JPH037606B2 - - Google Patents
Info
- Publication number
- JPH037606B2 JPH037606B2 JP5719387A JP5719387A JPH037606B2 JP H037606 B2 JPH037606 B2 JP H037606B2 JP 5719387 A JP5719387 A JP 5719387A JP 5719387 A JP5719387 A JP 5719387A JP H037606 B2 JPH037606 B2 JP H037606B2
- Authority
- JP
- Japan
- Prior art keywords
- molybdate
- moo
- aqueous solution
- containing aqueous
- added
- 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
Links
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 24
- 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 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 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 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 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
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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加圧
水素により二酸化モリブデンを製造する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing molybdenum dioxide from a molybdate-containing aqueous solution using pressurized hydrogen.
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MoO3
＋H2＝MoO2＋H2O、第２段階は、1100℃〜1200
℃でMoO2＋2H2＝Mo＋2H2Oすなわち、金属モ
リブデンを製造する工程で二酸化モリブデン
MoO2は製造される。
Molybdenum dioxide (MoO 2 ) is produced industrially by reducing ammonium paramolybdate or molybdenum oxide with hydrogen, and the reduction is generally carried out in two stages. The first stage is MoO3 at 600℃~800℃
+ H2 = MoO2 + H2O , second stage 1100℃~1200℃
MoO 2 + 2H 2 = Mo + 2H 2 O at °C, that is, molybdenum dioxide is
MoO2 is manufactured.
従来の方法はMoO2の製造は水素雰囲気中で
600℃〜800℃の反応温度で10時間を要する。又加
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
からアルカリ性での還元法が研究課題とされてい
る。
The traditional method is to produce MoO2 in a hydrogen atmosphere.
It takes 10 hours at a reaction temperature of 600°C to 800°C. A method using pressurized hydrogen has also been researched and reported;
Both are on the acidic side and have a low reduction rate from alkaline solutions. From the viewpoint of purification to high purity and corrosion of the reaction equipment, the alkaline reduction method is a research topic.
本発明の方法によれば、モリブデン酸塩含有水
溶液を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、加圧水素と反応させることを特徴とする二酸
化モリブデンの製造方法が提供される。
According to the method of the present invention, hydrazine or ascorbic acid is added to a molybdate-containing aqueous solution, a water-soluble organic solvent that dissolves in water in an arbitrary ratio is added, and the mixture is reacted with pressurized hydrogen. A manufacturing method is provided.
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テン等が挙げられる。
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加圧水素
を反応させて二酸化モリブデンに還元するが、こ
の場合、水素加圧は、30気圧以上、好ましくは50
気圧以上であり、反応温度は230℃以上、好まし
くは250℃〜300℃程度である。 The water-soluble organic solvent used in the present invention may be any solvent as long as it mixes arbitrarily with water and can precipitate molybdenum from an aqueous solution, such as lower alcohols and acetene.
The water-soluble organic solvent can be added before, after, or simultaneously with the addition of hydrazine or ascorbic acid, and its addition precipitates molybdate from the molybdate-containing aqueous solution. In the present invention, such a molybdate is reduced to molybdenum dioxide by reacting pressurized hydrogen in the presence of hydrazine or ascorbic acid. In this case, the hydrogen pressure is 30 atmospheres or more, preferably 50 atmospheres or more.
The reaction temperature is at least 230°C, preferably about 250°C to 300°C.
本発明によると反応温度にエネルギーの消費が
従来の600℃〜800℃が250℃程度の温度で済むこ
と、反応時間も８時間〜10時間要したのが２時間
〜３時間程度で済むこと、したがつて、水素の消
費量等コストの点で大きな効果がある。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 energy consumption for the reaction temperature can be reduced to about 250°C instead of the conventional 600°C to 800°C, and the reaction time can be reduced to about 2 to 3 hours instead of 8 to 10 hours. Therefore, there is a significant effect in terms of hydrogen consumption and costs. Further, the present invention is suitable for producing high-purity molybdenum.
Mo濃度100ｇ／ｌの（NH4）2MoO4溶液250ml
に「ヒドラジン水和物５ml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（500ml）
を添加しモリブデン酸塩を析出させた状態（PH
８）で加圧反応装置に装入し、反応温度250℃、
水素分圧50Kg／cm2、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
強い回折線のみが表れ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
つた。
250 ml of (NH 4 ) 2 MoO 4 solution with Mo concentration 100 g/l
For "when 5 ml of hydrazine hydrate was added and stirred" and "when 5 g of ascorbic acid was added and stirred", methanol was added in a liquid ratio of 1:2 (500 ml).
is added to precipitate molybdate (PH
Step 8): Charge the pressurized reactor and set the reaction temperature to 250°C.
The reaction was carried out under the conditions of hydrogen partial pressure 50 Kg/cm 2 , reaction time 150 minutes, and 700 rpm. The reaction solution was separated into solid and liquid, and the precipitate and filtrate were analyzed. The precipitate was found to be hydrazine water as a result of X-ray diffraction. In both the case of addition of hydrate and the case of addition of ascorbic acid, only extremely strong diffraction lines of MoO 2 appeared, indicating that it was reduced to MoO 2 .
No Mo was detected in the filtrate (PH9.2) either.
All of the Mo in the molybdate-containing aqueous solution is
It became clear that it was completely reduced to MoO 2 .
