0.000 claims description 36
- 238000010521 absorption reaction Methods 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 27
- 239000000428 dust Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 16
- 239000004744 fabric Substances 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 101
- 229910052742 iron Inorganic materials 0.000 abstract description 45
- 150000002910 rare earth metals Chemical class 0.000 abstract description 32
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 48
- 229910052777 Praseodymium Inorganic materials 0.000 description 48
- 238000005406 washing Methods 0.000 description 48
- 229910052692 Dysprosium Inorganic materials 0.000 description 42
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 42
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 42
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 36
- 239000002893 slag Substances 0.000 description 36
- 238000002156 mixing Methods 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000003350 kerosene Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229960002089 ferrous chloride Drugs 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 6
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004094 preconcentration Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- BOXVSFHSLKQLNZ-UHFFFAOYSA-K dysprosium(iii) chloride Chemical compound Cl[Dy](Cl)Cl BOXVSFHSLKQLNZ-UHFFFAOYSA-K 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000007131 hydrochloric acid regeneration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明涉及一种钕铁硼废料资源化回收系统及回收方法，所述钕铁硼废料资源化回收系统包括钕铁硼废料供给单元、酸浸单元、第一固液分离单元、酸浸液喷雾热解单元、水浸单元、第二固液分离单元、水浸液萃取单元与盐酸回收单元，通过酸浸液喷雾热解单元的设置实现了铁与稀土金属的有效分离，实现铁与稀土金属分别进行回收，工艺过程对环境友好，并通过稀土元素的回收产生巨大的经济效益。所述回收方法操作简单，通过对盐酸的回收减少了盐酸的用量以及盐酸的排放量。
The invention relates to a NdFeB waste recycling system and a recycling method. The NdFeB waste recycling system includes a NdFeB waste supply unit, an acid leaching unit, a first solid-liquid separation unit, and an acid leaching liquid spray. Pyrolysis unit, water leaching unit, second solid-liquid separation unit, water leaching liquid extraction unit and hydrochloric acid recovery unit, through the setting of acid leaching liquid spray pyrolysis unit, the effective separation of iron and rare earth metals is realized, and iron and rare earth metals are realized. Recycling is carried out separately, the process is environmentally friendly, and huge economic benefits are generated through the recovery of rare earth elements. The recovery method is simple to operate, and the consumption of hydrochloric acid and the discharge amount of hydrochloric acid are reduced by recovering the hydrochloric acid.
Description
Technical Field
The invention belongs to the technical field of resource recovery and environmental protection, relates to a waste material resource recovery system and a waste material resource recovery method, and particularly relates to a neodymium iron boron waste material resource recovery system and a neodymium iron boron waste material resource recovery method.
Background
The neodymium iron boron magnetic material is a permanent magnetic material with excellent performance, is called as 'permanent magnet king', and enables the permanent magnetic material to be reused unprecedentedly in the fields of electronics, communication, medical equipment, aerospace, automobile industry, industrial automation and the like with high strength magnetism and relatively low cost. However, due to the production process and the use factor, the utilization rate of the raw materials for producing the ndfeb magnetic material is only about 75%, that is, about 25% of the ndfeb waste is generated during the production of the ndfeb magnetic material.
The mass fraction of rare earth in the neodymium iron boron waste material is about 33%, the mass fraction of boron is about 1%, and the balance is iron and added noble metals such as cobalt, dysprosium, praseodymium and the like, so that the neodymium iron boron waste material can be used as a secondary resource for recovering the rare earth and other valuable metal elements. The neodymium iron boron waste is comprehensively utilized to the maximum extent, the utilization rate of resources is improved, the environment is protected, and the recovery of rare earth elements from the neodymium iron boron waste can bring great economic benefit and social benefit.
The method for recovering the neodymium iron boron waste comprises a wet method and an active method, and mainly comprises a hydrochloric acid optimum dissolution method, a full extraction method, a sulfuric acid-double salt method, a direct reduction-slag gold melting method and an electroreduction-extraction method.
The hydrochloric acid optimum dissolution method is to dissolve the rare earth in the neodymium iron boron waste preferentially by hydrochloric acid under the condition of controlling acid decomposition, and to obtain rare earth products by the processes of oxidizing roasting, acid dissolution impurity removal, extraction separation, precipitation firing and the like. However, the method needs to oxidize metals such as neodymium, iron and the like into metal oxides through high-temperature oxidizing roasting, and has high energy consumption; and ammonia water is required to be added for regulation and control in the optimal dissolution process of the hydrochloric acid, so that a large amount of ammonia nitrogen wastewater is generated.
The total extraction method utilizes hydrochloric acid to completely dissolve rare earth elements, cobalt, iron and the like in the waste, and obtains a product through the processes of iron removal by oxidation, extraction separation, precipitation, ignition and the like. Specifically, the total extraction method comprises the steps of performing total dissolution by using hydrochloric acid, oxidizing ferrous ions into ferric ions to extract and remove iron from the ferric ions, performing multi-stage extraction to obtain neodymium oxide and dysprosium oxide, and recovering cobalt from the solution after iron and rare earth elements are removed by using carbonate, so that the recovery of rare earth metals and cobalt is realized. However, the process flow of the full extraction method is long, and the ferric ion solution obtained by extraction is difficult to treat.
The sulfuric acid-double salt method utilizes the difference of the properties of various chemical elements in the waste material, adopts H2SO4Dissolving, precipitating rare earth by sodium sulfate, converting sodium hydroxide, dissolving by hydrochloric acid, precipitating iron by double salt, extracting and separating and the like, thereby obtaining neodymium oxide, dysprosium oxide and cobalt oxide with higher purity. The impurity requirement of dysprosium oxide composite electrolysis for producing metal dysprosium is that the mass fraction of rare earth impurities in cobalt oxide is less than 0.01 percent. However, the sulfuric acid-double salt method uses caustic soda, sodium sulfate, hydrochloric acid and other media, the process flow is long, and a large amount of iron-containing salts are formed in the process flow, which is not beneficial to environmental protection.
The direct reduction-slag-metal melting separation method utilizes the difference of larger chemical activity between rare earth elements and iron elements in the neodymium iron boron waste materials, and recovers metal iron, cobalt alloy and slag rich in high rare earth oxide by the direct reduction-slag-metal melting separation method, thereby realizing the cooperative recovery of rare earth and other valuable metals. However, the slag of rare earth oxides still needs to be further extracted by a wet method.
The electro-reduction-extraction method continuously electro-reduces the waste neodymium iron boron decomposition liquid in an electrolytic tank, and the decomposition liquid after electro-reduction enters an extraction tank for extraction separation and iron removal. The electro-reduction-extraction method can realize industrial production, the recovery rate of the rare earth is 98.13 percent, and the recovered rare earth feed liquid can be directly extracted and separated, but the method has high operation cost and large equipment investment, and also has the same environmental pollution problem as the full extraction method and the hydrochloric acid optimal solution method.
Therefore, the neodymium iron boron waste recycling system and the recycling method are simple to operate, high in rare earth recovery rate and environment-friendly, the neodymium iron boron waste recycling cost and the environmental pollution damage are reduced, and huge economic benefits can be generated for the rare earth elements.
Disclosure of Invention
The invention aims to provide a neodymium iron boron waste recycling system and a recycling method, wherein the neodymium iron boron waste recycling system can effectively separate iron and rare earth metals, can respectively recycle the iron and the rare earth metals, is environment-friendly in the recycling process, and can generate great economic benefit through recycling the rare earth elements. The method is simple to operate, and the consumption of the hydrochloric acid and the discharge amount of the hydrochloric acid are reduced by recovering the hydrochloric acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a neodymium iron boron waste recycling system, which comprises a neodymium iron boron waste supply unit, an acid leaching unit, a first solid-liquid separation unit, an acid leaching solution spray pyrolysis unit, a water leaching unit, a second solid-liquid separation unit, a water leaching solution extraction unit and a hydrochloric acid recycling unit.
