JPH02289428A - New molybdic acid solution - Google Patents
New molybdic acid solutionInfo
- Publication number
- JPH02289428A JPH02289428A JP10858889A JP10858889A JPH02289428A JP H02289428 A JPH02289428 A JP H02289428A JP 10858889 A JP10858889 A JP 10858889A JP 10858889 A JP10858889 A JP 10858889A JP H02289428 A JPH02289428 A JP H02289428A
- Authority
- JP
- Japan
- Prior art keywords
- molybdic acid
- acid solution
- soln
- present
- solution
- 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
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 title claims abstract description 70
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 abstract description 17
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 abstract description 13
- 229940010552 ammonium molybdate Drugs 0.000 abstract description 13
- 235000018660 ammonium molybdate Nutrition 0.000 abstract description 13
- 239000011609 ammonium molybdate Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003729 cation exchange resin Substances 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 3
- 238000007747 plating Methods 0.000 abstract description 3
- -1 ammonium ions Chemical class 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 229920005990 polystyrene resin Polymers 0.000 abstract description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 67
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010420 shell particle 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
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規なモリブデン酸溶液に関し、各種触媒、顔
′Ｐ；１、染料、セラミックス、メツキ材料等に有用な
モリブデン酸を提供することを１的とするものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel molybdic acid solution, and aims to provide molybdic acid useful for various catalysts, face 1, dyes, ceramics, plating materials, etc. This is the first objective.
（従来の技１＃）
三酸化モリブデンは、通常モリブデン酸アンモニウムを
焼成、熱分解することにより製造される。(Conventional Technique 1#) Molybdenum trioxide is usually produced by calcining and thermally decomposing ammonium molybdate.
この三酸化モリブデンは触媒として最もよく使用される
が、触媒用担体にこれを保持させるような場合には、湿
式法、即ちモリブデン酸アンモニウムを一旦溶液とし、
触媒用担体に浸漬した後、乾燥させてモリブデン酸アン
モニウムを析出さゼ、更にこれを熱処理して三酸化モリ
ブデンとする方法が一般的に行われている。This molybdenum trioxide is most often used as a catalyst, but when holding it in a catalyst carrier, a wet method is used, that is, once ammonium molybdate is made into a solution,
A commonly used method is to immerse the catalyst carrier in a catalyst carrier, then dry it to precipitate ammonium molybdate, which is then heat-treated to form molybdenum trioxide.
しかしこの方法によれば、モリブデン酸アンモニウムが
結晶質であるために、乾燥、析出時にこれがモリブデン
酸アンモニウム特有の形態で担体に晶析するため、熱処
理後に生成する三酸化モリブデン粉本もこの結晶形を引
き継いだ形骸粒子となり、以て均一な触媒が得られない
という間趙がある。However, according to this method, since ammonium molybdate is crystalline, it crystallizes on the carrier in a form peculiar to ammonium molybdate during drying and precipitation, so the molybdenum trioxide powder produced after heat treatment also has this crystal form. However, it is said that the catalyst becomes a mere shell particle that has taken over the process, making it impossible to obtain a uniform catalyst.
従って、触媒制御が厳密な分野に於いては、この方法に
より触媒担体に三酸化モリブデンを保持させることは極
めて困龍である。Therefore, in fields where catalyst control is strict, it is extremely difficult to retain molybdenum trioxide on a catalyst carrier using this method.
更に、モリブデン酸アンモニウムを使用することで、熱
処理に際しては刺激性のアンモニアガスが多量に発生し
、作業環境上も好適であるとはいえなかった。Furthermore, the use of ammonium molybdate generates a large amount of irritating ammonia gas during heat treatment, which is not suitable for the working environment.
一方、モリブデン酸アンモニウム以外の二酸化モリブデ
ン用原料として、オルトモリブデン酸（ＨｅＭｏ０４及
びＨ，、Ｍｏｂ、−ｕ２ｏ）が知られているが、これら
のものもモリブデン酸アンモニウムと同様に結晶質であ
るばかりでなく、溶解度が極めて低いことより、高濃度
の溶液で利用する場合には不適であった。On the other hand, orthomolybdic acid (HeMo04 and H, Mob, -u2o) is known as a raw material for molybdenum dioxide other than ammonium molybdate, but these are also crystalline like ammonium molybdate. Because of its extremely low solubility, it was unsuitable for use in highly concentrated solutions.
