CN102021334A - Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process - Google Patents
Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process Download PDFInfo
- Publication number
- CN102021334A CN102021334A CN201010587695XA CN201010587695A CN102021334A CN 102021334 A CN102021334 A CN 102021334A CN 201010587695X A CN201010587695X A CN 201010587695XA CN 201010587695 A CN201010587695 A CN 201010587695A CN 102021334 A CN102021334 A CN 102021334A
- Authority
- CN
- China
- Prior art keywords
- gallium
- mother liquor
- resin
- vanadium
- bayer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 103
- 239000012452 mother liquor Substances 0.000 title claims abstract description 91
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 79
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000004131 Bayer process Methods 0.000 title claims abstract description 50
- 238000001556 precipitation Methods 0.000 title claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 168
- 239000011347 resin Substances 0.000 claims abstract description 104
- 229920005989 resin Polymers 0.000 claims abstract description 104
- 238000005406 washing Methods 0.000 claims abstract description 54
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 52
- 229910021513 gallium hydroxide Inorganic materials 0.000 claims abstract description 44
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 claims abstract description 44
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 40
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 33
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 33
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 229910052788 barium Inorganic materials 0.000 claims abstract description 21
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 35
- 239000011734 sodium Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 30
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 27
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 24
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 2
- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000003480 eluent Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 description 16
- 235000011149 sulphuric acid Nutrition 0.000 description 16
- 238000005342 ion exchange Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- BPAABJIBIBFRST-UHFFFAOYSA-N [V].[V].[V].[Ga] Chemical compound [V].[V].[V].[Ga] BPAABJIBIBFRST-UHFFFAOYSA-N 0.000 description 2
- 229910000999 vanadium-gallium Inorganic materials 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- CLBBORVVTAFIRZ-UHFFFAOYSA-N gallium vanadium Chemical compound [V].[Ga] CLBBORVVTAFIRZ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for extracting gallium and vanadium from seed precipitation mother liquor of a Bayer process, which is used for recovering gallium and vanadium. The method is characterized by using an ion exchange resin for absorbing the seed precipitation mother liquor of the Bayer process, and comprising the following steps of: (1) absorbing the seed precipitation mother liquor of the Bayer process with the ion exchange resin; (2) washing the saturated resin; (3) adding BaO to eluent and precipitating vanadium in the form of barium vanadate; (4) adding NaOH to solution in which vanadium precipitates and precipitating gallium in the form of gallium hydroxide; (5) dissolving the gallium hydroxide with a NaOH solution and generating a sodium gallate solution; and (6) electrolyzing the sodium gallate solution to prepare metal gallium. In the method, gallium and vanadium are recovered from the seed precipitation mother liquor in the aluminium oxide production process of the Bayer process by the processes of resin adsorption, washing, leaching, vanadium precipitation, gallium precipitation, gallium dissolution, electrolysis and the like. The method has the advantages of simple process, convenience for operation, lower cost and high recovery rate.
Description
Technical field
The present invention relates to from Bayer-process seed-separating mother liquor, extract the method for gallium and vanadium, be used for the recovery of gallium and vanadium.
Background technology
The gallium resource is very rare, and the occurring in nature gallium mainly is present in the bauxite, and the primary gallium more than 90% is to extract from the process of producing aluminum oxide in the world, and therefore, the aluminum oxide flow process is a kind of important gallium resource.In addition, the gallium in the alumina producing flow process can be separated out with aluminium hydroxide in decomposition course, thereby influences the alumina product quality, and it is extracted, and the alumina product quality is improved to some extent; If can form new product, produce favorable economic benefit, it is single to alleviate the alumina producer product, improves the ability that aluminum oxide enterprise resists the market risk.
The method of extracting gallium from the alumina producing flow process has multiple, in industrial application chemical method (lime method, carbonatation process), electrochemical process (amalgam electrolysis method and substitution method), extraction process and ion exchange method has been arranged.Wherein ion exchange method need not to add any reagent in sodium aluminate solution because its flow process is brief, easy to operate, is acknowledged as the best method that reclaims gallium from bayer liquors, also is present main method in industrial application.Vanadium is that a kind of ion exchange method reclaims the major impurity in the gallium process, and vanadium also is a kind of higher metal that is worth, if can when reclaiming gallium vanadium also be recycled, then can produce better economic benefit.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, and the method for extracting gallium and vanadium from Bayer-process seed-separating mother liquor that a kind of flow process is simple, easy to operate, the rate of recovery is high is provided.
The objective of the invention is to be achieved through the following technical solutions.
Extract the method for gallium and vanadium in the Bayer-process seed-separating mother liquor, it is characterized in that spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, its process may further comprise the steps:
(1) spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, and gallium, vanadium negatively charged ion are adsorbed on the resin, and the mother liquor after the absorption returns production system;
(2) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin is carried out drip washing again, make the gallium of resin absorption, vanadium negatively charged ion enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium and the vanadium of mother liquor;
(3) in leacheate, add BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein;
(4) add NaOH in the solution behind the precipitation vanadium, gallium is precipitated with the form of gallium hydroxide;
(5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again;
(6) sodium solution gallate is carried out electrolysis, make gallium.
Extract the method for gallium and vanadium in the Bayer-process seed-separating mother liquor, it is characterized in that adopting two kinds of different ion exchange resin that Bayer-process seed-separating mother liquor is successively adsorbed, be characterised in that its process may further comprise the steps:
(1) with two kinds of different ion exchange resin Bayer-process seed-separating mother liquor is successively adsorbed, gallium, vanadium negatively charged ion are adsorbed in respectively on a kind of resin, and the mother liquor after the absorption returns production system;
(2) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin is carried out drip washing again, make the gallium of resin absorption, vanadium negatively charged ion enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium and the vanadium of mother liquor;
(3) in the leacheate that contains vanadium, add BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein;
(4) in the leacheate that contains gallium, add NaOH, gallium is precipitated with the form of gallium hydroxide;
(5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again;
(6) sodium solution gallate is carried out electrolysis, make gallium.
Extract the method for gallium and vanadium in the Bayer-process seed-separating mother liquor, it is characterized in that leaching process adds BaO earlier in Bayer-process seed-separating mother liquor, spent ion exchange resin adsorbs seed precipitation solution again, and its process may further comprise the steps:
(1) in Bayer-process seed-separating mother liquor, adds BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein;
(2) spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, and gallium is adsorbed on the resin, and the mother liquor after the absorption returns production system;
(3) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin are carried out drip washing again, make the gallium of resin absorption enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium of mother liquor;
(4) in leacheate, add NaOH, gallium is precipitated with the form of gallium hydroxide;
(5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again;
(6) sodium solution gallate is carried out electrolysis, make gallium.
Method of the present invention, when it is characterized in that spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, adsorption temp is 40～60 ℃, resin and mother liquor duration of contact are 15～60min.
Method of the present invention, when it is characterized in that with diluted acid saturated resin being washed, dilute acid concentration is 3%～5%, when saturated resin being carried out drip washing with concentrated acid, concentrated acid concentration is 5%～20%, and concentrated acid and saturated resin duration of contact are 30～60min, and the drip washing temperature is 20～40 ℃.
Method of the present invention, when it is characterized in that in Bayer-process seed-separating mother liquor, adding the BaO precipitation, Na in the add-on of BaO and the mother liquor
2CO
3Mol ratio be 0.1～1.0, temperature of reaction is 40 ℃～60 ℃, the reaction times is 15min～120min, stirring velocity is 100r/min～400r/min.
Method of the present invention, when it is characterized in that in leacheate adding BaO vanadium being precipitated with the form of vanadic acid barium, V in the BaO of adding and the leacheate
2O
5Mol ratio be 2～3, temperature of reaction is 20～40 ℃, the reaction times is 30～60min.
Method of the present invention, when it is characterized in that in leacheate adding NaOH gallium being precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 1～3 in the NaOH of adding and the leacheate, and temperature of reaction is 20～40 ℃, and the reaction times is 60～90min.
Method of the present invention, when it is characterized in that gallium hydroxide dissolves with NaOH solution, the concentration of NaOH solution is 2.5～3.5mol/L, and liquid-solid ratio is 3～5, and temperature of reaction is 40～60 ℃, and the reaction times is 30～60min.
Method of the present invention, when it is characterized in that sodium solution gallate carried out electrolysis, electrolysis temperature is 20～40 ℃, electrolysis time is 6～12h, thereby makes gallium.
Method of the present invention is characterized in that ion exchange resin is resin.
Method of the present invention is characterized in that related acid can be sulfuric acid, hydrochloric acid or nitric acid.
Several method of the present invention is with process recovery gallium and vanadium wherein such as the drip washing after resin absorption, washing of the seed precipitation solution in the alumina producing Bayer process process, precipitation, heavy gallium, molten gallium, electrolysis.Flow process is simple, easy to operate, cost is lower, the rate of recovery is high.
Description of drawings
Fig. 1 is a kind of process flow sheet of the present invention.
Fig. 2 is a kind of process flow sheet of the present invention.
Fig. 3 is a kind of process flow sheet of the present invention.