The neodymium iron boron waste material supply unit is connected with the acid leaching unit and is used for providing neodymium iron boron waste materials for the acid leaching unit; the first solid-liquid separation unit is connected with the acid leaching unit and is used for separating acid leaching liquid generated by the acid leaching unit from solid; the pickle liquor spray pyrolysis unit is connected with the first solid-liquid separation unit and is used for spray pyrolysis of the pickle liquor conveyed by the first solid-liquid separation unit; the water leaching unit is connected with the pickle liquor spray pyrolysis unit and is used for leaching solid materials generated by spray pyrolysis of pickle liquor; the second solid-liquid separation unit is connected with the water leaching unit and is used for solid-liquid separation of water leaching feed liquid; the water extract extraction unit is connected with the second solid-liquid separation unit and is used for extracting water extract obtained by solid-liquid separation; the hydrochloric acid recovery unit is connected with the acid leaching solution spray pyrolysis unit and the acid leaching unit and used for recovering hydrochloric acid generated by the acid leaching solution spray pyrolysis unit and conveying the hydrochloric acid to the acid leaching unit to perform acid leaching on the neodymium iron boron waste material.
The method comprises the steps of dissolving valuable elements such as iron, neodymium, praseodymium and dysprosium in neodymium iron boron waste materials by high-temperature hydrochloric acid, so that the valuable elements are separated from silicon and other insoluble impurities; then FeCl in the pickle liquor is subjected to spray pyrolysis of the pickle liquor2Decomposition to HCl and insoluble Fe2O3Meanwhile, chlorine salts of neodymium, praseodymium and dysprosium are not decomposed, so that the separation of Fe from neodymium, praseodymium and dysprosium is ensured by water immersion, and the difficulty of subsequent separation and purification of neodymium, praseodymium and dysprosium is reduced; and HCl generated by decomposition can be used as an acid source of the acid leaching unit after being recovered, so that the cyclic utilization of the HCl is realized.
Preferably, neodymium iron boron waste material feed unit is including the ball mill and the neodymium iron boron waste material conveyer that connect gradually, and neodymium iron boron waste material conveyer conveys the neodymium iron boron waste material after the ball-milling to the pickling unit.
The invention improves the specific surface area of the neodymium iron boron waste through ball milling treatment, thereby being beneficial to acid leaching of the neodymium iron boron waste. The neodymium iron boron waste conveyor includes but is not limited to a belt conveyor and/or a screw conveyor, and those skilled in the art can reasonably select the conveyor according to the process requirement.
Preferably, the acid leaching unit comprises a hydrochloric acid leaching device and an acid leaching liquid conveying device, the neodymium iron boron waste conveyor is connected with a feed inlet of the hydrochloric acid leaching device, and the acid leaching liquid conveying device is used for conveying the acid leaching liquid to the first solid-liquid separation unit.
The hydrochloric acid leaching device is a device capable of realizing hydrochloric acid leaching, and comprises but is not limited to a hydrochloric acid leaching kettle; the acid leach liquor delivery means includes, but is not limited to, an acid leach liquor delivery pump.
Preferably, the hydrochloric acid leaching device is an indirect heating hydrochloric acid leaching kettle, and the heat source of the indirect heating hydrochloric acid leaching kettle is low-pressure steam; the indirect heating hydrochloric acid leaching kettle is made of hydrochloric acid resistant materials, including but not limited to lining glass and/or graphite.
Preferably, the first solid-liquid separation unit comprises an acid leaching solution filter press, an acid leaching solution storage device and an acid leaching solution conveying device which are connected in sequence, and the acid leaching solution conveying device is connected with the acid leaching solution spray pyrolysis unit.
The pickle liquor storage device is a device capable of storing pickle liquor, and comprises but is not limited to a pickle liquor buffer tank; the pickle liquor conveying device comprises but is not limited to a buffer tank discharge pump.
Preferably, the pickle liquor spray pyrolysis unit comprises a spray pyrolysis device, a gas-solid separation device and a powder conveyor; the pickle liquor conveying device is connected with a feed inlet of the spray pyrolysis device; the discharge hole of the spray pyrolysis device is connected with the feed inlet of the gas-solid separation device; the solid outlet of the gas-solid separation device is connected with the powder conveyor, and the gas outlet of the gas-solid separation device is connected with the hydrochloric acid recovery unit.
The powder conveyor comprises a belt conveyor and/or a screw conveyor, and is used for collecting solid powder separated in a gas-solid separation device and conveying the solid powder to a water immersion unit, and a person skilled in the art can reasonably select the powder conveyor according to process requirements.
Preferably, the pickle liquor spray pyrolysis unit further comprises a heat exchange concentration device and a concentrated liquor conveying device; the feed inlet of the heat exchange concentration device is connected with the pickle liquor conveying device, the feed liquor outlet of the heat exchange concentration device is connected with the feed inlet of the spray pyrolysis device through the concentrated liquor conveying device, the gas outlet of the gas-solid separation device is connected with the gas inlet of the heat exchange concentration device, and the gas outlet of the heat exchange concentration device is connected with the hydrochloric acid recovery unit.
Concentrated solution conveyor includes but not limited to the concentrated solution delivery pump, the concentrated solution delivery pump not only can carry the concentrated solution to the spray pyrolysis device, can also improve the outstanding effect of concentrated solution and high-temperature gas through setting up the circulation concentrated solution of branch road, improves the concentrated efficiency of heat transfer concentration. The heat exchange concentration device is a gas-liquid contact heat exchange device, and a person skilled in the art can reasonably select the type number according to needs, and the invention is not limited too much here.
In the invention, the gas obtained by the gas-solid separation device has higher temperature, and the consumption of absorption liquid is increased when the gas is directly absorbed; the high-temperature gas heats the pickle liquor through the arrangement of the heat exchange concentration device, so that the preconcentration of the pickle liquor is realized, the energy consumption of the subsequent spray pyrolysis is reduced, and the high-temperature gas can be recovered without excessive absorption liquid after being cooled. Therefore, the energy consumption of the neodymium iron boron waste recovery is greatly reduced by arranging the heat exchange concentration device.
Preferably, the spray pyrolysis device is a spray pyrolysis furnace with a bottom heating, and a feed inlet of the spray pyrolysis furnace is arranged at the bottom of the tower.
The bottom-heating spray pyrolysis furnace is a pyrolysis furnace which is heated at the bottom and is fed from the bottom, namely an upper-spraying type pyrolysis furnace with an upper-spraying type spray dryer structure, and the fuel used by the pyrolysis furnace is natural gas. In the spray pyrolysis process, the high-temperature flue gas and the pickle liquor needing spray pyrolysis flow in parallel, so that the controllability of the spray pyrolysis temperature is ensured, and the generation of an overheated area is effectively avoided, thereby realizing FeCl2While decomposing, the chloride salts of neodymium, praseodymium and dysprosium are hardly decomposed.
Preferably, the gas-solid separation device comprises a cyclone separator and a bag-type dust collector which are sequentially connected, an inlet of the cyclone separator is connected with a discharge port of the spray pyrolysis device, an air outlet of the bag-type dust collector is connected with an air inlet of the heat exchange concentration device, and a discharge port of the cyclone separator and the bag-type dust collector is connected with the powder conveyor.
Preferably, the cloth bag used by the cloth bag dust remover is a temperature-resistant cloth bag which can resist the temperature of more than 350 ℃.
Preferably, the material of the temperature-resistant cloth bag comprises a ceramic sintering net and/or a metal sintering net.
Preferably, the hydrochloric acid recovery unit comprises a hydrochloric acid absorption tower, a tail gas conveying device and a tail gas purification device which are connected in sequence.
The tail gas purification device comprises a tail gas purification tower and a purification liquid circulating pump; the gas inlet of hydrochloric acid absorption tower is connected with the gas outlet of heat exchange concentration device, the gas outlet of hydrochloric acid absorption tower is connected with the gas inlet of tail gas purification tower through tail gas conveying device, the tower bottom purification liquid of tail gas purification tower is connected with the liquid inlet of hydrochloric acid absorption tower through purification liquid circulating pump, and the liquid outlet of hydrochloric acid absorption tower is connected with the hydrochloric acid inlet of hydrochloric acid pickling device.
According to the invention, the hydrochloric acid recovery unit is arranged to realize the recovery of the acid-containing gas generated by spray pyrolysis, so that the consumption and discharge of hydrochloric acid are reduced, the environmental protection is realized, and the environmental burden of enterprises is reduced. When the recovered hydrochloric acid amount cannot meet the hydrochloric acid amount required by acid leaching of the neodymium iron boron waste, acid leaching can be performed in a manner of externally supplementing hydrochloric acid.
