CN102092786A - Method for cleanly preparing vanadium oxides - Google Patents

Method for cleanly preparing vanadium oxides Download PDF

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CN102092786A
CN102092786A CN2009102423989A CN200910242398A CN102092786A CN 102092786 A CN102092786 A CN 102092786A CN 2009102423989 A CN2009102423989 A CN 2009102423989A CN 200910242398 A CN200910242398 A CN 200910242398A CN 102092786 A CN102092786 A CN 102092786A
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vanadate
vanadium
metavanadate
gas
potassium
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CN102092786B (en
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李平
徐红彬
张懿
李佐虎
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Abstract

The invention discloses a method for cleanly preparing vanadium oxides, comprising the following steps of: with vanadate as a raw material and reducible gases as reducing agents, making the vanadate react with the reducible gases at the temperature of 300-1500 DEG C for 0.5-8h to obtain low-valent vanadate and a byproduct of NaOH; cooling and then washing a reaction mixer with water; hydrolyzing the washed product at the temperature of 20-200 DEG C for 0-6h; and filtering the hydrolysate and then drying the hydrolysate at the temperature of 80-300 DEG C for 0-24h to obtain vanadium oxides (V2O5, V2O3 and VO2) and a byproduct of vanadium-containing alkaline solution for cycle use. Meanwhile, the preparation of the vanadium oxides and the discharge of non-polluted products are realized and the problems of the vanadium and high-ammonium contained wastewater and the like in the industrial production method are solved. The vanadium acid and alkali salts comprise metavanadate, ortho-vanadate and pyrovandate which are respectively sodium metavanadate or potassium metavanadate, sodium orthovanadate or potassium orthovanadate and sodium pyrovanadate or potassium pyrovanadate; and the reducing gases include hydrogen gas, natural gas, ammonia gas, coal gas or a mixer of the hydrogen gas, the natural gas, the ammonia gas and the coal gas.