Embodiment
Extract the method for gallium and vanadium from Bayer-process seed-separating mother liquor, its process may further comprise the steps:
I is adsorbed Bayer-process seed-separating mother liquor with chelating ion exchange resin:
(1) with chelating ion exchange resin Bayer-process seed-separating mother liquor is adsorbed, gallium, vanadium negatively charged ion are adsorbed on the resin, and the mother liquor after the absorption returns production system; (2) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin is carried out drip washing again, make the gallium of resin absorption, vanadium negatively charged ion enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium and the vanadium of mother liquor; (3) in leacheate, add BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein; (4) add NaOH in the solution behind the precipitation vanadium, gallium is precipitated with the form of gallium hydroxide; (5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again; (6) sodium solution gallate is carried out electrolysis, make gallium.
II is successively adsorbed Bayer-process seed-separating mother liquor with two kinds of different chelating ion exchange resins:
(1) with two kinds of different chelating ion exchange resins Bayer-process seed-separating mother liquor is successively adsorbed, gallium, vanadium negatively charged ion are adsorbed in respectively on a kind of resin, and the mother liquor after the absorption returns production system; (2) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin is carried out drip washing again, make the gallium of resin absorption, vanadium negatively charged ion enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium and the vanadium of mother liquor; (3) in the leacheate that contains vanadium, add BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein; (4) in the leacheate that contains gallium, add NaOH, gallium is precipitated with the form of gallium hydroxide; (5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again; (6) sodium solution gallate is carried out electrolysis, make gallium.
III adds BaO earlier in Bayer-process seed-separating mother liquor, with chelating ion exchange resin seed precipitation solution is adsorbed again:
(1) in Bayer-process seed-separating mother liquor, adds BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein; (2) spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, and gallium is adsorbed on the resin, and the mother liquor after the absorption returns production system; (3) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin are carried out drip washing again, make the gallium of resin absorption enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium of mother liquor; (4) in leacheate, add NaOH, gallium is precipitated with the form of gallium hydroxide; (5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again; (6) sodium solution gallate is carried out electrolysis, make gallium.
When spent ion exchange resin adsorbed Bayer-process seed-separating mother liquor, adsorption temp was 40～60 ℃, and resin and mother liquor duration of contact are 15～60min; When with diluted acid saturated resin being washed, dilute acid concentration is 3%～5%, and when with concentrated acid saturated resin being carried out drip washing, concentrated acid concentration is 5%～20%, and concentrated acid and saturated resin duration of contact are 30～60min, and the drip washing temperature is 20～40 ℃; When in Bayer-process seed-separating mother liquor, adding the BaO precipitation, Na in the add-on of BaO and the mother liquor
2CO
3Mol ratio be 0.1～1.0, temperature of reaction is 40 ℃～60 ℃, the reaction times is 15min～120min, stirring velocity is 100r/min～400r/min; In leacheate, add BaO when vanadium is precipitated with the form of vanadic acid barium, V in the BaO of adding and the leacheate
2O
5Mol ratio be 2～3, temperature of reaction is 20～40 ℃, the reaction times is 30～60min; Add NaOH when gallium is precipitated with the form of gallium hydroxide in leacheate, the mol ratio of Ga concentration is 1～3 in the NaOH of adding and the leacheate, and temperature of reaction is 20～40 ℃, and the reaction times is 60～90min; When gallium hydroxide dissolved with NaOH solution, the concentration of NaOH solution was 2.5～3.5mol/L, and liquid-solid ratio is 3～5, and temperature of reaction is 40～60 ℃, and the reaction times is 30～60min; When sodium solution gallate was carried out electrolysis, electrolysis temperature was 20～40 ℃, and electrolysis time is 6～12h, thereby makes gallium.
Several method of the present invention is with process recovery gallium and vanadium wherein such as the drip washing after resin absorption, washing of the seed precipitation solution in the alumina producing Bayer process process, precipitation, heavy gallium, molten gallium, electrolysis.Flow process is simple, easy to operate, cost is lower, the rate of recovery is high.
Embodiment 1
Spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, and adsorption temp is 40 ℃, and resin and mother liquor duration of contact are 30min, and the gallium adsorption rate reaches 98.10%, and the vanadium adsorption rate reaches 60.23%;
With dilute sulphuric acid saturated resin is washed, dilute sulphuric acid concentration is 3%, when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 10%, and the vitriol oil and saturated resin duration of contact are 30min, and the drip washing temperature is 20 ℃, after the drip washing in the solution Ga concentration be 1.51g/L, V
2O
5Concentration is 1.01g/L;
Add BaO in the leacheate vanadium is precipitated with the form of vanadic acid barium, V in the BaO of adding and the leacheate
2O
5Mol ratio be 2, temperature of reaction is 20 ℃, the reaction times is 30min, the precipitation rate is 95.56%;
Add NaOH in the solution of precipitation behind the vanadium gallium is precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 1 in the NaOH of adding and the leacheate, and temperature of reaction is 20 ℃, and the reaction times is 60min, obtains the gallium hydroxide solid precipitation;
Gallium hydroxide is with the dissolving of NaOH solution, and the concentration of NaOH solution is 2.5mol/L, and liquid-solid ratio is 3, and temperature of reaction is 40 ℃, and the reaction times is 60min, and obtaining Ga concentration is 40.56g/L;
Sodium solution gallate is carried out electrolysis, and electrolysis temperature is 30 ℃, and electrolysis time is 8h, thereby makes gallium.
Embodiment 2
Spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, and adsorption temp is 30 ℃, and resin and mother liquor duration of contact are 45min, and the gallium adsorption rate reaches 98.33%, and the vanadium adsorption rate reaches 61.23%;
With dilute sulphuric acid saturated resin is washed, dilute sulphuric acid concentration is 3%, when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 15%, and the vitriol oil and saturated resin duration of contact are 45min, and the drip washing temperature is 30 ℃, after the drip washing in the solution Ga concentration be 1.45g/L, V
2O
5Concentration is 1.11g/L;
Add BaO in the leacheate vanadium is precipitated with the form of vanadic acid barium, V in the BaO of adding and the leacheate
2O
5Mol ratio be 2.5, temperature of reaction is 30 ℃, the reaction times is 45min, the precipitation rate is 95.01%;
Add NaOH in the solution of precipitation behind the vanadium gallium is precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 2 in the NaOH of adding and the leacheate, and temperature of reaction is 40 ℃, and the reaction times is 60min, obtains the gallium hydroxide solid precipitation;
Gallium hydroxide is with the dissolving of NaOH solution, and the concentration of NaOH solution is 3mol/L, and liquid-solid ratio is 4, and temperature of reaction is 40 ℃, and the reaction times is 60min, and obtaining Ga concentration is 43.11g/L;
Sodium solution gallate is carried out electrolysis, and electrolysis temperature is 30 ℃, and electrolysis time is 8h, thereby makes gallium.
Embodiment 3
The spent ion exchange resin I is adsorbed Bayer-process seed-separating mother liquor, and adsorption temp is 50 ℃, and resin and mother liquor duration of contact are 45min, and the vanadium adsorption rate reaches 95.06%;
With dilute sulphuric acid the saturated resin I is washed, dilute sulphuric acid concentration is 3%, and when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 15%, and the vitriol oil and saturated resin duration of contact are 45min, and the drip washing temperature is 20 ℃, V in the solution after the drip washing
2O
5Concentration is 3.51g/L;
Add BaO in the leacheate I vanadium is precipitated with the form of vanadic acid barium, V in the BaO of adding and the leacheate
2O
5Mol ratio be 2.5, temperature of reaction is 30 ℃, the reaction times is 45min, the precipitation rate is 95.76%;
The spent ion exchange resin II is proceeded absorption to seed precipitation solution, and adsorption temp is 50 ℃, and resin and mother liquor duration of contact are 60min, and the gallium adsorption rate reaches 98.62%;
With dilute sulphuric acid the saturated resin II is washed, dilute sulphuric acid concentration is 3%, when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 15%, the vitriol oil and saturated resin duration of contact are 45min, and the drip washing temperature is 20 ℃, after the drip washing in the solution Ga concentration be 1.65g/L;
Add NaOH in the leacheate II gallium is precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 2 in the NaOH of adding and the leacheate, and temperature of reaction is 20 ℃, and the reaction times is 60min, obtains the gallium hydroxide solid precipitation;
Gallium hydroxide is with the dissolving of NaOH solution, and the concentration of NaOH solution is 3.5mol/L, and liquid-solid ratio is 4, and temperature of reaction is 40 ℃, and the reaction times is 60min, and obtaining Ga concentration is 42.56g/L;
Sodium solution gallate is carried out electrolysis, and electrolysis temperature is 30 ℃, and electrolysis time is 8h, thereby makes gallium.
