CN105734296B - A kind of method of comprehensive utilization of neodymium iron boron waste material acid leaching residue - Google Patents
A kind of method of comprehensive utilization of neodymium iron boron waste material acid leaching residue Download PDFInfo
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- CN105734296B CN105734296B CN201610246932.3A CN201610246932A CN105734296B CN 105734296 B CN105734296 B CN 105734296B CN 201610246932 A CN201610246932 A CN 201610246932A CN 105734296 B CN105734296 B CN 105734296B
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- rare earth
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- cobalt
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- 239000002253 acid Substances 0.000 title claims abstract description 69
- 238000002386 leaching Methods 0.000 title claims abstract description 66
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 38
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 57
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 46
- 239000010941 cobalt Substances 0.000 claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 rare earth sulfate Chemical class 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 238000000746 purification Methods 0.000 claims description 19
- 238000006722 reduction reaction Methods 0.000 claims description 19
- 239000002075 main ingredient Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000009991 scouring Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 235000014413 iron hydroxide Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005360 mashing Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 230000003292 diminished effect Effects 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004073 vulcanization 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
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of method of comprehensive utilization of neodymium iron boron waste material acid leaching residue, neodymium iron boron waste material acid leaching residue is mixed in neutralization reactor with from the neodymium iron boron waste material acid leaching residue acid leaching liquor obtained by acidleach, separation circuit, neutralizer and neutralization residue are received into obtain in neutralize slip filtering, neutralizer is used as the raw material for preparing iron oxide red;Residue will be neutralized and be mixed and added into the acid-leaching reaction that sulfuric acid enters with acidleach residue eluate obtained by acidleach process, acid leaching liquor and acidleach residue are obtained after filtering, acid leaching liquor is used to neutralize dispensing, acidleach residue is mixed with the later stage eluate of iron oxide red preparation section institute output and slurry is made into, then make the rare earth sulfate dissolution in acidleach residue through filtering, washing, send Extraction of rare eart process to be used to prepare rare-earth products gained filter eluate after separation.Realize the comprehensive utilization to iron, trace rare-earth and cobalt resource in neodymium iron boron waste material acid leaching residue, and realize efficiently separating and being enriched with to its middle rare earth and cobalt element.
Description
Technical field
The invention belongs to industrial solid castoff technical field of comprehensive utilization, and in particular to a kind of neodymium iron boron waste material acid leaching residue
Method of comprehensive utilization.
Background technology
Neodymium iron boron waste material acid leaching residue is to use excellent molten method production breakdown neodymium iron boron waste material institute during neodymium iron boron waste material carries neodymium
The acid-soaked waste residue of generation, its Main Ingredients and Appearance is Fe2O3, REO, Co etc..Currently without suitable method of comprehensive utilization, some enterprises
Sold as iron-smelting raw material, store up processing or being done, not only occupied ground, and pollution environment.
The content of the invention
In order to comprehensively utilize the valuable resource in neodymium iron boron waste material acid leaching residue, environmental pollution is eliminated, the present invention proposes one
Plant the method for comprehensive utilization of neodymium iron boron waste material acid leaching residue.Realize to iron, trace rare-earth and cobalt money in neodymium iron boron waste material acid leaching residue
The comprehensive utilization in source, has been made the iron oxide red commercial pigments of satisfactory quality and has realized to its middle rare earth and cobalt element
