CN102050491B - Production method of vanadium trioxide - Google Patents
Production method of vanadium trioxide Download PDFInfo
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- CN102050491B CN102050491B CN2010105631204A CN201010563120A CN102050491B CN 102050491 B CN102050491 B CN 102050491B CN 2010105631204 A CN2010105631204 A CN 2010105631204A CN 201010563120 A CN201010563120 A CN 201010563120A CN 102050491 B CN102050491 B CN 102050491B
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- vanadous oxide
- vanadium
- vanadate
- working method
- solid carbon
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- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 title abstract 7
- 238000000034 method Methods 0.000 claims abstract description 49
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 12
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 14
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 230000003068 static effect Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 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 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- HJIYJLZFNBHCAN-UHFFFAOYSA-N [V].[C] Chemical compound [V].[C] HJIYJLZFNBHCAN-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A production method of vanadium trioxide is characterized in that ammonium polyvanadate or vanadium pentoxide with the particle size of 0.01-5 mm and solid carbon are mixed according to the weight ratio of 100: 40-100: 1, adding the mixture into a heating furnace, heating at 800-1150 ℃ for 1-5 h, carrying out reduction reaction on the materials in the heating furnace to generate vanadium trioxide, cooling the materials under a closed condition to room temperature, and discharging. The advantages are that: compared with the dynamic method for preparing vanadium trioxide by using gas as a reducing agent, the method for preparing vanadium trioxide by using the solid reducing agent and the static reduction method has the advantages of low manufacturing cost, simple process, strong operability, high safety coefficient, no gas leakage danger, capability of obtaining a high-quality vanadium trioxide product, high vanadium grade of the vanadium trioxide product reaching more than 67 percent, and realization of industrial production.
Description
Technical field
The invention belongs to the oxide compound preparing technical field of vanadium at a low price, particularly relate to a kind of working method of vanadous oxide.
Background technology
Vanadous oxide and Vanadium Pentoxide in FLAKES, vanadium carbide, vanadium nitride, carbon vanadium nitride, ammonium vanadate, vanadic acid sodium etc. belong to the important compound of vanadium together, and it can be applicable to industry fields such as metallurgy, electronics, chemical industry.
The alternative Vanadium Pentoxide in FLAKES of vanadous oxide prepares vanadium iron, also can process vanadium carbide to vanadous oxide or vanadium nitride directly adds in the molten steel, improves the mechanical property of steel.Also available vanadous oxide prepares the vanadium metal powder.In addition, vanadous oxide also can directly be used to produce electronic products such as thermoelectric converter.
JP84/61141622 discloses with ammonia and has made the method that reductive agent reduction Vanadium Pentoxide in FLAKES prepares vanadous oxide.Its reaction conditions is: at 0.01～0.15MPa; Under 450～650 ℃ of temperature, carry out hybrid reaction to the ammonia of 1～20 times of mole ratio of raw material and Vanadium Pentoxide in FLAKES, keep reaction times 1～6h; Making the Vanadium Pentoxide in FLAKES decomposition-reduction is vanadous oxide; Its shortcoming is that the ammonia consumption is big, and cost is high, has spillage risk.
CN200610020405.7 discloses a kind of method of producing vanadium sesquioxide powder.Its method is powder ammonium vanadate or Vanadium Pentoxide in FLAKES to be joined as furnace charge add in the hot fluidized bed furnace boiler tube, makes the filling ratio of boiler tube reach 10%～55%, feeds industrial gas; Be heated to 600～650 ℃; Insulation reduction 3～9 minutes, secluding air is cooled to come out of the stove below 100 ℃, obtains product.Its shortcoming is that required industrial gas consumption is big, complex manufacturing.
In sum, existing vanadous oxide working method employed reductive agent in heat-processed all is a gas, complex manufacturing, and the gas consumption is big, and production cost is high, and SF is low.
Summary of the invention
The technical problem that the present invention will solve provides a kind of working method of vanadous oxide; This method adopts solid reductant; Static conditions is the preparation vanadous oxide down; Production cost is low, technology is simple, workable, SF is high, quality product is excellent, simultaneously can realize suitability for industrialized production, be with a wide range of applications.
Technical solution of the present invention is:
A kind of working method of vanadous oxide; With granularity is that ammonium poly-vanadate or Vanadium Pentoxide in FLAKES and the solid carbon of 0.01～5mm joins in the process furnace according to weight ratio 100:40～100:1; Heating temperature is 800 ~ 1150 ℃; Recovery time is 1 ~ 5h, makes material that reduction reaction take place in process furnace and generates vanadous oxide, and cooled materials to room temperature is come out of the stove in confined conditions.
The working method of above-mentioned vanadous oxide, described ammonium poly-vanadate join earlier in the process furnace, and described solid carbon fits over around the ammonium poly-vanadate.