このような現状に於いて、三酸化モリブデン用原料、触
媒製造川原Ｈ１また高濃度のモリブデン酸が要望される
ような分野に於いて利用できる優れたモリブデン原料の
出現が望まれているのが現状である。Under these circumstances, there is a desire for the emergence of an excellent molybdenum raw material that can be used in fields where molybdenum trioxide raw materials, catalyst production Kawahara H1, and high concentration molybdic acid are required. It is.
（発明が解決しようとする課題）
本発明者らはこれらの実状に鑑み、モリブデン成分のみ
を含有し、且つ高濃度の成分組成を有するモリブデン酸
の溶液を１）るべく、各種モリブデン酸原料について鋭
意検討を重ねた結果、本発明に到達したものである。(Problems to be Solved by the Invention) In view of these actual circumstances, the present inventors have investigated various molybdic acid raw materials in order to 1) create a solution of molybdic acid containing only a molybdenum component and having a highly concentrated component composition. As a result of extensive research, the present invention was arrived at.
（ａｌＤを解決するための手段）
即ち、本発明は９０°Ｃで２時間の熱処理条件下に於い
て、三酸化モリブデンを生成することを特徴とする新規
なモリブデン酸溶液に関する。(Means for solving alD) That is, the present invention relates to a novel molybdic acid solution that is characterized in that it produces molybdenum trioxide under heat treatment conditions at 90° C. for 2 hours.
（作 用） 以下、本発明を更に詳細に説明する。(for production) The present invention will be explained in more detail below.
本発明のモリブデン酸溶液は、モリブデン酸成分のみを
含有する新規な物質である。The molybdic acid solution of the present invention is a novel substance containing only molybdic acid components.
従来、モリブデン酸成分のみを含有する可溶性物質とし
ては、一般にＡルトモリブデンＮ！（ＨＪａ０４及び■
１．！Ｍ００４・ト０）が知られており、それぞれ結晶
質の固体である。Conventionally, as a soluble substance containing only molybdic acid component, A-rutomolybdenum N! (HJa04 and ■
1. ! M004 and M00) are known, and each is a crystalline solid.
また、それらの水に対する溶解度は、２５°Ｃにおいて
、！Ｉｏｎ、、とじて各々０．１９及び０．２７！ｉｆ
１％であり、前述の様に所１ｉＴｌ難溶性物質である。Also, their solubility in water at 25°C is ! Ion,, respectively 0.19 and 0.27! if
1%, and as mentioned above, it is a poorly soluble substance.
υＣっで、これらを二酸化モリブデン原料の溶液として
使用することは、工業的に非常に困難であり、実際に於
いても利用されていない。It is industrially very difficult to use these as solutions of molybdenum dioxide raw materials, and they are not used in practice.
本発明者らは、イオン交換法によるモリブデン酸溶液の
製造について種々検討を重ねた結果、モリブデン酸アン
モニウム等のモリブデン酸塩の溶液を、強酸型の陽イオ
ン交換樹脂に接触し、溶液中のアンモニウムイオン等の
カチオンをプロトンに交換することにより、高濃度のモ
リブデン酸成分を含有するモリブデン酸溶液が得られる
ことを見い出した。As a result of various studies on the production of molybdic acid solutions by the ion exchange method, the present inventors have found that by contacting a solution of a molybdate salt such as ammonium molybdate with a strong acid type cation exchange resin, the ammonium in the solution is It has been discovered that a molybdic acid solution containing a high concentration of molybdic acid components can be obtained by exchanging cations such as ions with protons.
