JP2583064B2 - Method for producing 18-molybdodiphosphate - Google Patents
Method for producing 18-molybdodiphosphateInfo
- Publication number
- JP2583064B2 JP2583064B2 JP62167790A JP16779087A JP2583064B2 JP 2583064 B2 JP2583064 B2 JP 2583064B2 JP 62167790 A JP62167790 A JP 62167790A JP 16779087 A JP16779087 A JP 16779087A JP 2583064 B2 JP2583064 B2 JP 2583064B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- molybdophosphoric
- purity
- reducing agent
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 48
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 description 31
- 235000011007 phosphoric acid Nutrition 0.000 description 22
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 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 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- -1 electrolysis Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
Landscapes
- Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ドーソン（Dawson）構造のヘテロポリ酸と
して知られる18−モリブド二リン酸の効率的製造法に関
するもので、さらに詳しくは、12−モリブドリン酸とリ
ン酸の反応によって18−モリブド二リン酸を製造するに
際し、高純度に、かつ迅速に製造するための改良法に関
するものである。The present invention relates to a method for efficiently producing 18-molybdodiphosphate known as a Dawson-structured heteropolyacid, and more particularly to 12-molybdodiphosphate. The present invention relates to an improved method for producing 18-molybdodiphosphoric acid by reaction between molybdophosphoric acid and phosphoric acid with high purity and promptly.
（従来の技術） 18−モリブド二リン酸は一般式H6P2Mo18O62・nH2O
（ｎは33もしくは37、以後P2Mo18と略記する場合もあ
る）で表されるヘテロポリ酸である。これらは酸触媒と
して、また、酸化触媒あるいは導電体として、多く利用
されている。(Prior art) 18-molybdodiphosphoric acid has the general formula H 6 P 2 Mo 18 O 62 · nH 2 O
(N is 33 or 37, and may be abbreviated as P 2 Mo 18 hereinafter). These are widely used as an acid catalyst, an oxidation catalyst or a conductor.
その製造法は、古くから、モリブデン酸ソーダ等の水
溶液にリン酸と塩酸を加え還流条件で反応させたのち、
NH4CIを用いてアンモニウム塩として結晶を析出させ、
さらに、これを溶解させ、酸性条件で抽出するか、ある
いはイオン交換によってナトリウムを除去する方法であ
った。このため、工程が繁雑であり、ナトリウム除去等
の費用がかかっていた。ナトリウムの存在しない系での
方法としては、12−モリブドリン酸とリン酸から18−モ
リブド二リン酸を製造する方法も知られているが、この
反応は平衡反応であるため時間がかかり、しかも、純度
の低いものしか得られないという欠点があった。The production method has long been used, after adding phosphoric acid and hydrochloric acid to an aqueous solution such as sodium molybdate and reacting under reflux conditions.
Using NH 4 CI to precipitate crystals as ammonium salts,
Further, it is a method of dissolving this and extracting it under acidic conditions or removing sodium by ion exchange. For this reason, the process is complicated and costs such as sodium removal are required. As a method in a system in the absence of sodium, a method of producing 18-molybdodiphosphate from 12-molybdophosphoric acid and phosphoric acid is also known, but this reaction is an equilibrium reaction and takes time, and There was a drawback that only low purity products could be obtained.
（発明が解決しようとする問題点） 本発明は、ナトリウム等の存在しない簡素な系で、し
かも、収率よく高純度の18−モリブド二リン酸を得る方
法を提供することを目的としてなされたものである。(Problems to be Solved by the Invention) An object of the present invention is to provide a method for obtaining a high-purity 18-molybdodiphosphate in a simple system free of sodium or the like and with high yield. Things.
（問題点を解決するための手段） 本発明者らは、ナトリウム等の存在しない系で18−モ
リブド二リン酸を得る方法を鋭意検討した結果、還元剤
の存在下に、12−モリブドリン酸とリン酸を水溶液中で
反応させ、しかも、12−モリブドリン酸を20％重量％以
上の濃度でリン酸と反応させることにより、高収率で18
−モリブド二リン酸が得られることを見出だし、本発明
をなすに至った。(Means for Solving the Problems) The present inventors have intensively studied a method for obtaining 18-molybdophosphoric acid in a system free of sodium or the like, and as a result, in the presence of a reducing agent, 12-molybdophosphoric acid. By reacting phosphoric acid in an aqueous solution and reacting 12-molybdophosphoric acid with phosphoric acid at a concentration of 20% by weight or more, a high yield of 18
-It was found that molybdodiphosphate was obtained, which led to the present invention.