The working method of above-mentioned vanadous oxide, described Vanadium Pentoxide in FLAKES in advance with the solid carbon mixing.
The working method of above-mentioned vanadous oxide, said solid carbon are a kind of in Graphite Powder 99, coke, coke powder, the coal or two kinds.
The working method of above-mentioned vanadous oxide, the material of described process furnace are nickelalloy, and the process furnace material is selected nickelalloy, more helps carrying out smoothly of reduction reaction.
The working method of above-mentioned vanadous oxide, described ammonium poly-vanadate or Vanadium Pentoxide in FLAKES and solid carbon splendid attire mode adopt one or more layers splendid attire.
The working method of above-mentioned vanadous oxide, described type of heating are gas-fired heating, combustion of natural gas heating or electrically heated.
The working method of above-mentioned vanadous oxide, the type of cooling are naturally cooling, are cooled with circulating water or cooling under protection of inert gas.
The present invention has following advantage: with make reductive agent with gas, dynamic method prepares vanadous oxide and compares; Adopt solid reductant, quiescent state reduction to prepare vanadous oxide; Have low cost of manufacture, technology is simple, workable, SF is high, does not have advantages such as gas leakage danger, can obtain high-quality vanadous oxide product; Its full vanadium grade can reach more than 67%, can realize suitability for industrialized production simultaneously.
Description of drawings
Fig. 1 is the hybrid mode synoptic diagram of ammonium poly-vanadate and solid carbon.
Fig. 2 is the hybrid mode synoptic diagram of Vanadium Pentoxide in FLAKES and solid carbon.
Fig. 3 is a multilayer splendid attire mode synoptic diagram.
Embodiment
Illustrate specific embodiments of the present invention below.
Embodiment 1:
With granularity is that the ammonium poly-vanadate of 0.01～5mm is joined reductive agent-Graphite Powder 99 outward and joined in the process furnace of nickelalloy material, and Graphite Powder 99 is allocated into around ammonium poly-vanadate, and is as shown in Figure 1.The weight ratio 10:4 of described ammonium poly-vanadate and Graphite Powder 99, Heating temperature is 800 ℃, and the recovery time is 5h, makes material that reduction reaction take place in process furnace and generates vanadous oxide, and naturally cooling material to room temperature is come out of the stove in confined conditions.The vanadous oxide product ∑ V67.39% that makes, the recovery of vanadium is 99.3%.
Embodiment 2:
With granularity is that the ammonium poly-vanadate of 0.01～5mm is joined the reductive agent Graphite Powder 99 outward and joined in the process furnace of nickelalloy material, and Graphite Powder 99 is allocated into around ammonium poly-vanadate, and is as shown in Figure 1.The weight ratio 100:1 of described ammonium poly-vanadate and Graphite Powder 99, Heating temperature is 1150 ℃, and the recovery time is 1h, makes material that reduction reaction take place in process furnace and generates vanadous oxide, and cooled materials to room temperature is come out of the stove under protection of inert gas.The vanadous oxide product ∑ V67.03% that makes, the recovery of vanadium is 99.1%.
Embodiment 3:
With granularity is that the ammonium poly-vanadate of 0.01～5mm is joined reductive agent-coke outward, and wherein coke is allocated into around ammonium poly-vanadate, and is as shown in Figure 1; The weight ratio 4:1 of described ammonium poly-vanadate and coke; Join in the process furnace of nickelalloy material, Heating temperature is 1000 ℃, and the recovery time is 1h; Make material that reduction reaction take place in process furnace and generate vanadous oxide, cooled materials to room temperature is come out of the stove under protection of inert gas.The vanadous oxide product ∑ V67.58% that makes, the recovery of vanadium is 99.6%.
Embodiment 4
The Vanadium Pentoxide in FLAKES that with granularity is 0.01～5mm joins in the process furnace of nickelalloy material after reductive agent-Graphite Powder 99 mixes according to weight ratio 5:2; As shown in Figure 2; Heating temperature is 1150 ℃; Recovery time is 1h, makes material that reduction reaction take place in process furnace and generates vanadous oxide, is cooled with circulating water material to room temperature in confined conditions and comes out of the stove.The vanadous oxide product ∑ V67.45% that makes, the recovery of vanadium is 99.5%.
Embodiment 5:
With granularity is Vanadium Pentoxide in FLAKES and the reductive agent-coke powder of 0.01～5mm; Join together in the process furnace of nickelalloy material after mixing according to weight ratio 100:1; As shown in Figure 2, Heating temperature is 800 ℃, and the recovery time is 5h; Make material that reduction reaction take place in process furnace and generate vanadous oxide, cooled materials to room temperature is come out of the stove under protection of inert gas.The vanadous oxide product ∑ V67.11% that makes, the recovery of vanadium is 99.1%.
