CN1290772C - Preparation of vanadium pentoxide - Google Patents
Preparation of vanadium pentoxide Download PDFInfo
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- CN1290772C CN1290772C CN 200410099101 CN200410099101A CN1290772C CN 1290772 C CN1290772 C CN 1290772C CN 200410099101 CN200410099101 CN 200410099101 CN 200410099101 A CN200410099101 A CN 200410099101A CN 1290772 C CN1290772 C CN 1290772C
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002893 slag Substances 0.000 claims abstract description 35
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 30
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 6
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000002912 waste gas Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 5
- 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 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a preparation method of vanadium pentoxide. With the method, after being mixed, vanadium slag and industrial salts are ground to be powder, and 30 to 50%liquid caustic soda and coke powder are added to the powder and are sufficiently mixed with the powder. After calcination is carried out for 1 to 6 hours at 600 to 1000 DEG C, a calcination material is put into water and the mixture is stirred and filtered to remove impurities. The pH value of an obtained aqueous solution is regulated from 2 to 3 by diluted sulfuric acid. The aqueous solution is filtered and dried to obtain vanadium pentoxide crystals. The preparation method of vanadium pentoxide has the advantages of high yield, simple reaction operation, easy operation and convenient industrial production, a chlorine gas which is generated in a reaction participates in the reaction as a reactant, the generation of a waste gas is avoided, and water soluble sodium metavanadate can be generated by vanadium in the vanadium slag through multiple ways.
Description
(I) technical field
The invention relates to a preparation method of vanadium pentoxide, belonging to the field of inorganic chemistry.
(II) background of the invention
Vanadium pentoxide is also known as vanadic anhydride, the english name being Vanadium pentaoxide; vanadiumpentaoxide; vanadic anhydride. CAS number 1314-62-1. The appearance was yellowish red crystalline powder. Molecular formula V2O5Molecular weight 183.88. The relative density was 3.357. Melting point 690 ℃. Boiling point 1750 deg.C. Has low solubility in water (1 g in 125ml water), and can be dissolved in concentrated acid to obtain red-yellow solution and alkali to obtain vanadate.
Vanadium pentoxide is an important inorganic chemical raw material. The coating is used as a jacket for manufacturing special vanadium iron alloy steel and an electrode of an iron melting furnace in the metallurgical industry and a contact agent in the glass and ceramic industry; the catalyst is used as a catalyst for decarburization and desulfurization in the synthetic ammonia industry, and is used as a corrosion inhibitor for equipment corrosion prevention in a petrochemical device;in the chemical industry are catalysts for the synthesis of chemical raw materials such as sulfuric acid, nitric acid and phthalic anhydride. It can also be used for producing coloring materials for dyes and ceramics, paints, UV-opaque glasses, photographic developers. People are predicted to be widely applied to the aspects of medicines, pesticides, plant diseases prevention and the like.
The production method of vanadium pentoxide varies depending on the source of the raw material. At present, the production methods used at home and abroad are summarized as an alkali fusion method, a salt fusion method and an ion exchange resin method. The alkali fusion method is to use vanadium fine powder and soda ash to roast at high temperature to generate sodium metavanadate, add sulfuric acid to neutralize under heating and stirring, and then prepare vanadium pentoxide. The method is suitable for raw materials with high vanadium content, or the raw materials need to be pretreated, and the raw materials are easy to agglomerate in the roasting process. The salt melting method is to perform ball milling on vanadium ore and industrial salt and then perform oxidizing roasting to obtain sodium metavanadate, and then perform acidification with hydrochloric acid to obtain a vanadium pentoxide product. This is currently the most commonly used method in the industry. However, this method has a problem in that it is necessary to solve the environmental pollution caused by the discharge of waste water and exhaust gas. Although the calcium roasting method is adopted to solve the problem of the generation of polluted waste gas, the limestone exists in the form of calcium salt after being roasted, the conditions required in the post-treatment are higher, and certain difficulty is brought to the production. The ion exchange resin method solves the pollution problem of hydrochloric acid wastewater, but the ion exchange resin has higher cost and is difficult to produce on a large scale, and the regeneration of the ion exchange resin also needs certain expenditure.
Disclosure of the invention
Aiming at the problems in the preparation of vanadium pentoxide in the prior art, the invention provides a preparation method of vanadium pentoxide with less environmental pollution, low cost and high yield.
The technical scheme adopted by the invention for achieving the aim of the invention is as follows:
a preparation method of vanadium pentoxide comprises the following steps: mixing vanadium slag and industrial salt, grinding into powder, adding liquid caustic soda and coke powder with the concentration of 30-50%, fully mixing, roasting at 600-1000 ℃ for 1-6 hours, adding the roasted material into water, stirring, filtering to remove slag, adjusting the pH of the obtained aqueous solution to 2-3 by using dilute sulfuric acid, filtering, and drying to obtain the vanadium pentoxide crystal.