また本発明により製造された二酸化モリブデン
（MoO2）と工業的に製造された高純度の二酸化
モリブデン（MoO2）と比較した結果、Ｘ線回折
により同定された。折出物の粒度は1μから28μで
8μにピークのある粒度分布を示した。 Further, as a result of comparing molybdenum dioxide (MoO 2 ) produced according to the present invention with industrially produced high-purity molybdenum dioxide (MoO 2 ), it was identified by X-ray diffraction. The particle size of the precipitates ranges from 1μ to 28μ.
It showed a particle size distribution with a peak at 8μ.
比較例 １
還元剤（ヒドラジン水和物又はアスコルビン
酸）を添加しない場合について、Mo濃度100
ｇ／ｌの（NH4）2MoO4溶液250mlにメタノール
を液比１：２（500ml）を添加しモリブデン酸塩を
析出させた状態（PH8.2）で加圧反応装置に装入
し反応温度250℃、水素分圧50Kg／cm2、反応時間
150分、700rpmの条件で反応を行い、反応溶液を
個液分離し析出物とろ液を分析した。析出物につ
いてはＸ線回折の結果、MoO3の回折線の他に
Ａ，Ｓ，Ｔ，Ｍに該当しない回折線を示し、
MoO2には還元されていない事が明らかとなつ
た。またろ液についてはMoは検出されず、モリ
ブデン酸塩含有水溶液中のMoは
（NH4）6MO7O24，4H2Oの形で結晶したものと考
えられる。Comparative Example 1 Mo concentration 100 without adding reducing agent (hydrazine hydrate or ascorbic acid)
Add methanol to 250 ml of g/l (NH 4 ) 2 MoO 4 solution at a liquid ratio of 1:2 (500 ml) to precipitate molybdate (PH 8.2), then charge the mixture into a pressurized reactor and react. Temperature 250℃, hydrogen partial pressure 50Kg/cm 2 , reaction time
The reaction was carried out for 150 minutes at 700 rpm, the reaction solution was separated into individual liquids, and the precipitate and filtrate were analyzed. Regarding the precipitate, the results of X-ray diffraction showed diffraction lines that do not correspond to A, S, T, and M in addition to the diffraction line of MoO 3 ,
It became clear that it was not reduced to MoO 2 . Moreover, Mo was not detected in the filtrate, and it is considered that Mo in the molybdate-containing aqueous solution was crystallized in the form of (NH 4 ) 6 MO 7 O 24 , 4H 2 O.
比較例 ２
低級アルコール又はアセトンを添加しない場合
についてMo濃度100ｇ／ｌの（NH4）2MoO4溶液
250mlに「ヒドラジン水和物５ml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H2O500mlを加え（PH８）
加圧反応装置に操入し反応温度250℃、水素分圧
50Kg／cm2、反応時間150分、700rpmの条件で反応
を行い、反応溶液を個液分離し、析出物とろ液を
分析した、析出物についてはＸ線回折の結果、
「ヒドラジン水和物５ml添加した場合」と「アス
コルビン酸５ｇ添加した場合」いずれも青い粉末
でモリブデンブルー（Mo2O3・3MoO3・6H2O）
が生成したものと考えられ、MoO2の強い回折線
も表れた。Comparative Example 2 (NH 4 ) 2 MoO 4 solution with a Mo concentration of 100 g/l without adding lower alcohol or acetone
Add 500 ml of H 2 O to 250 ml for "When 5 ml of hydrazine hydrate was added and stirred" and "When 5 g of ascorbic acid was added and stirred" (PH 8)
Operated in a pressurized reactor, reaction temperature 250℃, hydrogen partial pressure
The reaction was carried out under the conditions of 50Kg/cm 2 , reaction time 150 minutes, and 700 rpm, the reaction solution was separated into individual liquids, and the precipitate and filtrate were analyzed.
"When adding 5 ml of hydrazine hydrate" and "When adding 5 g of ascorbic acid" Both are blue powder and molybdenum blue (Mo 2 O 3 3MoO 3 6H 2 O)
The strong diffraction lines of MoO 2 also appeared.
モリブデン酸塩含有水溶液中のMoはMoO2と
して30％〜40％が還元された。 30% to 40% of Mo in the molybdate-containing aqueous solution was reduced as MoO2 .
Claims (1)
いて二酸化モリ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、加圧水素と反応
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 using pressurized hydrogen 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 molybdate-containing aqueous solution is reacted with pressurized hydrogen. Method for producing molybdenum dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5719387A JPS63222015A (en) | 1987-03-12 | 1987-03-12 | Production of molybdenum dioxide from molybdate-containing aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5719387A JPS63222015A (en) | 1987-03-12 | 1987-03-12 | Production of molybdenum dioxide from molybdate-containing aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63222015A JPS63222015A (en) | 1988-09-14 |
| JPH037606B2 true JPH037606B2 (en) | 1991-02-04 |
Family
ID=13048649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5719387A Granted JPS63222015A (en) | 1987-03-12 | 1987-03-12 | Production of molybdenum dioxide from molybdate-containing aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63222015A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072469A2 (en) * | 2003-07-22 | 2009-06-24 | H.C. Starck Inc. | Method of making MoO2 powders, products made from MoO2 powders, deposition of MoO2 thin films, and methods of using such materials |
| US7754185B2 (en) | 2004-06-29 | 2010-07-13 | H.C. Starck Inc. | Method of making MoO2 powders, products made from MoO2 powders, deposition of MoO2 thin films, and methods of using such materials |
| CN108585046B (en) * | 2018-04-23 | 2019-10-15 | 西安交通大学 | A kind of high length-diameter ratio molybdenum dioxide nanotube and preparation method thereof |
-
1987
- 1987-03-12 JP JP5719387A patent/JPS63222015A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63222015A (en) | 1988-09-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |