CN101503760B - Method for extracting zinc from zinc oxide ore ammonia leaching solution - Google Patents
Method for extracting zinc from zinc oxide ore ammonia leaching solution Download PDFInfo
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- CN101503760B CN101503760B CN200910094205XA CN200910094205A CN101503760B CN 101503760 B CN101503760 B CN 101503760B CN 200910094205X A CN200910094205X A CN 200910094205XA CN 200910094205 A CN200910094205 A CN 200910094205A CN 101503760 B CN101503760 B CN 101503760B
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- Prior art keywords
- zinc
- extraction
- phase
- zinc oxide
- ammonia
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011701 zinc Substances 0.000 title claims abstract description 43
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 36
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 29
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002386 leaching Methods 0.000 title claims description 19
- 238000000605 extraction Methods 0.000 claims abstract description 63
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- 239000003350 kerosene Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 8
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 17
- 230000005501 phase interface Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 3
- 229960001763 zinc sulfate Drugs 0.000 abstract description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 3
- 239000000839 emulsion Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000003607 modifier Substances 0.000 abstract 2
- MJUVQSGLWOGIOB-UHFFFAOYSA-N 2-[(Z)-hydroxyiminomethyl]-4-nonylphenol Chemical compound OC1=C(C=N/O)C=C(C=C1)CCCCCCCCC MJUVQSGLWOGIOB-UHFFFAOYSA-N 0.000 abstract 1
- 229940095054 ammoniac Drugs 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 238000004070 electrodeposition Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- YWACCMLWVBYNHR-UHFFFAOYSA-N 7-(5-ethylnonan-2-yl)quinolin-8-ol Chemical compound C1=CC=NC2=C(O)C(C(C)CCC(CC)CCCC)=CC=C21 YWACCMLWVBYNHR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
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- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for extracting zinc from ammonia lixivium of zinc oxide ores. The method is to adopt an aldoxime extractant (2-hydroxy-5-nonyl benzaldoxime), a modifier (isoamyl alcohol or mixed alcohol) and 260<#> sulfonated kerosene or aviation kerosene to form an organic extract phase, extract Zn<2+> from ammonia lixivium of zinc oxide ores, and use sulfuric acid for back-extraction to make zinc in the ammonia lixivium separated and enriched into zinc sulfate. The method is characterized by adopting the synergic action of the aldoxime extractant and the modifier (the isoamyl alcohol or the mixed alcohol) to strengthen zinc extraction in an ammoniac solution and maintain the stability of an extraction system, adopting the sulfuric acid as a pH regulator of an extracted water phase, fully mixing the organic phase and the water phase when efficiently extracting the zinc and performing quick phase splitting, having a clear phase interface, and generating no emulsion or a third phase. The organic phase can be recycled, and the organic extract phase can make Zn<2+> in the water phase subjected to high-efficiency extraction, separation and enrichment. The method can efficiently, quickly and cleanly separate and enrich the zinc in the ammonia lixivium of the zinc oxide ores.
Description
Technical field
The present invention relates to metallurgical technology field, specifically is the method for extracting zinc from the zinc oxide ore ammonia leaching solution.
Background technology
At present, zinc oxide ore all adopts the method for hydrometallurgy to handle more than 80%.The zinc oxide ore hydrometallurgy is mainly with acidleach-extraction-electrodeposition method, but for the high zinc oxide ore of calcium magnesium basic gangue content because of sour consumption is big, be difficult to handle with pickling process.This class zinc oxide ore is suitable for the ammonia leaching, but for the low ore of grade, its leach liquor zinc concentration is low, can't dock with existing electrodeposition process, need carry out separation and concentration.Extraction process is the proper method of separation and concentration, but the extraction difficulty of zinc is big in the ammonia solution.
The extraction of zinc is more common in the acidic solution, its extraction agent commonly used comprises alkylphosphonic acid carboxylic acid type (as P204, P507), carboxylic acid extractant (as Vetatic 911, Kelex 100), neutral complexing extractant (as TBP), amine extractant (as TOA, N235, N236) etc.But deficiencies such as above-mentioned extraction agent extracting zinc in ammonia solution exists, and extraction efficiency is low, the branch phase velocity slow, easy emulsification are not seen the report of commercial application.
Summary of the invention
The purpose of this invention is to provide a kind of at the method for zinc oxide ore ammonia leaching solution with aldoxime kind of extractants extracting and separating enrichment zinc.Can improve percentage extraction, adjustable extraction process simultaneously makes phase-splitting fast behind organic phase and the water thorough mixing, forms clear phase interface, does not produce emulsification or generation third phase.
