CN106319227A - Comprehensive utilization method for acid leaching slag of neodymium iron boron waste - Google Patents
Comprehensive utilization method for acid leaching slag of neodymium iron boron waste Download PDFInfo
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- CN106319227A CN106319227A CN201610709079.4A CN201610709079A CN106319227A CN 106319227 A CN106319227 A CN 106319227A CN 201610709079 A CN201610709079 A CN 201610709079A CN 106319227 A CN106319227 A CN 106319227A
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- iron boron
- neodymium iron
- roasting
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- hydrogen peroxide
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- -1 neodymium iron boron Chemical compound 0.000 title claims abstract description 47
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 238000002386 leaching Methods 0.000 title claims abstract description 32
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 239000002893 slag Substances 0.000 title abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 78
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000012065 filter cake Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000005591 charge neutralization Effects 0.000 claims abstract description 3
- 230000001264 neutralization Effects 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 19
- 239000012046 mixed solvent Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000284 extract Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000005712 crystallization Effects 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000001351 cycling Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000007602 hot air drying Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 3
- 230000001960 triggered Effects 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 description 25
- 239000000706 filtrate Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910000460 iron oxide Inorganic materials 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 230000000977 initiatory Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052904 quartz Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 230000002378 acidificating Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N Neodymium Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- 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
Abstract
The invention discloses a comprehensive utilization method for acid leaching slag of neodymium iron boron waste. According to the method, a certain proportion of mixed leaching agent is dissolved in a neutralization reactor to obtain a filter cake and filter liquor; and then, after the filter cake is dried, oxygen supply roasting is conducted, the waste is triggered to be crushed to become fine powder, the single iron substance in the waste is basically converted into ferric iron under oxidation of hydrogen peroxide and the high-temperature roasting action, rare earth elements are very easily converted into rare earth oxide, and after roasting, the fine powder is subjected to acid leaching again, and a needed product is obtained. The method is characterized in that the neodymium iron boron more thoroughly becomes the rare earth oxide through the joint action of oxidability and the faint acid performance of hydrogen peroxide and hydrochloric acid, and the waste is expanded, burst and pulverized through inflation of hydrogen; and then, oxygen supply roasting is conducted under the situation of incomplete dehydrogenation, and the waste is further triggered to be crushed to become the fine powder. According to method, the grinding procedure is not needed, oxidization is thorough, and compared with a common acid leaching method, the comprehensive utilization method saves more energy and is more environment-friendly.
Description
Technical field
The invention belongs to the technical field of industrial waste resource recycling, be specifically related to a kind of neodymium iron boron waste material acid leaching residue
Method of comprehensive utilization.
Background technology
Neodymium iron boron waste material is one of current rare earth permanent magnet spent material, and its shape typically has powdery, granular, block, pureed, has
Water content is many, some moisture content less, and the volatilizable component content of most neodymium iron boron waste material is relatively low, and it basic composition is:
The B of about 1%, the Fe of 70% and the higher rare earth element of 20% value utilized above.Neodymium iron boron waste material does not have Rare Earth Mine institute
The complicated ingredient contained, rare earth ore is the grandidierite containing multiple valuable mineral, and rare earth oxide content only has a few percent
To hundreds of thousands divide several, therefore before smelting must ore dressing, and neodymium iron boron waste material content of rare earth is far above mineral content, and does not has
There are other complicated ingredients, it is seen then that although neodymium iron boron waste material is not natural Rare Earth Mine, but are strictly more preferable than natural superfine Rare Earth Mine
The resource refined." a kind of method separating and recovering valuable element from neodymium iron boron waste material " (patent No.:
201110058039.5) and " a kind of use ion exchange be enriched with low rare earth concentration eluate method " (application number:
201410059517.8) can be seen that in that Fe cycling of elements is the actual conversion of trivalent Fe after once grinding and a roasting
Rate is the highest, has higher Fe in acid leaching liquor2+Content, it is still necessary to add excess after leachate is readjusted pH
Chemical oxidizing agent；In actual production process, by adding chemical oxidizing agent in the acidic leaching liquid system of the big scale of construction with weight
Newly precipitate Fe3+, its effect is the most undesirable.In the production process of neodymium-iron-boron magnetic material, produce substantial amounts of waste residue, in order to save
Resource, it is to avoid the waste of rare earth resources, reduces industrial refuse simultaneously, protects environment, it is necessary to neodymium iron boron waste material is carried out synthesization
Utilize.