Efficiently separate and be enriched with, be the further comprehensive utilization of rare earth and cobalt element, prepare rare earth oxide and cobalt compound is established
Basis.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of method of comprehensive utilization of neodymium iron boron waste material acid leaching residue, it is characterised in that carry out according to the following steps：Neodymium iron boron gives up
Expect the leaching and separation of iron, rare earth and cobalt element in acid leaching residue：
Step one：By neodymium iron boron waste material acid leaching residue in neutralization reactor with from the neodymium obtained by acidleach, separation circuit
Iron boron waste material acid leaching residue acid leaching liquor is mixed, and it is 70 DEG C -100 DEG C to control neutral temperature, and the neutralization reaction time is 180-360min,
Reaction end pH value is 0.5, is consumed the free acid in acid leaching liquor, iron, rare earth in neodymium iron boron waste material acid leaching residue and
Cobalt element obtains preliminary dissolution；
Step 2：Slurry in neutralization reactor is filtered under the conditions of 70 DEG C -100 DEG C and receives neutralizer and to neutralize residual
Slag, the Main Ingredients and Appearance of neutralizer is iron and the sulfate of cobalt, as the raw material for preparing iron oxide red, neutralizes residue Main Ingredients and Appearance and is
Silica, iron oxide, rare earth oxide, rare earth sulfate and micro cobalt；
Step 3：Residue will be neutralized and send acidleach process, with iron oxide red preparation section institute output in acid-leaching reaction device
Later stage eluate presses solid-to-liquid ratio 1:1.5-1:2.5 mixing, then add the concentrated sulfuric acid in 70 DEG C -100 by 1.5-1.9 times of theoretical amount
Acid-leaching reaction is carried out under the conditions of DEG C, it is 180-360 min to control the acid-leaching reaction time, iron therein, rare earth and cobalt is entered one
Walk dissolution, reaction terminate through filtering receive Main Ingredients and Appearance be iron and cobalt sulfate acid leaching liquor and acidleach residue；
Step 4：Step 1: the course of reaction described in three is strong acid hot environment, rare earth sulfate dissolves on this condition
Degree is relatively low, and most of form preservation with soluble-salt will neutralize residue through step 3 acidleach institute in residue obtained by step 2
Later stage eluate of the acidleach residue with iron oxide red preparation section institute output in plasm scouring groove again is obtained in mixing under normal temperature condition
And slurry is made into, dissolve the rare earth sulfate in acidleach residue and enter liquid phase, Main Ingredients and Appearance then is made through filtering, washing
Eluate and acidleach residue for rare earth sulfate, eluate middle rare earth content send rare earth to carry between 1-3g/L
Process is taken to be used to prepare rare-earth products；
The preparation of iron oxide red：
Step（1）：Neutralizer obtained by step 2 is returned into former process, using iron filings, iron sheet or reduced iron powder as reducing agent, in
Reduction reaction is carried out under the conditions of 50 DEG C -80 DEG C, makes Fe therein3+It is converted into Fe2+, it is that sulfuric acid is sub- that Main Ingredients and Appearance, which is made, through filtering
Solution after the reduction of iron；
Step（2）：By part steps（1）Gained copperas solution send first class purification process, and bicarbonate is added thereto
Ammonium or ammonium carbonate, 30-180min is reacted under the conditions of 50 DEG C -80 DEG C, rare earth therein is converted into carbonated rare earth precipitation；Again plus
Enter ammonium sulfide or hydrogen sulfide, 30-180min is reacted under the conditions of 50 DEG C -80 DEG C, the heavy metals such as cobalt therein is converted into vulcanization
Thing is precipitated；After reaction terminates filtering receive must purify after copperas solution and Main Ingredients and Appearance be carbonated rare earth, the precipitation of cobalt sulfide
Thing.Secondary purification process is sent by copperas solution after purification, adding appropriate ammoniacal liquor makes a small amount of ferrous iron be converted into hydroxide
Iron, while making ferrous hydroxide be converted into iron hydroxide by the contact with air, is incubated precipitation under the conditions of 50 DEG C -80 DEG C
30-180min, rare earth, the cobalt foreign ion of further adsorbent solution residual, the sulfuric acid for receiving pure is filtered in reaction after terminating sub-