更に、このようにして得られたモリブデン酸溶液は、例
えばこれを３５℃で乾燥すると非晶質のモリブデン酸を
生成すること、またこれを９０°Ｃで２時間の熱処理す
ると三酸化モリブデンを生成するという特徴をイＩする
。Furthermore, the molybdic acid solution obtained in this way produces amorphous molybdic acid when it is dried at 35°C, and molybdenum trioxide is produced when it is heat-treated at 90°C for 2 hours. I like the characteristic of doing.
このような低温で三酸化モリブデンを生成することは、
従来モリブデン酸アンモニウムからの三酸化モリブデン
の生成が２００９Ｃ以上であったことと比較して、大い
に異なる点である。Producing molybdenum trioxide at such low temperatures is
This is very different from the conventional production of molybdenum trioxide from ammonium molybdate, which was 2009C or higher.
尚、本発明のモリブデン酸溶液がらの三酸化モリブデン
の生成に於ける条件は、温度と時間との相間関係にあり
、例えば８０°Ｃでは４時間以上、１００℃では０．５
時間以上の熱処理条件で二酸化モリブデンが生成する。The conditions for the production of molybdenum trioxide from the molybdic acid solution of the present invention are related to temperature and time, for example, 4 hours or more at 80°C and 0.5 hours at 100°C.
Molybdenum dioxide is generated under heat treatment conditions that last for more than 30 minutes.
この二つの特徴は、従来より知られているモリブデン酸
には全く見られなかったものであり、本発明のモリブデ
ン酸溶液が新規なものであることを示すものである。These two characteristics were not found at all in conventionally known molybdic acids, and indicate that the molybdic acid solution of the present invention is novel.
本発明のモリブデン酸溶液が、＋ｎｒ故この様な特徴を
示すのかは、未だ充分には解明されていないが、本発明
者らは凡そ以下のように推定している。Although it has not yet been fully elucidated why the molybdic acid solution of the present invention exhibits such characteristics due to +nr, the present inventors roughly estimate as follows.
即ち、本発明のモリブデン酸溶液は、モリブデン原子及
び酸素原子が水溶液中で多数縮合したポリモリブデン酸
多核鈷体イオンを形成しているものと推定される。That is, it is presumed that the molybdic acid solution of the present invention forms a polymolybdate polynuclear ion in which a large number of molybdenum atoms and oxygen atoms are condensed in an aqueous solution.
本発明のモリブデン酸溶液を低温で脱水した場合、晶析
現象を起こすことなく１１１ｉ濃度のモリブデン酸溶液
となり、この場合に徐々にその粘性が増加する。When the molybdic acid solution of the present invention is dehydrated at low temperature, it becomes a molybdic acid solution with a concentration of 111i without causing any crystallization phenomenon, and in this case, its viscosity gradually increases.
濃縮濃度に特に上限はなく、濃縮を進めるに従って溶液
はゾル状の形態を示す。There is no particular upper limit to the concentrated concentration, and as the concentration progresses, the solution takes on a sol-like form.
而して本発明のモリブデン酸？８液が、９０’Ｃで２時
間の熱処理条件下に於いて、三酸化モリブデンを生成す
るという理由は、高度に縮合したモリブデン酸の多核錯
体イオンが熱的に不安定なため、加熱によりさらに縮合
が進み、最終的に三酸化モリブデンを生成するためと考
えられる。So what about the molybdic acid of the present invention? The reason why Molybdenum trioxide is produced in Liquid 8 under heat treatment conditions at 90'C for 2 hours is because the polynuclear complex ions of highly condensed molybdic acid are thermally unstable. This is thought to be because condensation progresses and molybdenum trioxide is finally produced.
本発明のモリブデン酸溶液は、例えば以下の方法によっ
て製造することができる。The molybdic acid solution of the present invention can be produced, for example, by the following method.
モリブデン酸原料としては、バラモリブデン酸アンモニ
ウム、オルトモリブデン酸ナトリウム、オルトモリブデ
ン酸カリウム等のモリブデン酸塩が使用できる。As the molybdic acid raw material, molybdate salts such as ammonium rosemolybdate, sodium orthomolybdate, and potassium orthomolybdate can be used.
本発明では先ずこれらの原料を水に溶解し溶液とするが
、その濃度は、飽和溶解度以下であればよい。In the present invention, these raw materials are first dissolved in water to form a solution, but the concentration may be below the saturation solubility.