Summary of the invention
(1) to solve the technical problem that
The present invention is in order to overcome traditional rare earth to reclaim energy resource consumption height, and easily causes water pollution, it is impossible to scale metaplasia
The shortcoming produced, the technical problem to be solved in the present invention is to provide a kind of mixed solvent solvent extraction method and hydrogen adsorption crush method so that
Without mechanical disruption neodymium iron boron, more environmental protection, mixed solvent oxidation acidifying substance more efficiently, reclaims more thorough neodymium iron boron and gives up
The method of comprehensive utilization of material acid leaching residue.
(2) technical scheme
In order to solve above-mentioned technical problem, the invention provides the comprehensive utilization side of such a neodymium iron boron waste material acid leaching residue
Method, specifically includes following steps:
A. neodymium iron boron waste material is put in retort, after machinery smashs 10 minutes to pieces, be passed through distilled water and hydrogen peroxide simultaneously, its
The concentration of middle hydrogen peroxide be the volume ratio of 2mol/L, distilled water and hydrogen peroxide be 1:10-20, solid-to-liquid ratio is 1:2.5-4, reaction temperature
Degree, for 20-30 DEG C, is passed through oxygen, flow velocity 10m in whipping process3/h-30m3/h。
B. the hydrochloric acid that concentration is 4mol/L is passed through in step a in the material of preliminary oxidation, mixed solvent volume ratio hydrochloric acid:
Hydrogen peroxide: distilled water=3:1:10-20, extraction temperature is 20-50 DEG C, and extraction time is 1-8h.
C. the slip after acidleach in step b is thrown and under the conditions of 30-50 DEG C, carry out filter pressing, after filter pressing completes to pressure filter
Filtrate stand-by, the main component of filtrate is rare earth chloride and FeCl3, take out filter cake placement hot air drying stove and dry,
Dry temperature and be 120-180 DEG C.The main component of filter cake is B, Fe, rare earth metal and a small amount of SiO2, in not after having dried
Rule caking shape.
D. the filter cake after drying is thrown to NdFeB hydrogen breaker, first lead to the oxygen of argon removing device, prevent hydrogen
Explosion, then it is passed through hydrogen, in the case of incomplete dehydrogenation, initiation is crushed and becomes fine powder by filter cake, and the flow velocity that is passed through of hydrogen is
20-50m3/ h, operation temperature is 25-35 DEG C.Filter cake is during inhaling hydrogen, and rich neodymium therein inhales hydrogen-expansion prior to major event, makes filter
Alloy intercrystalline fracture in cake, so hydrogenation powder major part is single crystal grain.
E. being transported in roaster carry out roasting by inhaling the fine powder after hydrogen crushes, the temperature of oxygen supply calcining process is at 750-
900 DEG C, roasting time 1-5h, oxygen gas flow rate 10-30m3/h。
F. the fine powder after roasting is thrown into and retort carries out acidleach again, isolate the filter cake after acidleach and secondary leaches
Liquid, concentration of hydrochloric acid used by acidleach is 4mol/L again, and hydrogen peroxide concentration is 2mol/L, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide:
Distilled water=5:1:10-20, leaching extraction is temperature required for 30-50 DEG C.After the acidleach of acidleach-drying-suction hydrogen-roasting-again
Filtrate, the Fe of more than 95% is converted into Fe3+, and the rare earth metal of more than 98% is converted into rare earth chloride.
G. a leachate and secondary leachate being poured in neutralization retort, adding concentration is the NaOH solution of 5mol/L
After regulation pH to 6.0-7.0, adding extractant N503 and extract leachate, the volume fraction of extractant N503 is 40%-60%, extraction
Adding NaCl solid during taking, solid-to-liquid ratio is 200-400:1, stirs 1.5h-6h, and standing separation is biphase, reclaims organic facies, then
Add hydrochloric acid back extraction, regulate pH to 1.5-3.0, cycling extraction and back extraction 1-3 time respectively, obtain FeCl3Solution, test leaching
Go out liquid Fe3+The content of ion is less than 0.5%.
H. the FeCl extracted to step g3It is the NaOH solution of 5mol/L that solution adds concentration, and stirring reaction is until no longer
Till producing precipitation, extract and separate goes out solid phase Fe (OH)3Precipitation is thrown to rotary roasting furnace, and high-temperature roasting obtains iron oxide red
Fe203, sintering temperature is 450-550 DEG C, and roasting time is 2-6h.
I. step g extract after remaining inorganic phase solution pour evaportor into, treat moisture drying to 1%-5%,
Material is poured into crystallization tank crystallization and i.e. obtains rare-earth metal chloride.
As the preferred embodiment of the present invention, in step a, the volume ratio of distilled water and hydrogen peroxide is 1:15, reaction temperature
Degree is 27 DEG C, and solid-to-liquid ratio is 1:3, oxygen gas flow rate 20m3/h。
As the preferred embodiment of the present invention, in step b, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distilled water=3:
1:15, extraction temperature is 35 DEG C, and mixing time is 3h, and reaction pH is adjusted to 2.0.
As the preferred embodiment of the present invention, in step c, pressure filter used is belt filter press, passes through compression roller
High pressure dehydrate rate reaches more than 90%, and drying temperature is 160 DEG C.
As the preferred embodiment of the present invention, in step d, it is 40m that hydrogen is passed through flow velocity3/ h, operation temperature is 30
℃。
As the preferred embodiment of the present invention, in step e, oxygen supply sintering temperature is 800 DEG C, and roasting time is 3h,
Oxygen gas flow rate 20m3/h。
As the preferred embodiment of the present invention, in step f, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distilled water=
5:1:14, leaching extraction is temperature required is 38 DEG C.
As the preferred embodiment of the present invention, in step g, the volume fraction of extractant 503 is 55%, and solid-to-liquid ratio is
300:1, neutralizes stirring 2.5h, regulates pH to 2.0 under room temperature.
As the preferred embodiment of the present invention, in step h, sintering temperature is 500 DEG C, and roasting time is 3h.
(3) beneficial effect
Beneficial effects of the present invention: 1. use the mixed solvent of hydrogen peroxide and hydrochloric acid in step a and step b, hydrogen peroxide has
There are faintly acid and oxidisability, and hydrochloric acid can make up the weakly acidic shortcoming of hydrogen peroxide, this oxidation being conducive to rare earth metal and acid
Solve.2. step d use vacuum hydrogen to crush this mode of neodymium iron boron so that without long-time grinding material, increase air powder
Dust content, prevents the generation of occupation disease, and the most energy-conservation and environmental protection is without long-time roasting neodymium iron boron.3. hydrochloric acid and hydrogen peroxide are all
Being regular industrial raw material, convenient sources and cheap, cost is relatively low.4. technological process is simple, is all popular response equipment, passes through
Reclaim neodymium iron boron, be greatly improved the utilization rate of rare earth, save non-renewable energy resources.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue, specifically includes following steps:
A. neodymium iron boron waste material 100Kg is put in retort, after machinery smashs 10 minutes to pieces, be passed through distilled water and dioxygen simultaneously
Water, wherein the concentration of hydrogen peroxide be the volume ratio of 2mol/L, distilled water and hydrogen peroxide be 1:10, solid-to-liquid ratio is 1:2.5, reaction temperature
Degree is 20 DEG C, must be passed through oxygen in whipping process, and flow velocity is 10m3/h。。
B. the hydrochloric acid that concentration is 4mol/L is passed through in step a in the material of preliminary oxidation, mixed solvent volume ratio hydrochloric acid:
Hydrogen peroxide: distilled water=3:1:10, extraction temperature is 20 DEG C, and extraction time is 1h.
C. the slip after acidleach in step b is thrown and under the conditions of 30 DEG C, carry out filter pressing, after filter pressing completes to pressure filter
Filtrate is stand-by, and the main component of filtrate is rare earth chloride and FeCl3, take out filter cake placement hot air drying stove and dry, dry
Dry temperature is 120 DEG C.The main component of filter cake is B, Fe, rare earth metal and a small amount of SiO2, in irregular knot after having dried
Block.