Ferrous solution and the sediment that Main Ingredients and Appearance is iron hydroxide, the sediment produced by first class purification and secondary purification return to acidleach work
Sequence is recycled；
Step（3）：By step（2）The pure copperas solution of gained is combined in reactor with oxidation in multifunctional oxygen
The later stage eluate of iron oxide red preparation section institute output is diluted to 5-30g/L, controls 10 DEG C -25 DEG C of solution temperature, adds thereto
0.9-1.5 times of ammoniacal liquor of theoretical amount, control ph is 9-10.5, and then outward appearance is made in shallow pale brown in blowing air oxidation 30-90min
Color, crystal seed with well suspended；
Step（4）：Add water it is appropriate crystal seed in reactor be combined to multifunctional oxygen be diluted, and adjust slurry with sulfuric acid
PH value is 3-4, and step is added in manner of cocurrent flow after crystal seed slurry temperature is promoted into 80 DEG C -90 DEG C（1）It is molten after gained reduction
Liquid and ammoniacal liquor, while blowing air is aoxidized, it is that ferrous sulfate concentration is 10-20 g/L in 3-4, slurry to control co-current process pH value,
Stop the dropwise addition of solution after reduction when coloured light is similar to standard sample, continue blowing air oxidation, and slurry pH value is controlled with ammoniacal liquor
For 3-4, when Fe concentration is less than 0.1g/L in slurry, reaction terminates；
Step（5）：By step（4）Gained iron oxide red slurry filtration, receive iron oxide red wet cake and Fe concentration are less than
0.1g/L, rare earth oxide concentration more than 0.3g/L, cobalt concentration more than 0.25g/L iron oxide red mother liquor, by gained oxygen
Change iron oxide red mother liquor to close with iron, the leaching of rare earth and cobalt element and separating step (4) gained eluate in neodymium iron boron waste material acid leaching residue
And rare earth and cobalt abstraction process are sent to for preparing rare earth and cobalt product；
Step（6）：By step（5）Gained iron oxide red wet cake is sent in pickling reactor and mixed with acid eluate, in normal temperature
Under the conditions of, control ph between 1.5-3, after being sufficiently stirred for filter, then it is scrubbed receive pickling rear oxidation iron oxide red wet cake and
Acid eluate containing rare earth sulfate, acid eluate recycle to rare earth concentration reach more than 0.1g/L when and neodymium iron boron waste material
Iron, the leaching of rare earth and cobalt element and separating step in acid leaching residue（4）Gained eluate, which merges, is sent to rare earth and cobalt abstraction process
For preparing rare earth and cobalt product；
Step（7）：Pickling rear oxidation iron oxide red wet cake is mixed into mashing with clear water, then with Filter Press and washed, is made
Obtain the washing rear oxidation iron oxide red wet cake that sulphates content is less than 0.05%；
Step（8）：Send drying system to dry iron oxide red wet cake and iron oxide red finished product is made.
Iron, rare earth and cobalt in neodymium iron boron waste material acid leaching residue described in iron, the leaching of rare earth and cobalt element and separating step one
Elements Leaching and separation method：Neodymium iron boron waste material acid leaching residue is leached in strong acid hot environment, becomes rare earth sulfuric acid salt solubility
It is small and be enriched in acidleach residue, then acidleach residue and water are mixed in plasm scouring groove again by the way of washing dissolution
Close, make rare earth sulfate dissolution, the eluate of rare earth sulfate must be contained by being received through separation, small in eluate middle rare earth concentration
When 1.5g/L, eluate can be returned to again plasm scouring groove and recycled, until eluate middle rare earth concentration is more than 2.0
Extraction of rare eart process is sent to during g/L again.
The present invention proposes a kind of method of comprehensive utilization of neodymium iron boron waste material acid leaching residue.In order to comprehensively utilize neodymium iron boron waste material
Valuable resource in acid leaching residue, eliminates environmental pollution, realizes to iron, trace rare-earth and cobalt money in neodymium iron boron waste material acid leaching residue
The comprehensive utilization in source, has been made the iron oxide red commercial pigments of satisfactory quality and has realized to its middle rare earth and cobalt element
Efficiently separate and be enriched with, be the further comprehensive utilization of rare earth and cobalt element, prepare rare earth oxide and cobalt compound is established
Basis.
