JPH0623046B2 - Method for producing molybdenum dioxide from molybdate-containing aqueous solution - Google Patents
Method for producing molybdenum dioxide from molybdate-containing aqueous solutionInfo
- Publication number
- JPH0623046B2 JPH0623046B2 JP63024885A JP2488588A JPH0623046B2 JP H0623046 B2 JPH0623046 B2 JP H0623046B2 JP 63024885 A JP63024885 A JP 63024885A JP 2488588 A JP2488588 A JP 2488588A JP H0623046 B2 JPH0623046 B2 JP H0623046B2
- Authority
- JP
- Japan
- Prior art keywords
- molybdate
- aqueous solution
- containing aqueous
- molybdenum dioxide
- producing molybdenum
- 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.)
- Expired - Lifetime
Links
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims description 14
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims description 12
- 239000007864 aqueous solution Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、モリブデン酸塩含有水溶液から二酸化モリブ
デンを製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing molybdenum dioxide from a molybdate-containing aqueous solution.
二酸化モリブデン（ＭｏＯ2）の製造は、工業的にはパ
ラモリブデン酸アンモニウムや酸化モリブデンを水素で
還元する方法で一般に還元は２段階に行われる。第１段
階は、600℃〜800℃で次の反応が起こる ＭｏＯ３＋Ｈ２＝ＭｏＯ２＋Ｈ２Ｏ 第２段階は1,100℃〜1,200℃で次の反応が起きる ＭｏＯ２＋２Ｈ２Ｏ＝Ｍｏ＋２Ｈ２Ｏ 〔発明が解決しようとする問題点〕 従来の方法でＭｏＯ２の製造は水素雰囲気中で600℃〜8
00℃の反応温度で８時間程度を要する。また、加圧水素
による方法も研究され報告されているが、いずれも酸性
側でアルカリ性溶液からは還元率が低い。高純度への精
製及び反応装置の腐蝕の点等から中性もしくはアルカリ
性での還元法が研究課題とされている。The production of molybdenum dioxide (MoO 2 ) is industrially a method of reducing ammonium paramolybdate or molybdenum oxide with hydrogen, and the reduction is generally performed in two steps. The first stage is the following reaction at 600 ° C. to 800 ° C. MoO 3 + H 2 = MoO 2 + H 2 O The second stage is the following reaction at 1,100 ° C. to 1,200 ° C. MoO 2 + 2H 2 O = Mo + 2H 2 O [Problems to be Solved by the Invention] Production of MoO 2 by a conventional method is carried out in a hydrogen atmosphere at 600 ° C. to 8 ° C.
It takes about 8 hours at a reaction temperature of 00 ° C. Also, methods using pressurized hydrogen have been studied and reported, but all have a low reduction rate from an alkaline solution on the acidic side. From the viewpoints of purification to high purity and corrosion of the reactor, a neutral or alkaline reduction method is a research subject.
本発明の方法によれば、密閉反応容器を用いてモリブデ
ン酸塩含有水溶液にヒドラジン又はアスコルビン酸を加
え、水と任意の割合で溶解する水溶性有機溶媒を添加
し、230℃〜270℃の蒸気圧下で、二酸化モリブデンを製
造する方法で、水素ガスを使用しないことを特徴とす
る。According to the method of the present invention, hydrazine or ascorbic acid is added to a molybdate-containing aqueous solution using a closed reaction vessel, water and a water-soluble organic solvent that dissolves at an arbitrary ratio are added, and steam at 230 ° C. to 270 ° C. A method for producing molybdenum dioxide under pressure, which is characterized in that hydrogen gas is not used.
本発明で用いる水溶性有機溶媒としては、水と任意に混
ざり、水溶液中からモリブデンを沈澱させ得るものであ
ればよく、このようなものとしては、低級アルコールや
アセトン等が挙げられる。The water-soluble organic solvent used in the present invention may be any one that can be arbitrarily mixed with water to precipitate molybdenum from the aqueous solution, and examples of such a solvent include lower alcohol and acetone.
この水溶性有機溶媒は、ヒドラジン又はアスコルビン酸
の添加前、添加後、あるいは同時に添加することがで
き、このものの添加により、モリブデン酸塩含有水溶液
から、モリブデン酸塩が沈澱する。本発明では、このよ
うなモリブデン酸塩をヒドラジン又はアスコルビン酸の
存在下で230℃〜270℃の蒸気圧下で反応させて二酸化モ
リブデンに還元する。This water-soluble organic solvent can be added before, after, or simultaneously with the addition of hydrazine or ascorbic acid, and the addition of this causes the molybdate to precipitate from the molybdate-containing aqueous solution. In the present invention, such a molybdate is reacted in the presence of hydrazine or ascorbic acid under a vapor pressure of 230 ° C to 270 ° C to reduce it to molybdenum dioxide.
本発明によると反応温度にエネルギーの消費が従来の60
0℃〜800℃が、250℃程度の温度ですむこと、反応時間
も８時間程度要したのが、２時間〜３時間ですむこと、
高価な水素ガスを全く使用せず、添加物が還元を行うも
のであるから、経済的にも大きな効果がある。また本発
明は高純度モリブデンの製造に好適である。According to the present invention, the reaction temperature consumes energy of 60% or less.
From 0 ℃ to 800 ℃, a temperature of about 250 ℃ is required, and a reaction time of about 8 hours is required from 2 hours to 3 hours.
Since an expensive hydrogen gas is not used at all and the additive reduces, it has a great economical effect. Further, the present invention is suitable for producing high-purity molybdenum.
Ｍｏ濃度100 ｇ／のモリブデン酸アンモニウム溶液25
0 mlに「ヒドラジン水和物5 mlを添加して撹拌した場
合」と「アスコルビン酸５ｇを添加して撹拌した場合」
についてメタノールを液比１：２（500 ml）を添加しモ
リブデン酸塩を析出させた状態（ｐＨ８）で密閉反応装
置に装入し、反応温度250℃、反応時間150分、700rpmの
条件で反応を行い、反応溶液を固液分離し、析出物とろ
液を分析した結果、析出物についてはＸ線回折の結果、
ヒドラジン水和物添加の場合と、アスコルビン酸添加の
場合、いずれもＭｏＯ２の極めて強い回析線のみが表れ
ＭｏＯ２に還元されていた。ろ液（ｐＨ9.2）について
も双方のＭｏは検出されず、モリブデン酸塩含有水溶液
中のＭｏのすべてがＭｏＯ２に完全に還元されているこ
とが明らかとなった。Ammonium molybdate solution with Mo concentration of 100 g / 25
“When adding 5 ml of hydrazine hydrate and stirring” to 0 ml and “when adding 5 g of ascorbic acid and stirring”
Regarding the above, methanol was added to a liquid ratio of 1: 2 (500 ml) and molybdate was deposited in a closed reactor (pH 8), and the reaction was carried out under the conditions of a reaction temperature of 250 ° C., a reaction time of 150 minutes and 700 rpm. The reaction solution was subjected to solid-liquid separation, and the precipitate and the filtrate were analyzed. As a result, the precipitate was analyzed by X-ray diffraction,
In the case of hydrazine hydrate added, in the case of ascorbic acid added, either only a very strong diffraction lines of MoO 2 has been reduced to appear MoO 2. Neither Mo was detected in the filtrate (pH 9.2) either, which revealed that all of Mo in the molybdate-containing aqueous solution was completely reduced to MoO 2 .
〔比較例〕１ Ｍｏ濃度100 ｇ／のモリブデン酸アンモニウム溶液25
0 mlにメタノールを液比１：２（500 ml）を添加しモリ
ブデン酸塩を析出させた状態で密閉反応装置に装入し、
反応温度250℃、反応時間150 分、700rpmの条件で反応
を行い、反応溶液を固液分離し、析出物とろ液を分析
し、析出物についてはＸ線回折の結果、ＭｏＯ２への還
元は70% となった。Comparative Example 1 Ammonium molybdate solution with Mo concentration of 100 g / 25
Methanol was added to 0 ml in a liquid ratio of 1: 2 (500 ml), and molybdate was deposited in a closed reactor,
The reaction was carried out under the conditions of a reaction temperature of 250 ° C., a reaction time of 150 minutes, and 700 rpm, the reaction solution was subjected to solid-liquid separation, and the precipitate and the filtrate were analyzed. As a result of the X-ray diffraction of the precipitate, reduction to MoO 2 was confirmed. It became 70%.