D. the filter cake after drying is thrown to NdFeB hydrogen breaker, first lead to the oxygen of argon removing device, prevent hydrogen
Explosion, then it is passed through hydrogen, in the case of incomplete dehydrogenation, initiation is crushed and becomes fine powder by filter cake, and the flow velocity that is passed through of hydrogen is
20m3/ h, operation temperature is 25 DEG C.
E. by inhale hydrogen broken after fine powder be transported in roaster carry out roasting, the temperature of oxygen supply calcining process at 750 DEG C,
Roasting time 1h, oxygen gas flow rate 10m3/h。
F. the fine powder after roasting is thrown into and retort carries out acidleach again, isolate the filter cake after acidleach and filtrate, then
Concentration of hydrochloric acid used by secondary acidleach is 4mol/L, and hydrogen peroxide concentration is 2mol/L, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distillation
Water=5:1:10, leaching extraction is temperature required is 30 DEG C.Filtrate after the acidleach of acidleach-drying-suction hydrogen-roasting-again, 95%
Above Fe is converted into Fe3+, and the rare earth metal Re of more than 98% is converted into rare earth chloride.
G. merging acidleach for the first time and pouring into of second time acidleach neutralizes in retort, adding concentration is the NaOH of 5mol/L
After solution regulation pH to 6.0-7.0, adding extractant N503 and extract eluate, the volume fraction of extractant N503 is 40%, extraction
Adding NaCl solid during taking, solid-to-liquid ratio is 200:1, stirs 1.5h, and standing separation is biphase, reclaims organic facies, adds salt
Acid back extraction, regulates pH to 1.5, cycling extraction and back extraction 1 time respectively, tests leachate Fe3+The content of ion is less than
0.5%.
H. the FeCl extracted to step g3It is the NaOH solution of 5mol/L that solution adds concentration, and stirring reaction is until no longer
Till producing precipitation, extract and separate goes out solid phase Fe (OH)3Precipitation is thrown to rotary roasting furnace, and high-temperature roasting obtains 53.6Kg's
Iron oxide red Fe203, sintering temperature is 450 DEG C, and roasting time is 2h.
I. step g extract after remaining inorganic phase solution pour evaportor into, treat moisture drying to 1%, by thing
Material is poured crystallization tank crystallization into and is i.e. obtained rare-earth metal chloride 23.5Kg.
Embodiment 2
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue, specifically includes following steps:
A. neodymium iron boron waste material 100Kg is put in retort, after machinery smashs 10 minutes to pieces, be passed through distilled water and dioxygen simultaneously
Water, wherein the concentration of hydrogen peroxide be the volume ratio of 2mol/L, distilled water and hydrogen peroxide be 1:20, solid-to-liquid ratio is 1:4, reaction temperature
It is 30 DEG C, whipping process must be passed through oxygen, flow velocity 30m3/h。
B. the hydrochloric acid that concentration is 4mol/L is passed through in step a in the material of preliminary oxidation, mixed solvent volume ratio hydrochloric acid:
Hydrogen peroxide: distilled water=3:1:20, extraction temperature is 50 DEG C, and extraction time is 8h.
C. the slip after acidleach in step b is thrown and under the conditions of 50 DEG C, carry out filter pressing, after filter pressing completes to pressure filter
Filtrate is stand-by, and the main component of filtrate is rare earth chloride and FeCl3, take out filter cake placement hot air drying stove and dry, dry
Dry temperature is 180 DEG C.The main component of filter cake is B, Fe, rare earth metal and a small amount of SiO2, in irregular knot after having dried
Block.
D. the filter cake after drying is thrown to NdFeB hydrogen breaker, first lead to the oxygen of argon removing device, prevent hydrogen
Explosion, then it is passed through hydrogen, in the case of incomplete dehydrogenation, initiation is crushed and becomes fine powder by filter cake, and the flow velocity that is passed through of hydrogen is
50m3/ h, operation temperature is 35 DEG C.