すなわち、本発明は、12−モリブドリン酸とリン酸を
水溶液中で反応させるに際し、12−モリブドリン酸に対
し還元剤を４電子還元相当より少ない範囲で存在させ、
12−モリブドリン酸を20重量％以上の濃度でリン酸と反
応させることを特徴とする18−モリブド二リン酸の製造
法である。That is, in the present invention, when reacting 12-molybdophosphoric acid and phosphoric acid in an aqueous solution, a reducing agent is present in 12-molybdophosphoric acid in a range smaller than that of four-electron reduction,
A method for producing 18-molybdodiphosphoric acid, comprising reacting 12-molybdophosphoric acid with phosphoric acid at a concentration of 20% by weight or more.
還元剤が存在すると、反応速度が増加し、高収率とな
る。このような優れた効果がどのような作用機構に基づ
くか、その理由は明らかではないが、12−モリブドリン
酸とリン酸から18−モリブド二リン酸が生成する平衡反
応で、還元剤は18−モリブド二リン酸の生成を有利にし
ているものと考えられる。対象となる還元剤は12−モリ
ブドリン酸を還元できるものであればよく、ヒドラジ
ン、アスコルビン酸、亜硫酸ソーダ等があげられるが、
電解、水素還元でもよく、これらに限定されるものでは
ない。とくに精製による除去のいらないヒドラジン、電
解、水素による還元が望ましい。使用する還元剤の量
は、12−モリブドリン酸に対し４電子還元相当以上の還
元剤を加えると、還元剤の優れた効果がなくなるだけで
なく、12−モリブドリン酸はリン酸と反応しなくなるた
め、12−モリブドリン酸に対し４電子還元相当より少な
い範囲で使用する。好ましくは18−モリブド二リン酸の
生成と純度を高くする観点から、１電子還元以上４電子
還元相当より少ない範囲で選ばれる。The presence of the reducing agent increases the reaction rate and results in high yield. It is not clear why such an excellent effect is based on the mechanism of action, but it is an equilibrium reaction in which 18-molybdophosphoric acid is formed from 12-molybdophosphoric acid and phosphoric acid, and the reducing agent is 18-molybdophosphoric acid. It is believed that the production of molybdodiphosphate is favored. The reducing agent of interest may be any one that can reduce 12-molybdophosphoric acid, and includes hydrazine, ascorbic acid, sodium sulfite, and the like.
Electrolysis and hydrogen reduction may be used, but the present invention is not limited to these. In particular, reduction by hydrazine, electrolysis, and hydrogen, which do not require removal by purification, is desirable. The amount of reducing agent to be used is such that when a reducing agent equivalent to four-electron reduction or more is added to 12-molybdophosphoric acid, not only the excellent effect of the reducing agent is lost, but also 12-molybdophosphoric acid does not react with phosphoric acid. , 12-Molybdophosphoric acid is used in a range less than the equivalent of four-electron reduction. Preferably, from the viewpoint of increasing the production and purity of 18-molybdodiphosphate, it is selected in a range from one-electron reduction to less than four-electron reduction.
還元剤の添加は、12−モリブドリン酸とリン酸の水溶
液に調整時に加えることもできるし、また、反応時に回
分的に加えることもできる。The reducing agent can be added to the aqueous solution of 12-molybdophosphoric acid and phosphoric acid at the time of preparation, or can be added batchwise during the reaction.
リン酸とは、メタリン酸、ピロリン酸、オルトリン
酸、三リン酸、四リン酸、五酸化リンであり、水中でリ
ン酸イオンを生じるものである。Phosphoric acid is metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, and phosphorus pentoxide, and generates phosphate ions in water.
12−モリブドリン酸とリン酸の比率は広く選択できる
が、12−モリブドリン酸100重量部に対し20〜100重量部
の範囲で行う。好ましくは12−モリブドリン酸300重量
部に対しリン酸100重量部の比率付近が、未反応物が少
なく有利である。Although the ratio of 12-molybdophosphoric acid to phosphoric acid can be selected widely, the reaction is carried out in the range of 20 to 100 parts by weight per 100 parts by weight of 12-molybdophosphoric acid. Preferably, the ratio of about 100 parts by weight of phosphoric acid to 300 parts by weight of 12-molybdophosphoric acid is advantageous because there are few unreacted substances.