Embodiment 4
The spent ion exchange resin I is adsorbed Bayer-process seed-separating mother liquor, and adsorption temp is 50 ℃, and resin and mother liquor duration of contact are 60min, and the vanadium adsorption rate reaches 95.82%;
With dilute sulphuric acid the saturated resin I is washed, dilute sulphuric acid concentration is 3%, and when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 15%, and the vitriol oil and saturated resin duration of contact are 60min, and the drip washing temperature is 30 ℃, V in the solution after the drip washing
2O
5Concentration is 3.66g/L;
Add BaO in the leacheate I vanadium is precipitated with the form of vanadic acid barium, V in the BaO of adding and the leacheate
2O
5Mol ratio be 3, temperature of reaction is 40 ℃, the reaction times is 60min, the precipitation rate is 95.94%;
The spent ion exchange resin II is proceeded absorption to seed precipitation solution, and adsorption temp is 50 ℃, and resin and mother liquor duration of contact are 60min, and the gallium adsorption rate reaches 98.75%;
With dilute sulphuric acid the saturated resin II is washed, dilute sulphuric acid concentration is 3%, when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 15%, the vitriol oil and saturated resin duration of contact are 45min, and the drip washing temperature is 30 ℃, after the drip washing in the solution Ga concentration be 1.68g/L;
Add NaOH in the leacheate II gallium is precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 3 in the NaOH of adding and the leacheate, and temperature of reaction is 30 ℃, and the reaction times is 60min, obtains the gallium hydroxide solid precipitation;
Gallium hydroxide is with the dissolving of NaOH solution, and the concentration of NaOH solution is 3.5mol/L, and liquid-solid ratio is 5, and temperature of reaction is 40 ℃, and the reaction times is 60min, and obtaining Ga concentration is 43.25g/L;
Sodium solution gallate is carried out electrolysis, and electrolysis temperature is 30 ℃, and electrolysis time is 8h, thereby makes gallium.
Embodiment 5
Add BaO in the Bayer-process seed-separating mother liquor vanadium is precipitated with the form of vanadic acid barium, Na in the add-on of BaO and the mother liquor
2CO
3Mol ratio be 0.5, temperature of reaction is 50 ℃, the reaction times is 50min, stirring velocity is 200r/min;
Separate, obtain the vanadic acid precipitated barium;
Spent ion exchange resin is proceeded absorption to seed precipitation solution, and adsorption temp is 50 ℃, and resin and mother liquor duration of contact are 45min, and the gallium adsorption rate reaches 98.23%;
With dilute sulphuric acid saturated resin is washed, dilute sulphuric acid concentration is 3%, when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 15%, the vitriol oil and saturated resin duration of contact are 45min, and the drip washing temperature is 20 ℃, after the drip washing in the solution Ga concentration be 1.64g/L;
Add NaOH in the leacheate gallium is precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 2 in the NaOH of adding and the leacheate, and temperature of reaction is 30 ℃, and the reaction times is 60min, obtains the gallium hydroxide solid precipitation;
Gallium hydroxide is with the dissolving of NaOH solution, and the concentration of NaOH solution is 3mol/L, and liquid-solid ratio is 4, and temperature of reaction is 40 ℃, and the reaction times is 45min, and obtaining Ga concentration is 41.87g/L;
Sodium solution gallate is carried out electrolysis, and electrolysis temperature is 30 ℃, and electrolysis time is 8h, thereby makes gallium.
Embodiment 6
Add BaO in the Bayer-process seed-separating mother liquor vanadium is precipitated with the form of vanadic acid barium, Na in the add-on of BaO and the mother liquor
2CO
3Mol ratio be 1.0, temperature of reaction is 55 ℃, the reaction times is 100min, stirring velocity is 300r/min;
Separate, obtain the vanadic acid precipitated barium;
Spent ion exchange resin is proceeded absorption to seed precipitation solution, and adsorption temp is 50 ℃, and resin and mother liquor duration of contact are 60min, and the gallium adsorption rate reaches 98.57%;
With dilute sulphuric acid saturated resin is washed, dilute sulphuric acid concentration is 3%, when with the vitriol oil saturated resin being carried out drip washing, sulfuric acid concentration is 20%, the vitriol oil and saturated resin duration of contact are 60min, and the drip washing temperature is 20 ℃, after the drip washing in the solution Ga concentration be 1.73g/L;
Add NaOH in the leacheate gallium is precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 3 in the NaOH of adding and the leacheate, and temperature of reaction is 30 ℃, and the reaction times is 80min, obtains the gallium hydroxide solid precipitation;
Gallium hydroxide is with the dissolving of NaOH solution, and the concentration of NaOH solution is 3mol/L, and liquid-solid ratio is 5, and temperature of reaction is 50 ℃, and the reaction times is 60min, and obtaining Ga concentration is 43.10g/L;
Sodium solution gallate is carried out electrolysis, and electrolysis temperature is 30 ℃, and electrolysis time is 8h, thereby makes gallium.
Claims (12)
1. extract the method for gallium and vanadium in the Bayer-process seed-separating mother liquor, it is characterized in that spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, its process may further comprise the steps:
(1) spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, and gallium, vanadium negatively charged ion are adsorbed on the resin, and the mother liquor after the absorption returns production system;
(2) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin is carried out drip washing again, make the gallium of resin absorption, vanadium negatively charged ion enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium and the vanadium of mother liquor;
(3) in leacheate, add BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein;
(4) add NaOH in the solution behind the precipitation vanadium, gallium is precipitated with the form of gallium hydroxide;
(5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again;
(6) sodium solution gallate is carried out electrolysis, make gallium.