Technical scheme of the present invention is: with 2-hydroxyl-5 nonyls-benzaldoxime is extraction agent, and kerosene is that thinner is formed organic phase, and extraction agent 5%-15% (volume ratio), thinner 65%-90% (volume ratio) add properties-correcting agent C in the organic phase
5-C
9Alcohols material, with the strengthening extraction separating effect, improve the steady dissolution of aldoxime kind of extractants in thinner simultaneously, properties-correcting agent consumption 5%-20% (volume ratio); The zinc oxide ore ammonia leaching solution makes zinc be able to separation and concentration through extraction, back extraction and forms solution of zinc sulfate.Raffinate returns ammonia and soaks operation.Return the extraction operation after the regeneration of back extraction organic phase.
Properties-correcting agent is selected primary isoamyl alcohol or C for use
7-C
9Alcohol mixture.Thinner selects 260 for use
#Sulfonated kerosene or aviation kerosene.
For above-mentioned zinc oxide ore ammonia leaching solution, according to zinc concentration wherein, free ammonia (NH
3) concentration and ammonium ion (NH
4 +) the concentration difference, adopting 2-3mol/L sulfuric acid to regulate pH is 7.5-9, as water and extracted organic phase thorough mixing the zinc in the ammonia leaching solution is come together into organic phase with this, guarantee the efficient extraction of water zinc, make phase-splitting fast behind organic phase and the water thorough mixing simultaneously, phase interface is clear, does not produce emulsion or third phase.Load organic phases through after the suitable washing, is carried out back extraction with the sulfuric acid of 2-3mol/L, and strip liquor recycles as required, until its Zn
2+Concentration satisfies follow-up electrodeposition needs.
Above-mentioned raffinate can suitably add and returns zinc oxide ore ammonia behind the ammonia and soak operation, and the back extraction organic phase is through suitably recycling after the regeneration, and the electrodeposition raffinate replenishes sulfuric acid as strip liquor through suitably handling the back.The extraction operation does not produce the waste water that effluxes, and also can fully utilize the electrodeposition raffinate of electrodeposition operation simultaneously, realizes cleaner production.
The present invention adopts aldoxime extractants and alcohols material to be dissolved in kerosene composition organic phase, is particularly suitable for the ammonia leaching solution (C of lower concentration zinc
Zn2+=5-40g/L) in the separation and concentration of zinc.The zinc oxide ore ammonia leaching solution adopts sulfuric acid to regulate pH before extraction, can strengthen the complexing action between zine ion and extraction agent, improves percentage extraction, adjustable extraction process of while, make phase-splitting fast behind organic phase and the water thorough mixing, form clear phase interface, do not produce emulsification or generate third phase.
The present invention can produce following effect in the zinc separation and concentration process of zinc oxide ore ammonia leaching solution owing to have These characteristics:
1, with 2-hydroxyl-5 nonyls-benzaldoxime be extraction agent, with primary isoamyl alcohol or C
7-C
9Alcohol mixture is properties-correcting agent, is the organic phase that thinner is formed with kerosene that the zinc in the extracting and separating ammonia leaching solution can be realized the separation rapidly and efficiently of zinc in the Different Zinc concentration ammonia leaching solution, and extraction process does not produce emulsification or third phase, is easy to regulation and control.
2, strip liquor does not contain ammonia, can directly be connected with the operation of sophisticated zinc sulfate electrodeposition.
3, do not produce efflux wastewater, also can fully utilize the electrodeposition raffinate, realize cleaner production.
Embodiment
Embodiment 1:
At high contents of calcium and magnesium zinc oxide ore ammonia leaching solution 1
#, wherein zinc concentration is that 5.32g/L (presses Zn
2+Calculate), ammonium ion (NH
4 +) 1.5mol/L, free (NH
3) 2.5mol/L, 2mol/L sulfuric acid is transferred pH=8.6.With the extraction agent 2-hydroxyl-5 nonyls-benzaldoxime of 5% (volume percent), 5% properties-correcting agent C
7-C
9Alcohol mixture, 90% thinner 260
#Sulfonated kerosene is dissolved in properties-correcting agent and extraction agent in the lump and forms extracted organic phase in the kerosene, carries out the two-stage extraction.Load organic phases is through suitably using the back extraction of 3mol/L sulfuric acid after the washing.Reach 85% through first step extracting zinc percentage extraction, the total percentage extraction of two-stage extraction back zinc nearly 100%.Extraction and back extraction divide phase velocity fast, and phase interface is clear.