The tail gas conveying device comprises but is not limited to an acid-proof fan, and the tail gas conveying device can be reasonably selected by a person skilled in the art according to the process requirement.
Preferably, the water leaching unit comprises a water leaching device and a water leaching material liquid conveying device which are sequentially connected, a feed port of the water leaching device is connected with the powder conveyor, and a discharge port of the water leaching device is connected with the second solid-liquid separation unit through the water leaching material liquid conveying device.
The water leaching device is a device capable of performing water leaching and comprises but is not limited to a water leaching kettle; the water leaching feed liquid conveying device comprises but is not limited to a water leaching feed liquid discharge pump.
Preferably, the second solid-liquid separation unit comprises a water-soaked filter press.
Preferably, the second solid liquid separation unit further comprises a drying device, including but not limited to an oven. The drying device can dry a filter cake obtained by the water leaching filter press to obtain an iron oxide red product.
Preferably, the aqueous leach solution extraction unit comprises a rare earth chloride extraction plant. The rare earth metal chloride extraction device is an extraction reactor which is conventional in the field, and the invention is not limited to the excess.
Spray pyrolysis of pickle liquor to remove FeCl2Pyrolysis to insoluble Fe2O3The separation of Fe from neodymium, praseodymium, and dysprosium can be achieved by water immersion. After the water leaching is finished, the filter pressing is carried out, and Fe can be obtained2O3A filter cake as the main component and an aqueous extract with neodymium, praseodymium and dysprosium chloride salt as the main component. The obtained water extract can realize the separation of neodymium, praseodymium and dysprosium through conventional extraction treatment, thereby realizing the recycling of iron, neodymium, praseodymium and dysprosium in the neodymium iron boron waste material.
In a second aspect, the invention provides a recycling method for recycling neodymium iron boron waste by using the neodymium iron boron waste recycling system in the first aspect, and the recycling method comprises the following steps:
(1) performing acid leaching treatment on the neodymium iron boron waste material by hydrochloric acid, and performing solid-liquid separation to obtain a pickle liquor;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) to obtain acid-containing flue gas and solid materials;
(3) water leaching the solid material in the step (2), and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3).
Preferably, the method further comprises the step of washing the solid slag obtained after the solid-liquid separation in the step (1), wherein the residual rare earth elements in the solid slag can be dissolved by washing, so that the recovery rate of the rare earth elements is ensured. In this case, the pickle liquor in the step (1) is obtained by mixing the liquid obtained by the solid-liquid separation in the step (1) with a water washing liquid.
Preferably, the solid slag is washed with water in a liquid-solid ratio of (5-10):1, preferably 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but not limited to the values listed, and other values not listed within the range of values are equally applicable, said liquid-solid ratio being in mL/g.
Preferably, the method also comprises a step of washing the filter cake obtained in the step (3), wherein the residual rare earth elements in the filter cake are transferred to the water phase by the washing, so that the recovery rate of the rare earth elements is ensured. In this case, the rare earth metal chloride solution in the step (3) is obtained by mixing the liquid obtained by the solid-liquid separation in the step (3) and a filter cake water washing liquid.
Preferably, the liquid-to-solid ratio of water used to wash the filter cake to the filter cake is (10-15):1, preferably 10:1, 11:1, 12:1, 13:1, 14:1 or 15:1, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable, the liquid-to-solid ratio being in mL/g.
Preferably, the hydrochloric acid of step (1) has a concentration of 18 to 21 wt.%, and may be, for example, 18 wt.%, 18.5 wt.%, 19 wt.%, 19.5 wt.%, 20 wt.%, 20.5 wt.%, or 21 wt.%, but is not limited to the recited values, and other values not recited within the numerical ranges are equally applicable.
The hydrochloric acid has the function of dissolving valuable metal elements in the neodymium iron boron waste, the hydrochloric acid recovered by the hydrochloric acid recovery device is hydrochloric acid which reacts with Fe to generate ferrous chloride, and a person skilled in the art can adjust the usage amount of the hydrochloric acid according to the content of the elements in the treated neodymium iron boron waste so as to ensure that the hydrochloric acid can sufficiently pickle the valuable metal elements in the neodymium iron boron waste.
Preferably, the temperature of the acid leaching treatment in step (1) is 80-95 ℃, for example, 80 ℃, 82 ℃, 85 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃ or 95 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable; the time is 60-90min, for example 60min, 65min, 70min, 75min, 80min, 85min or 90min, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the temperature of the spray pyrolysis in step (2) is 300-350 ℃, and may be, for example, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The temperature of the spray pyrolysis is 300-350 ℃, and FeCl is generated at the temperature2Sufficient decomposition can be obtained, and the chlorine salt of neodymium, praseodymium, and dysprosium is hardly decomposed. When the temperature exceeds 350 ℃, the chloride decomposition rate of neodymium, praseodymium and dysprosium is increased, and the subsequent recovery rate of neodymium, praseodymium and dysprosium is reduced; when the temperature is lower than 300 ℃, FeCl2Can not be completely decomposed, the addition amount of hydrochloric acid is increased, and the subsequent separation difficulty of neodymium, praseodymium and dysprosium is increased.
Preferably, the temperature of the water immersion treatment in step (3) is 80-95 ℃, for example, 80 ℃, 82 ℃, 85 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃ or 95 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable; the time is 40-60min, for example 40min, 45min, 50min, 55min or 60min, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the drying temperature in step (4) is 150-180 ℃, such as 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ or 180 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
The extracting agent used for the extraction separation of the invention includes but is not limited to an extracting agent formed by mixing P507 and kerosene, and can be reasonably selected by a person skilled in the art according to the requirements of an extraction process.
Preferably, the recovery method further comprises the step of ball milling the neodymium iron boron waste materials to more than 200 meshes before the step (1).
The invention discloses a method for ball-milling and crushing neodymium iron boron waste materials to more than 200 meshes, which is characterized in that the neodymium iron boron waste materials after ball milling are sieved by a 200-mesh sieve, and the sieved neodymium iron boron waste materials are selected as subsequent treatment objects.
As a preferable embodiment of the recovery method according to the second aspect of the present invention, the recovery method includes the steps of:
(1) ball-milling and crushing the neodymium iron boron waste to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste for 60-90min by using hydrochloric acid with the concentration of 18-21 wt% at the temperature of 80-95 ℃, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) spray pyrolysis treatment is carried out on the pickle liquor obtained in the step (1) at the temperature of 300 ℃, (B) acid-containing flue gas and solid materials are obtained;
(3) water leaching the solid material in the step (2) for 40-60min at the temperature of 80-95 ℃, and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at the temperature of 150 ℃ and 180 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3).
Further preferably, the recovery method comprises the steps of:
(1) ball-milling and crushing the neodymium iron boron waste to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste for 60-90min by using hydrochloric acid with the concentration of 18-21 wt% at the temperature of 80-95 ℃, and carrying out solid-liquid separation; washing the solid obtained after the solid-liquid separation with water, and mixing the water washing liquid with the liquid obtained by the solid-liquid separation to obtain pickle liquor; the liquid-solid ratio of water to solid used for washing is (5-10) to 1, and the unit is mL/g;
(2) spray pyrolysis treatment is carried out on the pickle liquor obtained in the step (1) at the temperature of 300 ℃, (B) acid-containing flue gas and solid materials are obtained;
(3) water leaching the solid material in the step (2) for 40-60min at the temperature of 80-95 ℃, and performing solid-liquid separation to obtain a filter cake and a rare earth solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1); washing the filter cake obtained after solid-liquid separation with water, and mixing the washing liquid with the rare earth solution to obtain a rare earth metal chloride solution, wherein the liquid-solid ratio of the water used for washing the filter cake with water to the filter cake is (10-15):1, and the unit is mL/g;
(4) drying the filter cake obtained in the step (3) at the temperature of 150 ℃ and 180 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3).
The system refers to an equipment system, or a production equipment.
Compared with the prior art, the invention has the following beneficial effects:
(1) the system can realize effective separation of iron and rare earth metal through the arrangement of the pickle liquor spray pyrolysis unit, so that the iron and the rare earth metal can be respectively recovered; the hydrochloric acid recovery unit is arranged, so that the recovery process is environment-friendly, and great economic benefit is generated by recovering the rare earth elements;
(2) the recovery method provided by the invention is simple in process, the consumption of hydrochloric acid and the discharge amount of hydrochloric acid can be reduced by recovering hydrochloric acid, so that the recovery method is environment-friendly, and the recovery method is an environment-friendly and clean method.