Chemical reaction involved in the present invention：
Fe2O3 +3H2SO4→Fe2(SO4)3+3 H2O
RE2O3+3H2SO4+（n-3）H2O→RE2(SO4)3·nH2O
CoO+H2SO4→CoSO4+ H2O
RE2(SO4)3·nH2O+H2O→RE2(SO4)3+（n+1）H2O
Reduction and purification：
Fe2(SO4)3+Fe→3FeSO4
RE2(SO4)3 +6NH4HCO3→RE2(CO3)3+3(NH4)2SO4+3H2O+3CO2
CoSO4+ (NH4)2S →CoS+(NH4)2SO4
4FeSO4+8NH3+10H2O+O2→4Fe(OH)3+4(NH4)2SO4
It is prepared by iron oxide red：
FeSO4+2NH3·H2O→Fe(OH)2+(NH4)2SO4
4Fe(OH)2+O2+2H2O→4Fe(OH)3↓
H2SO4+ 2NH3→(NH4)2SO4
2Fe(OH)3→Fe2O3+3H2O
4FeSO4+O2+8NH3+4H2O→2Fe2O3+4(NH4)2SO4。
Brief description of the drawings
The specific embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is process chart of the invention.
Embodiment
Embodiment 1：
Raw materials used composition：Fe2O353.54%；REO1.00%；Co0.65%.
100kg neodymium iron boron waste material acid leaching residues are mixed in neutralization reactor with 295kg acid leaching liquors, it is 70 to control temperature
DEG C reaction 180min, reaction terminate after filter, a small amount of water washing, slag 69kg must be neutralized by receiving, neutralizer 355kg.Neutralizer is main
Composition is：Fe2（SO4）3 131.3kg；REO 0.4kg；Co 0.62kg；
By in 69kg and residue is mixed into slurry, Ran Houjia in acid-leaching reaction device with 105kg iron oxide red later stage eluates
Enter the concentrated sulfuric acid that 106kg concentration is 98%, the reaction time is 240min under the conditions of 70 DEG C, and reaction terminates under the conditions of 70 DEG C
Filtering, a small amount of water washing receives to obtain acid leaching liquor 295kg, wet basis acidleach residue 27kg.
27kg acidleach residue is added into eluate in plasm scouring groove again135kg, stirs into after slurry and filters, obtain rare earth oxygen
Compound concentration is 2.9g/L eluate, then using the washing function of filter press itself, carried out with iron oxide red later stage eluate
Washing, receives to obtain eluate135kg, rare earth oxide concentration is 0.8g/L, returns to dispensing in stock tank again, circulates residual for acidleach
The washing of slag.
Neutralizer 355kg is returned into former process, iron filings is added, reduction reaction is carried out under the conditions of 50 DEG C -80 DEG C, is made wherein
Fe3+It is converted into Fe2+, solution 520kg after reduction is made through filtering, containing FeSO4150.1kg, REO 0.4kg；Co 0.62kg；
Solution send first class purification process after 16kg is reduced, and ammonium hydrogen carbonate is added thereto, is reacted under the conditions of 50 DEG C
After 30min, add ammonium sulfide solution, maintain the temperature continue react 30min, reaction terminate after filtering receive ferrous sulfate is molten
Liquid 16kg, and Main Ingredients and Appearance are carbonated rare earth, the sediment 0.1kg of cobalt sulfide.
Copperas solution send addition 0.1kg ammoniacal liquor, Ran Hou under secondary purification process, stirring condition after 16kg is purified
Insulation precipitation 30min under the conditions of 80 DEG C.Reaction filters the copperas solution 16kg for receiving pure after terminating, and Main Ingredients and Appearance is hydrogen
The sediment 0.05kg of iron oxide.The common 0.15kg of sediment produced by first class purification and secondary purification is returned into acidleach process to follow
Ring is used.
Copperas solution pure 16kg is combined in reactor in multifunctional oxygen to use iron oxide red later stage eluate
5g/L is diluted to, 10 DEG C of solution temperature is controlled, 0.9 times of ammoniacal liquor of theoretical amount is added thereto, control ph is 9.0, then leads to sky
Gas aoxidizes 30min, and outward appearance is made in sundown, crystal seed slurry with well suspended.
