CN101979336B - Method for simultaneously treating waste water and recovering rare earth of rare earth separation plant - Google Patents
Method for simultaneously treating waste water and recovering rare earth of rare earth separation plant Download PDFInfo
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- CN101979336B CN101979336B CN2010102733884A CN201010273388A CN101979336B CN 101979336 B CN101979336 B CN 101979336B CN 2010102733884 A CN2010102733884 A CN 2010102733884A CN 201010273388 A CN201010273388 A CN 201010273388A CN 101979336 B CN101979336 B CN 101979336B
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- rare earth
- waste water
- oxalic acid
- ammonia
- oxide
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 89
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 72
- 239000002351 wastewater Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000000926 separation method Methods 0.000 title claims abstract description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003916 acid precipitation Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 239000000292 calcium oxide Substances 0.000 claims abstract description 11
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract 3
- 239000002893 slag Substances 0.000 claims description 17
- -1 rare earth oxalate Chemical class 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000007127 saponification reaction Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 201000002282 venous insufficiency Diseases 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 12
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000001110 calcium chloride Substances 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract 3
- 239000000463 material Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 8
- 235000011941 Tilia x europaea Nutrition 0.000 description 8
- 239000004571 lime Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- PYEJXBWRVNYIFO-UHFFFAOYSA-H C(C(=O)[O-])(=O)[O-].[Nd+3].[Pr+3].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] Chemical compound C(C(=O)[O-])(=O)[O-].[Nd+3].[Pr+3].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] PYEJXBWRVNYIFO-UHFFFAOYSA-H 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- TVXXPIQTTCLGHP-UHFFFAOYSA-N dysprosium;oxalic acid Chemical compound [Dy].OC(=O)C(O)=O TVXXPIQTTCLGHP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- RVNCZYOIAUWWCB-UHFFFAOYSA-N oxalic acid;terbium Chemical compound [Tb].OC(=O)C(O)=O RVNCZYOIAUWWCB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder 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
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
Classifications
-
- 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 method for simultaneously treating oxalic acid precipitation waste water and ammonia-nitrogen waste water and recovering rare earth of a rare earth separation plant. The method is characterized by comprising the following steps of: treating the oxalic acid precipitation waste water by using calcium carbonate; precipitating rare earth dissolved in the oxalic acid precipitation waste water; recovering with calcium oxalate together; obtaining a mixture of calcium oxide and rare earth oxide by burning; treating the ammonia-nitrogen waste water generated in a rare earth separating process by using the calcium oxide in the mixture; generating calcium chloride by dissolving the calcium oxide, simultaneously generating ammonia water from ammonia nitrogen in the ammonia-nitrogen waste water, and generating rare earth hydrate from the rare earth; obtaining rare earth-containing filter residue by filtering and separating; returning filtrate to an extraction line for saponifying an organic extractant; obtaining rare earth material liquid by dissolving the filter residue by using an acid; and returning the rare earth material liquid for use. The method of the invention can treat the oxalic acid precipitation waste water and the ammonia-nitrogen waste water generated in various rare earth separation processes and has a simple process. Acidic waste water is treated, resource is saved, environmental pollution is reduced, rare earth is recovered, waste is utilized comprehensively and simultaneously good economic benefit is achieved.
Description
Technical field
The present invention relates to a kind of method that Rare Earth Separation factory waste water reclaims rare earth simultaneously of handling, belong to the technology for treating industrial waste water field.
Background technology
The waste water that Rare Earth Separation factory production process produces is divided into acid waste water (mainly contain a kind of in oxalic acid, hydrochloric acid, nitric acid, sulfuric acid, the acetic acid or several) and ammoniated wastewater (mainly contain a kind of in ammonium chloride, ammonium oxalate, an ammonium nitrate, ammonium sulfate, ammonium acetate, the ammoniacal liquor or several) usually.Acid waste water mainly results from the process of the rare earth feed liquid of separate purifying (often being rare earth chloride liquid) with oxalic acid precipitation, and ammoniated wastewater mainly results from the waste water that organic phase saponification in the rare earth extraction sepn process is abandoned water (ammoniacal liquor saponification commonly used) and separated rare earth feed liquid (often being rare earth chloride liquid) the carbon ammonium precipitation process generation of purifying.
