CN101817558A - Production method of vanadium trioxide - Google Patents
Production method of vanadium trioxide Download PDFInfo
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- CN101817558A CN101817558A CN 201010137595 CN201010137595A CN101817558A CN 101817558 A CN101817558 A CN 101817558A CN 201010137595 CN201010137595 CN 201010137595 CN 201010137595 A CN201010137595 A CN 201010137595A CN 101817558 A CN101817558 A CN 101817558A
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Abstract
The invention discloses a production method of vanadium trioxide, comprising the following steps: heating in a reducing atmosphere or under inert gas protection at the temperature of 600-900 DEG C, and keeping reduction time for 5-60 minutes; and naturally cooling or forcibly cooling under an isolated air condition. The method has the advantages that amino-containing vanadate is taken as a raw material and heated by industrial microwave, and an appropriate amount of reductant can be added or not, thus greatly saving usage amount of the reductant, shortening reduction time, reducing reduction temperature, simplifying production process, lowering production cost, and obtaining high-purity vanadium trioxide.
Description
Technical field
The invention belongs to the oxide compound production technology of vanadium, particularly relate to a kind of production method of powdery vanadous oxide.
Background technology
Vanadous oxide has at aspects such as temperature-sensitive, air-sensitive temperature sensor and magnetic switches widely to be used, also be the raw material of preparation vanadium iron, vanadium nitrogen compound and chemical catalyst, Kuai Sufazhan vanadium oxide battery is a raw material manufacturing with highly purified vanadous oxide in recent years.Producing the method for vanadous oxide, generally is the direct-reduction process that adopts additional reducing agent in the prior art, makes by decomposition-reduction under high temperature or the High Temperature High Pressure.Be raw material with Vanadium Pentoxide in FLAKES, ammonium meta-vanadate or ammonium poly-vanadate normally, used reductive agent comprises pure hydrogen, ammonia, methane, carbon monoxide or industrial coal etc.Because reducing gas is difficult to obtain and price is more expensive, the recovery time is long, and some needs special sealing equipment, and its industrial application is restricted.
It is raw material that Chinese patent 94111901.7 discloses with the ammonium vanadate of certain particle size or Vanadium Pentoxide in FLAKES, joins in the outer heating container, as reductive agent, reduces 30min at least with industrial gas under 900 ℃ of conditions, the preparation vanadous oxide.The shortcoming of this method is: the reduction temperature height, and required industrial gas consumption temple, and the high temperature material in the production unit can influence the quality of subsequent product because the catalysis reason cause that carbon content increases in the product.
It is raw material that Japanese Patent 86/141622 discloses with the Vanadium Pentoxide in FLAKES, uses ammonia as reductive agent, the method for decomposition-reduction under the stainless steel tube mesohigh.The shortcoming that this method exists is: need reduce under condition of high voltage, for up to 4 hours, to having relatively high expectations of equipment.
" Chengdu Univ. of Science ﹠ Technology's journal " 1984 the 3rd phase P27～30 introduced six ammonium vanadate under ammonia flow in stainless steel tube, under 850 ± 50 ℃ of conditions, reduced 1～2 hour, made vanadous oxide.The shortcoming of this method is: the reduction temperature height, the recovery time is long, the cost height.
" mining metallurgical engineering " 2005 the 25th volumes the 6th phase P61-63 has introduced ammonium meta-vanadate under the condition of life coal gas as reductive agent, carries out decomposition-reduction in the reacting in rotary kiln device, reduces at least 50 minutes under 700 ± 50 ℃ of conditions, can make vanadous oxide.The shortcoming of this method is: reduction temperature is higher, and the recovery time is longer.
Russia's preparation vanadous oxide is raw material with the Vanadium Pentoxide in FLAKES nearly all, and reductive agent has ammonia and vanadium metal etc.People such as Yankelevich had announced that they were raw material with the Vanadium Pentoxide in FLAKES in 1974, and ammonia prepares the method for vanadous oxide as reductive agent, and this technology is 450 ℃ of temperature, and ammonia flow is under the condition of 4L/h, reduces 3 hours, makes vanadous oxide.The shortcoming of this method is: the recovery time is long, and the ammonia consumption is big, and there is spillage risk in the cost height.
Above-mentioned prior art all needs a large amount of additional reducing agents in heat-processed, and employed reductive agent all is purer gas, generally only limiting to laboratory or small-sized production uses, be difficult to satisfy large batch of industrial production, its industrial application is restricted, and complex manufacturing, reduction apparatus is made and the production cost height.
Summary of the invention
The present invention aims to provide a kind of production method that can add or not add the vanadous oxide of other reductive agents less, and its reduction temperature is low, and the recovery time is short, and production cost is low, and technology is simple.
Technical scheme of the present invention is: will contain amino vanadate and place industrial microwave oven; under reducing atmosphere or under the protection of inert gas, heat; Heating temperature is 600～900 ℃, and the recovery time is 5～60 minutes, carries out naturally cooling or force cooling under the secluding air condition.
