JPS62197317A - Production of vanadium suboxide - Google Patents
Production of vanadium suboxideInfo
- Publication number
- JPS62197317A JPS62197317A JP3975386A JP3975386A JPS62197317A JP S62197317 A JPS62197317 A JP S62197317A JP 3975386 A JP3975386 A JP 3975386A JP 3975386 A JP3975386 A JP 3975386A JP S62197317 A JPS62197317 A JP S62197317A
- Authority
- JP
- Japan
- Prior art keywords
- vanadium
- reaction vessel
- gas
- nh4vo3
- temperature
- 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
Links
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 claims abstract description 12
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 23
- 239000007858 starting material Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims 1
- 229910003206 NH4VO3 Inorganic materials 0.000 abstract description 14
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000006693 Cassia laevigata Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000735631 Senna pendula Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940124513 senna glycoside Drugs 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔利用される技術分野〕
この発明は各種センナに用いられる機能的材料、合金製
造材料、又は触媒に用いられる素材としてのパナジクム
低級酸化物殊にＶｌｉＯ１３又はＶ２Ｏ４を製造する方
法に関する。Detailed Description of the Invention [Technical field to be used] This invention is for producing panazicum lower oxides, especially VliO13 or V2O4, as functional materials used in various types of senna, alloy production materials, or materials used in catalysts. Regarding the method.
従来Ｖ６Ｏ１３’Ｐ Ｖ２Ｏ４を製造する方法としては
ＮＨ４ＶＯ３を加熱熱分解して、ＶｚＯｓを製造し、こ
れＫ フＩＩ シェフ （ＣＨｓＣＨ＝ Ｃ＝ Ｃ）ｈ
） 、ＮＨａ 又に２８０２を別途供給し、還元する
方法が知られているが、工程が２工程になる。The conventional method for producing V2O4 is to thermally decompose NH4VO3 to produce VzOs.
), NHa, and a method of separately supplying 2802 and reducing it is known, but it requires two steps.
またバナジウム酸塩に鉄、ニッケル、コバルトを添加し
、更に還元ガス（水素、硫化水素等）を用いて５５０乃
至６５’Ｏｔ：に加熱減圧してＶ６Ｏ１３を製造してい
ることが特公昭４５−１４４０９号特許公報によって知
られているが、添加金属が目的物中に残り、純度の高い
ものが得られない。It is also known that V6O13 is produced by adding iron, nickel, and cobalt to vanadate salts, and then heating and reducing the pressure to 550 to 65'Ot using reducing gas (hydrogen, hydrogen sulfide, etc.). Although this method is known from Patent Publication No. 14409, the added metal remains in the target product, making it impossible to obtain a product with high purity.
またＶ６Ｏ１３を製造する方法として、Ｖ ｚ Ｏｓと
Ｖ２Ｏ５を当量混合し、封管中加熱して得られる方法も
知られているが、それぞれＶ２Ｏ５、Ｖ２Ｏ３を先ず製
造し、後Ｖ、Ｏ，とＶ２Ｏ５とを反応させ、る２工程に
なるだけでなく固相反応であるため、反応にも時間を要
する。Another known method for producing V6O13 is to mix equivalent amounts of VzOs and V2O5 and heat them in a sealed tube. Not only is it a two-step reaction in which the
この発明は従来ＮＨ４ＶＯ，を焼成するときに熱分解し
て、 ＶｚＯｓを製造するときに発生するＮＨａガスに
着目し、このＮＨａを利用し、ＮＨ４ＶＯａを焼成冷却
する一連の過程において、他から還元ガスを供給するこ
となく、工程を簡素化し、廉価に目的物を製造するため
の方法を市場に提供するためである。This invention focuses on the NHa gas generated when VzOs is produced by thermally decomposing it when NH4VO is conventionally fired, and utilizes this NHa to generate reducing gas from other sources in a series of firing and cooling processes of NH4VOa. This is to provide the market with a method for simplifying the process and manufacturing the desired product at a low cost without having to supply it.
この発明は出発物質としてメタバナジン酸アンモニア
（ＮＨ４ＶＯ５） （Ｑ単味乃至前記ＮＨ４ＶＯ３と五
酸化バナジウム（ＶｚＯｓ）との混合物を不活性耐熱反
応容器に外気が侵入できないように装入し、温度上昇速
度０．５乃至３０℃／ｍで３８０乃至Ｔ５０′ｃまで加
熱し、前記出発物質中のＮＨ４ＶＯ３が熱分解して発生
するアンモニアガス（ＮＨｓガス）によって、前記反応
容器中の空気を反応容器外に追い出し、かつ前記容器中
の圧力を外気より高く約３ａｔｍ以内に保持しながら３
０分乃至３時間その状態を保持し、反応容器中の前記Ｎ
Ｈａガスによって、ＮＨ４ＶＯ３より熱分解して生成し
たもの、乃至は出発物質中に含まれる製造目的物よりも
高級のバナジウム酸化物を還元し、後これを外気と接触
しないようにしながら冷却することを特徴とするバナジ
ウム低級酸化物の製法とすることによって問題点を解決
した。This invention uses ammonia metavanadate as a starting material.
(NH4VO5) (Q alone or the mixture of NH4VO3 and vanadium pentoxide (VzOs) was charged into an inert heat-resistant reaction container so that outside air could not enter, and the temperature was increased to 380°C at a temperature increase rate of 0.5 to 30°C/m. The air in the reaction vessel is expelled from the reaction vessel by the ammonia gas (NHs gas) generated by thermal decomposition of NH4VO3 in the starting material, and the pressure in the vessel is reduced to outside air. 3 while holding within about 3 atm higher.
This state is maintained for 0 minutes to 3 hours, and the N in the reaction vessel is
By using Ha gas, the vanadium oxide produced by thermal decomposition of NH4VO3 or the vanadium oxide higher than the production target contained in the starting material is reduced, and then it is cooled while avoiding contact with the outside air. The problem was solved by using a unique manufacturing method for vanadium lower oxide.
叙上の方法を更に具体的に説明すれば、例えば内壁面が
磁器製品で内張り、又は加熱炉の中に磁器製などの反応
容器、若（は全体が磁器製のロータリーキルンなどの中
に所定量の出発物質（原材料） トＬ、 テＮＨ４ＶＯ
３又に２１５ ％以内Ｖ２Ｏ５全混合したものを装入し
、これらの反応容器に外気が侵入しないようにし、反応
容器中の温度上昇速度が前述の０．５乃至３Ｑ’Ｃ／ｍ
の範囲内で加熱し、前記反応容器中の温度が３８０乃至
７５０ ’ＣＫなるまで加熱する。To explain the above method more specifically, for example, the inner wall surface is lined with a porcelain product, or a reaction vessel made of porcelain is placed in a heating furnace, or a predetermined amount is placed in a rotary kiln made entirely of porcelain. Starting materials (raw materials) for L, NH4VO
A total mixture of V2O5 of 215% or less is charged in three prongs, and outside air is prevented from entering these reaction vessels, and the temperature rise rate in the reaction vessels is kept within the range of 0.5 to 3Q'C/m as mentioned above.
The temperature in the reaction vessel is 380 to 750 CK.
この加熱方法は内部燃焼以外ならば特に限定はなく、電
気炉、高周波、電磁波、外部燃焼式など適宜の方法で行
う。This heating method is not particularly limited as long as it is other than internal combustion, and may be performed using an appropriate method such as an electric furnace, high frequency, electromagnetic waves, or external combustion.
このようＫして、反応温度に達したならばその状態を３
０分乃至３時間程度保持される。K in this way, and when the reaction temperature is reached, the state is changed to 3
It is maintained for about 0 minutes to 3 hours.
前記の加熱開始より反応温度を保持する間に反応容器中
のＮＨ４ＶＯｓは熱分解を起し、ＮＨａガスを発生し、
反応容器中のガス圧は上昇するが、調圧弁によって、反
応容器中のガス圧を約３ａｔｍ以下に保持し、余分のガ
スを系外に放出し、−緒に反応容器中の空気も外部に追
い出す。While maintaining the reaction temperature from the start of heating, NH4VOs in the reaction vessel undergoes thermal decomposition, generating NHa gas,
The gas pressure in the reaction vessel increases, but the pressure regulating valve maintains the gas pressure in the reaction vessel below approximately 3 atm, releases excess gas to the outside of the system, and simultaneously releases the air in the reaction vessel to the outside. kick out
このような状態において、反応容器中でＮＨ４０Ｖａ、
より熱分解したＶ６Ｏ１３又はＶ２０’４よりも高級の
バナジウム酸化物例えばＶ ２０ ｓなどは先のＮＨ３
カスによって還元し、前記の製造目的物たるＶ６Ｏ１３
又はＶ２Ｏ４となる。Under such conditions, NH40Va,
Vanadium oxides higher than thermally decomposed V6O13 or V20'4, such as V 20 s, are
V6O13, which is the target product of the above production, is reduced by the residue.
Or it becomes V2O4.
その後反応容器を外気が侵入しないようにしながら冷却
し、冷却後目的物たる前記バナジウム低級酸化物を反応
容器より取り出す。Thereafter, the reaction vessel is cooled while preventing outside air from entering, and after cooling, the objective lower vanadium oxide is taken out from the reaction vessel.
前述の反応容器冷却時に外部より今年活性ガスを吹き込
んで冷却しても、また不活性ガスが充満している別個の
容器中で前記の還元して製造されたバナジウム低級酸化
物を冷却し、反応容器を次のバッチに用い、熱エネルギ
ーを有効に利用するようにしても、この発明の方法とし
ては同一である。Even if an active gas is blown into the reaction vessel from the outside to cool it, the vanadium lower oxide produced by the reduction is cooled in a separate vessel filled with an inert gas, and the reaction continues. Even if the container is used for the next batch and the thermal energy is utilized effectively, the method of the present invention remains the same.
このようＫこの発明の方法においては、不活性により、
かつ内部圧力を前記の範囲とすることによって、何ら外
部から還元ガスを供給することな造コストを低減できる
。In this way, in the method of this invention, due to inertness,
Moreover, by setting the internal pressure within the above range, manufacturing costs can be reduced without supplying any reducing gas from the outside.
Ａ、 ＶｓＯｌｇを製造する場合
実験例１゜
環状炉中に直径？５，１ｍ、長さ５０ｃｌＬの磁器製ス
リーブよりなる反応容器を横置し、この中に出発物質（
原材１１’ｒ ） タルＮＨ４ＶＯ３’ｔ ２００９
人し、両端を閉止して、前記反応容器を軸線周りに回転
させながら、環状炉中の温度を上昇させ、前記反応容器
中の温度上昇速度１．８で７ｍとし、反応温度４４０ピ
まで加熱し、後反応温度を３時間保持した。A. When producing VsOlg Experimental example 1゜Diameter in annular furnace? A reaction vessel made of a porcelain sleeve with a length of 5.1 m and 50 clL was placed horizontally, and the starting material (
Raw material 11'r) Tal NH4VO3't 2009
Then, with both ends closed, the temperature in the annular furnace was increased while rotating the reaction vessel around the axis, and the temperature in the reaction vessel was increased to 7 m at a temperature increase rate of 1.8, and heated to a reaction temperature of 440 psi. The post-reaction temperature was maintained for 3 hours.
後室温まで冷却して製品を反応容器よりとり出した。After cooling to room temperature, the product was taken out from the reaction vessel.
前記の加熱開始後、冷却完了までの全過程において、反
応容器中に空気が入らないよう忙した。During the entire process from the start of heating to the completion of cooling, care was taken to prevent air from entering the reaction vessel.
また反応容器中の圧力が丁度３ａｔｍ以上になったとき
は逆上調圧弁を押し開いて、内部発生ガスを放出させた
。而してＶｓＯ□３を得た。Further, when the pressure in the reaction vessel reached exactly 3 atm or more, the reverse pressure regulating valve was pushed open to release the internally generated gas. Thus, VsO□3 was obtained.
実験例２゜
実験例１．と同じ設備を用い、出発物質として重量比テ
ＮＨ４ＶＯ３ヲ９０ ｍ 、Ｖ２Ｏ５ヲ１０ 郡全体ト
Ｌ。Experimental example 2゜Experimental example 1. Using the same equipment as the starting materials, the weight ratios were 90 m of NH4VO3 and 10 m of V2O5.
て合計５００ｙの原材料を用い、温度上昇速度２．０℃
／馴とし、反応温度４７０℃、反応温度保持時間３時間
とし、その他は実験例１と同様の方法とし、Ｖ６Ｏ１３
を得た。Using a total of 500y of raw materials, the temperature rise rate was 2.0℃.
/ acclimatized, reaction temperature was 470°C, reaction temperature holding time was 3 hours, other methods were the same as in Experimental Example 1, V6O13
I got it.
Ｂ、 Ｖ２Ｏ４を製造する場合
実験例６゜
実験例１．と同一の設備を用い、出発物質としてＮＨ４
ＶＯ３’ｌ ６００ ｆ！ ！！ ’ＪＥ Ｌ、温度上
昇速度２３１／馴、反応温度７００ｔとし、その他実験
例１゜と同様の方法とし、Ｖ２Ｏ４を得た。B. When producing V2O4 Experimental example 6゜Experimental example 1. using the same equipment as NH4 as the starting material.
VO3'l 600f! ! ! V2O4 was obtained by using the same method as in Experimental Example 1, except that the temperature rise rate was 231/cm2, the reaction temperature was 700 t, and the reaction temperature was 700 t.
実験例４゜
容量１００ｋｇ用の実験用ロータリーキルンを用い、Ｎ
Ｈ４ＶＯａを５０ｑ、入れ、温度上昇速度２５．６”Ｃ
／ ｍ、反応温度６３０℃とし、他は実験例１．と同様
としＶ２Ｏ４を得た。Experimental Example 4 Using an experimental rotary kiln with a capacity of 100 kg, N
Add 50q of H4VOa, temperature rise rate 25.6”C
/ m, reaction temperature was 630°C, and other conditions were as in Experimental Example 1. V2O4 was obtained in the same manner as above.
Ｃ０比較実験
実験例５゜
実験例１．と同一の設備を用いＮＨ４ＶＯ３を６００１
、温度上昇速度ｉ 、Ｑ ’Ｃ／ ｗとし、反応温度３
５０″Ｃとし、他は実験例１、と同一の方法を実施した
ところ、製品はＶａｎｓ ｓの外、Ｖ２Ｏ３、及びその
他のバナジウム酸化物を含有したものであった。C0 Comparative Experiment Experimental Example 5゜Experimental Example 1. NH4VO3 using the same equipment as 6001
, temperature increase rate i, Q'C/w, reaction temperature 3
When the temperature was 50''C and the same method as in Experimental Example 1 was carried out, the product contained Vans S, V2O3, and other vanadium oxides.
実験例６゜
出発物質としてＶ２Ｏ５のみを４００ｙ、温度上昇速度
２．０℃／Ｗ、反応温度４５０″Ｃ１その他、実験例１
．と同一の方法を実施したところ、全く反応はなく Ｖ
ｚＯｓそのま〜であった。Experimental Example 6゜400y using only V2O5 as the starting material, temperature increase rate 2.0℃/W, reaction temperature 450''C1, etc. Experimental Example 1
．． When the same method as V was carried out, there was no reaction at all.
zOs was just like that.