It is 3 that sulfuric acid adjustment pH value is added into crystal seed slurry, then adds ferrous sulfate in solution after reduction, adjustment slurry
Concentration is 20g/L, and crystal seed slurry temperature is promoted to after 80 DEG C and adds solution and ammoniacal liquor after reduction in manner of cocurrent flow, is led to simultaneously
Air oxidation.It is that ferrous sulfate concentration is 20g/L in 3, slurry to control co-current process pH value.When coloured light is similar to 130# standard samples
When stop the dropwise addition of solution after reduction, continue blowing air oxidation, and slurry pH value controlled as 3 using ammoniacal liquor.When Fe concentration in slurry
During less than 0.1g/L, reaction terminates.Iron oxide red mother liquor 1300kg is received to obtain in filtering, separation（Wherein contain Fe0.10kg, rare-earth oxidation
Thing 0.34kg, cobalt 0.57kg）, iron oxide red wet cake 160kg.
Iron oxide red wet cake is sent in pickling reactor and mixed with acid eluate, under normal temperature condition, control ph exists
1.5, filter, wash after stirring, receive to obtain pickling rear oxidation iron oxide red wet cake 160kg and the acid eluate containing rare earth sulfate.Will
Acid eluate, which is recycled to rare earth concentration, reaches more than 0.1g/L, stops recycling, often handles 100kg neodymium iron boron waste materials,
Averagely can output acid eluate 90kg, 0.01kg containing rare earth oxide, cobalt 0.01kg.Iron oxide red acid eluate and iron oxide red mother liquor and wash
Go out liquidRare earth and cobalt abstraction process are sent after merging, rare earth therein, cobalt is extracted and is prepared into corresponding compound products.
160kg pickling rear oxidation iron oxide red wet cakes are mixed into mashing with clear water, then with Filter Press and washed, sulphur is made
Phosphate content is less than 0.05% washing rear oxidation iron oxide red wet cake, send drying system to dry and iron oxide red finished product 82kg, product is made
Meet GB/T1863-2008 iron oxide red product standards.
Embodiment 2
Raw materials used composition：Fe2O367.53%；REO0.85%；
1000kg neodymium iron boron waste material acid leaching residues are mixed in neutralization reactor with 3410kg acid leaching liquors, control the temperature to be
100 DEG C, the time is 360min, and reaction terminates to filter under the conditions of 90 DEG C, a small amount of water washing, and slag 600kg must be neutralized by receiving, and be neutralized
Liquid 3850kg.Neutralizer main component is：Fe2（SO4）3 1665kg；REO 3.80kg；
By in 600kg and residue is mixed into slurry in acid-leaching reaction device with 1500kg iron oxide red later stage eluates, then
The concentrated sulfuric acid that 1560kg concentration is 98% is added, the reaction time is 180min under the conditions of 90 DEG C, and reaction terminates after 100 DEG C of bars
Filtered under part, a small amount of water washing receives to obtain acid leaching liquor 3410kg, wet basis acidleach residue 250kg.
250kg acidleach residue is added into eluate in plasm scouring groove again300kg, stirs into after slurry and filters, obtain rare earth
Oxide concentration is 1.5g/L eluate, then using the washing function of filter press itself, entered with iron oxide red later stage eluate
Row washing, receives to obtain eluate300kg, rare earth oxide concentration is 0.3g/L, returns to dispensing in stock tank again, circulates for acidleach
The washing of residue.
Neutralizer 3850kg is returned into former process, iron sheet is added, reduction reaction is carried out under the conditions of 50 DEG C -80 DEG C, makes it
In Fe3+It is converted into Fe2+, solution 6500kg after reduction is made through filtering, containing FeSO41900kg, REO 3.80kg；
Solution send first class purification process after 260kg is reduced, and ammonium carbonate is added thereto, is reacted under the conditions of 80 DEG C
After 120min, ammonium sulfide solution is added, maintains the temperature to continue to react 180min, ferrous sulfate is received to obtain in filtering after reaction terminates
Solution 260kg, and Main Ingredients and Appearance are carbonated rare earth, the sediment 1.90kg of cobalt sulfide.
Copperas solution send addition 2.0kg ammoniacal liquor under secondary purification process, stirring condition after 260kg is purified, then
The insulation precipitation 180min under the conditions of 50 DEG C.Reaction filters the copperas solution 260kg for receiving pure, Main Ingredients and Appearance after terminating
For the sediment 1.0kg of iron hydroxide.The common 2.90kg of sediment produced by first class purification and secondary purification is returned into acidleach work
Sequence is recycled.