2. extract the method for gallium and vanadium in the Bayer-process seed-separating mother liquor, it is characterized in that adopting two kinds of different ion exchange resin that Bayer-process seed-separating mother liquor is successively adsorbed, be characterised in that its process may further comprise the steps:
(1) with two kinds of different ion exchange resin Bayer-process seed-separating mother liquor is successively adsorbed, gallium, vanadium negatively charged ion are adsorbed in respectively on a kind of resin, and the mother liquor after the absorption returns production system;
(2) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin is carried out drip washing again, make the gallium of resin absorption, vanadium negatively charged ion enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium and the vanadium of mother liquor;
(3) in the leacheate that contains vanadium, add BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein;
(4) in the leacheate that contains gallium, add NaOH, gallium is precipitated with the form of gallium hydroxide;
(5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again;
(6) sodium solution gallate is carried out electrolysis, make gallium.
3. extract the method for gallium and vanadium in the Bayer-process seed-separating mother liquor, it is characterized in that leaching process adds BaO earlier in Bayer-process seed-separating mother liquor, spent ion exchange resin adsorbs seed precipitation solution again, and its process may further comprise the steps:
(1) in Bayer-process seed-separating mother liquor, adds BaO, vanadium is precipitated with the form of vanadic acid barium, and then handle the vanadium that reclaims wherein;
(2) spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, and gallium is adsorbed on the resin, and the mother liquor after the absorption returns production system;
(3) first water and diluted acid wash saturated resin, remove the mother liquor that is attached on the resin, with concentrated acid saturated resin are carried out drip washing again, make the gallium of resin absorption enter leacheate, and the circulation of the resin after the drip washing is used for adsorbing the gallium of mother liquor;
(4) in leacheate, add NaOH, gallium is precipitated with the form of gallium hydroxide;
(5) gallium hydroxide with the dissolving of NaOH solution, generates sodium solution gallate again;
(6) sodium solution gallate is carried out electrolysis, make gallium.
4. according to claim 1,2 or 3 described methods, when it is characterized in that spent ion exchange resin adsorbs Bayer-process seed-separating mother liquor, adsorption temp is 40～60 ℃, and resin and mother liquor duration of contact are 15～60min.
5. according to claim 1,2 or 3 described methods, when it is characterized in that saturated resin being washed with diluted acid, dilute acid concentration is 3%～5%, when saturated resin being carried out drip washing with concentrated acid, concentrated acid concentration is 5%～20%, concentrated acid and saturated resin duration of contact are 30～60min, and the drip washing temperature is 20～40 ℃.
6. according to claim 1,2 or 3 described methods, when it is characterized in that in Bayer-process seed-separating mother liquor, adding the BaO precipitation, Na in the add-on of BaO and the mother liquor
2CO
3Mol ratio be 0.1～1.0, temperature of reaction is 40 ℃～60 ℃, the reaction times is 15min～120min, stirring velocity is 100r/min～400r/min.
7. according to claim 1,2 or 3 described methods, when it is characterized in that in leacheate, adding BaO vanadium being precipitated with the form of vanadic acid barium, V in the BaO of adding and the leacheate
2O
5Mol ratio be 2～3, temperature of reaction is 20～40 ℃, the reaction times is 30～60min.
8. according to claim 1,2 or 3 described methods, when it is characterized in that in leacheate adding NaOH gallium being precipitated with the form of gallium hydroxide, the mol ratio of Ga concentration is 1～3 in NaOH that adds and the leacheate, and temperature of reaction is 20～40 ℃, and the reaction times is 60～90min.
9. according to claim 1,2 or 3 described methods, when it is characterized in that gallium hydroxide dissolves with NaOH solution, the concentration of NaOH solution is 2.5～3.5mol/L, and liquid-solid ratio is 3～5, and temperature of reaction is 40～60 ℃, and the reaction times is 30～60min.
10. according to claim 1,2 or 3 described methods, when it is characterized in that sodium solution gallate carried out electrolysis, electrolysis temperature is 20～40 ℃, and electrolysis time is 6～12h, thereby makes gallium.
11., it is characterized in that ion exchange resin is resin according to claim 1,2 or 3 described methods.
