CN1818144A - Vanadium removal for electrolytic stoste in metal gallium electrolysis - Google Patents
Vanadium removal for electrolytic stoste in metal gallium electrolysis Download PDFInfo
- Publication number
- CN1818144A CN1818144A CN 200510104602 CN200510104602A CN1818144A CN 1818144 A CN1818144 A CN 1818144A CN 200510104602 CN200510104602 CN 200510104602 CN 200510104602 A CN200510104602 A CN 200510104602A CN 1818144 A CN1818144 A CN 1818144A
- Authority
- CN
- China
- Prior art keywords
- electrolytic solution
- vanadium
- solution
- gallium
- vanadium removal
- 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.)
- Granted
Links
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 58
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 33
- 238000005868 electrolysis reaction Methods 0.000 title claims description 22
- 229910052751 metal Inorganic materials 0.000 title description 2
- 239000002184 metal Substances 0.000 title description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 9
- 239000004571 lime Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910001679 gibbsite Inorganic materials 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000003513 alkali Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention is about the removal of the vanadium from the electrolyte in the production of the gallium. The process is: (1) adding the hydrogen peroxide into the electrolyte to oxidize the S2- to SO42-; (2) adding the Al(OH)3 to 2-50g/l; (3) adding the white lime to 5-100g/l, mix it for 8-12h in the 50-60 DEG C to remove the vanadium; (4) decreasing the temperature to 20-40 DEG C to separate the solid and the liquid. The process can improve the current yield for extracting the vanadium by the resin, so it can reuse the electrolyte to decrease the cost.
Description
Technical field
The present invention relates to the vanadium removal method of electrolytic solution in a kind of gallium electrolysis production, belong to the dissipated metal field of metallurgy.
Background technology
Adopting resin method to reclaim gallium is one of state-of-the-art method in current all gallium production methods, gallium finally obtains by electrolysis gallium salt brine solution, owing to the resin choice reason, the content of vanadium that causes electrolytic solution is than higher, make its actual electrolysis deposition potential exceed the deposition potential of gallium, cause the preferential reduction of vanadium in the electrolytic process, make the pole plate blackout, reduced the overpotential of hydrogen evolution, so that cause gallium on pole plate, to deposit difficulty, problems such as current efficiency is low are seriously restricting the further raising of quality and output.
Vanadium exists with the vanadic acid sodium form in electrolytic solution, owing to produce oxygen continuously on the anode in the electrolytic solution, owing to electrochemical reason, make vanadium on electrolytic solution and pole plate, produce the circulation change of valence state, consumed electric energy, influenced gallium separating out at negative electrode, even gallium can come out in electrolysis, and is also too much because of the sponge gallium, quality can not get guaranteeing, also need to handle the sponge gallium more again, obtain qualified gallium.With the milk of lime vanadium removal can only be lower at the mother liquor free alkali concentration (NaOH content≤100g/l) down effectively, and can cause the greater loss of gallium.The high more vanadium removal effect of free alkali concentration is poor more, how therefrom effectively vanadium to be removed under the situation of not losing gallium content in the electrolytic solution, is the problem that presses for solution in producing at present.Resolve vanadium in the electrolytic solution remove technology after, not only can improve the output of gallium greatly, reduce the cost of unit gallium because vanadium is removed in the electrolytic solution, the electrolysis lean liquor just can the Returning process repeated use, has reduced production cost.
Summary of the invention
The object of the present invention is to provide the vanadium removal method of electrolytic solution in a kind of gallium electrolysis production, reduce the content of vanadium in the electrolytic solution, improve Faradaic current efficient and production capacity that resin method extracts gallium, can make the electrolysis lean liquor obtain recycling, reduce production costs.
The vanadium removal method of electrolytic solution in the gallium electrolysis production of the present invention, carry out according to the following step successively:
Reaction system is: 1.5～5CaOAl
2O
32～5.8V
2O
54～19H
2O;
(1) in electrolytic solution, adds hydrogen peroxide, make S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, make solution oxide aluminium content reach 2～50g/l;
(3) add white lime in above-mentioned solution and reach 5～100g/l, violent stirring is 8～12 hours under 50～60 ℃ temperature, carries out the vanadium removal reaction;
(4) solution temperature is reduced to 20～40 ℃, implements solid-liquid separation, go out vanadium slag, obtain the electrolytic solution of vanadium low levels.
Wherein, the add-on of hydrogen peroxide is that 8～12% of electrolytic solution volume suits, and the concentration of hydrogen peroxide is chosen as 50%.