Copperas solution pure 260kg is combined in reactor in multifunctional oxygen to use iron oxide red later stage eluate
30g/L is diluted to, 25 DEG C of solution temperature is controlled, 1.1 times of ammoniacal liquor of theoretical amount are added thereto, control ph is 10.5, Ran Houtong
Air oxidation 90min, is made outward appearance in sundown, crystal seed slurry with well suspended.
It is 4 that sulfuric acid adjustment pH value is added into crystal seed slurry, then adds ferrous sulfate in solution after reduction, adjustment slurry
Concentration is 10g/L, and crystal seed slurry temperature is promoted to after 90 DEG C and adds solution and ammoniacal liquor after reduction in manner of cocurrent flow, is led to simultaneously
Air oxidation.It is that ferrous sulfate concentration is 10g/L in 4, slurry to control co-current process pH value.When coloured light is similar to 190# standard samples
When stop the dropwise addition of solution after reduction, continue blowing air oxidation, and slurry pH value controlled as 4 using ammoniacal liquor.When Fe concentration in slurry
During less than 0.1g/L, reaction terminates.Iron oxide red mother liquor 9000kg is received to obtain in filtering, separation（Wherein 0.75kg containing Fe, rare earth oxygen
Compound 3.44kg）, iron oxide red wet cake 2000kg.
Iron oxide red wet cake is sent in pickling reactor and mixed with acid eluate, under normal temperature condition, control ph 3,
Filter, wash after being sufficiently stirred for, receive to obtain pickling rear oxidation iron oxide red wet cake 2000kg and the acid eluate containing rare earth sulfate.Will
Acid eluate, which is recycled to rare earth concentration, reaches 0.12g/L, stops recycling, often handles 1000kg neodymium iron boron waste materials, puts down
Can output acid eluate 850kg, 0.102kg containing rare earth oxide.Iron oxide red acid eluate and iron oxide red mother liquor and eluateClose
And after send rare earth and cobalt abstraction process, extract rare earth therein, cobalt and be simultaneously prepared into corresponding compound products.
2000kg pickling rear oxidation iron oxide red wet cakes are mixed into mashing with clear water, then with Filter Press and washed, are made
Sulphates content is less than 0.05% washing rear oxidation iron oxide red wet cake, send drying system to dry and iron oxide red finished product 1050kg is made,
Product meets GB/T1863-2008 iron oxide red product standards.
Claims (2)
1. a kind of method of comprehensive utilization of neodymium iron boron waste material acid leaching residue, it is characterised in that carry out according to the following steps：
The leaching and separation of iron, rare earth and cobalt element in neodymium iron boron waste material acid leaching residue：
Step (1)：By neodymium iron boron waste material acid leaching residue in neutralization reactor with from the neodymium iron boron obtained by acidleach, separation circuit
Waste material acid leaching residue acid leaching liquor is mixed, and it is 70 DEG C -100 DEG C to control neutral temperature, and the neutralization reaction time is 180-360min, reaction
Endpoint pH is 0.25-0.5, is consumed the free acid in acid leaching liquor, iron, rare earth in neodymium iron boron waste material acid leaching residue and
Cobalt element obtains preliminary dissolution；
Step (2)：Slurry in neutralization reactor is filtered under the conditions of 70 DEG C -100 DEG C and receives to obtain neutralizer and neutralization residue, in
Main Ingredients and Appearance with liquid is iron and the sulfate of cobalt, as the raw material for preparing iron oxide red, and it is dioxy to neutralize residue Main Ingredients and Appearance
SiClx, iron oxide, rare earth oxide, rare earth sulfate and micro cobalt；
Step (3)：Residue will be neutralized and send acidleach process, with the later stage of iron oxide red preparation section institute output in acid-leaching reaction device
Eluate presses solid-to-liquid ratio 1:1.5-1:2.5 mixing, then add the concentrated sulfuric acid in 70 DEG C of -100 DEG C of bars by 1.5-1.9 times of theoretical amount
Acid-leaching reaction is carried out under part, it is 180-360 min to control the acid-leaching reaction time, makes iron therein, rare earth and cobalt further molten