12., it is characterized in that related acid can be sulfuric acid, hydrochloric acid or nitric acid according to claim 1,2 or 3 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010587695XA CN102021334A (en) | 2010-12-15 | 2010-12-15 | Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010587695XA CN102021334A (en) | 2010-12-15 | 2010-12-15 | Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102021334A true CN102021334A (en) | 2011-04-20 |
Family
ID=43863109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010587695XA Pending CN102021334A (en) | 2010-12-15 | 2010-12-15 | Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102021334A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321802A (en) * | 2011-08-25 | 2012-01-18 | 西安蓝晓科技有限公司 | New method for extracting gallium from Bayer mother liquor through chelating resin |
| CN102534214A (en) * | 2012-01-18 | 2012-07-04 | 西安蓝晓科技新材料股份有限公司 | New method for recycling gallium from Bayer mother solution by using chelate resin |
| CN103014379A (en) * | 2012-12-26 | 2013-04-03 | 中南大学 | Process for extracting vanadium from stone coal vanadium mine |
| CN103740940A (en) * | 2013-12-14 | 2014-04-23 | 中国铝业股份有限公司 | Processing method for lime slag generated during purifying process of gallium pregnant solution |
| CN103805794A (en) * | 2013-12-30 | 2014-05-21 | 中国神华能源股份有限公司 | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash |
| CN103833057A (en) * | 2014-03-24 | 2014-06-04 | 连云港乐园新材料科技有限公司 | Production method for high-purity aluminum oxide |
| TWI488684B (en) * | 2013-05-14 | 2015-06-21 | Inst Nuclear Energy Res | A Method for Purification of Gallium - 69 Isotopes |
| CN105420495A (en) * | 2015-11-17 | 2016-03-23 | 中国铝业股份有限公司 | Uranium separation method during gallium treatment in aluminum oxide production through Bayer process |
| CN109179467A (en) * | 2018-09-30 | 2019-01-11 | 中铝山东有限公司 | A method of gallium is removed to the low pregnant Bayer process liquor of concentration containing gallium |
| CN113088724A (en) * | 2021-04-06 | 2021-07-09 | 攀枝花学院 | Method for leaching gallium in vanadium extraction tailings |
| CN114507778A (en) * | 2022-03-18 | 2022-05-17 | 郑州轻工业大学 | Comprehensive utilization method of vanadium slag in metal gallium production process |
| CN115109951A (en) * | 2022-06-28 | 2022-09-27 | 郑州轻工业大学 | Comprehensive utilization method for sulfuric acid desorption gallium-containing liquid in alumina production |
| CN117305592A (en) * | 2023-08-16 | 2023-12-29 | 永新县稀贵矿业冶化有限责任公司 | Method for extracting vanadium from vanadium-containing alkaline residue and synergistic harmless utilization of vanadium-containing alkaline residue and secondary aluminum ash |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61215215A (en) * | 1985-03-22 | 1986-09-25 | Miyoshi Oil & Fat Co Ltd | Separation of gallium from aqueous solution of aluminate |
| CN88103282A (en) * | 1987-06-02 | 1988-12-21 | 皮奇尼铅公司 | The method of extraction and gallium-purifying from Bayer-liquid |
| CN101560602A (en) * | 2008-04-16 | 2009-10-21 | 北京西桥有机材料技术有限责任公司 | Method for recycling gallium from alumina seed separation mother liquid using ion exchange method |
| CN101708864A (en) * | 2009-12-18 | 2010-05-19 | 中国铝业股份有限公司 | Method for extracting vanadium pentoxide in Bayer-process seed-separating mother liquor |
-
2010
- 2010-12-15 CN CN201010587695XA patent/CN102021334A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61215215A (en) * | 1985-03-22 | 1986-09-25 | Miyoshi Oil & Fat Co Ltd | Separation of gallium from aqueous solution of aluminate |
| CN88103282A (en) * | 1987-06-02 | 1988-12-21 | 皮奇尼铅公司 | The method of extraction and gallium-purifying from Bayer-liquid |
| CN101560602A (en) * | 2008-04-16 | 2009-10-21 | 北京西桥有机材料技术有限责任公司 | Method for recycling gallium from alumina seed separation mother liquid using ion exchange method |
| CN101708864A (en) * | 2009-12-18 | 2010-05-19 | 中国铝业股份有限公司 | Method for extracting vanadium pentoxide in Bayer-process seed-separating mother liquor |
Non-Patent Citations (1)
| Title |
|---|
| 《湿法冶金》 20060331 冯峰等 拜耳法种分母液组成对树脂吸附镓的影响 30-32 1-12 第25卷, 第1期 2 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321802A (en) * | 2011-08-25 | 2012-01-18 | 西安蓝晓科技有限公司 | New method for extracting gallium from Bayer mother liquor through chelating resin |
| CN102534214A (en) * | 2012-01-18 | 2012-07-04 | 西安蓝晓科技新材料股份有限公司 | New method for recycling gallium from Bayer mother solution by using chelate resin |
| CN102534214B (en) * | 2012-01-18 | 2014-03-12 | 西安蓝晓科技新材料股份有限公司 | Method for recycling gallium from Bayer mother solution by using chelate resin |
| CN103014379A (en) * | 2012-12-26 | 2013-04-03 | 中南大学 | Process for extracting vanadium from stone coal vanadium mine |
| TWI488684B (en) * | 2013-05-14 | 2015-06-21 | Inst Nuclear Energy Res | A Method for Purification of Gallium - 69 Isotopes |
| CN103740940A (en) * | 2013-12-14 | 2014-04-23 | 中国铝业股份有限公司 | Processing method for lime slag generated during purifying process of gallium pregnant solution |
| CN103805794A (en) * | 2013-12-30 | 2014-05-21 | 中国神华能源股份有限公司 | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash |
| CN103805794B (en) * | 2013-12-30 | 2015-04-08 | 中国神华能源股份有限公司 | Recovery method for extracting gallium from aluminum oxide coarse-fine liquid by using acid-process fly ash |
| CN103833057A (en) * | 2014-03-24 | 2014-06-04 | 连云港乐园新材料科技有限公司 | Production method for high-purity aluminum oxide |
| CN105420495A (en) * | 2015-11-17 | 2016-03-23 | 中国铝业股份有限公司 | Uranium separation method during gallium treatment in aluminum oxide production through Bayer process |
| CN109179467A (en) * | 2018-09-30 | 2019-01-11 | 中铝山东有限公司 | A method of gallium is removed to the low pregnant Bayer process liquor of concentration containing gallium |
| CN113088724A (en) * | 2021-04-06 | 2021-07-09 | 攀枝花学院 | Method for leaching gallium in vanadium extraction tailings |
| CN114507778A (en) * | 2022-03-18 | 2022-05-17 | 郑州轻工业大学 | Comprehensive utilization method of vanadium slag in metal gallium production process |
| CN115109951A (en) * | 2022-06-28 | 2022-09-27 | 郑州轻工业大学 | Comprehensive utilization method for sulfuric acid desorption gallium-containing liquid in alumina production |
| CN117305592A (en) * | 2023-08-16 | 2023-12-29 | 永新县稀贵矿业冶化有限责任公司 | Method for extracting vanadium from vanadium-containing alkaline residue and synergistic harmless utilization of vanadium-containing alkaline residue and secondary aluminum ash |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102021334A (en) | Method for extracting gallium and vanadium from seed precipitation mother liquor of Bayer process | |
| CN110527836A (en) | A kind of method that ion-exchange recycles valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| CN103789552B (en) | Method for recovering rhenium from high-temperature alloy pickle liquor | |
| CN111285403B (en) | Purification treatment method of manganese sulfate solution | |
| CN102417194B (en) | Method for deeply removing magnesium through chelating resin for extracting lithium from salt lake brine | |
| CN106435197B (en) | A kind of SCR denitration dead catalyst valuable metal alkaline extraction retracting device and technique | |
| CN109881012B (en) | Treatment method for recycling tungsten from tungsten metallurgy dephosphorization residues | |
| CN111187907B (en) | Method for purifying manganese sulfate solution | |
| CN109929997B (en) | Method for producing germanium concentrate by using N235 extracting agent | |
| CN111410216A (en) | Method for extracting lithium from water with high magnesium-lithium ratio and preparing lithium carbonate | |
| CN102965506B (en) | Method for removing aluminum from rare earth solution by benzoate precipitation method | |
| CN103014379B (en) | Process for extracting vanadium from stone coal vanadium mine | |
| CN101503350A (en) | Method for recycling acid and valuable metal from oxalic acid wastewater | |
| CN105274345B (en) | Method for separating and recovering cobalt and manganese in cobalt-manganese waste | |
| CN109626632A (en) | A kind of method of leaded waste acid recycling | |
| CN105950877A (en) | Method for recovering vanadium in impurity removing slag by using vanadium precipitation waste water | |
| CN103572062A (en) | Method for recovering vanadium from desilication slag | |
| CN115849451A (en) | Method for recycling uranium-containing waste liquid | |
| CN114277264A (en) | Method for extracting and recovering germanium | |
| CN106892479B (en) | Method for recovering oxalic acid and hydrochloric acid from rare earth oxalic acid precipitation wastewater | |
| CN112645413B (en) | Method for treating rare earth oxalate precipitation wastewater | |
| CN108893623B (en) | Method for back extracting lithium from loaded organic phase after lithium-containing brine extraction | |
| CN109280770B (en) | Method for recovering scandium and titanium from scandium-containing titanic acid immersion liquid | |
| CN109626414B (en) | Method for recovering thallium and rhenium from smelting waste acid | |
| CN111471874A (en) | Method for extracting and separating arsenic and iron by chloride system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110420 |