First, FeO.V in the vanadium slag2O5Reacting with sodium chloride to generate chlorine and sodium metavanadate:
the produced chlorine reacts with vanadium pentoxide in the vanadium slag to obtain vanadium oxychloride, and the vanadium oxychloride can react with sodium hydroxide to generate sodium metavanadate, so that the production of waste gas is avoided, and the pollution is reduced:
and the redundant vanadium pentoxide can also react with sodium hydroxide to generate sodium metavanadate:
and finally, dissolving the roasted material in water, filtering to remove residues to obtain a sodium metavanadate solution, and reacting the sodium metavanadate with sulfuric acid to obtain vanadium pentoxide crystals:
the mass ratio of the vanadium slag to the industrial salt is 100: 1-6, the mass of the liquid caustic soda is 5-20% of that of the industrial salt, and the mass of the coke powder is 1-10% of that of the vanadium slag.
The concentration of the liquid caustic soda is preferably 30%.
The concentration of the dilute sulfuric acid is preferably 30 percent
Specifically, the method comprises the following steps: mixing 100 parts by mass of vanadium slag and 3.5 parts by mass of industrial salt, grinding into powder, adding 0.5 part by mass of 30% liquid caustic soda and 1 part by mass of coke powder, fully mixing, roasting at 700 ℃ for 3 hours, putting the roasted material into 100 parts by mass of water, stirring, filtering to remove slag, adjusting the pH value of the obtained aqueous solution to 2 by using 30% dilute sulfuric acid, filtering, and drying to obtain the vanadium pentoxide crystal.
Or, the method is as follows: mixing 100 parts by mass of vanadium slag and 4 parts by mass of industrial salt, grinding into powder, adding 0.25 part by mass of 48% liquid caustic soda and 8 parts by mass of coke powder, fully mixing, roasting at 900 ℃ for 2 hours, putting the roasted material into 100 parts by mass of water, stirring, filtering to remove slag, adjusting the pH value of the obtained aqueous solution to be 2 by using 20% dilute sulfuric acid, filtering, and drying to obtain the vanadium pentoxide crystal.
The preparation method of vanadium pentoxide has the following beneficial effects: (1) chlorine generated by the reaction is used as a reactant to participate in the reaction, so that the generation of waste gas is avoided; (2) the vanadium in the vanadium slag is generated into water-soluble sodium metavanadate through various ways, and the yield is high; (3) the reaction operation is simple, the operation is easy, and the industrial production is convenient.
(IV) detailed description of the preferred embodiments
The invention is further described below with reference to specific examples:
example 1:
mixing 100 g of vanadium slag and 3.5 g of industrial salt, grinding into powder by using a ball mill, adding 0.5 g of 30% liquid caustic soda and 1 g of coke powder, fully mixing, placing into a high-temperature converter to roast at 700 ℃, after 3 hours, placing the roasted material into 100 ml of water, stirring, filtering and deslagging, adjusting the pH of an aqueous solution dissolved with sodium metavanadate to be approximately equal to 2 by using 30% dilute sulfuric acid, obtaining 3.9 g of vanadium pentoxide with the yield of 90%. The vanadium slag is a product of Panzhihua new steel vanadium limited company, the same as the following.
Example 2:
mixing 100 g of vanadium slag with 4 g of industrial salt, grinding into powder, adding 0.25 g of 48% liquid caustic soda and 8 g of coke powder, fully mixing, roasting at 900 ℃ in a high-temperature converter for 2 hours, adding the roasted material into 100 g of water, stirring, filtering to remove slag, adjusting the pH of the obtained aqueous solution to be approximatelyequal to 2 by using 20% dilute sulfuric acid, filtering, and drying in vacuum to obtain 3.8 g of vanadium pentoxide crystals with the yield of 88%.
Example 3:
mixing 100 g of vanadium slag and 6 g of industrial salt, grinding into powder, adding 0.6 g of 42% liquid caustic soda and 10 g of coke powder, fully mixing, roasting at 600 ℃ in a high-temperature converter for 5 hours, adding the roasted material into 100 g of water, stirring, filtering to remove slag, adjusting the pH of the obtained aqueous solution to be approximately equal to 3 by using 10% dilute sulfuric acid, filtering, and drying in vacuum to obtain 4.0 g of vanadium pentoxide crystals with the yield of 93%.
Example 4:
mixing 100 g of vanadium slag and 5 g of industrial salt, grinding into powder, adding 1.0 g of 30% liquid caustic soda and 5 g of coke powder, fully mixing, roasting at 800 ℃ in a high-temperature converter for 4 hours, adding the roasted material into 100 g of water, stirring, filtering to remove residues, adjusting the pH of the obtained aqueous solution to be approximately equal to 2.5 by using 30% dilute sulfuric acid, filtering, and vacuum drying to obtain 4.2 g of vanadium pentoxide crystals with the yield of 95%.
Example 5:
mixing 100 g of vanadium slag with 4 g of industrial salt, grinding into powder, adding 0.4 g of 46% liquid caustic soda and 7 g of coke powder, fully mixing, roasting at 900 ℃ in a high-temperature converter for 2 hours, adding the roasted material into 100 g of water, stirring, filtering to remove slag, adjusting the pH of the obtained aqueous solution to be approximately equal to 2 by using 30% dilute sulfuric acid, filtering, and drying in vacuum to obtain 3.7 g of vanadium pentoxide crystals with the yield of 85%.
Example 6:
mixing 100 g of vanadium slag with 5 g of industrial salt, grinding into powder, adding 0.3 g of 48% liquid caustic soda and 6 g of coke powder, fully mixing, roasting at 600 ℃ in a high-temperature converter for 6 hours, adding the roasted material into 100 g of water, stirring, filtering to remove residues, adjusting the pH of the obtained aqueous solution to be approximately equal to 2 by using 20% dilute sulfuric acid, filtering, and drying in vacuum to obtain 3.8 g of vanadium pentoxide crystals with the yield of 87%.
Example 7:
mixing 100 g of vanadium slag with 2 g of industrial salt, grinding into powder, adding 0.2 g of 40% liquid caustic soda and 8 g of coke powder, fully mixing, roasting at 700 ℃ in a high-temperature converter for 3 hours, adding the roasted material into 100 g of water, stirring, filtering to remove slag, adjusting the pH of the obtained aqueous solution to be approximately equal to 3 by using 30% dilute sulfuric acid, filtering, and drying in vacuum to obtain 3.8 g of vanadium pentoxide crystals with the yield of 88%.
Example 8:
mixing 100 g of vanadium slag with 1 g of industrial salt, grinding into powder, adding 0.2 g of 30% liquid caustic soda and 6 g of coke powder, fully mixing, roasting at 1000 ℃ in a high-temperature converter for 1 hour, putting the roasted material into 100 g of water, stirring, filtering to remove slag, adjusting the pH of the obtained aqueous solution to be approximately equal to 3 by using 30% dilute sulfuric acid, filtering, and drying in vacuum to obtain 3.6 g of vanadium pentoxide crystals with the yield of 83%.
Claims (5)
1. A preparation method of vanadium pentoxide is characterized by comprising the following steps:
mixing vanadium slag and industrial salt, grinding into powder, adding liquid caustic soda and coke powder with the concentration of 30-50%, fully mixing, roasting at 600-1000 ℃ for 1-6 hours, adding the roasted material into water, stirring, filtering to remove slag, adjusting the pH of the obtained aqueous solution to 2-3 by using dilute sulfuric acid, filtering and drying to obtain the vanadium pentoxide crystal; the mass ratio of the vanadium slag to the industrial salt is 100: 1-6, the mass of the liquid caustic soda is 5-20% of that of the industrial salt, and the mass of the coke powder is 1-10% of that of the vanadium slag.
2. The method according to claim 1, wherein the concentration of the liquid caustic soda is 30%.
3. The method for producing vanadium pentoxide according to claim 1, wherein the concentration of the dilute sulfuric acid is 30%.
4. The method of claim 1, wherein the force method comprises:
mixing 100 parts by mass of vanadium slag and 3.5 parts by mass of industrial salt, grinding into powder, adding 0.5 part by mass of 30% liquid caustic soda and 1 part by mass of coke powder, fully mixing, roasting at 700 ℃ for 3 hours, putting the roasted material into 100 parts by mass of water, stirring, filtering to remove slag, adjusting the pH value of the obtained aqueous solution to 2 by using 30% dilute sulfuric acid, filtering, and drying to obtain the vanadium pentoxide crystal.
5. The method for preparing vanadium pentoxide according to claim 1, wherein said method comprises:
mixing 100 parts by mass of vanadium slag and 4 parts by mass of industrial salt, grinding into powder, adding 0.25 part by mass of 48% liquid caustic soda and 8 parts by mass of coke powder, fully mixing, roasting at 900 ℃ for 2 hours, putting the roasted material into 100 parts by mass of water, stirring, filtering to remove slag, adjusting the pH value of the obtained aqueous solution to be 2 by using 20% dilute sulfuric acid, filtering, and drying to obtain the vanadium pentoxide crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410099101 CN1290772C (en) | 2004-12-28 | 2004-12-28 | Preparation of vanadium pentoxide |
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|---|---|---|---|
| CN 200410099101 CN1290772C (en) | 2004-12-28 | 2004-12-28 | Preparation of vanadium pentoxide |
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| CN1644511A CN1644511A (en) | 2005-07-27 |
| CN1290772C true CN1290772C (en) | 2006-12-20 |
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| CN 200410099101 Expired - Fee Related CN1290772C (en) | 2004-12-28 | 2004-12-28 | Preparation of vanadium pentoxide |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101899582A (en) * | 2010-07-30 | 2010-12-01 | 四川省川威集团有限公司 | Method for extracting vanadium pentoxide from vanadium slag |
| CN102502570B (en) * | 2011-11-29 | 2013-04-10 | 芜湖人本合金有限责任公司 | Production method of medical sodium metavanadate |
| CN102531059A (en) * | 2011-12-21 | 2012-07-04 | 攀枝花钢企欣宇化工有限公司 | Method for treating waste sulfuric acid containing chlorine |
| CN113578396A (en) * | 2021-08-18 | 2021-11-02 | 国能龙源催化剂江苏有限公司 | High-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak regulation and preparation method thereof |
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