Go out, reaction terminate through filtering receive Main Ingredients and Appearance be iron and cobalt sulfate acid leaching liquor and acidleach residue；By gained Ore Leaching
Liquid storage is used as neutralizing proportion liquid；
Step (4)：Step（1）、（3）Described course of reaction is strong acid hot environment, and rare earth sulfate dissolves on this condition
Degree is relatively low, and most of form preservation with soluble-salt is in residue, by step（2）Gained neutralizes residue through step（3）Acidleach
Later stage eluate of the gained acidleach residue in plasm scouring groove again with iron oxide red preparation section institute output is under normal temperature condition afterwards
Mix and make into slurry, dissolve the rare earth sulfate in acidleach residue and enter liquid phase, be then made main through filtering, washing
Composition is the eluate and acidleach residue of rare earth sulfate, and eluate middle rare earth content is sent dilute between 1-3g/L
Native abstraction process is used to prepare rare-earth products；
The preparation of iron oxide red：
Step（1）：By step（2）Gained neutralizer returns former process, using iron filings, iron sheet or reduced iron powder as reducing agent, in 50
Reduction reaction is carried out under the conditions of DEG C -80 DEG C, makes Fe therein3+It is converted into Fe2+, it is ferrous sulfate that Main Ingredients and Appearance, which is made, through filtering
Reduction after solution；
Step（2）：By part steps（1）Gained copperas solution send first class purification process, thereto add ammonium hydrogen carbonate or
Ammonium carbonate, 30-180min is reacted under the conditions of 50 DEG C -80 DEG C, rare earth therein is converted into carbonated rare earth precipitation；Add sulphur
Change ammonium or hydrogen sulfide, react 30-180min under the conditions of 50 DEG C -80 DEG C, cobalt heavy metal therein is converted into sulfide precipitation；
After reaction terminates filtering receive must purify after copperas solution and Main Ingredients and Appearance be carbonated rare earth, the sediment of cobalt sulfide；
Secondary purification process is sent by copperas solution after purification, adding appropriate ammoniacal liquor makes a small amount of ferrous iron be converted into hydroxide
Iron, while making ferrous hydroxide be converted into iron hydroxide by the contact with air, is incubated precipitation under the conditions of 50 DEG C -80 DEG C
30-180min, rare earth, the cobalt foreign ion of further adsorbent solution residual, the sulfuric acid for receiving pure is filtered in reaction after terminating sub-
Ferrous solution and the sediment that Main Ingredients and Appearance is iron hydroxide, the sediment produced by first class purification and secondary purification return to acidleach work
Sequence is recycled；
Step（3）：By step（2）The pure copperas solution of gained is combined in reactor use iron oxide red in multifunctional oxygen
The later stage eluate of preparation section institute output is diluted to 5-30g/L, controls 10 DEG C -25 DEG C of solution temperature, adds thereto theoretical
Measure 0.9-1.5 times of ammoniacal liquor, control ph is 9-10.5, then blowing air oxidation 30-90min be made outward appearance in sundown,
Crystal seed with well suspended；
Step（4）：Add water it is appropriate crystal seed in reactor be combined to multifunctional oxygen be diluted, and adjust slurry pH value with sulfuric acid
For 3-4, step is added in manner of cocurrent flow after crystal seed slurry temperature is promoted into 80 DEG C -90 DEG C（1）Gained reduction after solution and
Ammoniacal liquor, while blowing air is aoxidized, it is that ferrous sulfate concentration is 10-20 g/L in 3-4, slurry to control co-current process pH value, works as color
Light stops the dropwise addition of solution after reduction to standard sample when similar, continue blowing air oxidation, and control slurry pH value as 3- using ammoniacal liquor
4, when Fe concentration is less than 0.1g/L in slurry, reaction terminates；
Step（5）：By step（4）Gained iron oxide red slurry filtration, receive iron oxide red wet cake and Fe concentration be less than 0.1g/L,