次いで、これを予め再生してプロトン型にしておいた強
酸型陽イオン交換１１詣に接触させる。Next, this is brought into contact with a strong acid type cation exchanger 11 which has been previously regenerated into a proton type.
強Ｗ！望陽イオン交換樹脂は、スルホン酸基を有する架
橋ポリスチレン系の樹脂を使用し、例えばその種類とし
て夕゛イヤイ４７５ＫＩＢ（三菱化成■製商品名）、八
ｍｂ＠ｒｌｉｔ＠ＩＲ−１２０（Ｖｌ−ム・アンド・ハ
づ社製商品名）、Ｄ。Strong W! The desired cation exchange resin uses a cross-linked polystyrene resin having a sulfonic acid group, and its types include, for example, Yuyai 475KIB (trade name manufactured by Mitsubishi Chemical Corporation), 8mb@rlit@IR-120 (Vl-M)・Product name manufactured by And Hazu Co., Ltd.), D.
ｖｅｘ ５０Ｍ（９”つ・プミ６１）社製商品名）等が
挙げられる。vex 50M (product name manufactured by 9'' Pumi 61), etc.
また、このイオン交換樹脂との接触方法には特段限定は
なく、種々の方法があるが、通常工業的に利用されてい
るカラム方式が最も好適である。Further, there is no particular limitation on the method of contacting with the ion exchange resin, and there are various methods, but a column method, which is usually used industrially, is most suitable.
更に、その場合に空間速度などの各１！１条件は、原料
モリブデン酸塩の陽イオンがプロトンに充分に交換され
る範囲内であればよい。Furthermore, in that case, each 1:1 condition such as space velocity may be within a range where the cations of the raw molybdate are sufficiently exchanged with protons.
交換処理時の温度に関しては、生成した本発明のモリブ
デン酸溶液から二酸化モリブデンの生成を防止するため
、５０℃以下で行うことが望ましい。Regarding the temperature during the exchange treatment, it is desirable to perform the exchange treatment at a temperature of 50° C. or lower in order to prevent the formation of molybdenum dioxide from the generated molybdic acid solution of the present invention.
この様にして得ることがでさる本発明のモリブデン酸溶
液は、その成分として不純物を殆ど含まない純粋なモリ
ブデン酸溶液である。The molybdic acid solution of the present invention that can be obtained in this manner is a pure molybdic acid solution containing almost no impurities as its components.
また１本発明のモリブデン酸溶液は、その用途に合わせ
て濃縮することができる。Furthermore, the molybdic acid solution of the present invention can be concentrated depending on its use.
この場合に濃縮方法としては、減圧下、低温で水分を除
去する方法を採用することが望ましい。In this case, as the concentration method, it is desirable to employ a method of removing water under reduced pressure and at low temperature.
また、５０℃以下の温度で本発明のモリブデン酸溶液の
乾燥を行えば、水可溶性の非晶質モリブデン酸粉末を得
ることができ、この粉末を再度水に溶解させれば、任意
の濃度のモリブデン酸溶液を調製することも可能となる
。Furthermore, if the molybdic acid solution of the present invention is dried at a temperature of 50°C or lower, water-soluble amorphous molybdic acid powder can be obtained, and if this powder is redissolved in water, an arbitrary concentration can be obtained. It also becomes possible to prepare molybdic acid solutions.
（発明の効果）
本発明のモリブデン酸溶液の特徴とその効果を列挙する
と以下の通りである。(Effects of the Invention) The characteristics and effects of the molybdic acid solution of the present invention are listed below.
第一に、本発明のモリブデン酸溶液は、約９０°Ｃとい
う比較的低温で二酸化モリブデンを生成することである
。First, the molybdic acid solution of the present invention produces molybdenum dioxide at relatively low temperatures of about 90°C.
従来のモリブデン酸アンモニウムの熱分解法による二酸
化モリブデンの製造では、少なくともモリブデン酸アン
モニウムを２００℃以上の高温で焼成しなければならな
かったが、本発明のモリブデン酸溶液を使用すれば、容
易に三酸化モリブデンをｔ２＞ることかでき、工業ヒ有
益であるぽかりでなく、アンモニア等の分解ガスを発生
することもないことより作業環境上でも好適である。In the conventional production of molybdenum dioxide using the thermal decomposition method of ammonium molybdate, at least ammonium molybdate had to be calcined at a high temperature of 200°C or higher. Molybdenum oxide can be removed by t2>, which is advantageous for industrial use, and does not generate decomposed gases such as ammonia, which is suitable for the working environment.
第二に、本発明のモリブデン酸溶液は、例えばこれを３
５°Ｃで乾燥するとＸ線回折的に非晶質のモリブデン酸
を生成し、この性質より触媒用担体に本発明のモリブデ
ン酸を保持させるような場合には、均一な組成の触媒を
得ることができ、従って触媒制御が厳密な分野に於いて
は、本発明のモリブデン酸溶液は触媒用二酸化モリブデ
ン原料として有益である。Secondly, the molybdic acid solution of the present invention can be prepared by e.g.
When dried at 5°C, amorphous molybdic acid is produced by X-ray diffraction, and based on this property, when the molybdic acid of the present invention is retained in a catalyst carrier, a catalyst with a uniform composition can be obtained. Therefore, in fields where catalyst control is strict, the molybdic acid solution of the present invention is useful as a raw material for molybdenum dioxide for catalysts.
また、本発明のモリブデン酸溶液は、非晶質のモリブデ
ン酸のコーティングＦＩＩ％を得ることを目的とするよ
うな場合、本発明品を各種の基材に塗布することができ
、均−且つ摩擦係数の低い非常に滑りのよい膜が得られ
、各種基材の表面改質に使用することができる。In addition, the molybdic acid solution of the present invention can be applied to various base materials evenly and frictionally when the purpose is to obtain a coating FII% of amorphous molybdic acid. A very slippery film with a low coefficient can be obtained and can be used for surface modification of various substrates.
従って、従来では不可能であったフィルム等の基材にも
容易にコーティングが可能となる。Therefore, it becomes possible to easily coat base materials such as films, which was previously impossible.
第三に、本発明のモリブデン酸溶液は、非常に高濃度の
溶液まで調製が可能である点である。Thirdly, the molybdic acid solution of the present invention can be prepared up to a very high concentration.
本発明のモリブデン酸の濃縮液は、そのＭｏｂ、濃度が
高くなるほど粘稠な液体となり、濃度が約５０！ｉｈ［
％となっても粘稠なゾル状の溶液としてその安定性を保
持している。The concentrated solution of molybdic acid of the present invention becomes a viscous liquid as the Mob concentration increases, and the concentration is about 50! ih[
%, it maintains its stability as a viscous sol-like solution.
これは難溶性のオルトモリブデン酸と格段に異なる性質
であり、更に通常三酸化モリブデン原料として使用され
ているバラモリブデン酸アンモニウムの溶解度（Ｎｏ、
３として３１重量％（２５℃））を邊かに土建るもので
ある。This property is significantly different from that of poorly soluble orthomolybdic acid, and the solubility (No.
3, 31% by weight (at 25°C)) is placed in the vicinity.
従うて、本発明のモリブデン酸溶液は、高濃度のモリブ
デン酸が所望される分野に於いては非常に有益である。Therefore, the molybdic acid solution of the present invention is very useful in fields where high concentrations of molybdic acid are desired.
例えば、本発明のモリブデン酸溶液を触媒の担体に保持
させる場合に於いては、高濃度でのモリブデン酸の保持
が容易となる。For example, when the molybdic acid solution of the present invention is retained on a catalyst carrier, molybdic acid can be easily retained at a high concentration.
以上の様な優れたａ能を有する本発明の新規なモリブデ
ン酸溶液は、二酸化モリブデン原料等に有用なものであ
り、各種の触媒、顔料、染料、セラミックス、メツキ材
料等多くの分野に幅広い用途を有するものである。The novel molybdic acid solution of the present invention, which has excellent a-ability as described above, is useful as a raw material for molybdenum dioxide, and has a wide range of applications in many fields such as various catalysts, pigments, dyes, ceramics, and plating materials. It has the following.
（実施例）
以下に本発明の実施例を掲げて更に説明を行なうが１本
発明はこれらに限定されるものではない。(Example) The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.
また実施例に於いて、％は特に断らない限り全て！ｉ量
％を表す。Also, in the examples, all percentages are shown unless otherwise specified! Represents i amount%.
実施例１
バラモリブデン酸アンモニウム１０００部を水７１５３
部に溶解させ、Ｗｏｏ、濃度として１０．０％の溶液を
調製した。Example 1 1000 parts of ammonium rosemolybdate was added to 7153 parts of water.
A solution with a concentration of 10.0% was prepared.
この溶液のＰＨは５．４であった。The pH of this solution was 5.4.
この溶液を予め塩酸により再生しておいた９！ｌ酸型陽
イオン交換樹脂（υ−ム・アン１・ハース社製、商品名
アンハゝ−ライ）［Ｒ−１２０Ｂ）の５００ｍ１を充填
したカラムに、上方より流速４２ｍ１／ｗｉｎ（空間速
度０．０８４ｍ１ｎ−’に対応）で通過させてイオン交
換を行なった。This solution was previously regenerated with hydrochloric acid9! A column filled with 500 ml of a l-acid type cation exchange resin (manufactured by υ-Mean Haas Co., Ltd., trade name Anha-Rye) [R-120B] was charged from above at a flow rate of 42 m1/win (space velocity 0. 084m1n-') to perform ion exchange.
尚、カラム通通液の液温は２０℃で一定とし、ｐＨは０
．８〜１．０の範囲内で一定であった。The temperature of the liquid flowing through the column was kept constant at 20°C, and the pH was 0.
．． It was constant within the range of 8 to 1.0.
このようにして供給開始後、通過液のＰＨが上昇し始め
るまでの通過液１５４０部が本発明のモリブデン酸溶液
として得られた。In this manner, 1540 parts of the permeate was obtained as the molybdic acid solution of the present invention after the start of supply until the pH of the permeate began to rise.
この本発明のモリブデン酸溶液の分析を行った結果、）
ｌｏｏ、として９．２％を含有する溶液であり、残留ア
ンモニア濃度は、１．ｌｐｐｍであった。As a result of analyzing this molybdic acid solution of the present invention,
This is a solution containing 9.2% as LOOO, and the residual ammonia concentration is 1. It was lppm.
上述の操作によって得られるた本発明のモリブデン酸溶
液を、次いで３５℃で通風乾燥し、粉末を調製してこれ
をＸ線回折の測定に供した。The molybdic acid solution of the present invention obtained by the above operation was then dried with ventilation at 35° C. to prepare a powder, which was subjected to X-ray diffraction measurements.
尚、Ｘ線回折の測定は、測定装置として−ＩＵす製ＲＡ
Ｄ−１ａ型を使用し、Ｃｕ管球を用いて３０にν、２０
−＾の条件で行った・
また、比較のためにオルトモリブデン酸の粉末を同様に
Ｘ線回折の測定に供した。In addition, for the measurement of X-ray diffraction, the measuring device is RA made by IU.
Using D-1a type, ν to 30, 20 using Cu tube.
The test was carried out under the following conditions: For comparison, orthomolybdic acid powder was similarly subjected to X-ray diffraction measurements.
これらの結果を第１図及び第２図に示した。These results are shown in FIGS. 1 and 2.
第１図及び第２図の結果から明らかなように、本発明の
モリブデン酸溶液を低温乾燥しで得られる粉末品は非晶
質の物質である。As is clear from the results shown in FIGS. 1 and 2, the powder product obtained by drying the molybdic acid solution of the present invention at low temperature is an amorphous substance.
これに対してオルトモリブデン酸粉末は結晶質であり、
本発明のような非晶質のモリブデン酸とは明確に区別で
きる。On the other hand, orthomolybdic acid powder is crystalline;
It can be clearly distinguished from amorphous molybdic acid as used in the present invention.