E. by inhale hydrogen broken after fine powder be transported in roaster carry out roasting, the temperature of oxygen supply calcining process at 900 DEG C,
Roasting time 5h, oxygen gas flow rate 30m3/h。
F. the fine powder after roasting is thrown into and retort carries out acidleach again, isolate the filter cake after acidleach and filtrate, then
Concentration of hydrochloric acid used by secondary acidleach is 4mol/L, and hydrogen peroxide concentration is 2mol/L, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distillation
Water=5:1:20, leaching extraction is temperature required is 50 DEG C.Filtrate after the acidleach of acidleach-drying-suction hydrogen-roasting-again, 95%
Above Fe is converted into Fe3+, and the rare earth metal Re of more than 98% is converted into rare earth chloride.
G. merging acidleach for the first time and pouring into of second time acidleach neutralizes in retort, adding concentration is the NaOH of 5mol/L
After solution regulation pH to 6.0-7.0, adding extractant N503 and extract eluate, the volume fraction of extractant N503 is 60%, extraction
Adding NaCl solid during taking, solid-to-liquid ratio is 400:1, stirs 6h, and standing separation is biphase, reclaims organic facies, adds hydrochloric acid
Back extraction, regulates pH to 3.0, cycling extraction and back extraction 3 times respectively, tests leachate Fe3+The content of ion is less than 0.5%.
H. the FeCl extracted to step g3It is the NaOH solution of 5mol/L that solution adds concentration, and stirring reaction is until no longer
Till producing precipitation, extract and separate goes out solid phase Fe (OH)3Precipitation is thrown to rotary roasting furnace, and high-temperature roasting obtains 58.6Kg's
Iron oxide red Fe203, sintering temperature is 550 DEG C, and roasting time is 6h.
I. step g extract after remaining inorganic phase solution pour evaportor into, treat moisture drying to 5%, by thing
Material is poured crystallization tank crystallization into and is i.e. obtained rare-earth metal chloride 25.5Kg.
Embodiment 3
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue, specifically includes following steps:
A. neodymium iron boron waste material 100Kg is put in retort, after machinery smashs 10 minutes to pieces, be passed through distilled water and dioxygen simultaneously
Water, wherein the concentration of hydrogen peroxide be the volume ratio of 2mol/L, distilled water and hydrogen peroxide be 1:15, solid-to-liquid ratio is 1:3.5, reaction temperature
Degree is 27 DEG C, must be passed through oxygen, flow velocity 20m in whipping process3/h。
B. the hydrochloric acid that concentration is 4mol/L is passed through in step a in the material of preliminary oxidation, mixed solvent volume ratio hydrochloric acid:
Hydrogen peroxide: distilled water=3:1:15, extraction temperature is 35 DEG C, and extraction time is 3h.
C. the slip after acidleach in step b is thrown and under the conditions of 40 DEG C, carry out filter pressing, after filter pressing completes to pressure filter
Filtrate is stand-by, and the main component of filtrate is rare earth chloride and FeCl3, take out filter cake placement hot air drying stove and dry, dry
Dry temperature is 160 DEG C.The main component of filter cake is B, Fe, rare earth metal and a small amount of SiO2, in irregular knot after having dried
Block.
D. the filter cake after drying is thrown to NdFeB hydrogen breaker, first lead to the oxygen of argon removing device, prevent hydrogen
Explosion, then it is passed through hydrogen, in the case of incomplete dehydrogenation, initiation is crushed and becomes fine powder by filter cake, and the flow velocity that is passed through of hydrogen is
40m3/ h, operation temperature is 30 DEG C.
E. by inhale hydrogen broken after fine powder be transported in roaster carry out roasting, the temperature of oxygen supply calcining process at 800 DEG C,
Roasting time 3h, oxygen gas flow rate 20m3/h。
F. the fine powder after roasting is thrown into and retort carries out acidleach again, isolate the filter cake after acidleach and filtrate, then
Concentration of hydrochloric acid used by secondary acidleach is 4mol/L, and hydrogen peroxide concentration is 2mol/L, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distillation
Water=5:1:14, leaching extraction is temperature required is 38 DEG C.Filtrate after the acidleach of acidleach-drying-suction hydrogen-roasting-again, 95%
Above Fe is converted into Fe3+, and the rare earth metal Re of more than 98% is converted into rare earth chloride.
G. merging acidleach for the first time and pouring into of second time acidleach neutralizes in retort, adding concentration is the NaOH of 5mol/L
After solution regulation pH to 6.0-7.0, adding extractant N503 and extract eluate, the volume fraction of extractant N503 is 50%, extraction
Adding NaCl solid during taking, solid-to-liquid ratio is 300:1, stirs 2.5h, and standing separation is biphase, reclaims organic facies, adds salt
Acid back extraction, regulates pH to 2.0, cycling extraction and back extraction 2 times respectively, tests leachate Fe3+The content of ion is less than
0.5%.
H. the FeCl extracted to step g3It is the NaOH solution of 5mol/L that solution adds concentration, and stirring reaction is until no longer
Till producing precipitation, extract and separate goes out solid phase Fe (OH)3Precipitation is thrown to rotary roasting furnace, and high-temperature roasting obtains iron oxide red
68.2Kg Fe20368.2Kg, sintering temperature is 500 DEG C, and roasting time is 3h.
I. step g extract after remaining inorganic phase solution pour evaportor into, treat moisture drying to 3%, by thing
Material is poured crystallization tank crystallization into and is i.e. obtained rare-earth metal chloride 32.5Kg.
In the present invention, embodiment one obtains iron oxide red Fe203For 53.6Kg, the response rate is 53.6%, obtains rare earth metal
Chloride 23.5Kg, the response rate is 23.5%；Embodiment two obtains Fe203For 58.6Kg, the response rate is 58.6%, obtains dilute
Earth metal chloride 25.5Kg, the response rate is 25.5%；Embodiment three obtains iron oxide red Fe203For 68.2Kg, the response rate is
68.2%, obtain rare-earth metal chloride 32.5Kg, the response rate is 32.5%.
At present, in the method for comprehensive utilization of existing neodymium iron boron waste material acid leaching residue, the response rate of iron oxide red is about 40%, and dilute
The muriatic response rate of earth metal is about 18%, and compared to general recovery process, the response rate of the present invention is apparently higher than biography
The recovery process of system, meanwhile, technological process is the most fairly simple, is all popular response equipment, by reclaiming neodymium iron boron, greatly carries
The high utilization rate of rare earth, saves non-renewable energy resources.
Embodiment described above only have expressed the preferred embodiment of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to making some deformation, improve and substitute, these broadly fall into this
Bright protection domain.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. the method for comprehensive utilization of a neodymium iron boron waste material acid leaching residue, it is characterised in that specifically include following steps:
A. neodymium iron boron waste material is put in retort, after machinery smashs 10 minutes to pieces, is passed through distilled water and hydrogen peroxide simultaneously and stirs,
Whipping process is passed through oxygen, flow velocity 10-30m3/ h, wherein the concentration of hydrogen peroxide is the body of 2mol/L, distilled water and hydrogen peroxide
Long-pending ratio is 1:10-20, and solid-to-liquid ratio is 1:2.5-4, and reaction temperature is 20-30 DEG C；
B. the hydrochloric acid that concentration is 4mol/L is passed through in the material of step a, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distilled water
=3:1:10-20, extraction temperature is 20-50 DEG C, and extraction time is 1-8h；
C. being thrown by the slip in step b and carry out filter pressing under the conditions of 30-50 DEG C to pressure filter, filter pressing is once soaked after completing
Going out liquid, taking-up filter cake is positioned over hot air drying stove dries, and dries temperature and is 120-180 DEG C；
D. the filter cake after drying is thrown to NdFeB hydrogen breaker, first lead to the oxygen in argon removing device, then be passed through hydrogen
Causing filter cake to be broken into fine powder, the flow velocity that is passed through of hydrogen is 20-50m3/ h, operation temperature is 25-35 DEG C；
E., fine powder is transported in roaster carry out roasting, and the temperature of oxygen supply roasting is 750-900 DEG C, roasting time 1-5h, oxygen
Gas velocity 10-30m3/h；
F. the fine powder after roasting is thrown into and retort carries out acidleach again, isolate the filter cake after acidleach and secondary leachate,
Concentration of hydrochloric acid used by acidleach is 4mol/L again, and hydrogen peroxide concentration is 2mol/L, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: steam
Distilled water=5:1:10-20, leaching extraction is temperature required for 30-50 DEG C；
G. a leachate and secondary leachate are poured in neutralization retort, add the NaOH solution that concentration is 5mol/L and neutralize
Leachate, is adjusted to pH to 6.0-7.0, adds extractant N503 and extracts leachate, and the volume fraction of extractant N503 is 40%-
60%, extraction process adds NaCl solid, solid-to-liquid ratio is 200-400:1, stirs 1.5-6h, and standing separation is biphase, and recovery has
Machine phase, adds hydrochloric acid back extraction, regulates pH to 1.5-3.0, cycling extraction and back extraction 1-3 time respectively, obtains FeCl3Liquid；
H. the FeCl extracted to step g3It is the NaOH solution of 5mol/L that solution adds concentration, and stirring reaction is until no longer producing
Till precipitation, filter to isolate Fe (OH)3Precipitation, then thrown to rotary roasting furnace, sintering temperature is 450-550 DEG C, roasting
The burning time is 2-6h；
I. the remaining inorganic phase solution after step g being extracted pours evaportor into, after moisture drying to 1%-5%, falls
Enter crystallization tank and obtain rare-earth metal chloride.
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that step a
In, the volume ratio of distilled water and hydrogen peroxide is 1:15, and reaction temperature is 27 DEG C, and solid-to-liquid ratio is 1:3, flow velocity 20m3/h。
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that step b
In, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distilled water=3:1:15, extraction temperature is 35 DEG C, and extraction time is 3h.
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that step c
In pressure filter used be belt filter press, the dehydration rate of filter cake reaches more than 90%, and drying temperature is 160 DEG C.
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that in step
In d, it is 40m that hydrogen is passed through flow velocity3/ h, operation temperature is 30 DEG C.
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that in step
In e, oxygen supply sintering temperature is 800 DEG C, and roasting time is 3h, oxygen gas flow rate 20m3/h。
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that in step
In f, mixed solvent volume ratio hydrochloric acid: hydrogen peroxide: distilled water=5:1:14, leaching extraction is temperature required is 38 DEG C.
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that in step
In g, the volume fraction of extractant 503 is 55%, and extraction solid-to-liquid ratio is 300:1, neutralizes stirring 2.5h, regulate pH to 2.0 under room temperature.
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue the most according to claim 1, it is characterised in that in step
In h, sintering temperature is 500 DEG C, and roasting time is 3h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012315A (en) * | 2017-03-31 | 2017-08-04 | 赣州市恒源科技股份有限公司 | A kind of method that utilization rare earth raffinate leaches neodymium iron boron waste material rare earth elements |
| CN111349798A (en) * | 2020-03-17 | 2020-06-30 | 中国科学院过程工程研究所 | Neodymium iron boron waste recycling system and method |
| CN113621809A (en) * | 2021-08-09 | 2021-11-09 | 四川省乐山锐丰冶金有限公司 | Method for reducing and leaching bastnaesite by utilizing neodymium iron boron reclaimed materials |
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2016
- 2016-08-23 CN CN201610709079.4A patent/CN106319227A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012315A (en) * | 2017-03-31 | 2017-08-04 | 赣州市恒源科技股份有限公司 | A kind of method that utilization rare earth raffinate leaches neodymium iron boron waste material rare earth elements |
| CN111349798A (en) * | 2020-03-17 | 2020-06-30 | 中国科学院过程工程研究所 | Neodymium iron boron waste recycling system and method |
| CN111349798B (en) * | 2020-03-17 | 2021-08-27 | 中国科学院过程工程研究所 | Neodymium iron boron waste recycling system and method |
| CN113621809A (en) * | 2021-08-09 | 2021-11-09 | 四川省乐山锐丰冶金有限公司 | Method for reducing and leaching bastnaesite by utilizing neodymium iron boron reclaimed materials |
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