また、本発明を実施するには、12−モリブドリン酸の
濃度が水溶液中で20重量％以上で行う必要がある。還元
剤が存在する条件下では、12−モリブドリン酸の濃度が
20重量％未満では、リン酸との反応性が還元剤の存在に
より、むしろ低下する。したがって、水溶液の12−モリ
ブドリン酸の濃度は、20重量％以上、12−モリブドリン
酸の飽和溶解度（室温では約80重量％）以下の範囲内か
ら選ばれる。好ましくは反応速度の大きい飽和溶解度付
近の高濃度で行う。Further, in order to carry out the present invention, it is necessary that the concentration of 12-molybdophosphoric acid be 20% by weight or more in an aqueous solution. Under conditions where a reducing agent is present, the concentration of 12-molybdophosphate is
Below 20% by weight, the reactivity with phosphoric acid is rather reduced due to the presence of the reducing agent. Therefore, the concentration of 12-molybdophosphoric acid in the aqueous solution is selected from the range of not less than 20% by weight and not more than the saturated solubility of 12-molybdophosphoric acid (about 80% by weight at room temperature). Preferably, the reaction is performed at a high concentration near the saturation solubility where the reaction rate is high.
本発明を実施するには、12−モリブドリン酸、リン
酸、水および還元剤を加えた溶液を撹拌しつつ行うこと
ができる。また、12−モリブドリン酸は酸化モリブデン
（VI）とリン酸を水溶液中で加熱、撹拌することで生成
することが知られており、酸化モリブデンとリン酸を反
応させ、12−モリブドリン酸を生成させつつ、12−モリ
ブドリン酸に対し４電子還元相当より少ない範囲の還元
剤を添加することで、本発明を実施することもできる。
反応温度は水溶液の凝固点以上の温度であればよく、加
圧して、100℃以上の温度で反応を行うこともできる
が、好ましくは室温から100℃以下の温度範囲で行う。The present invention can be carried out while stirring a solution containing 12-molybdophosphoric acid, phosphoric acid, water and a reducing agent. Also, it is known that 12-molybdophosphoric acid is produced by heating and stirring molybdenum oxide (VI) and phosphoric acid in an aqueous solution. On the other hand, the present invention can be practiced by adding a reducing agent in a range less than the equivalent of four-electron reduction to 12-molybdophosphoric acid.
The reaction temperature may be any temperature higher than the freezing point of the aqueous solution, and the reaction can be carried out at a temperature of 100 ° C. or higher by applying pressure. However, the reaction is preferably performed in a temperature range from room temperature to 100 ° C. or lower.
反応に要する時間は、反応温度、還元剤の量、溶液濃
度によって異なるが、通常、数時間から数十時間の範囲
で、90％以上の18−モリブド二リン酸が得られる。純度
をさらに高めるため数百時間に及ぶ場合もある。反応に
よって生成した18−モリブド二リン酸は、この純度で使
用が可能な場合、還元水溶液として、そのまま、各種用
途に、例えば、酸触媒として反応に用いることもできる
し、濃縮後、析出させ、固体として用いることもでき
る。酸化状態のものが望ましい場合は、水溶液の状態で
過酸化水素水で容易に酸化することができ、酸化状態の
水溶液あるいは濃縮後、晶析させ、固体として使用する
こともできる。さらに純度の高い18−モリブド二リン酸
とする場合、再結晶することで99％以上の純度のものを
得ることができる。The time required for the reaction varies depending on the reaction temperature, the amount of the reducing agent, and the concentration of the solution. Usually, 90% or more of 18-molybdodiphosphate is obtained in a range of several hours to several tens of hours. It can take hundreds of hours to further increase purity. When 18-molybdodiphosphoric acid produced by the reaction can be used with this purity, it can be used as a reduced aqueous solution as it is for various applications, for example, it can be used as an acid catalyst in the reaction, and after concentration, it is precipitated. It can also be used as a solid. When an oxidized state is desirable, it can be easily oxidized with aqueous hydrogen peroxide in the form of an aqueous solution, and can also be used as a solid by crystallization after oxidized aqueous solution or concentration. When 18-molybdodiphosphoric acid having a higher purity is used, a crystal having a purity of 99% or more can be obtained by recrystallization.