Drawings
Fig. 1 is a schematic structural diagram of a neodymium iron boron waste recycling system provided in embodiment 1 of the present invention;
fig. 2 is a schematic structural diagram of a neodymium iron boron waste recycling system provided in embodiment 2 of the present invention.
Wherein: 1, a ball mill; 2, a neodymium iron boron waste conveyor; 3, pickling the kettle with hydrochloric acid; 4, acid leaching liquid conveying pump; 5, acid leaching liquor filter press; 6, a pickle liquor buffer tank; 7, a buffer tank discharge pump; 8, a spray pyrolysis furnace; 9, a cyclone separator; 10, a bag-type dust collector; 11, a powder conveyor; 12, a heat exchange concentration device; 13, a concentrated solution delivery pump; 14, a hydrochloric acid absorption tower; 15, an acid-resistant fan; 16, a tail gas purification tower; 17, a purifying liquid circulating pump; 18, a water immersion kettle; 19, a water leaching feed liquid discharge pump; 20, a water leaching material filter press; 21, a rare earth metal chloride extraction reactor; 22, an oven.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This embodiment provides a neodymium iron boron waste recycling system, neodymium iron boron waste recycling system's schematic diagram is shown in fig. 1, including neodymium iron boron waste supply unit, acid leaching unit, first solid-liquid separation unit, acid leaching liquid spray pyrolysis unit, water leaching unit, second solid-liquid separation unit, water leaching liquid extraction unit and hydrochloric acid recovery unit.
The neodymium iron boron waste material supply unit comprises a ball mill 1 and a neodymium iron boron waste material conveyor 2 which are connected in sequence, and the neodymium iron boron waste material subjected to ball milling is conveyed to the acid leaching unit through the neodymium iron boron waste material conveyor 2.
The acid leaching unit comprises a hydrochloric acid leaching kettle 3 and an acid leaching liquid delivery pump 4, a neodymium iron boron waste conveyor 2 is connected with a feed inlet of the hydrochloric acid leaching kettle 3, and the acid leaching liquid delivery pump 4 is used for delivering acid leaching liquid to the first solid-liquid separation unit.
The first solid-liquid separation unit comprises an acid leaching liquid filter press 5, an acid leaching liquid buffer tank 6 and a buffer tank discharge pump 7 which are connected in sequence, and the buffer tank discharge pump 7 is connected with the acid leaching liquid spray pyrolysis unit.
The pickle liquor spray pyrolysis unit comprises a spray pyrolysis furnace 8 with a bottom for heating and feeding, a cyclone separator 9, a bag-type dust collector 10 and a powder conveyor 11; the buffer tank discharge pump 7 is connected with a feed inlet of the spray pyrolysis furnace 8; the discharge hole of the spray pyrolysis furnace 8 is connected with the feed inlet of the cyclone separator 9; the solid outlets of the cyclone separator 9 and the bag-type dust collector 10 are connected with the powder conveyor 11, and the gas outlet of the bag-type dust collector 10 is connected with the hydrochloric acid recovery unit. The cloth bag used by the cloth bag dust collector 10 is a temperature-resistant cloth bag which can resist the temperature of more than 350 ℃.
The hydrochloric acid recovery unit comprises a hydrochloric acid absorption tower 14, an acid-resistant fan 15 and a tail gas purification device which are sequentially connected, wherein the tail gas purification device comprises a tail gas purification tower 16 and a purification liquid circulating pump 17. The gas inlet of the hydrochloric acid absorption tower 14 is connected with the gas outlet of the bag-type dust collector 10, the gas outlet of the hydrochloric acid absorption tower 14 is connected with the gas inlet of the tail gas purification tower 16 through an acid-resistant fan 15, the tower bottom purification liquid of the tail gas purification tower 16 is connected with the liquid inlet of the hydrochloric acid absorption tower 14 through a purification liquid circulating pump 17, and the liquid outlet of the hydrochloric acid absorption tower 14 is connected with the hydrochloric acid inlet of the hydrochloric acid leaching kettle 3.
The water leaching unit comprises a water leaching kettle 18 and a water leaching material liquid discharging pump 19 which are sequentially connected, a feed port of the water leaching kettle 18 is connected with the powder conveyor 11, and a discharge port of the water leaching kettle 18 is connected with the second solid-liquid separation unit through the water leaching material liquid discharging pump 19.
The second solid-liquid separation unit comprises a water-soaked material filter press 20 and an oven 22. The aqueous extraction unit includes a rare earth chloride extraction reactor 21. The oven 22 is capable of drying the filter cake obtained by the water soak filter press 20 to obtain the iron oxide red product.
When the recovery system provided by the embodiment is applied to recover the neodymium iron boron waste, valuable elements of iron, neodymium, praseodymium and dysprosium in the neodymium iron boron waste are dissolved through high-temperature hydrochloric acid, so that separation of valuable elements and incompatible impurities such as silicon is realized; then FeCl2 in the pickle liquor is decomposed into HCl and insoluble Fe2O3 through spray pyrolysis of the pickle liquor, and meanwhile, chlorine salts of neodymium, praseodymium and dysprosium are not decomposed, so that the separation of Fe from neodymium, praseodymium and dysprosium through water leaching is ensured, and the difficulty of subsequent separation and purification of neodymium, praseodymium and dysprosium is reduced; and HCl generated by decomposition can be used as an acid source of the acid leaching unit after being recovered, so that the cyclic utilization of the HCl is realized. When the recovered HCl can not meet the amount of HCl used in acid leaching, acid leaching can be carried out by externally adding hydrochloric acid into the hydrochloric acid leaching kettle 3.
Example 2
This embodiment provides a neodymium iron boron waste recycling system, neodymium iron boron waste recycling system's schematic diagram is shown in fig. 2, including neodymium iron boron waste supply unit, pickling unit, first solid-liquid separation unit, pickling liquid spray pyrolysis unit, water logging unit, second solid-liquid separation unit, water logging extraction unit and hydrochloric acid recovery unit.
Compared with the embodiment 1, the pickle liquor spray pyrolysis unit of the embodiment is also internally provided with a heat exchange concentration device 12 and a concentrated liquor delivery pump 13; the feed inlet and the buffer tank discharge pump 7 of heat transfer enrichment facility 12 are connected, and the feed liquid export of heat transfer enrichment facility 12 passes through concentrate delivery pump 13 and is connected with the feed inlet of spray pyrolysis stove 8, and the gas outlet of sack cleaner 10 is connected with the gas inlet of heat transfer enrichment facility 12, and the gas outlet of heat transfer enrichment facility 12 is connected with hydrochloric acid absorption tower 14 in the hydrochloric acid recovery unit.
The setting of heat transfer enrichment facility 12 is passed through to this embodiment, makes high-temperature gas heat the pickle liquor, has realized the preconcentration of pickle liquor to reduce the energy consumption of follow-up spray pyrolysis, need not too much absorption liquid can be retrieved after the high-temperature gas cooling moreover. Therefore, the energy consumption of the neodymium iron boron waste recovery is greatly reduced by the arrangement of the heat exchange concentration device 12 in the embodiment.
The neodymium iron boron waste recycling system provided by the invention is used for recycling neodymium iron boron waste, and the element composition of the neodymium iron boron waste is shown in table 1.
TABLE 1
Application example 1
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the embodiment 1, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) ball-milling and crushing the neodymium iron boron waste materials to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste materials for 75min at 88 ℃ by using hydrochloric acid with the concentration of 19 wt%, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 320 ℃ to obtain acid-containing flue gas and solid materials;
(3) soaking the solid material in the step (2) in water at 88 ℃ for 50min, and carrying out solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at 160 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3) by using a mixed extracting agent of P507 and kerosene.
The recovery rate of iron is 98.2 percent by measuring the content of iron in the iron oxide red product; the total recovery rate of neodymium, praseodymium and dysprosium can reach 97.5 percent through extraction and separation.
Application example 2
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) ball-milling and crushing the neodymium iron boron waste materials to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste materials for 75min at 88 ℃ by using hydrochloric acid with the concentration of 19 wt%, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 320 ℃ to obtain acid-containing flue gas and solid materials;
(3) soaking the solid material in the step (2) in water at 88 ℃ for 50min, and carrying out solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at 160 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3) by using a mixed extracting agent of P507 and kerosene.
The recovery rate of iron is 98.2 percent by measuring the content of iron in the iron oxide red product; the total recovery rate of neodymium, praseodymium and dysprosium can reach 97.5 percent through extraction and separation.
Application example 3
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) ball-milling and crushing the neodymium iron boron waste materials to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste materials for 85min at 85 ℃ by using hydrochloric acid with the concentration of 19 wt%, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 310 ℃ to obtain acid-containing flue gas and solid materials;
(3) water leaching the solid material in the step (2) for 55min at 85 ℃, and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at 160 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3) by using a mixed extracting agent of P507 and kerosene.
The iron recovery rate is 97.8 percent by measuring the iron content in the iron oxide red product; the total recovery rate of neodymium, praseodymium and dysprosium can reach 97.3 percent through extraction and separation.
Application example 4
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) ball-milling and crushing the neodymium iron boron waste materials to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste materials for 65min at 90 ℃ by using hydrochloric acid with the concentration of 20 wt%, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 340 ℃ to obtain acid-containing flue gas and solid materials;
(3) water leaching the solid material in the step (2) for 45min at 90 ℃, and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at 170 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3) by using a mixed extracting agent of P507 and kerosene.
The recovery rate of iron is 98.4 percent by measuring the content of iron in the iron oxide red product; the total recovery rate of neodymium, praseodymium and dysprosium can reach 97.7 percent through extraction and separation.
Application example 5
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) ball-milling and crushing the neodymium iron boron waste materials to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste materials for 90min at a temperature of 80 ℃ by using hydrochloric acid with a concentration of 18 wt%, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 300 ℃ to obtain acid-containing flue gas and solid materials;
(3) water leaching the solid material in the step (2) for 40min at 95 ℃, and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at the temperature of 150 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3) by using a mixed extracting agent of P507 and kerosene.
The iron recovery rate is 97.5 percent by measuring the iron content in the iron oxide red product; the total recovery rate of neodymium, praseodymium and dysprosium can reach 97.0 percent through extraction and separation.
Application example 6
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) ball-milling and crushing the neodymium iron boron waste materials to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste materials for 60min at a temperature of 95 ℃ by using hydrochloric acid with a concentration of 21 wt%, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 350 ℃ to obtain acid-containing flue gas and solid materials;
(3) water leaching the solid material in the step (2) for 60min at the temperature of 80 ℃, and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at 180 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3) by using a mixed extracting agent of P507 and kerosene.
The recovery rate of iron is 98.5 percent by measuring the content of iron in the iron oxide red product; the total recovery rate of neodymium, praseodymium and dysprosium can reach 97.8 percent through extraction and separation.
Example 7
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) weighing 1000Kg of neodymium iron boron waste, wherein the molar weight of Fe is 7.39Kmol, and the total molar weight of Nd, Pr and Dy is 1.25 Kmol; ball-milling the neodymium iron boron waste materials to be crushed into particles with the particle size of more than 200 meshes, mixing the ball-milled neodymium iron boron waste materials with 4133kg of hydrochloric acid with the concentration of 18 wt%, and carrying out acid leaching at 95 ℃ for 60min, wherein in the process, valuable metal elements such as iron, neodymium, praseodymium, dysprosium and the like in the waste materials are dissolved to form chlorides; solid-liquid separation, washing solid slag with water, wherein the ratio of the washing water amount to the slag amount is 5:1, the wet weight of the filtered slag is 440Kg, the water content is 51 percent, and the filtered slag is discharged as insoluble silica slag; mixing the water washing liquid with the liquid obtained by solid-liquid separation to obtain pickle liquor;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 300 ℃, wherein ferrous chloride is completely decomposed and oxidized into ferric oxide, and chlorides of neodymium, praseodymium and dysprosium are not hydrolyzed; the high-temperature HCl-containing flue gas sequentially enters a cyclone separator 9 and a high-temperature bag-type dust collector 10 and then enters a pre-concentrator, and dust recovery and cooling are realized in the process to obtain acid-containing flue gas and solid materials;
(3) recycling acid-containing flue gas to obtain 3370Kg of hydrochloric acid with the concentration of 18 wt%, circulating the obtained hydrochloric acid to the step (1) for acid leaching treatment, sending the absorbed tail gas into a tail gas purification tower 16 by an acid-resistant tail gas fan, purifying the tail gas with water by a circulating pump of the tail gas purification tower 16 to reach the standard and discharging, and circularly pumping the purified liquid to a hydrochloric acid absorption tower 14 by the tail gas purification tower 16 after the purified liquid reaches a certain concentration for HCl absorption; water leaching the solid material in the step (2) for 60min at the temperature of 80 ℃, dissolving neodymium, praseodymium and dysprosium chloride into a liquid phase in the process, performing solid-liquid separation to obtain a filter cake and a rare earth solution, washing the filter cake with water, wherein the liquid-solid ratio of the washing water to the filter cake is 10:1mL/g, and mixing the washing liquid with the rare earth solution to obtain a rare earth metal chloride solution;
(4) drying the washed filter cake obtained in the step (3) at 160 ℃ to obtain 595Kg of iron oxide red product, wherein the content of ferric oxide is 98.5 percent, and the yield of iron reaches 99.2 percent; and (3) extracting and separating the rare earth chloride solution obtained in the step (3) by using a mixed extractant of P507 and kerosene to obtain 1300Kg of neodymium chloride solution with the mass concentration of 15%, 400Kg of praseodymium chloride solution with the mass concentration of 15% and 300Kg of dysprosium chloride solution with the mass concentration of 15%, wherein the total yield of the rare earth chloride reaches 99.0%.
Example 8
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) weighing 1000Kg of neodymium iron boron waste, wherein the molar weight of Fe is 7.39Kmol, and the total molar weight of Nd, Pr and Dy is 1.25 Kmol; ball milling the neodymium iron boron waste to obtain powder with the particle size of more than 200 meshes, mixing the ball milled neodymium iron boron waste with hydrochloric acid, and performing acid leaching at 80 ℃ for 90min, wherein the hydrochloric acid is 21 wt% hydrochloric acid obtained by mixing 3370Kg of 18 wt% hydrochloric acid obtained in example 7 with 570Kg of 36 wt% hydrochloric acid; in the process, valuable metal elements such as iron, neodymium, praseodymium, dysprosium and the like in the waste are dissolved to form chloride; solid-liquid separation, washing the solid slag with water, wherein the ratio of the washing water amount to the slag amount is 6:1, the wet weight of the filtered slag is 438Kg, the water content is 50%, and the filtered slag is discharged as insoluble silica slag; mixing the water washing liquid with the liquid obtained by solid-liquid separation to obtain pickle liquor;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at the temperature of 310 ℃, wherein ferrous chloride is completely decomposed and oxidized into ferric oxide, and chlorides of neodymium, praseodymium and dysprosium are not hydrolyzed; the high-temperature HCl-containing flue gas sequentially enters a cyclone separator 9 and a high-temperature bag-type dust collector 10 and then enters a pre-concentrator, and dust recovery and cooling are realized in the process to obtain acid-containing flue gas and solid materials;
(3) recycling acid-containing flue gas to obtain 3200Kg of hydrochloric acid with the concentration of 21 wt%, circulating the obtained hydrochloric acid to the step (1) for acid leaching treatment, sending the absorbed tail gas into a tail gas purification tower 16 by an acid-resistant tail gas fan, purifying the tail gas with water by a circulating pump of the tail gas purification tower 16 to reach the standard and discharging, and circularly pumping the purified liquid to a hydrochloric acid absorption tower 14 by the tail gas purification tower 16 after reaching a certain concentration for HCl absorption; water leaching the solid material in the step (2) for 40min at 95 ℃, dissolving neodymium, praseodymium and dysprosium chloride into a liquid phase in the process, performing solid-liquid separation to obtain a filter cake and a rare earth solution, washing the filter cake with water, wherein the liquid-solid ratio of the washing water to the filter cake is 11:1mL/g, and mixing the washing liquid with the rare earth solution to obtain a rare earth metal chloride solution;
(4) drying the washed filter cake obtained in the step (3) at 160 ℃ to obtain 590Kg of iron oxide red product, wherein the content of the ferric oxide is 98.7 percent, and the yield of the iron reaches 98.6 percent; and (3) extracting and separating the rare earth chloride solution obtained in the step (3) by using a mixed extractant of P507 and kerosene to obtain 1220Kg of neodymium chloride solution with the mass concentration of 16%, 375Kg of praseodymium chloride solution with the mass concentration of 16% and 280Kg of dysprosium chloride solution with the mass concentration of 16%, wherein the total yield of the rare earth chloride reaches 98.9%.
Example 9
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) weighing 1000Kg of neodymium iron boron waste, wherein the molar weight of Fe is 7.39Kmol, and the total molar weight of Nd, Pr and Dy is 1.25 Kmol; ball milling the neodymium iron boron waste to obtain powder with the particle size of more than 200 meshes, mixing the ball milled neodymium iron boron waste with hydrochloric acid, and carrying out acid leaching at 85 ℃ for 80min, wherein the hydrochloric acid is 21 wt% hydrochloric acid obtained in 3200Kg obtained in example 8, 36 wt% hydrochloric acid obtained in example 8 and water with the concentration of 19 wt% obtained by mixing 550 Kg; in the process, valuable metal elements such as iron, neodymium, praseodymium, dysprosium and the like in the waste are dissolved to form chloride; solid-liquid separation, washing solid slag with water, wherein the ratio of the washing water amount to the slag amount is 7:1, the wet weight of the filtered slag is 439Kg, the water content is 50 percent, and the filtered slag is discharged as insoluble silica slag; mixing the water washing liquid with the liquid obtained by solid-liquid separation to obtain pickle liquor;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 320 ℃, wherein ferrous chloride is completely decomposed and oxidized into ferric oxide, and chlorides of neodymium, praseodymium and dysprosium are not hydrolyzed; the high-temperature HCl-containing flue gas sequentially enters a cyclone separator 9 and a high-temperature bag-type dust collector 10 and then enters a pre-concentrator, and dust recovery and cooling are realized in the process to obtain acid-containing flue gas and solid materials;
(3) recycling acid-containing flue gas to obtain 3100Kg of hydrochloric acid with the concentration of 20 wt%, circulating the obtained hydrochloric acid to the step (1) for acid leaching treatment, sending the absorbed tail gas into a tail gas purification tower 16 by an acid-resistant tail gas fan, purifying the tail gas with water by a circulating pump of the tail gas purification tower 16 to reach the standard and discharging, and circularly pumping the purified liquid to a hydrochloric acid absorption tower 14 by the tail gas purification tower 16 after the purified liquid reaches a certain concentration for absorbing HCl; water leaching the solid material in the step (2) for 45min at 90 ℃, dissolving neodymium, praseodymium and dysprosium chloride into a liquid phase in the process, performing solid-liquid separation to obtain a filter cake and a rare earth solution, washing the filter cake with water, wherein the liquid-solid ratio of the washing water to the filter cake is 12:1mL/g, and mixing the washing liquid with the rare earth solution to obtain a rare earth metal chloride solution;
(4) drying the washed filter cake obtained in the step (3) at 170 ℃ to obtain 592Kg of iron oxide red product, wherein the content of the ferric oxide is 98.6 percent, and the yield of the iron reaches 98.8 percent; and (3) extracting and separating the rare earth chloride solution obtained in the step (3) by using a mixed extractant of P507 and kerosene to obtain 1150Kg of neodymium chloride solution with the mass concentration of 17%, 350Kg of praseodymium chloride solution with the mass concentration of 17% and 260Kg of dysprosium chloride solution with the mass concentration of 17%, wherein the total yield of the rare earth chloride reaches 98.5%.
Example 9
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) weighing 1000Kg of neodymium iron boron waste, wherein the molar weight of Fe is 7.39Kmol, and the total molar weight of Nd, Pr and Dy is 1.25 Kmol; ball milling the neodymium iron boron waste to obtain powder with the particle size of more than 200 meshes, mixing the ball milled neodymium iron boron waste with hydrochloric acid, and carrying out acid leaching at 85 ℃ for 80min, wherein the hydrochloric acid is 21 wt% hydrochloric acid obtained in 3200Kg obtained in example 8, 36 wt% hydrochloric acid obtained in example 8 and water with the concentration of 19 wt% obtained by mixing 550 Kg; in the process, valuable metal elements such as iron, neodymium, praseodymium, dysprosium and the like in the waste are dissolved to form chloride; solid-liquid separation, washing solid slag with water, wherein the ratio of the washing water amount to the slag amount is 7:1, the wet weight of the filtered slag is 439Kg, the water content is 50 percent, and the filtered slag is discharged as insoluble silica slag; mixing the water washing liquid with the liquid obtained by solid-liquid separation to obtain pickle liquor;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 320 ℃, wherein ferrous chloride is completely decomposed and oxidized into ferric oxide, and chlorides of neodymium, praseodymium and dysprosium are not hydrolyzed; the high-temperature HCl-containing flue gas sequentially enters a cyclone separator 9 and a high-temperature bag-type dust collector 10 and then enters a pre-concentrator, and dust recovery and cooling are realized in the process to obtain acid-containing flue gas and solid materials;
(3) recycling acid-containing flue gas to obtain 3100Kg of hydrochloric acid with the concentration of 20 wt%, circulating the obtained hydrochloric acid to the step (1) for acid leaching treatment, sending the absorbed tail gas into a tail gas purification tower 16 by an acid-resistant tail gas fan, purifying the tail gas with water by a circulating pump of the tail gas purification tower 16 to reach the standard and discharging, and circularly pumping the purified liquid to a hydrochloric acid absorption tower 14 by the tail gas purification tower 16 after the purified liquid reaches a certain concentration for absorbing HCl; water leaching the solid material in the step (2) for 50min at 90 ℃, dissolving neodymium, praseodymium and dysprosium chloride into a liquid phase in the process, performing solid-liquid separation to obtain a filter cake and a rare earth solution, washing the filter cake with water, wherein the liquid-solid ratio of the washing water to the filter cake is 12:1mL/g, and mixing the washing liquid with the rare earth solution to obtain a rare earth metal chloride solution;
(4) drying the washed filter cake obtained in the step (3) at 170 ℃ to obtain 592Kg of iron oxide red product, wherein the content of the ferric oxide is 98.6 percent, and the yield of the iron reaches 98.8 percent; and (3) extracting and separating the rare earth chloride solution obtained in the step (3) by using a mixed extractant of P507 and kerosene to obtain 1150Kg of neodymium chloride solution with the mass concentration of 17%, 350Kg of praseodymium chloride solution with the mass concentration of 17% and 260Kg of dysprosium chloride solution with the mass concentration of 17%, wherein the total yield of the rare earth chloride reaches 98.5%.