〔比較例〕２ Ｍｏ濃度100 ｇ／のモリブデン酸アンモニウム溶液25
0 mlにヒドラジン5 mlを添加しＨ２Ｏを液比１：２（50
0 ml）を加えて密閉反応装置に装入し、反応温度250
℃、反応時間150 分、700rpmの条件で反応を行い反応溶
液を固液分離し、析出物とろ液を分析し、析出物につい
てはＸ線回折の結果ＭｏＯ２への還元は31% となった。[Comparative Example] 2 Ammonium molybdate solution with Mo concentration of 100 g / 25
Add 5 ml of hydrazine to 0 ml and add H 2 O at a liquid ratio of 1: 2 (50
(0 ml) and charged into a closed reactor, reaction temperature 250
The reaction solution was subjected to solid-liquid separation under the conditions of ℃, reaction time of 150 minutes and 700 rpm, and the precipitate and the filtrate were analyzed. The result of X-ray diffraction on the precipitate was 31% reduction to MoO 2 . .
Claims (1)
ブデンを製造する場合、モリブデン酸塩含有水溶液にヒ
ドラジン又はアスコルビン酸と、水溶性有機溶媒を添加
し密閉容器を用いて230℃〜270℃で反応させるモリブデ
ン酸塩含有水溶液から二酸化モリブデンの製造法。1. When producing molybdenum dioxide from a molybdate-containing aqueous solution, hydrazine or ascorbic acid and a water-soluble organic solvent are added to the molybdate-containing aqueous solution and the mixture is reacted at 230 ° C. to 270 ° C. in a closed container. A method for producing molybdenum dioxide from an aqueous solution containing molybdate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63024885A JPH0623046B2 (en) | 1988-02-04 | 1988-02-04 | Method for producing molybdenum dioxide from molybdate-containing aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63024885A JPH0623046B2 (en) | 1988-02-04 | 1988-02-04 | Method for producing molybdenum dioxide from molybdate-containing aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01201029A JPH01201029A (en) | 1989-08-14 |
| JPH0623046B2 true JPH0623046B2 (en) | 1994-03-30 |
Family
ID=12150642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63024885A Expired - Lifetime JPH0623046B2 (en) | 1988-02-04 | 1988-02-04 | Method for producing molybdenum dioxide from molybdate-containing aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0623046B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851006B (en) * | 2010-06-08 | 2011-08-31 | 南开大学 | Method for preparing MoS2 microspheres by solvent hot method |
| CN114471442A (en) * | 2021-12-20 | 2022-05-13 | 广东省科学院资源利用与稀土开发研究所 | Nano dye wastewater adsorption material and preparation method thereof |
-
1988
- 1988-02-04 JP JP63024885A patent/JPH0623046B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01201029A (en) | 1989-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3971843A (en) | Process for liquid/liquid extraction of gallium | |
| HU179296B (en) | Process for separaring gallium | |
| JPS6241721A (en) | Method of recovering iron oxide | |
| US4278567A (en) | Process for preparation of copper-iron-aluminum hydrogenation catalyst | |
| US3969478A (en) | Process for separation of tungsten and molybdenum by extraction | |
| ES425528A1 (en) | Method for recovering a liquid-phase oxidation catalyst for preparation of terephthalic acid | |
| CA1132996A (en) | Process for producing naphthoquinone | |
| US4062927A (en) | Process for the preparation of a hydroxylamine salt | |
| US4528175A (en) | Production of chromium (III) compounds | |
| Pregaglia et al. | Catalysis by cobalto-cyano complexes in non-aqueous solvents | |
| US3956474A (en) | Process for producing ammonium metatungstate from ammonium tungstate by digestion in silica | |
| JPH0623046B2 (en) | Method for producing molybdenum dioxide from molybdate-containing aqueous solution | |
| DE68927649T2 (en) | Process for the preparation of 3 ', 4'-anhydrovinblastine | |
| US4376105A (en) | Process for producing nitrous oxide | |
| US3655719A (en) | Amino carbonate adducts and method of making same | |
| US3446574A (en) | Preparation of the rare earth sesquicarbonates | |
| JPH037606B2 (en) | ||
| US3950505A (en) | Preparation of manganous hydroxide | |
| US4438080A (en) | Process for oxidizing thallium (I) to thallium (III) | |
| CA2006963A1 (en) | Precious metal salt solutions and precious metal catalysts | |
| CN117401715A (en) | A method for preparing ammonium metatungstate and ammonium paratungstate from crude sodium tungstate solution | |
| US4769488A (en) | Batch or semicontinuous pseudocumene oxidation and catalyst recovery and recycle | |
| US4876385A (en) | Batch or semicontinuous pseudocumene oxidation and catalyst recovery and recycle | |
| US4008306A (en) | Method of recovering manganese values from a mixture obtained by catalytically oxidizing a paraffin with gaseous oxygen | |
| CN113213537B (en) | Method for separating and preparing vanadium trioxide from mixed solution of vanadium and chromium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |