CN1491898A - Preparation method and application of vanadyl sulfate - Google Patents
Preparation method and application of vanadyl sulfate Download PDFInfo
- Publication number
- CN1491898A CN1491898A CNA021338086A CN02133808A CN1491898A CN 1491898 A CN1491898 A CN 1491898A CN A021338086 A CNA021338086 A CN A021338086A CN 02133808 A CN02133808 A CN 02133808A CN 1491898 A CN1491898 A CN 1491898A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- vanadyl sulfate
- preparation
- steps
- preparing
- 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
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- 229910000352 vanadyl sulfate Inorganic materials 0.000 title claims abstract description 28
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 229940041260 vanadyl sulfate Drugs 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000005484 gravity Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of vanadyl sulfate, which comprises a, adding V into sulfuric acid2O3And V2O5(ii) a b. Filtering, and evaporating and crystallizing the filtrate; c. removing crystal water to obtain VOSO4Light blue powder. Compared with the existing process route, the method omits the steps of heating dissolution, cooling dilution, reduction and the like, and has the advantages of mild reaction conditions, simple process, low cost and stable product quality. And directly taking the filtrate obtained from the steps a and b as a raw material for preparing the electrolyte of the vanadium battery.
Description
The technical field is as follows:
the invention relates to a preparation method and application of vanadyl sulfate, in particular to application of vanadyl sulfate in preparation of an all-vanadium ion battery.
Background art:
maria Skyllas-Kazacos, the university of New Nanwegian, Australia (UNSW) chemical engineering and Industrial chemistry college, published research results for vanadium batteries beginning in 1985, primarily using vanadyl sulfate as the active material of the battery. Vanadium batteries are considered to be a more competitive chemical power source than lead batteries and have a great market potential. The existing technical route for synthesizing vanadyl sulfate is as follows: v2O5→ sulfuric acid dissolution by heating → dilution by cooling → addition of reducing agent (oxalic acid or sulfurous acid, etc.)>reduction → evaporative crystallization → dehydration → VOSO4Light blue powder. Vanadyl sulfate is also a chemical raw material and is used for coloring agents of glass, ceramics and the like, and the synthetic technical route adopts the method. In the above technical scheme, V2O5Heating is required in the sulfuric acid to dissolve V, and at the same time, V is dissolved by using an excessive amount of sulfuric acid2O5Resulting in the formation of a product with a large amount of residual free acidH in liquid+Concentrations of up to 2mol/L are disadvantageous for evaporative crystallization and, due to the use of reducing agents, impurities introduced by the reducing agents are not easily removed, such as: the oxalic acid is used as a reducing agent, and the excessive oxalic acid is not easy to remove; sulfurous acid is used as a reducing agent, is unstable and is easy to release a large amount of SO in the reaction process2And the environment is polluted.
The method has complex process and higher cost, but is widely applied and is used up to now.
The invention content is as follows:
aiming at the defects of the prior art, the preparation method of vanadyl sulfate is provided, and has the advantages of simple process and low cost. Compared with the prior art, V is2O5And V2O3When the sodium sulfate is dissolved in dilute sulfuric acid, heating is not needed, so that the equipment investment can be reduced, and meanwhile, the cooling and diluting step is omitted, so that the production time can be greatly reduced, and the productivity is improved; because the reduction reaction in the original technical route generates heat and gas, the reaction is violent, the production process becomes simple after the reduction reaction is omitted, and simultaneously, because a reducing agent is not needed, impurities introduced by the reducing agent are not needed, the content of free acid in the product is low, H is H+The concentration is about 0.1mol/L, the evaporation crystallization process becomes simple, and the evaporation crystallization process does not need to be carried out under the vacuum condition and at higher temperature, thereby reducing the energy consumption and saving the equipment investmentAnd the product quality is stable.
The technical scheme of the invention is as follows: the preparation process of vanadyl sulfate includes adding V to sulfuric acid2O3And V2O5(ii) a b. Filtering, and evaporating and crystallizing the filtrate; c. removing crystal water to obtain VOSO4Light blue powder.
The technical route of the invention is as follows:
V2O3and V2O5→ dissolution in sulfuric acid → filtration → evaporative crystallization → dehydration of VOSO4Light blue colored powder
The main reaction equation:
the existing technical route for synthesizing vanadyl sulfate is as follows: v2O5→ sulfuric acid is heated, dissolved, cooled and diluted → reducing agent (oxalic acid or sulfurous acid) is added → evaporation crystal dehydration → VOSO4Light blue powder.
The main reaction equation is as follows:
oxalic acid isused as a reducing agent:
or taking sulfurous acid as a reducing agent:
the preparation method of the invention omits the steps of heating, cooling, diluting, reducing and the like, and has the advantages of mild reaction conditions, simple process, low cost and stable product quality.
The specific implementation mode of the invention is as follows: the preparation process of vanadyl sulfate includes adding V to sulfuric acid2O3And V2O5(ii) a b. Filtering, and evaporating and crystallizing the filtrate; c. removing crystal water to obtain VOSO4Light blue powder. In the step a, the sulfuric acid is diluted by concentrated sulfuric acid with the specific gravity of 1.84 to form 1: 1 dilute sulfuric acid; raw material V2O3、V2O5、H2SO4The weight ratio of: 32.4-54.3: 27.2: 68.6-92, wherein the sulfuric acid is concentrated sulfuric acid with specific gravity of 1.84, and V2O362-68% of TV, and V2O5The purity is more than or equal to 98 percent; the vanadyl sulfate solution obtained by the step a and the step b can be directly used as a raw material for preparing the electrolyte of the vanadium battery.
The invention is further illustrated by the following examples:
example one
Get V2O3(V2O362% of TV) and V with purity of 98%2O527g of H having a specific gravity of 1.842SO485g, diluting sulfuric acid with distilled water at a ratio of 1: 1, adding V2O3Then gradually add intoV2O5Stirring, cooling and filtering to obtain blue vanadyl sulfate solution, and testing; pH 1.2, vanadium concentration 4.2mol/L, ratio of tetravalent vanadium to total vanadium V (IV)The ratio/TV is more than 99 percent. Heating, evaporating and crystallizing to obtain a blue crystal, drying the crystal at 80 ℃ for 5 hours, dehydrating, and testing: TV 30%. Preparing electrolyte with vanadium concentration of 2mol/L from the prepared vanadyl sulfate according to the requirements of the vanadium redox battery, and putting the electrolyte into an electrolytic cell for a charge-discharge experiment: the charging plateau was 1.7V and the discharging plateau was 1.4V.
Example two
Get V2O3(V2O365% of TV) 74g, and V with a purity of 98.5%2O527g of H having a specific gravity of 1.842SO437g, diluting sulfuric acid with distilled water in a ratio of 1: 1, adding V2O3And V2O5Stirring, cooling and filtering to obtain blue vanadyl sulfate solution, and testing; the pH is 0.92, the vanadium concentration is 4.2mol/L, and the ratio V (IV)/TV of tetravalent vanadium to total vanadium is>99%. Heating, evaporating and crystallizing to obtain a blue crystal, drying the crystal at 80 ℃ for 5 hours, dehydrating, and testing: 30.2 percent of TV. Preparing electrolyte with vanadium concentration of 2mol/L from the prepared vanadyl sulfate according to the requirements of the vanadium redox battery, and putting the electrolyte into an electrolytic cell for a charge-discharge experiment: the charging plateau was 1.7V and the discharging plateau was 1.4V.
Claims (4)
1. A preparation method of vanadyl sulfate is characterized by comprising the following steps:
comprising a, adding V to sulfuric acid2O3And V2O5；
b. Filtering, and evaporating and crystallizing the filtrate;
c. removing crystal water to obtain VOSO4Light blue powder.
2. The method for preparing vanadyl sulfate according to claim 1, wherein: in step a, the sulfuric acid is diluted 1: 1 by concentrated sulfuric acid with a specific gravity of 1.84.
3. The method for preparing vanadyl sulfate according to claim 1, wherein: in step a, feed V2O3、V2O5、H2SO4The weight ratio of: 32.4-54.3: 27.2: 68.6-92, wherein the sulfuric acid is concentrated sulfuric acid with specific gravity of 1.84, and V2O362-68% of TV, and V2O5The purity is more than or equal to 98 percent.
4. The vanadyl sulfate solution obtained by steps a and b of the preparation method of claim 1 can be directly used as a raw material for preparing the electrolyte of the vanadium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021338086A CN1204053C (en) | 2002-09-25 | 2002-09-25 | Preparation method and application of vanadyl sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021338086A CN1204053C (en) | 2002-09-25 | 2002-09-25 | Preparation method and application of vanadyl sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1491898A true CN1491898A (en) | 2004-04-28 |
| CN1204053C CN1204053C (en) | 2005-06-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021338086A Expired - Fee Related CN1204053C (en) | 2002-09-25 | 2002-09-25 | Preparation method and application of vanadyl sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204053C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007049126A1 (en) * | 2005-10-24 | 2007-05-03 | Highveld Steel And Vanadium Corporation Limited | Process for the preparation of an electrolyte |
| CN100438190C (en) * | 2005-03-29 | 2008-11-26 | 攀钢集团攀枝花钢铁研究院 | All-vanadium ion flow battery electrolyte and preparation method thereof |
| CN101648727B (en) * | 2008-08-14 | 2011-06-15 | 比亚迪股份有限公司 | Method for preparing vanadyl sulfate |
| CN102354762A (en) * | 2011-09-30 | 2012-02-15 | 承德万利通实业集团有限公司 | Method for manufacturing high-purity vanadium battery electrolyte |
| CN102969521A (en) * | 2012-12-10 | 2013-03-13 | 贵州省岑巩县银峰矿业有限公司 | Method for preparing positive electrode electrolyte of vanadium battery |
| CN103199293A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadium sulfate solution for vanadium cell |
| CN103303976A (en) * | 2013-06-04 | 2013-09-18 | 青岛清阳新材料发展有限公司 | Preparation method of active substance, vanadyl sulfate, of vanadium battery |
| CN103319326A (en) * | 2012-03-23 | 2013-09-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for vanadyl oxalate |
| CN103427103A (en) * | 2013-07-29 | 2013-12-04 | 大连博融新材料有限公司 | Production method for electrolyte for high-purity all-vanadium flow batteries |
| CN104934623A (en) * | 2015-05-20 | 2015-09-23 | 大连博融新材料有限公司 | Production method and application of vanadium cell electrolyte crystal |
| CN106450401A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadyl sulfate by utilizing waste vanadium electrolyte |
| CN110627122A (en) * | 2019-10-24 | 2019-12-31 | 成都先进金属材料产业技术研究院有限公司 | Preparation of VO by solid phase method2Method for phase change materials |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101126124B (en) * | 2007-07-06 | 2011-08-17 | 北京普能世纪科技有限公司 | Method for preparing high-purity electrolyte for vanadium battery from stone-like coal |
-
2002
- 2002-09-25 CN CNB021338086A patent/CN1204053C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438190C (en) * | 2005-03-29 | 2008-11-26 | 攀钢集团攀枝花钢铁研究院 | All-vanadium ion flow battery electrolyte and preparation method thereof |
| WO2007049126A1 (en) * | 2005-10-24 | 2007-05-03 | Highveld Steel And Vanadium Corporation Limited | Process for the preparation of an electrolyte |
| JP2009512622A (en) * | 2005-10-24 | 2009-03-26 | ハイベルド スティール アンド バナディウム コーポレーション リミテッド | Preparation method of electrolyte |
| CN101648727B (en) * | 2008-08-14 | 2011-06-15 | 比亚迪股份有限公司 | Method for preparing vanadyl sulfate |
| CN102354762B (en) * | 2011-09-30 | 2015-09-30 | 承德万利通实业集团有限公司 | A kind of preparation method of high-purity vanadium battery electrolyte |
| CN102354762A (en) * | 2011-09-30 | 2012-02-15 | 承德万利通实业集团有限公司 | Method for manufacturing high-purity vanadium battery electrolyte |
| CN103319326A (en) * | 2012-03-23 | 2013-09-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for vanadyl oxalate |
| CN103319326B (en) * | 2012-03-23 | 2015-05-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for vanadyl oxalate |
| CN102969521A (en) * | 2012-12-10 | 2013-03-13 | 贵州省岑巩县银峰矿业有限公司 | Method for preparing positive electrode electrolyte of vanadium battery |
| CN103199293A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadium sulfate solution for vanadium cell |
| CN103303976A (en) * | 2013-06-04 | 2013-09-18 | 青岛清阳新材料发展有限公司 | Preparation method of active substance, vanadyl sulfate, of vanadium battery |
| CN103427103A (en) * | 2013-07-29 | 2013-12-04 | 大连博融新材料有限公司 | Production method for electrolyte for high-purity all-vanadium flow batteries |
| CN104934623A (en) * | 2015-05-20 | 2015-09-23 | 大连博融新材料有限公司 | Production method and application of vanadium cell electrolyte crystal |
| CN106450401A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadyl sulfate by utilizing waste vanadium electrolyte |
| CN106450401B (en) * | 2016-11-11 | 2019-08-30 | 攀钢集团攀枝花钢铁研究院有限公司 | A method of vanadic sulfate is prepared using discarded V electrolyte |
| CN110627122A (en) * | 2019-10-24 | 2019-12-31 | 成都先进金属材料产业技术研究院有限公司 | Preparation of VO by solid phase method2Method for phase change materials |
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| Publication number | Publication date |
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| CN1204053C (en) | 2005-06-01 |
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