Description

A kind of clean method for preparing of barium oxide
Technical field
The present invention relates to a kind of barium oxide (V 2O 5, V 2O 3, VO 2) the preparation method, the clean method for preparing of gaseous reducing agent low temperature reduction vanadate barium oxide specifically
Background technology
Barium oxide is mainly used in metallurgy, electronics, chemical industry, the petroleum industries such as catalyzer of tinting material, sulfuric acid and the petrochemical complex production usefulness of producing alloy, glass and ceramic industry.
Barium oxide comprises vanadic anhydride (V 2O 5), vanadium trioxide (V 2O 3) and vanadium dioxide (VO 2) etc., different oxide production methods is different.For V 2O 5, mainly contain alkaline process, acid system and chlorinating roasting according to the mineral difference.Alkaline process is that navajoite stone obtains sodium metavanadate through soda roasting, and US4039582 adopts sodium metavanadate solution to obtain ammonium metavanadate behind ammonium chloride or ammonium sulfate precipitation, obtains V after the thermal decomposition 2O 5This method advantage is a good product quality, and shortcoming is to contain the high ammonium waste water of vanadium in the production process to be difficult to solve.The salt method is to carry out oxidizing roasting after navajoite stone and the common salt balling-up to obtain sodium metavanadate, makes V with effect of sulfuric acid again 2O 5Acid system then is the dissolving with hydrochloric acid navajoite sodium metavanadate that gets made of stones, makes V with effect of sulfuric acid again 2O 5The environmental pollution of salt method and acid system ground chlorine and hydrogenchloride is comparatively serious, and difficulty of governance is big.For V 2O 3, CN1052460C has announced can be by reducing agent reduction V such as industrial gas, hydrogen, carbon carbon monoxide alive 2O 5Make with ammonium vanadate; Also can be at 1750 ℃ of lower thermal decomposition V 2O 5Make; US3410652 has announced that can calcine ammonium vanadate under secluding air makes.For VO 2, can be by V 2O 5With V 2O 3, C, CO, SO 2Or the reaction of the reducing agent such as oxalic acid makes, and CN152965 has announced with barium oxide powder art and cationic surfactant and stirred in absolute ethyl alcohol, makes after hydro-thermal.
Summary of the invention
Develop a kind of cleaning preparation technology of barium oxide brand-new, that have commercial viability, prepare respectively V 2O 5, V 2O 3, VO 2, and realize barium oxide preparation and non-pollutant discharge, solve problems such as containing the high ammonium waste water of vanadium in the industrial process.
Basic ideas of the present invention are that the vanadate that adopts the roasting of navajoite crystal soda method to obtain is a raw material, obtain presoma with reducing gas reduction under 300~1500 ℃, main component is tervalent vanadium compound or quaternary vanadium compound, and washing back solid product obtains the alkaline solution that barium oxide and by product contain vanadium after 20~200 ℃ of following hydrolysis, drying.
The present invention includes following steps:
(1) vanadate reduces in reduction furnace, and reduction temperature is 300~1500 ℃, and the recovery time is 0.5~8h, and reduzate cools off at protective atmosphere.
(2) reduzate washs at normal temperatures, and washed product is trivalent or quaternary vanadate, and the washing by product is the alkaline solution that contains a small amount of vanadium.
(3) washed product hydrolysis 0~6h in 20~200 ℃ of water, obtaining hydrolysate after the filtration is the moisture barium oxide of different valence state, by product is the alkaline solution that contains a small amount of vanadium.
(4) by product is circulated to the calcining process use.
(5) moisture barium oxide can obtain different valence state barium oxide (V behind 80~300 ℃ of drying 0~24h 2O 5, V 2O 3, VO 2).
Specific embodiments
Embodiment 1
The reduction of 1000g sodium metavanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 500 ℃, and the recovery time is 5h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, washed product obtains V at 100 ℃ of lower dry 12h at 80 ℃ of lower hydrolysis 3h after hydrolysate filters 2O 5The washing hydrolysising by-product recycles for containing vanadium NaOH solution.
At V 2O 5In the sample, V 2O 5Main content greater than 98.0%, Na content less than 0.5%.
Embodiment 2
The reduction of 1000g sodium metavanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 600 ℃, and the recovery time is 4h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, washed product under nitrogen atmosphere, 120 ℃ of pressurized hydrolysis 3h, obtains VO at 150 ℃ of lower dry 6h after hydrolysate filters 2The washing hydrolysising by-product recycles for containing vanadium NaOH solution.
At VO 2In the sample, VO 2Main content is greater than 98.0%, and Na content is less than 0.5%.
Embodiment 3
The reduction of 1000g sodium metavanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 700 ℃, and the recovery time is 3h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, washed product is under protective atmosphere, and 150 ℃ of lower pressurized hydrolysis 3h obtain V at 150 ℃ of lower dry 6h after hydrolysate filters 2O 3The washing hydrolysising by-product recycles for containing vanadium NaOH solution.
At V 2O 3In the sample, V 2O 3Main content greater than 99.0%, Na content less than 0.5%.
Embodiment 4
The reduction of 1000g sodium metavanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 800 ℃, and the recovery time is 3h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, 80 ℃ of lower hydrolysis 3h of washed product obtain V at 100 ℃ of lower dry 4h after hydrolysate filters 2O 3The washing hydrolysising by-product recycles for containing vanadium NaOH solution.
At V 2O 3In the sample, V 2O 3Main content greater than 99.0%, Na content less than 0.5%.
Embodiment 5
The reduction of 1000g potassium metavanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 600 ℃, and the recovery time is 4h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, be hydrolyzed 3h under 90 ℃ of lower protective atmospheres of washed product, obtain VO at 100 ℃ of lower dry 10h after hydrolysate filters 2The washing hydrolysising by-product recycles for containing vanadium KOH solution.
At VO 2In the sample, VO 2Main content is greater than 98.0%, and K content is less than 0.5%.
Embodiment 6
The reduction of 1000g potassium metavanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 800 ℃, and the recovery time is 2h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, 150 ℃ of lower pressurized hydrolysis 1h of washed product obtain V at 150 ℃ of lower dry 6h after hydrolysate filters 2O 5The washing hydrolysising by-product recycles for containing vanadium KOH solution.
At V 2O 5In the sample, V 2O 5Main content greater than 98.0%, K content less than 0.5%.
Embodiment 7
The reduction of 1000g sodium vanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 1100 ℃, and the recovery time is 2h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, 80 ℃ of lower hydrolysis 3h of washed product obtain V at 150 ℃ of lower dry 6h after hydrolysate filters 2O 5The washing hydrolysising by-product recycles for containing vanadium NaOH solution.
At V 2O 5In the sample, V 2O 5Main content greater than 99.0%, Na content less than 0.5%.
Embodiment 8
The reduction of 1000g sodium vanadate is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 1300 ℃, and the recovery time is 8h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, 80 ℃ of lower hydrolysis 3h of washed product obtain V at 100 ℃ of lower dry 8h after hydrolysate filters 2O 3The washing hydrolysising by-product recycles for containing vanadium NaOH solution.
At V 2O 3In the sample, V 2O 3Main content greater than 99.0%, Na content less than 0.5%.
Embodiment 9
The positive potassium vanadate reduction of 1000g is carried out in box reduction furnace, adopts hydrogen as reducing gas, and reduction temperature is 1500 ℃, and the recovery time is 6h, and hydrogen flowing quantity is 0.6L/min in the reduction process.
Adopt cold water washing after the reduzate cooling, 150 ℃ of lower pressurized hydrolysis 3h of washed product obtain V at 100 ℃ of lower dry 8h after hydrolysate filters 2O 5The washing hydrolysising by-product recycles for containing vanadium KOH solution.
At V 2O 5In the sample, V 2O 5Main content greater than 99.0%, K content less than 0.5%.