Rare-earth oxalate enhancing solubleness along with acidity in acidic aqueous solution increases.This is because exist in the system:
RE
2(C
2O
4)
3＝2RE
3++3C
2O
4 2-
H
++C
2O
4 2-＝HC
2O
4
RE
2(C
2O
4)
3→〔RE(C
2O
4)n〕
3-2n，(n＝1、2、3)
Because HC
2O
4 -Be weak electrolyte, ionizing power a little less than, if acidity increases, H in the ie in solution
+Concentration increases, then the C that comes out of rare-earth oxalate ionization
2O
4 2-With H
+In conjunction with generating HC
2O
4 -Increase, reduced C in the solution
2O
4 2-Concentration so balance moves right, causes the solubleness of rare-earth oxalate to increase; Because the oxalic acid that adds during deposition is excessive, a large amount of excessive C are arranged in the solution
2O
4 2-, along with RE
2(C
2O
4)
3Continuous dissolving, thereby make RE
2(C
2O
4)
3Be converted into (RE (C
2O
4) n)
3-2n(n=1,2,3), and then rare earth solubleness is obviously increased, promptly the loss of rare earth is big more.
These waste water acid concentrations are high, and quantity discharged is big, and environment is caused great pollution.It is acid that Rare Earth Separation enterprise generally adopts alkali (like caustic soda and normally used lime powder) neutral method to reduce waste water to this type waste water.Owing to also have a spot of REE in these acid waste waters, during these REEs cinder in caoxalate and lime etc. in the process of wastewater treatment gets into waste residue in.Because amount of impurities is many, kind is complicated, and rare earth gets into reasons such as mechanical impurity micropore, inconvenient recycling.And a large amount of waste residues that produced also need carry out drying etc. and dispose (it is moisture about 50% that these waste residues filter the back, and all the other staples are the mechanical impuritys such as cinder that bring in caoxalate and the sour insoluble lime, also have a small amount of rare earth and other inorganicss).Contain rare earth (butt is in REO) 1%-10% through detecting in this type waste residue, directly throwing aside these waste residues, not only to measure big intractability high, but also the valuable rare earth resources of loss.
Ammoniated wastewater discharges after removing ammonia nitrogen and filtered and recycled rare earth with heat after the milk of lime heightening pH value stripping and oxidation usually.The treating processes energy consumption is bigger, and index such as ammonia nitrogen, COD is difficult to reach the emission standard that country allows in the waste water.
By retrieval, do not see that processing Rare Earth Separation factory waste water reclaims the patent of rare earth simultaneously.
Summary of the invention
The object of the invention is exactly to be to provide a kind of method that reclaims rare earth when the Rare Earth Separation mesoxalic acid precipitates waste water and ammoniated wastewater of handling.Regulate rare earth oxalic acid precipitation waste water ph owing to use price far below the replacing lime with limestone of lime; Not only can reduce the wastewater treatment expense; And can reduce the quantity and the impurity introducing amount of waste residue; Be convenient to reclaim low levels rare earth and minimizing ammoniated wastewater adjusting pH value lime consumption in the waste residue, make waste residue and ammoniated wastewater obtain comprehensive utilization.
Main technical schemes of the present invention is; Rare earth oxalic acid precipitation waste water and calcium carbonate reaction reduce the acidity of waste water; Filter and collect and the middle slag (staple is caoxalate and rare earth oxalate) of washing; Middle slag obtains mixed oxide (staple is quicklime and rare earth oxide) through calcination; Mixed oxide soaks and the processing ammoniated wastewater that stirs with ammoniated wastewater, quicklime is changed into calcium chloride get into solution, and the rare earth in the ammoniated wastewater is converted into rare-earth hydroxide simultaneously, ammonia nitrogen is converted into ammoniacal liquor.Filter rear filtrate once more and return instead of part alkali do extraction production line saponification raw material, filter residue (staple is rare earth oxide and rare-earth hydroxide) washing back goes out to obtain rare earth feed liquid with acidleach and returns the production use.
Method of the present invention may further comprise the steps:
A) add in the lime carbonate in the rare earth oxalic acid precipitation waste water and the acid in the waste water; React to pH=1-4; Separation and Recovery contains the middle slag of rare earth, obtains containing the middle slag of caoxalate and rare earth, and said rare earth oxalic acid precipitation waste water is any one waste water that is produced with the oxalic acid precipitation rare earth;
B) slag obtains containing the mixed oxide of quicklime and rare earth oxide in the middle of through calcination;
C) add ammoniated wastewater in the mixed oxide, to pH=8-12;
D) liquid-solid separation obtains containing the lucium of rare earth oxide and rare-earth hydroxide, and filtrating is returned use;
E) lucium goes out with acidleach, obtains rare earth chloride liquid, returns to produce and uses.Wherein:
Step a) said rare earth oxalic acid precipitation waste water and calcium carbonate reaction through reducing waste water acidity, reduce the solubleness of rare earth oxalate in waste water to pH=1-4, reclaim the middle slag that contains rare earth with filtering separation.
The said rare earth oxalic acid precipitation of step a) waste water is that oxalic acid prepares the waste water that is produced when rare earth is total to hypostasis.
Slag was mainly contained the mixed oxide of quicklime and rare earth oxide 850-1000 ℃ of calcination in the middle of step b) was said.
Add ammoniated wastewater digestion in the said mixed oxide of step c), stirring reaction changes into calcium chloride with quicklime and gets into solution to pH=8-12, and the rare earth in the ammoniated wastewater is converted into rare-earth hydroxide simultaneously, ammonia nitrogen is converted into ammoniacal liquor.
The said liquid-solid separation of step d) is mainly contained the lucium of rare earth oxide and rare-earth hydroxide, and filtrating is returned the extraction line and made organic extractant saponification usefulness.
The said ammoniated wastewater of step d) comprises the arbitrary ammoniated wastewater that is produced in the Rare Earth Separation process.
Step e) is said to be gone out to comprise with a kind of or wherein mixing acid leaching more than two kinds in hydrochloric acid, sulfuric acid, nitric acid, the acetic acid with acidleach.
Relevant chemical reaction:
2H
++CaCO
3＝Ca
2++H
2O+CO
2↑
Ca
2++C
2O
4 2-＝CaC
2O
4↓
2CaC
2O
4+O
2＝2CaO+4CO
2↑
2RE
2(C
2O
4)
3+3O
2＝2RE
2O
3+12CO
2↑
CaO+H
2O＝Ca(OH)
2
2NH
4 ++Ca(OH)
2＝Ca
2++2NH
3·H
2O
NH
3·H
2O＝NH
4 ++OH
-
RE
3++3OH-＝RE(OH)
3↓
RE
2O
3+6H
+＝2RE
3++3H
2O
RE(OH)
3+3H
+＝RE
3++3H
2O
Adopt the present invention to handle Rare Earth Separation waste water; Reduced environmental pollution when not only handling waste water; The waste residue that can also utilize treatment of acidic wastewater to produce is simultaneously handled ammoniated wastewater through being used for replacing lime after reclaiming; Reduced and handled the consumption of lime that ammoniated wastewater consumes and the generation of waste residue, reclaimed the rare earth in acid waste water and the ammoniated wastewater, in waste ' s reclamation, can realize favorable economic benefit.
Description of drawings
Accompanying drawing is that the rare-earth process general flow chart is reclaimed in the wastewater treatment of Rare Earth Separation factory simultaneously.
Embodiment
Below be described further of the present invention with specific embodiment.
Embodiment one
Referring to Fig. 1, with C
Oxalic acid=12.7g/L, REO=0.73g/L praseodymium oxalate neodymium deposition waste water 5m
3When adding calcium carbonate reaction, suspension liquid is filtered and wash filter residue obtain middle slag to pH=1.5; Middle slag obtains mixed oxide 43.1kg 850-900 ℃ of calcination.The C that produces during this mixed oxide and Phosbloc are produced
Ammonium chloride=75g/L, REO=0.86g/L carbon ammonium precipitation filtrating 1m
3, filtrating is returned the extraction line be used for the organic extractant saponification to the pH=9 after-filtration at the stirring tank internal reaction, leach with sulfuric acid behind the residue washing, obtain rare earth feed liquid, return to produce and use.Meter reclaims rare earth and amounts to REO=4.1kg, rare earth yield 90.9%.
Embodiment two
Referring to Fig. 1, with C
Oxalic acid=16.9g/L, REO=0.78g/L oxalic acid dysprosium deposition waste water 5m
3When adding the lime carbonate hybrid reaction, suspension liquid is filtered and wash filter residue obtain middle slag to PH=4; Middle slag obtains mixed oxide 56.2kg 950-1000 ℃ of calcination.The C that produces in this mixed oxide and the extraction production line
Ammonium chloride=100g/L extraction saponification is abandoned water 1m
3, filtrating is returned the extraction line be used for the organic extractant saponification to the pH=8 after-filtration at the stirring tank internal reaction, leach with acetic acid behind the residue washing after the filtration, obtain rare earth feed liquid, return to produce and use.Meter reclaims rare earth and amounts to REO=3.7kg, rare earth yield 94.9%.
Embodiment three
Referring to Fig. 1, with C
Oxalic acid=8.6g/L, REO=0.41g/L oxalic acid terbium deposition waste water 5m
3When adding the lime carbonate hybrid reaction, suspension liquid is filtered and wash filter residue obtain middle slag to PH=2.5; Middle slag obtains mixed oxide 29.8kg 850-1000 ℃ of calcination.The C that produces in this mixed oxide and the extraction production line
Ammonium chloride=48.5g/L extraction saponification is abandoned water 1m
3, filtrating is returned the extraction line be used for the organic extractant saponification to pH≤12 after-filtration at the stirring tank internal reaction, leach with hydrochloric acid and nitric acid mixing acid behind the residue washing after the filtration, obtain rare earth feed liquid, return to produce and use.Meter reclaims rare earth and amounts to REO1.9kg, rare earth yield 92.7%.
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the aim and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (6)
1. handle the method that Rare Earth Separation factory waste water reclaims rare earth simultaneously for one kind, may further comprise the steps:
A) add in the lime carbonate in the rare earth oxalic acid precipitation waste water and the acid in the waste water; React to pH=1-4; Separation and Recovery contains the middle slag of rare earth, obtains containing the middle slag of caoxalate and rare earth oxalate, and said rare earth oxalic acid precipitation waste water is any one waste water that is produced with the oxalic acid precipitation rare earth;
B) slag obtains containing the mixed oxide of quicklime and rare earth oxide in the middle of through calcination;
C) add ammoniated wastewater in the mixed oxide, to pH=8-12;
D) liquid-solid separation obtains containing the lucium of rare earth oxide and rare-earth hydroxide, and filtrating is returned use;
E) lucium goes out to obtain rare earth feed liquid with acidleach, returns to produce and uses.
2. the method for claim 1 is characterized in that, said rare earth oxalic acid precipitation waste water is that oxalic acid prepares the waste water that is produced when rare earth is total to hypostasis.
3. the method for claim 1 is characterized in that, middle slag obtains quicklime and rare earth oxide mixture 850-1000 ℃ of calcination.
4. the method for claim 1 is characterized in that, liquid-solid separation obtains containing the lucium of rare earth oxide and rare-earth hydroxide, and filtrating is returned the extraction line and made organic extractant saponification usefulness.
5. the method for claim 1 is characterized in that, ammoniated wastewater comprises the arbitrary ammoniated wastewater that is produced in the Rare Earth Separation process.
6. the method for claim 1 is characterized in that, goes out to comprise with a kind of or wherein mixing acid leaching more than two kinds in hydrochloric acid, sulfuric acid, nitric acid, the acetic acid with acidleach.
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|---|---|---|---|
| CN2010102733884A CN101979336B (en) | 2010-09-03 | 2010-09-03 | Method for simultaneously treating waste water and recovering rare earth of rare earth separation plant |
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|---|---|---|---|
| CN2010102733884A CN101979336B (en) | 2010-09-03 | 2010-09-03 | Method for simultaneously treating waste water and recovering rare earth of rare earth separation plant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167467B (en) * | 2011-03-21 | 2012-09-26 | 江苏华杉环保科技有限公司 | Deep treatment technology of high-ammonia nitrogen rare earth wet process-smelted saponifying wastewater |
| CN102676853B (en) * | 2012-05-28 | 2013-11-20 | 五矿（北京）稀土研究院有限公司 | Rare earth separation method with material linkage cyclic utilization function |
| CN102976525B (en) * | 2012-12-12 | 2013-11-20 | 南昌大学 | Method for treating and recycling rare earth oxalate precipitation mother solution |
| CN103288248B (en) * | 2013-07-01 | 2015-03-11 | 全南包钢晶环稀土有限公司 | Combined treatment method for rear earth smelting/separating wastewater |
| CN103408091B (en) * | 2013-07-19 | 2015-02-04 | 广州有色金属研究院 | Recovery method of rare earth oxalate precipitation wastewater |
| CN104211106B (en) * | 2014-09-01 | 2016-08-24 | 赣州鑫隆康稀土有限公司 | A kind of carbonated rare earth preparation method not producing ammonia nitrogen waste water |
| CN104357670B (en) * | 2014-11-04 | 2016-05-18 | 江西理工大学 | A kind of method of recycling with slag for comprehensive in rare earth oxalic acid waste water |
| CN104761444A (en) * | 2015-03-18 | 2015-07-08 | 南京格洛特环境工程股份有限公司 | Process of recycling oxalic acid from rare earth wet-method smelting oxalic acid precipitation waste water |
| CN105417819B (en) * | 2015-11-27 | 2018-10-12 | 内蒙古包钢和发稀土有限公司 | A kind of technique of efficient process rare earth sulfuric acid ammonium waste water |
| CN109607914A (en) * | 2018-12-11 | 2019-04-12 | 崔源发 | A kind of technique for treating industrial wastewater of rare metal |
| CN110776040B (en) * | 2019-11-04 | 2022-01-18 | 南昌航空大学 | Method for preparing 4N-grade calcium chloride by extracting and separating calcium saponification wastewater with rare earth |
| CN111197124A (en) * | 2020-01-08 | 2020-05-26 | 昆明理工大学 | Method for researching rare earth recovery |
| CN113046578B (en) * | 2021-02-08 | 2022-09-16 | 五矿（北京）稀土研究院有限公司 | Preparation method of low-impurity rare earth feed liquid |
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| JP3615943B2 (en) * | 1998-09-16 | 2005-02-02 | 三井金属鉱業株式会社 | Method for recovering rare earth elements from used rare earth abrasives |
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