本法によれば、とくに反応に要する時間に制約がない
場合、例えば、12−モリブドリン酸に対し、２電子還元
相当程度の還元剤存在下で60〜100℃で数時間反応後、
さらに、還元剤を加え、４電子還元相当未満となるよう
に調整し、室温で保持することで、純度98％以上の18−
モリブド二リン酸を再結晶の操作なしに得ることも可能
である。According to the present method, when there is no particular restriction on the time required for the reaction, for example, after reacting for 12 hours at 60 to 100 ° C. with 12-molybdophosphoric acid in the presence of a reducing agent equivalent to two-electron reduction,
Further, a reducing agent is added to adjust the amount to less than the equivalent of four-electron reduction, and the mixture is kept at room temperature to obtain 18-purity of 98% or more.
Molybdodiphosphoric acid can be obtained without recrystallization.
（発明の効果） 本法によれば、ナトリウム等が存在しない酸性条件で
反応することができ、直接酸型の18−モリブド二リン酸
を製造することができ、イオン交換等の設備、工程を省
略でき、簡素なプロセスとすることができる。また、生
成する18−モリブド二リン酸の純度も従来法に比べ極め
て高く、通常、そのまま触媒などに用いることもでき
る。さらに高純度の18−モリブド二リン酸とする場合で
も、再結晶等の操作コストを大きく低減できる。(Effects of the Invention) According to the present method, the reaction can be carried out under acidic conditions in which sodium or the like does not exist, 18-molybdodiphosphoric acid in an acid form can be directly produced, and equipment and steps for ion exchange and the like can be reduced. It can be omitted and can be a simple process. Further, the purity of 18-molybdodiphosphoric acid produced is much higher than that of the conventional method, and it can be usually used as it is for a catalyst or the like. Furthermore, even in the case of using 18-molybdodiphosphoric acid of high purity, the operation cost for recrystallization and the like can be greatly reduced.
（実施例および比較例） 実施例１ ガラス製反応器で12−モリブドリン酸（日本無機化学
工業（株）:H3PMo12O40・30H2O）1000g、85％リン酸（H
3PO4）16.25gを水500mlに溶解し、98％抱水ヒドラジン
（和光純薬製）10.82g（２電子還元剤相当）を加え、70
℃で24時間反応後、12−モリブドリン酸の反応率、およ
び18−モリブド二リン酸の純度を測定するため、過酸化
水素水で酸化し、日本電子製FX−200を用い、31P−NMR
スペクトルを測定した。その結果、12−モリブドリン酸
（PMo12と略記する）およびリン酸の反応率は各90％
で、選択的に18−モリブドニリン酸（P2Mo18と略記す
る）が生成し、その純度は、ほぼ90重量％であった。(Examples and Comparative Example) Example 1 glass reactor in 12-molybdophosphate (Nippon Inorganic Color & Chemical Co. (Ltd.): H 3 PMo 12 O 40 · 30H 2 O) 1000g, 85% phosphoric acid (H
3 PO 4) and 16.25g is dissolved in water 500 ml, 98% hydrazine hydrate (Wako Pure Chemical) 10.82 g of (2 corresponding electron reducing agent) was added, 70
℃ after 24 hours reaction, 12 the reaction rate of molybdophosphoric acid and 18-molybdophosphoric for measuring the purity of the diphosphate, oxidized with hydrogen peroxide, using a JEOL FX-200, 31 P-NMR
The spectrum was measured. As a result, 12 (abbreviated as PMo 12) molybdophosphate and reaction rate of the phosphoric acid is the 90%
As a result, 18-molybdonylic acid (abbreviated as P 2 Mo 18 ) was selectively produced, and its purity was approximately 90% by weight.
比較例１ ヒドラジンを添加せず実施例１と同様の操作で反応を
行った。反応後、過酸化水素水で酸化し、31P−NMRから
12−モリブドリン酸、リン酸の反応率、18−モリブド二
リン酸の純度を同様に測定した結果、12−モリブドリン
酸、リン酸の反応率39％、18−モリブド二リン酸純度は
39重量％であった。Comparative Example 1 A reaction was carried out in the same manner as in Example 1 without adding hydrazine. After the reaction, it is oxidized with aqueous hydrogen peroxide, and from 31 P-NMR
As a result of similarly measuring the reaction rate of 12-molybdophosphoric acid and phosphoric acid, and the purity of 18-molybdophosphoric acid, the reaction rate of 12-molybdophosphoric acid and phosphoric acid was 39%, and the purity of 18-molybdodiphosphate was
39% by weight.
比較例２ 比較例１と反応時間をかえた他は、同様の操作で1000
時間反応を行った。反応後、過酸化水素水で酸化し、31
P−NMRにより純度を測定した結果、18−モリブド二リン
酸の純度は62重量％であった。Comparative Example 2 The same operation as in Comparative Example 1 was repeated except that the reaction time was changed to 1000.
A time reaction was performed. After the reaction, it is oxidized with aqueous hydrogen peroxide, 31
As a result of measuring the purity by P-NMR, the purity of 18-molybdodiphosphate was 62% by weight.
実施例２ 実施例１と同様の操作で反応後、さらにヒドラジン9g
添加し、70℃で24時間反応後、室温で２週間放置した。
その後、実施例１と同様に過酸化水素水で酸化し、31P
−NMRを用い18−モリブド二リン酸の純度を測定したと
ころ、98重量％であった。Example 2 After reacting in the same manner as in Example 1, 9 g of hydrazine was further added.
The mixture was added, reacted at 70 ° C. for 24 hours, and left at room temperature for 2 weeks.
After that, it is oxidized with a hydrogen peroxide solution in the same manner as in Example 1, and 31 P
When the purity of 18-molybdodiphosphate was measured by using -NMR, it was 98% by weight.
実施例３〜５、比較例３ ヒドラジンの添加量を変更した以外は、実施例１と同
様の操作で反応を行った。Examples 3 to 5, Comparative Example 3 A reaction was carried out in the same manner as in Example 1, except that the amount of hydrazine added was changed.
31P−NMRから18−モリブド二リン酸（P2Mo18）の純度
を測定し、表１にまとめて示した。The purity of 18-molybdodiphosphate (P 2 Mo 18 ) was measured by 31 P-NMR, and the results are shown in Table 1.
比較例４ ガラス製反応器で12−モリブドリン酸1000g,リン酸1.
65gを水900mlに溶解し、ヒドラジン1.08gを添加し、70
℃で24時間反応を行った。反応後、31P−NMRから12−モ
リブドリン酸はほとんど反応していなかった。Comparative Example 4 1000 g of 12-molybdophosphoric acid, phosphoric acid 1.
Dissolve 65 g in water 900 ml, add hydrazine 1.08 g, 70
The reaction was performed at 24 ° C. for 24 hours. After the reaction, 31 P-NMR showed that 12-molybdophosphoric acid had hardly reacted.
実施例６ 実施例２で得た18−モリブド二リン酸水溶液を過酸化
水素水で酸化後、常圧、40℃でイソブテンの水和反応触
媒として用いたところ、初期反応速度0.543moI/I・ｈで
ｔ−BuOHを生成した。Example 6 The aqueous solution of 18-molybdodiphosphoric acid obtained in Example 2 was oxidized with an aqueous solution of hydrogen peroxide and then used as a catalyst for hydration of isobutene at normal pressure and 40 ° C. The initial reaction rate was 0.543moI / I · h produced t-BuOH.
Claims (1)
反応させるに際し、12−モリブドリン酸に対し還元剤を
４電子還元相当より少ない範囲で存在させ、12−モリブ
ドリン酸を20重量％以上の濃度でリン酸と反応させるこ
とを特徴とする18−モリブド二リン酸の製造法。When reacting 12-molybdophosphoric acid and phosphoric acid in an aqueous solution, a reducing agent is present in a range of less than four-electron reduction with respect to 12-molybdophosphoric acid, and 12-molybdophosphoric acid is added in an amount of 20% by weight or more. A method for producing 18-molybdodiphosphoric acid, characterized by reacting with phosphoric acid at a concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62167790A JP2583064B2 (en) | 1987-07-07 | 1987-07-07 | Method for producing 18-molybdodiphosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62167790A JP2583064B2 (en) | 1987-07-07 | 1987-07-07 | Method for producing 18-molybdodiphosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6414106A JPS6414106A (en) | 1989-01-18 |
| JP2583064B2 true JP2583064B2 (en) | 1997-02-19 |
Family
ID=15856160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62167790A Expired - Lifetime JP2583064B2 (en) | 1987-07-07 | 1987-07-07 | Method for producing 18-molybdodiphosphate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2583064B2 (en) |
-
1987
- 1987-07-07 JP JP62167790A patent/JP2583064B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6414106A (en) | 1989-01-18 |
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