Claims (6)

1. the clean method for preparing of a barium oxide comprises the steps:
At a certain temperature, vanadate and reducing gas one are reacted certain hour; After the cooling, with product wash, wash the afterproduct hydrolysed filtrate with water, drying obtains barium oxide (V 2O 5, V 2O 3, VO 2), accessory substance recycles for containing the vanadium aqueous slkali.
2. preparation method according to claim 1 is characterized in that: described vanadic acid alkali salt is metavanadate, positive vanadate and pyrovanadate: sodium metavanadate or potassium metavanadate, sodium vanadate or positive potassium vanadate, sodium pyrovanadate or pyrovanadic acid potassium.
3. preparation method according to claim 1 is characterized in that: described reducing gas is hydrogen, Sweet natural gas, coal gas, ammonia, methane or their mixture.
4. preparation method according to claim 1 is characterized in that: described insulating process is 300~1500 ℃ for the control holding temperature, and soaking time is 0.5~8h.
5. preparation method according to claim 1 is characterized in that: described hydrolytic process is hydrolyzed at 20~200 ℃ for the washing after product, and hydrolysis time is 0~6h.
6. preparation method according to claim 1 is characterized in that: described drying temperature is 80~300 ℃, and be 0~24h time of drying.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104120271A (en) * 2014-06-24 2014-10-29 中国科学院过程工程研究所 Clean production technique of vanadium oxide by vanadium slag carbocholine leaching-hydrogen reduction process
WO2016018165A1 (en) * 2014-07-31 2016-02-04 Instituto Superior Técnico Simplified process for preparing electrolyte for vanadium redox batteries
CN105969984A (en) * 2016-05-16 2016-09-28 武汉理工大学 Preparation method of vanadium trioxide
CN106006735A (en) * 2016-05-16 2016-10-12 武汉理工大学 Method for preparing vanadium trioxide through bone coal vanadium extracting vanadium-rich liquid
CN106629847A (en) * 2017-01-17 2017-05-10 中南大学 Method for preparing vanadium trioxide from sodium-vanadate salt

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3410652A (en) * 1968-01-24 1968-11-12 Union Carbide Corp Production of vanadium trioxide
CN1052460C (en) * 1994-09-15 2000-05-17 攀枝花钢铁(集团)公司 Method for producing V2O3
CN1162330C (en) * 2001-10-08 2004-08-18 中国科学院过程工程研究所 Clean production method of potassium chromate
CN101475217B (en) * 2008-01-04 2011-06-01 中国科学院过程工程研究所 Method for preparing pigment grade chromium hemitrioxide green by using gaseous reducing agent to reduce chromate salt under low temperature

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN104120271A (en) * 2014-06-24 2014-10-29 中国科学院过程工程研究所 Clean production technique of vanadium oxide by vanadium slag carbocholine leaching-hydrogen reduction process
CN104120271B (en) * 2014-06-24 2018-09-25 中国科学院过程工程研究所 A kind of process of vanadium slag carbon alkali leaching hydrogen reduction method clean manufacturing barium oxide
WO2016018165A1 (en) * 2014-07-31 2016-02-04 Instituto Superior Técnico Simplified process for preparing electrolyte for vanadium redox batteries
CN105969984A (en) * 2016-05-16 2016-09-28 武汉理工大学 Preparation method of vanadium trioxide
CN106006735A (en) * 2016-05-16 2016-10-12 武汉理工大学 Method for preparing vanadium trioxide through bone coal vanadium extracting vanadium-rich liquid
CN106629847A (en) * 2017-01-17 2017-05-10 中南大学 Method for preparing vanadium trioxide from sodium-vanadate salt
CN106629847B (en) * 2017-01-17 2021-03-26 中南大学 Method for preparing vanadium trioxide from sodium vanadate

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