Rare earth oxide concentration more than 0.3g/L, cobalt concentration more than 0.25g/L iron oxide red mother liquor, gained iron oxide red is female
Liquid merge with eluate obtained by iron in neodymium iron boron waste material acid leaching residue, the leaching of rare earth and cobalt element and separating step (4) be sent to it is dilute
Soil and cobalt abstraction process are used to prepare rare earth and cobalt product；
Step（6）：By step（5）Gained iron oxide red wet cake is sent in pickling reactor and mixed with acid eluate, in normal temperature condition
Under, control ph is filtered between 1.5-3 after being sufficiently stirred for, then scrubbed receives pickling rear oxidation iron oxide red wet cake and to contain
The acid eluate of rare earth sulfate, acid eluate recycle to rare earth concentration reach more than 0.1g/L when with neodymium iron boron waste material acidleach
Iron, the leaching of rare earth and cobalt element and separating step in slag（4）Rare earth and cobalt abstraction process are sent in the merging of gained eluate to be used for
Prepare rare earth and cobalt product；
Step（7）：Pickling rear oxidation iron oxide red wet cake is mixed into mashing with clear water, then with Filter Press and washed, sulphur is made
Phosphate content is less than 0.05% washing rear oxidation iron oxide red wet cake；
Step（8）：Send drying system to dry iron oxide red wet cake and iron oxide red finished product is made.
2. the method for comprehensive utilization of neodymium iron boron waste material acid leaching residue according to claim 1, it is characterised in that
Iron, the leaching of rare earth and cobalt element and separating step in neodymium iron boron waste material acid leaching residue（1）Described iron, rare earth and cobalt element
Leach and separation method：Neodymium iron boron waste material acid leaching residue is leached in strong acid hot environment, rare earth sulfuric acid salt solubility is diminished simultaneously
It is enriched in acidleach residue, then acidleach residue is mixed with water in plasm scouring groove again by the way of washing dissolution, made
Rare earth sulfate dissolution, the eluate of rare earth sulfate must be contained by being received through separation, be less than in eluate middle rare earth concentration
During 1.5g/L, eluate can be returned to again plasm scouring groove and recycled, until eluate middle rare earth concentration is more than 2.0
Extraction of rare eart process is sent to during g/L again.
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| CN107794373B (en) * | 2017-11-06 | 2019-01-22 | 孙东江 | The integrated conduct method of the useless magnetic material of neodymium iron boron |
| CN108950250B (en) * | 2018-08-01 | 2020-11-24 | 安徽金三隆再生资源有限公司 | Method for recovering rare earth in neodymium iron boron waste acid-soluble slag |
| CN109439912B (en) * | 2018-10-22 | 2020-09-08 | 江西理工大学 | One-step comprehensive recovery method for neodymium iron boron waste acid leaching residue through flash reduction |
| 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 |
| CN113104902A (en) * | 2021-04-07 | 2021-07-13 | 江西理工大学 | Method for preparing iron oxide red from magnetic material waste acid leaching residues |
| CN113104901B (en) * | 2021-04-13 | 2024-02-09 | 江西理工大学 | Method for preparing iron oxide yellow from rare earth waste acid leaching slag |
| CN113293307B (en) * | 2021-06-03 | 2023-08-15 | 中国科学院江西稀土研究院 | Method for extracting iron and cobalt from neodymium-iron-boron waste material, namely, iron tailings by using eugenolysis method with hydrochloric acid |
| CN115074530B (en) * | 2022-04-07 | 2023-07-18 | 江西理工大学 | Method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under hydrochloric acid system |
| CN114875241B (en) * | 2022-04-07 | 2023-07-25 | 江西理工大学 | Method for comprehensively recovering valuable metals from neodymium iron boron waste acid leaching residues under sulfuric acid system |
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| CN1295357C (en) * | 2005-05-08 | 2007-01-17 | 西安西骏新材料有限公司 | Recovery method of valuable element in neodymium iron boron waste material |
| CN102206755B (en) * | 2011-03-06 | 2013-08-21 | 林剑 | Method for separating and recovering valuable elements from neodymium-iron-boron wastes |
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