Embodiment 2:
At high contents of calcium and magnesium zinc oxide ore ammonia leaching solution 2
#, wherein zinc concentration 10.52g/L (presses Zn
2+Calculate), ammonium ion (NH
4 +) 1.8mol/L, free ammonia (NH
3) 2.0mol/L, 2mol/L sulfuric acid is transferred pH=8.7.With the extraction agent 2-hydroxyl-5 nonyls-benzaldoxime of 10% (volume percent), 15% properties-correcting agent primary isoamyl alcohol, 75% thinner aviation kerosene, properties-correcting agent and extraction agent be dissolved in the lump form extracted organic phase in the kerosene, carry out the two-stage extraction.Load organic phases is through suitably using the back extraction of 2mol/L sulfuric acid after the washing.Reach 80% through first step extracting zinc percentage extraction, the total percentage extraction of two-stage extraction back zinc nearly 100%.Extraction and back extraction divide phase velocity fast, and phase interface is clear.
Embodiment 3:
At certain zinc oxide ore ammonia leaching solution 3
#, wherein zinc concentration is that 41.56g/L (presses Zn
2+Calculate), ammonium ion (NH
4 +) 2.0mol/L, free (NH
3) 1.6mol/L, 3mol/L sulfuric acid is transferred pH=8.3.With the extraction agent 2-hydroxyl-5 nonyls-benzaldoxime of 15% (volume percent), 20% properties-correcting agent C
7-C
9Alcohol mixture, 65% thinner aviation kerosene are dissolved in properties-correcting agent and extraction agent in the lump and form extracted organic phase in the kerosene, carry out three grades of extractions.Load organic phases is through suitably using the back extraction of 2mol/L sulfuric acid after the washing.Reach through first step extracting zinc percentage extraction that the total percentage extraction of zinc is 96% after 60%, three grade of extraction.Extraction and back extraction divide phase velocity fast, and phase interface is clear.
Embodiment 4:
At zinc oxide ore leach liquor 4
#, wherein zinc concentration is that 20.18g/L (presses Zn
2+Calculate), ammonium ion (NH
4 +) 1.6mol/L, free (NH
3) 2.1mol/L, 3mol/L sulfuric acid is transferred pH=8.6.With the extraction agent 2-hydroxyl-5 nonyls-benzaldoxime of 15% (volume percent), 20% properties-correcting agent C
7-C
9Alcohol mixture, 65% thinner aviation kerosene, properties-correcting agent and extraction agent are dissolved in the lump forms extracted organic phase in the kerosene, recycle 20 batches with same organic phase collection at this routine feed liquid, and the one-level percentage extraction of every batch of feed liquid zinc is 72%-75%.Every batch of extraction back extraction divides phase velocity fast, and phase interface is clear, does not produce emulsification or third phase.
Claims (1)
1. the method for an extracting zinc from the zinc oxide ore ammonia leaching solution, it is characterized in that adopting 2-hydroxyl-5 nonyl benzene formoxime as extraction agent volume percent 5%-15%, with kerosene as diluent volume per-cent 65%-90%, mix and form organic phase, add primary isoamyl alcohol or the C of volume percent 5%-20% in the extracted organic phase
7-C
9Alcohol mixture adopts the pH regulator agent of sulfuric acid as the preceding water of ammonia leaching solution extraction as properties-correcting agent, regulates water pH=7.5-9, the zinc in the extracting and separating enrichment zinc oxide ore ammonia leaching solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910094205XA CN101503760B (en) | 2009-03-13 | 2009-03-13 | Method for extracting zinc from zinc oxide ore ammonia leaching solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910094205XA CN101503760B (en) | 2009-03-13 | 2009-03-13 | Method for extracting zinc from zinc oxide ore ammonia leaching solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101503760A CN101503760A (en) | 2009-08-12 |
| CN101503760B true CN101503760B (en) | 2011-05-25 |
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ID=40976136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910094205XA Expired - Fee Related CN101503760B (en) | 2009-03-13 | 2009-03-13 | Method for extracting zinc from zinc oxide ore ammonia leaching solution |
Country Status (1)
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|---|---|
| CN (1) | CN101503760B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880770B (en) * | 2010-07-30 | 2012-05-09 | 中南大学 | Application of extractant and method for extracting zinc from ammonia solution |
| CN103710547B (en) * | 2013-12-25 | 2016-03-30 | 昆明理工大学 | A kind of method of extracting zinc in zinc ammonia leaching solution |
| CN106119571B (en) * | 2016-06-29 | 2017-12-22 | 昆明理工大学 | It is a kind of to strengthen the method that zinc extracts in zinc ammonia solution with carbon dioxide |
| CN108728665A (en) * | 2018-05-04 | 2018-11-02 | 昆明理工大学 | A method of recycling copper from Water Quenching Slag |
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2009
- 2009-03-13 CN CN200910094205XA patent/CN101503760B/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN101503760A (en) | 2009-08-12 |
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Granted publication date: 20110525 Termination date: 20140313 |