The described vanadate raw material that contains amino can be ammonium meta-vanadate (NH
4VO
3), also can be industrial ammonium poly-vanadate ((NH
4)
2V
6O
16).It is feedstock production that employing contains amino vanadate, can add or not add other reductive agents less, utilizes to contain hydrogen self reduction that ammonia cracking that amino vanadate discharges produces, and adds the hot preparation vanadous oxide under protection of inert gas.
Described reductive agent comprises hydrogen, ammonia, methane, carbon monoxide (removed water-gas, because water-gas is the gas that generates by red-hot coke, major ingredient is carbon monoxide, hydrogen) and mixture thereof; Described rare gas element comprises nitrogen, argon gas and mixture thereof.
Described industrial microwave oven is industrial intermittent type microwave stove or industrial continuous-type microwave stove.Described microwave frequency preferred value is 2.45GHz or 915MHz.
With ammonium meta-vanadate (NH
4VO
3) the raw material net reaction that do not add reductive agent is:
6NH
4VO
3□3V
2O
3+9H
2O+2NH
3+2N
2
The invention has the beneficial effects as follows: utilize the industrial microwave heating technique to prepare vanadous oxide, microwave direct and interior of articles atom or the heating of molecule generation coupling absorption micro-wave energy self, can be rapidly heated and sintering, and produce a kind of " non-thermal effect " phenomenon, reduce activation energy, reduce firing temperature, but fast cooling behind the while microwave firing reduces thermal source and pollutes; It is the feedstock production vanadous oxide that employing contains amino vanadate; can be the suitably a small amount of additional reducing agent of this method; also can not add other reductive agents and directly utilize and contain hydrogen self reduction that ammonia cracking that amino vanadate discharges produces; heating can prepare vanadous oxide under protection of inert gas; saving reductive greatly uses; and shorter than adopting Vanadium Pentoxide in FLAKES to carry out the required time of reduction reaction as raw material, temperature is also lower.So, the vanadous oxide purity height of method of the present invention preparation, and saved the consumption of reductive agent greatly, shorten the recovery time, reduced reduction temperature, simplified production technique, reduced production cost, can be used for suitability for industrialized production simultaneously, be with a wide range of applications.
Embodiment
Introduce indefiniteness embodiment below.
Embodiment 1: the ammonium meta-vanadate of 1kg is placed industrial intermittent type microwave stove, and microwave frequency is 915MHz, and the temperature rise rate with 5 ℃～10 ℃/minute under normal pressure is heated to 800 ℃ of insulations 5 minutes, and shielding gas is an argon gas.Adopt the thermocouple temperature measurement mode, close to cool to the furnace below 180 ℃ behind the microwave source and come out of the stove, obtain the vanadous oxide powder.The vanadous oxide that makes is the black meal, and is loose porous, and from the XRD analysis result, product is pure phase V
2O
3Ratio after the employing oxidation characterizes the content of vanadium, the high more (V of the big more content of vanadium of ratio
2O
5/ V
2O
3Theoretical value is 1.21), record its oxidation than ratio (V
2O
5/ V
2O
3) be 1.209.The rate of recovery of vanadium is greater than 99.5%.
Embodiment 2: a certain amount of ammonium poly-vanadate is put into industrial continuous-type microwave stove continuously, and microwave frequency is 2.45GHz, adopts the infrared thermometer thermometric, and shielding gas is the mixed gas of argon gas-nitrogen.Heating makes the furnace high-temperature district reach 600 ℃ under normal pressure, makes material pass through this temperature province generation reduction reaction 60 minutes, and coming out of the stove below the cooling furnace charge to 100 ℃ obtains vanadous oxide.The vanadous oxide that makes is a black, and from the XRD analysis result, product is pure phase V
2O
3From the SEM photo, crystal shape is a dumbbell shape, and size is about about 2 μ m, uniform crystal particles.The grade that obtains vanadous oxide is greater than 99.7%, and the rate of recovery of vanadium is greater than 99.5%.
Embodiment 3: a certain amount of ammonium meta-vanadate is put into industrial continuous-type microwave stove continuously, and microwave frequency is 2.45GHz, adopts thermocouple temperature measurement, and shielding gas is a nitrogen.Normal pressure down heating makes the furnace high-temperature district reach 900 ℃, makes material pass through this temperature province generation reduction reaction 30 minutes, and coming out of the stove below the cooling furnace charge to 100 ℃ obtains vanadous oxide.The vanadous oxide that makes is a black, from the XRD analysis result, does not have other assorted peaks and occurs, and product is pure phase V
2O
3, the XRD figure spectrum during with 800 ℃ is the same, and not lower oxyvanadium compound occurs.Record its oxidation than ratio (V
2O
5/ V
2O
3) be 1.208.The grade that obtains vanadous oxide is greater than 99.7%, and the rate of recovery of vanadium is greater than 99.5%.