The solvent temperature of aluminium hydroxide preferably is controlled to be: 100～120 ℃
The vanadium removal methodological science of electrolytic solution is reasonable in the gallium electrolysis production of the present invention, simple, can be with the content of vanadium in the electrolytic solution (NaOH content is at 250g/l-300g/l) of high alkalinity from dropping to more than the 1000mg/l below the 40mg/l, satisfy the demand of gallium electrolysis process, by reducing the content of vanadium in the electrolytic solution, improved resin method and extracted the Faradaic current efficient and the production capacity of gallium, and can make the electrolysis lean liquor obtain recycling, reduced production costs.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The vanadium removal method of electrolytic solution in the gallium electrolysis production of the present invention, carry out according to the following step successively:
Reaction system is: 3CaOAl
2O
34V
2O
510H
2O;
(1) adding volume ratio in the electrolytic solution that contains NaOH 253g/l is 10% 50% hydrogen peroxide, makes S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, be warmed up to 110 ± 3 ℃ of dissolvings, make solution oxide aluminium content reach 30g/l;
(3) in above-mentioned solution, add white lime [Ca (OH)
2] 50g/l, under 55 ± 3 ℃ temperature, carried out violent stirring 10 hours, carry out the vanadium removal reaction;
(4) solution temperature is reduced to 25 ± 3 ℃, implements solid-liquid separation, go out vanadium slag, obtain the electrolytic solution of vanadium low levels, the content of vanadium is reduced to 28mg/l by 1146mg/l.
Embodiment 2
The vanadium removal method of electrolytic solution in the gallium electrolysis production of the present invention, carry out according to the following step successively:
Reaction system is: 2.5CaOAl
2O
34.5V
2O
512H
2O;
(1) adding volume ratio in the electrolytic solution that contains NaOH 266g/l is 11% 50% hydrogen peroxide, makes S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, be warmed up to 105 ± 3 ℃ of dissolvings, make solution oxide aluminium content reach 23g/l;
(3) add white lime in above-mentioned solution and reach 45g/l, violent stirring is 9 hours under 55 ± 2 ℃ temperature, carries out the vanadium removal reaction;
(4) solution temperature is reduced to 25 ± 3 ℃, implements solid-liquid separation, remove vanadium slag, obtain the electrolytic solution of vanadium low levels, the content of vanadium is reduced to 38mg/l by 1295mg/l.
Embodiment 3
The vanadium removal method of electrolytic solution in the gallium electrolysis production of the present invention, carry out according to the following step successively:
Reaction system is: 5CaOAl
2O
35V
2O
58H
2O;
(1) adding volume ratio in the electrolytic solution that contains NaOH 256g/l is 10% 50% hydrogen peroxide, makes S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, be warmed up to 160 ± 3 ℃ of dissolvings, make solution oxide aluminium content reach 40g/l;
(3) add white lime in above-mentioned solution and reach 30g/l, violent stirring is 8.5 hours under 53 ± 3 ℃ temperature, carries out the vanadium removal reaction;
(4) solution temperature is reduced to 35 ± 3 ℃, implements solid-liquid separation, remove vanadium slag, obtain the electrolytic solution of vanadium low levels, the content of vanadium is reduced to 36mg/l by 1270mg/l.
Embodiment 4
The vanadium removal method of electrolytic solution in the gallium electrolysis production of the present invention, carry out according to the following step successively:
Reaction system is: 4CaOAl
2O
33V
2O
515H
2O;
(1) adding volume ratio in the electrolytic solution that contains NaOH 280g/l is 9% 50% hydrogen peroxide, makes S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, be warmed up to 112 ± 3 ℃ of dissolvings, make solution oxide aluminium content reach 36g/l;
(3) add white lime in above-mentioned solution and reach 55g/l, violent stirring is 12 hours under 56 ± 3 ℃ temperature, carries out the vanadium removal reaction;
(4) solution temperature is reduced to 30 ± 3 ℃, implements solid-liquid separation, remove vanadium slag, obtain the electrolytic solution of vanadium low levels, the content of vanadium is reduced to 37mg/l by 1260mg/l.
Embodiment 5
The vanadium removal method of electrolytic solution in the gallium electrolysis production of the present invention, carry out according to the following step successively:
Reaction system is: 2CaOAl
2O
33.5V
2O
514H
2O;
(1) adding volume ratio in the electrolytic solution that contains NaOH 262g/l is 10% 50% hydrogen peroxide, makes S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, be warmed up to 115 ± 3 ℃ of dissolvings, make solution oxide aluminium content reach 32g/l;
(3) add white lime in above-mentioned solution and reach 50g/l, violent stirring is 9 hours under 54 ± 3 ℃ temperature, carries out the vanadium removal reaction;
(4) solution temperature is reduced to 33 ± 3 ℃, implements solid-liquid separation, remove vanadium slag, obtain the electrolytic solution of vanadium low levels.
Embodiment 6
The vanadium removal method of electrolytic solution in the gallium electrolysis production of the present invention, carry out according to the following step successively:
Reaction system is: 4.2CaOAl
2O
33.6V
2O
512H
2O;
(1) adding volume ratio in the electrolytic solution that contains NaOH 260g/l is 12% 50% hydrogen peroxide, makes S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, be warmed up to 117 ± 3 ℃ of dissolvings, make solution oxide aluminium content reach 28g/l;
(3) add white lime in above-mentioned solution and reach 70g/l, violent stirring is 11 hours under 55 ± 3 ℃ temperature, carries out the vanadium removal reaction;
(4) solution temperature is reduced to 32 ± 3 ℃, implements solid-liquid separation, remove vanadium slag, obtain the electrolytic solution of vanadium low levels.