Embodiment 6:
With granularity is Vanadium Pentoxide in FLAKES and the reductive agent-coke powder of 0.01～5mm; Join together in the process furnace of nickelalloy material after mixing according to weight ratio 5:1; As shown in Figure 2, Heating temperature is 800 ℃, and the recovery time is 5h; Make material that reduction reaction take place in process furnace and generate vanadous oxide, cooled materials to room temperature is come out of the stove under protection of inert gas.The vanadous oxide product ∑ V67.18% that makes, the recovery of vanadium is 99.1%.
Reductive agent among the foregoing description 1-embodiment 6 is a fixed carbon, both can adopt a kind of or two kinds (like coke and coal) in Graphite Powder 99, coke, coke powder, the coal; Ammonium poly-vanadate or Vanadium Pentoxide in FLAKES and solid carbon splendid attire mode adopt individual layer splendid attire mode, also can adopt multilayer splendid attire mode as shown in Figure 3, and Fig. 3 is an example with three layers; The type of heating of process furnace is the gas-fired heating, also can adopt combustion of natural gas heating or electrically heated; The type of cooling is a naturally cooling, also can adopt recirculated water cooling or cooling under protection of inert gas.
Claims (5)
1. the working method of a vanadous oxide is characterized in that may further comprise the steps:
A, be that ammonium poly-vanadate or Vanadium Pentoxide in FLAKES and the solid carbon of 0.01～5mm joins in the process furnace according to weight ratio 100:40～100:1 with granularity; Described ammonium poly-vanadate joins earlier in the process furnace, and described solid carbon fits over around the ammonium poly-vanadate; Described Vanadium Pentoxide in FLAKES in advance with the solid carbon mixing; Said solid carbon is a kind of in Graphite Powder 99, coke, coke powder, the coal or two kinds;
B, Heating temperature are 800 ~ 1150 ℃, and the recovery time is 1 ~ 5h, make material that reduction reaction take place in process furnace and generate vanadous oxide;
C, cooled materials to room temperature is come out of the stove in confined conditions.
2. the working method of vanadous oxide according to claim 1, the material that it is characterized in that process furnace among the said step a is a nickelalloy.
3. the working method of vanadous oxide according to claim 1 is characterized in that among the said step a that ammonium poly-vanadate or Vanadium Pentoxide in FLAKES and solid carbon splendid attire mode adopt the single or multiple lift splendid attire.
4. the working method of vanadous oxide according to claim 1 is characterized in that type of heating is gas-fired heating, combustion of natural gas heating or electrically heated among the said step b.
5. the working method of vanadous oxide according to claim 1, it is characterized in that among the said step c type of cooling be in confined conditions naturally cooling, be cooled with circulating water or cooling under protection of inert gas in confined conditions.
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| CN102050491B true CN102050491B (en) | 2012-04-18 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708554B (en) * | 2014-01-16 | 2015-05-20 | 江苏理工学院 | Preparation method of vanadium trioxide nanospheres |
| CN103922404B (en) * | 2014-04-30 | 2015-09-23 | 攀枝花学院 | Method for preparing vanadium trioxide from vanadium pentoxide |
| CN104495926A (en) * | 2015-01-05 | 2015-04-08 | 南通汉瑞新材料科技有限公司 | Vanadium trioxide and preparation method thereof |
| RU2653020C1 (en) * | 2016-11-08 | 2018-05-04 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Method for obtaining a composite of vanadium trioxide/carbon |
| CN110581284B (en) * | 2019-09-30 | 2020-12-08 | 陕西科技大学 | A preparation method of electrocatalytic functional V2O3@Co and its application |
| CN112408479A (en) * | 2020-12-13 | 2021-02-26 | 湖南众鑫新材料科技股份有限公司 | Process for preparing low-valence vanadium from ammonium metavanadate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136476A (en) * | 1999-01-29 | 2000-10-24 | Hydro-Quebec Corporation | Methods for making lithium vanadium oxide electrode materials |
| CN101157478A (en) * | 2007-09-18 | 2008-04-09 | 攀钢集团攀枝花钢铁研究院 | A kind of preparation method of ammonium polyvanadate |
| CN101717117A (en) * | 2009-12-29 | 2010-06-02 | 四川省川威集团有限公司 | Method for producing vanadium trioxide |
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- 2010-11-29 CN CN2010105631204A patent/CN102050491B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136476A (en) * | 1999-01-29 | 2000-10-24 | Hydro-Quebec Corporation | Methods for making lithium vanadium oxide electrode materials |
| CN101157478A (en) * | 2007-09-18 | 2008-04-09 | 攀钢集团攀枝花钢铁研究院 | A kind of preparation method of ammonium polyvanadate |
| CN101717117A (en) * | 2009-12-29 | 2010-06-02 | 四川省川威集团有限公司 | Method for producing vanadium trioxide |
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