Embodiment 4: a certain amount of ammonium meta-vanadate is placed industrial intermittent type microwave stove, microwave frequency is 2.45GHz, feed hydrogen, temperature rise rate with 5 ℃～10 ℃/minute under normal pressure is heated to 850 ℃ of insulations 10 minutes, adopt thermocouple temperature measurement, close to cool to the furnace below 100 ℃ behind the microwave source and come out of the stove, obtain vanadous oxide.The vanadous oxide that makes is a black, and from the XRD analysis result, product is pure phase V
2O
3Record its oxidation than ratio (V
2O
5/ V
2O
3) be 1.207.The grade that obtains vanadous oxide is greater than 99.6%, and the rate of recovery of vanadium is greater than 99.6%.
Claims (2)
1. the production method of vanadous oxide; it is characterized in that: will contain amino vanadate and place industrial microwave oven; under reducing atmosphere or under the protection of inert gas, heat; Heating temperature is 600～900 ℃; recovery time is 5～60 minutes, carries out naturally cooling or force cooling under the secluding air condition.
2. the production method of vanadous oxide according to claim 1, it is characterized in that: described microwave frequency value is 2.45GHz or 915MHz.
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| CN 201010137595 CN101817558A (en) | 2010-04-01 | 2010-04-01 | Production method of vanadium trioxide |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102468509A (en) * | 2010-11-16 | 2012-05-23 | 中国海洋石油总公司 | Method for preparing electrolyte for vanadium battery |
| CN102583537A (en) * | 2012-02-27 | 2012-07-18 | 南通汉瑞实业有限公司 | Production process of vanadium trioxide |
| CN104118910A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Method for selectively preparing vanadium oxides and recovering hydroxides through vanadate hydrogen reduction method |
| CN108314083A (en) * | 2018-04-04 | 2018-07-24 | 河钢股份有限公司承德分公司 | A method of by preparing vanadium trioxide containing vanadium solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118765A (en) * | 1994-09-15 | 1996-03-20 | 攀枝花钢铁(集团)公司 | Method for producing V2O3 |
| JP2004168560A (en) * | 2002-11-15 | 2004-06-17 | Sumitomo Electric Ind Ltd | Method for producing vanadium compound and method for producing vanadium electrolyte |
| CN1974408A (en) * | 2006-12-12 | 2007-06-06 | 攀枝花市久欣钛业有限责任公司 | Production process of vanadium tetraoxide |
| CN101028938A (en) * | 2006-03-03 | 2007-09-05 | 攀钢集团攀枝花钢铁研究院 | Method for producing vanadium trioxide |
-
2010
- 2010-04-01 CN CN 201010137595 patent/CN101817558A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118765A (en) * | 1994-09-15 | 1996-03-20 | 攀枝花钢铁(集团)公司 | Method for producing V2O3 |
| JP2004168560A (en) * | 2002-11-15 | 2004-06-17 | Sumitomo Electric Ind Ltd | Method for producing vanadium compound and method for producing vanadium electrolyte |
| CN101028938A (en) * | 2006-03-03 | 2007-09-05 | 攀钢集团攀枝花钢铁研究院 | Method for producing vanadium trioxide |
| CN1974408A (en) * | 2006-12-12 | 2007-06-06 | 攀枝花市久欣钛业有限责任公司 | Production process of vanadium tetraoxide |
Non-Patent Citations (2)
| Title |
|---|
| 《振动利用工程》 20050831 闻邦椿等 振动利用工程 科学出版社 第316页 1-2 , 第一版 1 * |
| 《过程工程学报》 20050430 蔡卫权等 微波技术在冶金中的应用 第228-232页 1-2 第5卷, 第2期 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102468509A (en) * | 2010-11-16 | 2012-05-23 | 中国海洋石油总公司 | Method for preparing electrolyte for vanadium battery |
| CN102468509B (en) * | 2010-11-16 | 2015-05-20 | 中国海洋石油总公司 | Method for preparing electrolyte for vanadium battery |
| CN102583537A (en) * | 2012-02-27 | 2012-07-18 | 南通汉瑞实业有限公司 | Production process of vanadium trioxide |
| CN102583537B (en) * | 2012-02-27 | 2014-03-05 | 南通汉瑞实业有限公司 | Production process of vanadium trioxide |
| CN104118910A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Method for selectively preparing vanadium oxides and recovering hydroxides through vanadate hydrogen reduction method |
| CN108314083A (en) * | 2018-04-04 | 2018-07-24 | 河钢股份有限公司承德分公司 | A method of by preparing vanadium trioxide containing vanadium solution |
| CN108314083B (en) * | 2018-04-04 | 2020-11-03 | 河钢股份有限公司承德分公司 | Method for preparing vanadium trioxide from vanadium-containing solution |
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Open date: 20100901 |