Claims (3)
1, the vanadium removal method of electrolytic solution in a kind of gallium electrolysis production is characterized in that carrying out according to the following step successively:
(1) in electrolytic solution, adds hydrogen peroxide, make S wherein
2-Be oxidized to SO
4 2-
(2) add aluminium hydroxide in the electrolytic solution after oxidation, make solution oxide aluminium content reach 2～50g/l;
(3) add white lime in above-mentioned solution and reach 5～100g/l, violent stirring is 8～12 hours under 50～60 ℃ temperature, carries out the vanadium removal reaction;
(4) solution temperature is reduced to 20～40 ℃, implements solid-liquid separation, go out vanadium slag, obtain the electrolytic solution of vanadium low levels.
2, the vanadium removal method of electrolytic solution in the gallium electrolysis production according to claim 1, the add-on that it is characterized in that hydrogen peroxide is 8～12% of an electrolytic solution volume.
3, the vanadium removal method of electrolytic solution in the gallium electrolysis production according to claim 2, the concentration that it is characterized in that hydrogen peroxide is 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101046022A CN100383289C (en) | 2005-12-22 | 2005-12-22 | Vanadium removal for electrolytic stoste in metal gallium electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101046022A CN100383289C (en) | 2005-12-22 | 2005-12-22 | Vanadium removal for electrolytic stoste in metal gallium electrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1818144A true CN1818144A (en) | 2006-08-16 |
| CN100383289C CN100383289C (en) | 2008-04-23 |
Family
ID=36918332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101046022A Active CN100383289C (en) | 2005-12-22 | 2005-12-22 | Vanadium removal for electrolytic stoste in metal gallium electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100383289C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011000A (en) * | 2010-12-09 | 2011-04-13 | 中国铝业股份有限公司 | Method for removing vanadium from gallium-enriched solution in resin-absorbed seed precipitation mother liquor |
| CN106702429A (en) * | 2016-12-22 | 2017-05-24 | 北京吉亚半导体材料有限公司 | Method for purifying and recovering caustic alkali for producing metal gallium through alkaline method |
| CN115652112A (en) * | 2022-11-22 | 2023-01-31 | 中铝矿业有限公司 | Reduce S in metal gallium adsorption mother liquor 2- Content process method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4362606A (en) * | 1980-11-06 | 1982-12-07 | Magyar Aluminiumipari Troszt | Process for simultaneous recovery of vanadium, molybdenum and gallium from alumina factory aluminate liquors |
| US4368108A (en) * | 1981-01-23 | 1983-01-11 | Rubinshtein Georgy M | Process for electrolytic recovery of gallium or gallium and vanadium from alkaline liquors resulting from alumina production |
| JPS5858239A (en) * | 1981-09-30 | 1983-04-06 | Sumitomo Alum Smelt Co Ltd | Manufacture of metallic gallium |
| JPS63496A (en) * | 1986-06-20 | 1988-01-05 | Mitsubishi Metal Corp | Method for purifying gallium electrolytic solution |
| CN1014318B (en) * | 1989-01-21 | 1991-10-16 | 郑州轻金属研究所 | Recovery of gallium from alumina production by dissolution process |
| CN1035484C (en) * | 1992-08-28 | 1997-07-23 | 北京科技大学 | Method for extracting gallium from vanadic slag containing gallium |
| CN1235201A (en) * | 1998-05-08 | 1999-11-17 | 湖南省煤炭科学研究所 | Method for adsorption of vanadium by resin |
| CN1557978A (en) * | 2004-02-02 | 2004-12-29 | 四川川投峨眉铁合金（集团）有限责任 | Production process for extracting vanadium and molybdenum from waste aluminum-based molybdenum catalyst by wet method |
-
2005
- 2005-12-22 CN CNB2005101046022A patent/CN100383289C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011000A (en) * | 2010-12-09 | 2011-04-13 | 中国铝业股份有限公司 | Method for removing vanadium from gallium-enriched solution in resin-absorbed seed precipitation mother liquor |
| CN106702429A (en) * | 2016-12-22 | 2017-05-24 | 北京吉亚半导体材料有限公司 | Method for purifying and recovering caustic alkali for producing metal gallium through alkaline method |
| CN115652112A (en) * | 2022-11-22 | 2023-01-31 | 中铝矿业有限公司 | Reduce S in metal gallium adsorption mother liquor 2- Content process method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100383289C (en) | 2008-04-23 |
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| ASS | Succession or assignment of patent right |
Owner name: CHINESE ALUMINIUM CO., LTD. Free format text: FORMER OWNER: SHANDONG ALUMINIUM INDUSTRY CO., LTD. Effective date: 20071026 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
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Effective date of registration: 20071026 Address after: 100082 No. 62 North Main Street, Beijing, Xizhimen Applicant after: Aluminum Corporation of China Limited Address before: Five 1 km 255052, Zhangdian District, Shandong, Zibo Applicant before: Shandong Aluminium Industry Co., Ltd. |
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