Example 10
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) weighing 1000Kg of neodymium iron boron waste, wherein the molar weight of Fe is 7.39Kmol, and the total molar weight of Nd, Pr and Dy is 1.25 Kmol; ball-milling the neodymium iron boron waste to obtain powder with the particle size of more than 200 meshes, mixing the ball-milled neodymium iron boron waste with hydrochloric acid, and performing acid leaching at 90 ℃ for 70min, wherein the hydrochloric acid is 20 wt% hydrochloric acid obtained in 3100Kg of example 9, 36 wt% hydrochloric acid obtained in 420Kg of example 9 and water with the concentration of 19 wt% obtained in 540Kg of example; in the process, valuable metal elements such as iron, neodymium, praseodymium, dysprosium and the like in the waste are dissolved to form chloride; solid-liquid separation, washing solid slag with water, wherein the ratio of the washing water amount to the slag amount is 8:1, the wet weight of the filtered slag is 440Kg, the water content is 51 percent, and the filtered slag is discharged as insoluble silica slag; mixing the water washing liquid with the liquid obtained by solid-liquid separation to obtain pickle liquor;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) at 330 ℃, wherein ferrous chloride is completely decomposed and oxidized into ferric oxide, and chlorides of neodymium, praseodymium and dysprosium are not hydrolyzed; the high-temperature HCl-containing flue gas sequentially enters a cyclone separator 9 and a high-temperature bag-type dust collector 10 and then enters a pre-concentrator, and dust recovery and cooling are realized in the process to obtain acid-containing flue gas and solid materials;
(3) recycling acid-containing flue gas to obtain 3330Kg of hydrochloric acid with the concentration of 19 wt%, circulating the obtained hydrochloric acid to the step (1) for acid leaching treatment, sending the absorbed tail gas into a tail gas purification tower 16 by an acid-resistant tail gas fan, purifying the tail gas with water by a circulating pump of the tail gas purification tower 16 to reach the standard and discharging, and circularly pumping the purified liquid to a hydrochloric acid absorption tower 14 by the tail gas purification tower 16 after the purified liquid reaches a certain concentration for HCl absorption; water leaching the solid material in the step (2) for 55min at 85 ℃, dissolving neodymium, praseodymium and dysprosium chloride into a liquid phase in the process, performing solid-liquid separation to obtain a filter cake and a rare earth solution, washing the filter cake with water, wherein the liquid-solid ratio of the washing water to the filter cake is 13:1mL/g, and mixing the washing liquid with the rare earth solution to obtain a rare earth metal chloride solution;
(4) drying the washed filter cake obtained in the step (3) at 150 ℃ to obtain 593Kg of iron oxide red product, wherein the content of ferric oxide is 98.5 percent, and the yield of iron reaches 98.8 percent; and (3) extracting and separating the rare earth chloride solution obtained in the step (3) by using a mixed extractant of P507 and kerosene to obtain 1085Kg of neodymium chloride solution with the mass concentration of 18%, 330Kg of praseodymium chloride solution with the mass concentration of 18% and 245Kg of dysprosium chloride solution with the mass concentration of 18%, wherein the total yield of the rare earth chloride reaches 98.3%.
Example 11
The application example provides a recovery method for recovering neodymium iron boron waste by using the neodymium iron boron waste resource recovery system provided in the application example 2, the element composition of the neodymium iron boron waste is shown in table 1, and the recovery method comprises the following steps:
(1) weighing 1000Kg of neodymium iron boron waste, wherein the molar weight of Fe is 7.39Kmol, and the total molar weight of Nd, Pr and Dy is 1.25 Kmol; ball-milling the neodymium iron boron waste to obtain powder with the particle size of more than 200 meshes, mixing the ball-milled neodymium iron boron waste with hydrochloric acid, and carrying out acid leaching at the temperature of 95 ℃ for 60min, wherein the hydrochloric acid is 18 wt% hydrochloric acid obtained by mixing 3330Kg of 19 wt% hydrochloric acid obtained in example 10, 422Kg of 36 wt% hydrochloric acid and 605Kg of water; in the process, valuable metal elements such as iron, neodymium, praseodymium, dysprosium and the like in the waste are dissolved to form chloride; solid-liquid separation, washing solid slag with water, wherein the ratio of the washing water amount to the slag amount is 10:1, the wet weight of the filtered slag is 441Kg, the water content is 50 percent, and the filtered slag is discharged as insoluble silica slag; mixing the water washing liquid with the liquid obtained by solid-liquid separation to obtain pickle liquor;
(2) spray pyrolysis is carried out on the pickle liquor obtained in the step (1) at the temperature of 350 ℃, at the moment, ferrous chloride is completely decomposed and oxidized into ferric oxide, and chlorides of neodymium, praseodymium and dysprosium are not hydrolyzed; the high-temperature HCl-containing flue gas sequentially enters a cyclone separator 9 and a high-temperature bag-type dust collector 10 and then enters a pre-concentrator, and dust recovery and cooling are realized in the process to obtain acid-containing flue gas and solid materials;
(3) recycling acid-containing flue gas to obtain 3600Kg of hydrochloric acid with the concentration of 18 wt%, circulating the obtained hydrochloric acid to the step (1) for acid leaching treatment, sending the absorbed tail gas into a tail gas purification tower 16 by an acid-resistant tail gas fan, purifying the tail gas with water by a circulating pump of the tail gas purification tower 16 to reach the standard and discharging, and circularly pumping the purified liquid to a hydrochloric acid absorption tower 14 by the tail gas purification tower 16 for absorbing HCl after the purified liquid reaches a certain concentration; water leaching the solid material in the step (2) for 50min at 90 ℃, dissolving neodymium, praseodymium and dysprosium chloride into a liquid phase in the process, performing solid-liquid separation to obtain a filter cake and a rare earth solution, washing the filter cake with water, wherein the liquid-solid ratio of the washing water to the filter cake is 15:1mL/g, and mixing the washing liquid with the rare earth solution to obtain a rare earth metal chloride solution;
(4) drying the washed filter cake obtained in the step (3) at 180 ℃ to obtain 590Kg of iron oxide red product, wherein the content of the ferric oxide is 98.8 percent, and the yield of the iron reaches 98.7 percent; and (3) extracting and separating the rare earth chloride solution obtained in the step (3) by using a mixed extractant of P507 and kerosene to obtain 973Kg of neodymium chloride solution with the mass concentration of 20%, 295Kg of praseodymium chloride solution with the mass concentration of 20% and 218Kg of dysprosium chloride solution with the mass concentration of 20%, wherein the total yield of the rare earth chloride reaches 98.0%.
In conclusion, the method utilizes the high-temperature hydrochloric acid regeneration cycle to ensure that all valuable components in the neodymium iron boron waste enter the liquid phase; the effective separation of iron and rare earth metal is realized by the arrangement of the pickle liquor spray pyrolysis unit; the hydrochloric acid recovery unit is arranged, so that the recovery process is environment-friendly, and great economic benefit is generated by recovering the rare earth elements; the recovery method provided by the invention is simple in process, the consumption of hydrochloric acid and the discharge amount of hydrochloric acid can be reduced by recovering hydrochloric acid, so that the recovery method is environment-friendly, and the recovery method is an environment-friendly and clean method. The recovery system and the recovery method are green recovery system and method.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (21)
1. The method for recycling the neodymium iron boron waste is characterized by comprising the following steps:
(1) performing acid leaching treatment on the neodymium iron boron waste material by hydrochloric acid, and performing solid-liquid separation to obtain a pickle liquor;
(2) carrying out spray pyrolysis treatment on the pickle liquor obtained in the step (1) to obtain acid-containing flue gas and solid materials;
(3) water leaching the solid material in the step (2), and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) to obtain an iron oxide red product; extracting and separating the rare earth metal chloride solution obtained in the step (3);
the recovery method is carried out in a neodymium iron boron waste recycling system, and the neodymium iron boron waste recycling system comprises a neodymium iron boron waste supply unit, an acid leaching unit, a first solid-liquid separation unit, an acid leaching solution spray pyrolysis unit, a water leaching unit, a second solid-liquid separation unit, a water leaching solution extraction unit and a hydrochloric acid recovery unit;
the neodymium iron boron waste material supply unit is connected with the acid leaching unit and is used for providing neodymium iron boron waste materials for the acid leaching unit;
the first solid-liquid separation unit is connected with the acid leaching unit and is used for separating acid leaching liquid generated by the acid leaching unit from solid;
the pickle liquor spray pyrolysis unit is connected with the first solid-liquid separation unit and is used for spray pyrolysis of the pickle liquor conveyed by the first solid-liquid separation unit;
the water leaching unit is connected with the pickle liquor spray pyrolysis unit and is used for leaching solid materials generated by spray pyrolysis of pickle liquor;
the second solid-liquid separation unit is connected with the water leaching unit and is used for solid-liquid separation of water leaching feed liquid;
the water extract extraction unit is connected with the second solid-liquid separation unit and is used for extracting water extract obtained by solid-liquid separation;
the hydrochloric acid recovery unit is connected with the acid leaching solution spray pyrolysis unit and the acid leaching unit and used for recovering hydrochloric acid generated by the acid leaching solution spray pyrolysis unit and conveying the hydrochloric acid to the acid leaching unit to perform acid leaching on the neodymium iron boron waste material.
2. The recycling method according to claim 1, wherein the neodymium iron boron waste material supply unit comprises a ball mill and a neodymium iron boron waste material conveyor which are connected in sequence, and the neodymium iron boron waste material conveyor conveys the milled neodymium iron boron waste material to the acid leaching unit.
3. The recycling method according to claim 2, wherein the acid leaching unit comprises an acid leaching device with hydrochloric acid and an acid leaching liquid conveying device, the neodymium iron boron waste material conveyor is connected with a feeding port of the acid leaching device with hydrochloric acid, and the acid leaching liquid conveying device is used for conveying acid leaching liquid to the first solid-liquid separation unit.
4. The recycling method according to claim 3, characterized in that the first solid-liquid separation unit comprises an acid leaching solution filter press, an acid leaching solution storage device and an acid leaching solution conveying device which are connected in sequence, wherein the acid leaching solution conveying device is connected with the acid leaching solution spray pyrolysis unit.
5. The recycling method according to claim 4, wherein the pickle liquor spray pyrolysis unit comprises a spray pyrolysis device, a gas-solid separation device and a powder conveyor; the pickle liquor conveying device is connected with a feed inlet of the spray pyrolysis device; the discharge hole of the spray pyrolysis device is connected with the feed inlet of the gas-solid separation device; the solid outlet of the gas-solid separation device is connected with the powder conveyor, and the gas outlet of the gas-solid separation device is connected with the hydrochloric acid recovery unit.
6. The recovery method of claim 5, wherein the pickle liquor spray pyrolysis unit further comprises a heat exchange concentration device and a concentrate delivery device; the feed inlet of the heat exchange concentration device is connected with the pickle liquor conveying device, the feed liquor outlet of the heat exchange concentration device is connected with the feed inlet of the spray pyrolysis device through the concentrated liquor conveying device, the gas outlet of the gas-solid separation device is connected with the gas inlet of the heat exchange concentration device, and the gas outlet of the heat exchange concentration device is connected with the hydrochloric acid recovery unit.
7. The recycling method according to claim 6, wherein the spray pyrolysis device is a bottom-heated spray pyrolysis furnace, and the feed inlet of the spray pyrolysis furnace is arranged at the bottom of the tower.
8. The recycling method of claim 7, wherein the gas-solid separation device comprises a cyclone separator and a bag-type dust collector which are connected in sequence, an inlet of the cyclone separator is connected with a discharge port of the spray pyrolysis device, an air outlet of the bag-type dust collector is connected with an air inlet of the heat exchange concentration device, and a discharge port of the cyclone separator and the bag-type dust collector is connected with the powder conveyor.
9. The recycling method according to claim 8, wherein the cloth bag used by the cloth bag dust remover is a temperature-resistant cloth bag which can resist the temperature of more than 350 ℃.
10. The recovery method according to claim 8, wherein the hydrochloric acid recovery unit comprises a hydrochloric acid absorption tower, a tail gas conveying device and a tail gas purifying device which are connected in sequence;
the tail gas purification device comprises a tail gas purification tower and a purification liquid circulating pump; the gas inlet of hydrochloric acid absorption tower is connected with the gas outlet of heat exchange concentration device, the gas outlet of hydrochloric acid absorption tower is connected with the gas inlet of tail gas purification tower through tail gas conveying device, the tower bottom purification liquid of tail gas purification tower is connected with the liquid inlet of hydrochloric acid absorption tower through purification liquid circulating pump, and the liquid outlet of hydrochloric acid absorption tower is connected with the hydrochloric acid inlet of hydrochloric acid pickling device.
11. The recycling method according to claim 10, wherein the water leaching unit comprises a water leaching device and a water leaching feed liquid conveying device which are connected in sequence, a feed inlet of the water leaching device is connected with the powder conveyor, and a discharge outlet of the water leaching device is connected with the second solid-liquid separation unit through the water leaching feed liquid conveying device.
12. The recovery method according to claim 1 or 11, wherein the second solid-liquid separation unit comprises a water-soaked filter press.
13. The recovery process of claim 12, wherein the second solid-liquid separation unit comprises a drying device.
14. A recovery process according to claim 1 or 13, characterised in that the aqueous leach solution extraction unit comprises a rare earth metal chloride extraction plant.
15. The recovery method according to claim 1, wherein the concentration of the hydrochloric acid of the step (1) is 18 to 21 wt%.
16. The recovery method according to claim 1, wherein the temperature of the acid leaching treatment in step (1) is 80-95 ℃ and the time is 60-90 min.
17. The recycling method as claimed in claim 1, wherein the temperature of the spray pyrolysis in the step (2) is 300-350 ℃.
18. The recycling method according to claim 1, wherein the temperature of the water immersion treatment in the step (3) is 80-95 ℃ and the time is 40-60 min.
19. The recycling method as set forth in claim 1, wherein the temperature for drying in step (4) is 150 ℃ to 180 ℃.
20. The recycling method according to claim 1, further comprising the step of ball milling the neodymium iron boron waste to 200 mesh or more before step (1).
21. The method according to claim 1, wherein the recovery method comprises the steps of:
(1) ball-milling and crushing the neodymium iron boron waste to a particle size of more than 200 meshes, then carrying out acid leaching treatment on the neodymium iron boron waste for 60-90min by using hydrochloric acid with the concentration of 18-21 wt% at the temperature of 80-95 ℃, and carrying out solid-liquid separation to obtain acid leaching solution;
(2) spray pyrolysis treatment is carried out on the pickle liquor obtained in the step (1) at the temperature of 300 ℃, (B) acid-containing flue gas and solid materials are obtained;
(3) water leaching the solid material in the step (2) for 40-60min at the temperature of 80-95 ℃, and performing solid-liquid separation to obtain a filter cake and a rare earth metal chloride solution; the hydrochloric acid obtained by recovering the acid-containing flue gas is reused for the acid leaching treatment in the step (1);
(4) drying the filter cake obtained in the step (3) at the temperature of 150 ℃ and 180 ℃ to obtain an iron oxide red product; and (4) extracting and separating the rare earth metal chloride solution obtained in the step (3).
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| CN115475444B (en) * | 2022-09-23 | 2023-11-21 | 江西万弘高新技术材料有限公司 | A hydrochloric acid-optimized washing and filtering device for NdFeB waste and its filtration method |
| CN115874069B (en) * | 2022-11-16 | 2025-02-11 | 中国科学院赣江创新研究院 | A method for leaching rare earth from NdFeB waste iron tailings |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399116A (en) * | 2015-11-16 | 2016-03-16 | 中国科学院过程工程研究所 | System for treating waste acid with organic matters and treatment method and application of system |
| WO2016058007A2 (en) * | 2014-10-10 | 2016-04-14 | Rare Element Resources, Ltd. | Processing for the extraction of rare earth elements |
| CN105734296A (en) * | 2016-04-20 | 2016-07-06 | 南阳东方应用化工研究所 | Comprehensive utilization method of neodymium iron boron waste acid leaching slag |
| CN205653510U (en) * | 2013-09-26 | 2016-10-19 | 安德里特斯公开股份有限公司 | Be used for palingenetic equipment of hydrochloric acid |
| CN106319227A (en) * | 2016-08-23 | 2017-01-11 | 赣州市恒源科技股份有限公司 | Comprehensive utilization method for acid leaching slag of neodymium iron boron waste |
| CN106834722A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | With extraction iron oxide, aluminum oxide, the method for scandium oxide in a kind of utilization cobalt hydroxide nickel fibers slag and titanium white waste acid |
-
2020
- 2020-03-17 CN CN202010186548.5A patent/CN111349798B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN205653510U (en) * | 2013-09-26 | 2016-10-19 | 安德里特斯公开股份有限公司 | Be used for palingenetic equipment of hydrochloric acid |
| WO2016058007A2 (en) * | 2014-10-10 | 2016-04-14 | Rare Element Resources, Ltd. | Processing for the extraction of rare earth elements |
| CN105399116A (en) * | 2015-11-16 | 2016-03-16 | 中国科学院过程工程研究所 | System for treating waste acid with organic matters and treatment method and application of system |
| CN105734296A (en) * | 2016-04-20 | 2016-07-06 | 南阳东方应用化工研究所 | Comprehensive utilization method of neodymium iron boron waste acid leaching slag |
| CN106319227A (en) * | 2016-08-23 | 2017-01-11 | 赣州市恒源科技股份有限公司 | Comprehensive utilization method for acid leaching slag of neodymium iron boron waste |
| CN106834722A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | With extraction iron oxide, aluminum oxide, the method for scandium oxide in a kind of utilization cobalt hydroxide nickel fibers slag and titanium white waste acid |
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