実験例Ｚ
実験例１．と同一の設備を用い、出発物質としてＮＨ４
ＶＯ３をｓ ｏ ｏ ｙ、温度上昇速Ｒ１０，４ｒ／ｓ
ｕｓ。Experimental example Z Experimental example 1. using the same equipment as NH4 as the starting material.
VO3 so o y, temperature rise rate R10, 4r/s
us.
反応温度５３０℃として、他は実験例１、と同一の方法
により、製品を得たところＶ２Ｏ４以外のバナジウム酸
化物例えばＶ２Ｏ４が混在した。When a product was obtained by the same method as in Experimental Example 1 except that the reaction temperature was 530°C, vanadium oxides other than V2O4, such as V2O4, were mixed.
実験例８゜
実験例１．と同一の設備を用い、出発物質としてＮＨ４
ＶＯａを３００ｙ、温度上昇速度３２℃／ Ｕｌ＋ 。Experimental example 8゜Experimental example 1. using the same equipment as NH4 as the starting material.
VOa is 300y, temperature rise rate is 32℃/Ul+.
反応温度１６０℃とし、その他は実験例１．と同一の方
法により製品を得たところ、還元が進み過ぎ一部にＶ２
Ｏ３が発生し、Ｖ２Ｏ４と混在した。The reaction temperature was 160°C, and the other conditions were as in Experimental Example 1. When the product was obtained using the same method as above, the reduction progressed too much and some parts showed V2.
O3 was generated and mixed with V2O4.
叙上の各実験例を一括表にすれば次に示す通りである。The following table shows the experimental examples described above.
− 前記光に示す実験例より次のことが指摘できる。 − The following points can be pointed out from the experimental examples shown in the above-mentioned light.
ｖａｏｔｓを製造するとき、
反応温度が３８０″Ｃ以下では還元が十分に進まずｓ
ＶｚＯｓが残留し、５００″Ｃ以上では還元が進みすぎ
、Ｖ２Ｏ４、Ｖ２Ｏ３ができ易くなる。When producing vaots, if the reaction temperature is below 380"C, reduction will not proceed sufficiently.
VzOs remains, and at temperatures above 500″C, reduction progresses too much and V2O4 and V2O3 are easily formed.
また反応容器中の圧力がｉ ａｔｍ以下では外気、特に
酸素を吸い込み酸化され易く、かつ１ａｔｍ以下で処理
するには気密装置や減圧ポンプを必要とし、方法が面倒
である。他方３ａｔｍ以上では安全面からも、反応容器
を耐圧性にしなければならずその方法を実施の為の設備
に特殊のものを必要とし、製品コストを押し上げるが、
この方法においては、特別な減圧ポンプも、耐圧容器も
必要とせずに実施できる。Furthermore, if the pressure in the reaction vessel is less than 1 atm, outside air, especially oxygen, is easily sucked in and oxidized, and processing at 1 atm or less requires an airtight device or a pressure reducing pump, making the method cumbersome. On the other hand, if the pressure is higher than 3 atm, the reaction vessel must be made pressure resistant from a safety standpoint, and special equipment is required to carry out the method, which increases product cost.
This method can be carried out without the need for special vacuum pumps or pressure vessels.
また温度上昇速度を０，５′ｃ／シ乃至７″”Ｃ／ ｍ
ｉｘ トしたために、ＮＨ４ＶＯ３の熱分解で発生する
ＮＨ，ガスによって、反応容器中の空気の追い出しと、
その後のＮＨ３ガスは反応温度に既に達したＶ６Ｏ１３
よりも高級のバナジウム酸化物との還元反応に有効に利
用されるが（実験例１．２．参照）、温度上昇速度が前
述の範囲よりも遅いときは反応容器中の温度が反応温度
に達する前に発生したＮＨａガスによる圧力が上昇して
、このＮｌｈガスが反応容器乃至は系外に放出され、発
生したＮＨｓガスが還元反応に充分利用されない。他方
温度上昇速度が７で／翔よりも速いと反応がＶ２Ｏ４ま
で進み、Ｖｉｓｔａが得られない。In addition, the temperature increase rate is set from 0.5'c/cm to 7''C/m.
ix, the air in the reaction vessel is expelled by the NH gas generated by the thermal decomposition of NH4VO3,
The subsequent NH3 gas is V6O13 which has already reached the reaction temperature.
(See Experimental Example 1.2.) However, when the rate of temperature rise is slower than the above range, the temperature in the reaction vessel reaches the reaction temperature. The pressure due to the previously generated NHa gas increases, and this Nlh gas is released from the reaction vessel or outside the system, and the generated NHs gas is not sufficiently utilized for the reduction reaction. On the other hand, if the temperature rise rate is faster than 7/sho, the reaction will proceed to V2O4 and Vista will not be obtained.
Ｖ２Ｏ４を製造する場合
反応温度が５８０℃以下では還元が十分に進まず、７５
０℃以上では還元が進み過ぎ、Ｖ２Ｏ３が一部に生成さ
れる。When producing V2O4, if the reaction temperature is below 580°C, the reduction will not proceed sufficiently, and the
At temperatures above 0°C, reduction proceeds too much and V2O3 is partially generated.
また温度上昇速度が１５乃至３０″Ｃ／ｍの＠みよりも
遅いと反応容器内のＮＨａガスの分圧が低く温度の高い
Ｖ２Ｏ４を得ることができず、また、この仏反上昇範囲
よりも速いとＭもガスの発生が激し鉋ぎＶ２Ｏ３まで一
部還元が進行し、やはり純度の高℃ｖ２０４が得られな
い。Furthermore, if the temperature rise rate is slower than 15 to 30"C/m, the partial pressure of NHa gas in the reaction vessel will be low and it will not be possible to obtain high temperature V2O4. If it is too fast, M will also generate a lot of gas, and the reduction will proceed partially to V2O3, making it impossible to obtain V204 with high purity.
その他ＶｓＯ１ａ 、Ｖ２Ｏ４の製法とも反応時間が３
Ｃ分以下では、充分な還元反応が得られないし、３時間
以上では、反応が進み過ぎたり、或は進ま九〜・ように
しても、加熱時間が長すぎ不経済である。Other VsO1a and V2O4 production methods require a reaction time of 3
If the heating time is less than C minutes, a sufficient reduction reaction cannot be obtained, and if the heating time is longer than 3 hours, the reaction may proceed too much, or even if heated, the heating time is too long and uneconomical.
また出発物質中にＮＨａ ＶＯｓの外、ｖ２ｏ、が１５
％以内であれば、光分ＮＨ４ＶＯ３から発生するＮＨａ
ガスによって、添加したＶ２Ｏ５も還元できるが、Ｖ２
Ｏ１Ｓｔ のみでは、加熱してもＮＨａガスは発生し
ない。実験例６．かもも明かなようＫ 、 Ｖ２Ｏ５の
混合比が大きくなると還元反応が充分に起らない。Also, in addition to NHa VOs, v2o is present in the starting material at 15
If it is within %, the NHa generated from the light NH4VO3
Added V2O5 can also be reduced by gas, but V2
With O1St alone, NHa gas is not generated even when heated. Experimental example 6. As is obvious, when the mixing ratio of K and V2O5 increases, the reduction reaction does not occur sufficiently.
前記実験例１．と６．により生成されたものをＸ＠を回
折した図を第１図及び牙２図に示した。Ａ Ｓ ＴＭカ
ード１９−１３９８と一致していることが判る。Said Experimental Example 1. and 6. Figures 1 and 2 show the diffraction diagrams of X@ generated by . It can be seen that it matches ASTM card 19-1398.
１ 図面はこの発明に係るものであり１，１−１図
は災、 験例１．のＸ線回折図、矛２図は実験例６．
のＸ巌回ｌ 折回である。1 The drawings are related to this invention, and Figure 1, 1-1 is a disaster.Example 1. The X-ray diffraction diagram and Figure 2 are from Experimental Example 6.
This is the
Claims (1)
４ＶＯ＿３）の単味乃至前記ＮＨ＿４ＶＯ＿３と五酸化
バナジウム（Ｖ＿２Ｏ＿５）との混合物を不活性耐熱反
応容器に外気が侵入できないように装入し、温度上昇速
度０．５乃至３０℃／ｍｉｎで３８０℃乃至７５０℃ま
で加熱し、前記出発物質中のＮＨ＿４ＶＯ＿３が熱分解
して発生するアンモニアガス（ＮＨ＿３ガス）によつて
前記反応容器中の空気を反応容器外に追い出し、かつ前
記容器中の圧力を外気より高く約３ａｔｍ以内に保持し
ながら３０分乃至３時間その状態を保持し、反応容器中
の前記ＮＨ＿３ガスによつて、ＮＨ＿４ＶＯ＿３より熱
分解して生成したもの、乃至は出発物質中に含まれる製
造目的物よりも高級のバナジウム酸化物を還元し、後こ
れを外気と接触しないようにしながら冷却することを特
徴とするバナジウム低級酸化物の製法。 ２）前記出発物質としてほゞ１００％メタバナジン酸ア
ンモニウムを用いることを特徴とする特許請求の範囲第
１項記載のバナジウム低級酸化物の製法。 ３）前記出発物質として、重量比でＮＨ＿４ＶＯ＿３に
対し、１５％以内の範囲でＶ＿２Ｏ＿５が混合されたも
のを用いる方法であることを特徴とする特許請求の範囲
第１項記載のバナジウム低級酸化物の製法４）前記温度
上昇速度は０．５乃至７℃／ｍｉｎであり、前記加熱温
度は３８０乃至５００℃として、目的物たるバナジウム
低級酸化物としてＶ＿６Ｏ＿１＿３を製造することを特
徴とする特許請求の範囲第１項記載のバナジウム低級酸
化物の製法。 ５）前記温度上昇速度は１５乃至３０℃／ｍｉｎ、前記
反応温度は５８０乃至７５０℃として目的物たるバナジ
ウム低級酸化物としてＶ＿２Ｏ＿４を製造することを特
徴とする特許請求の範囲第１項記載のバナジウム低級酸
化物の製法。 ６）不活性耐熱反応容器としては磁器製容器を用いるこ
とを特徴とする特許請求の範囲第項記載のバナジウム低
級酸化物の製法。[Claims] 1) Ammonia metavanadate (NH_
4VO_3) or a mixture of NH_4VO_3 and vanadium pentoxide (V_2O_5) were charged into an inert heat-resistant reaction vessel so that outside air could not enter, and the temperature was raised from 380°C to 380°C at a temperature increase rate of 0.5 to 30°C/min. It is heated to 750°C, and the air in the reaction vessel is expelled from the reaction vessel by ammonia gas (NH_3 gas) generated by thermal decomposition of NH_4VO_3 in the starting material, and the pressure in the vessel is lowered from outside air. The product is thermally decomposed from NH_4VO_3 by the NH_3 gas in the reaction vessel, or the production purpose contained in the starting materials. A method for producing a lower vanadium oxide, which is characterized by reducing a vanadium oxide higher than that of a vanadium oxide, and then cooling the vanadium oxide while avoiding contact with the outside air. 2) The method for producing a lower vanadium oxide according to claim 1, characterized in that substantially 100% ammonium metavanadate is used as the starting material. 3) The method uses, as the starting material, a mixture of V_2O_5 to NH_4VO_3 in a weight ratio within 15% of the vanadium lower oxide according to claim 1. Production method 4) The temperature increase rate is 0.5 to 7°C/min, and the heating temperature is 380 to 500°C to produce V_6O_1_3 as the target vanadium lower oxide. A method for producing a vanadium lower oxide according to item 1. 5) Vanadium according to claim 1, wherein the temperature increase rate is 15 to 30°C/min, and the reaction temperature is 580 to 750°C to produce V_2O_4 as the target vanadium lower oxide. Manufacturing method of lower oxides. 6) A method for producing a vanadium lower oxide according to claim 1, wherein a porcelain container is used as the inert heat-resistant reaction container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61039753A JPH0742114B2 (en) | 1986-02-25 | 1986-02-25 | Vanadium lower oxide manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61039753A JPH0742114B2 (en) | 1986-02-25 | 1986-02-25 | Vanadium lower oxide manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62197317A true JPS62197317A (en) | 1987-09-01 |
| JPH0742114B2 JPH0742114B2 (en) | 1995-05-10 |
Family
ID=12561710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61039753A Expired - Lifetime JPH0742114B2 (en) | 1986-02-25 | 1986-02-25 | Vanadium lower oxide manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742114B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2726545A1 (en) * | 1994-11-09 | 1996-05-10 | Peintures Jefco | VANADIUM DIOXIDE MICROPARTICLES, PROCESS FOR OBTAINING SUCH MICROPARTICLES AND THEIR USE, IN PARTICULAR FOR SURFACE COATINGS |
| US6042805A (en) * | 1994-11-29 | 2000-03-28 | Danionics A/S | Method for synthesizing an essentially V2 O5 -free vanadium oxide |
| KR100436709B1 (en) * | 2001-03-28 | 2004-06-22 | 삼성에스디아이 주식회사 | Process for preparing spherical nanosize vanadium oxide particle |
| CN103420421A (en) * | 2013-07-29 | 2013-12-04 | 大连博融新材料有限公司 | Production method of vanadium tetraoxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51109297A (en) * | 1975-02-21 | 1976-09-28 | Toraibahaa Kemishe Beruke Ag | |
| JPS5240919A (en) * | 1975-09-26 | 1977-03-30 | Matsushita Electric Ind Co Ltd | Chrominance signal record reproducing system |
-
1986
- 1986-02-25 JP JP61039753A patent/JPH0742114B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51109297A (en) * | 1975-02-21 | 1976-09-28 | Toraibahaa Kemishe Beruke Ag | |
| JPS5240919A (en) * | 1975-09-26 | 1977-03-30 | Matsushita Electric Ind Co Ltd | Chrominance signal record reproducing system |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2726545A1 (en) * | 1994-11-09 | 1996-05-10 | Peintures Jefco | VANADIUM DIOXIDE MICROPARTICLES, PROCESS FOR OBTAINING SUCH MICROPARTICLES AND THEIR USE, IN PARTICULAR FOR SURFACE COATINGS |
| WO1996015068A1 (en) * | 1994-11-09 | 1996-05-23 | Les Peintures Jefco | Vanadium dioxide microparticles, method for preparing same, and use thereof, in particular for surface coating |
| US6042805A (en) * | 1994-11-29 | 2000-03-28 | Danionics A/S | Method for synthesizing an essentially V2 O5 -free vanadium oxide |
| KR100436709B1 (en) * | 2001-03-28 | 2004-06-22 | 삼성에스디아이 주식회사 | Process for preparing spherical nanosize vanadium oxide particle |
| CN103420421A (en) * | 2013-07-29 | 2013-12-04 | 大连博融新材料有限公司 | Production method of vanadium tetraoxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0742114B2 (en) | 1995-05-10 |
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