また別に、本発明のモリブデン酸溶液を還流器を備えた
容器内で、攪拌を行ないながら９０℃で２時間加熱処理
を行ない、白色の沈殿を得た。Separately, the molybdic acid solution of the present invention was heated at 90° C. for 2 hours with stirring in a container equipped with a reflux device to obtain a white precipitate.
これを濾別後乾燥し、得られた粉末のＸ線回折の測定を
行なった。This was filtered and dried, and the resulting powder was subjected to X-ray diffraction measurements.
Ｘ線回折結果を第３図に示した。The X-ray diffraction results are shown in FIG.
この結果より明らかなように、本発明のモリブデン酸溶
液を９０℃で２時間熱処理したものは、二酸化モリブデ
ンのＸ線回折ピークを示している。As is clear from the results, the molybdic acid solution of the present invention heat-treated at 90° C. for 2 hours shows an X-ray diffraction peak of molybdenum dioxide.
これに対して、前記のオルトモリブデン酸粉末を同様に
９０℃で２時間熱処理に供してＸ線回折の測定を行った
が、このものは第２図に示したＸ線回折ピークと同一で
あり、三酸化モリブデンとはならなかった。In contrast, the above-mentioned orthomolybdic acid powder was similarly heat-treated at 90°C for 2 hours and subjected to X-ray diffraction measurements, which showed the same X-ray diffraction peak as shown in Figure 2. , it did not become molybdenum trioxide.
これらの結果から明らかな様に、本発明のモリブデン＃
溶液は非晶質モリブデン酸の溶液であり、約９０℃程度
の低温で容易に二酸化モリブデンを生成するという、従
来のものにない特徴を有する新規なモリブデン酸溶液で
あることが判る。As is clear from these results, the molybdenum #
The solution is a solution of amorphous molybdic acid, and it can be seen that it is a novel molybdic acid solution that has a characteristic not found in conventional molybdic acid solutions: it easily generates molybdenum dioxide at a low temperature of about 90°C.
尚、この本発明のモリブデン酸溶液を３５℃で通風乾燥
して得た粉末の分析を行った結果、Ｍａｎ、濃度は８１
．５％であり、これをＷｏｏ、濃度４０％となるように
水に溶解したが、このものは容易に水に溶解し、本発明
モリブデン酸溶液を再調製することができた。Incidentally, as a result of analyzing the powder obtained by drying the molybdic acid solution of the present invention with ventilation at 35°C, the Man concentration was 81.
．． This was dissolved in water to give a concentration of 40%, but it was easily dissolved in water and the molybdic acid solution of the present invention could be prepared again.
実施例２
実施例１で得た本発明のモリブデン酸溶液を用いて、脱
水濃縮操作を行い、本発明モリブデン酸溶液の高濃度品
を得た。Example 2 Using the molybdic acid solution of the present invention obtained in Example 1, a dehydration and concentration operation was performed to obtain a highly concentrated molybdic acid solution of the present invention.
濃縮方法は、本発明のモリブデン酸溶液をロータリーエ
バポレーターに移し、アスピレータ−による減圧下、３
５℃で加温を行いながら脱水濃縮を行なった。The concentration method involves transferring the molybdic acid solution of the present invention to a rotary evaporator, and under reduced pressure using an aspirator.
Dehydration and concentration were performed while heating at 5°C.
濃縮操作の途中で溶液の採取を行ない、 Ｍｏｏ、濃度
と液温２０℃における溶液粘度を測定した。A solution was sampled during the concentration operation, and the Moo, concentration, and solution viscosity at a liquid temperature of 20°C were measured.
また、これの１ｉ１！間経過後の溶液状態（液安定性）
を観察した。Also, this 1i1! Solution state after a period of time (liquid stability)
observed.
この結果を第１表に示した。The results are shown in Table 1.
第１表の結果から明らかなように、本発明のモリブデン
酸溶液は、高濃度まで流動性ある溶液とすることが可能
であり、しかも高濃度となっても溶液の安定性に優れる
ものである。As is clear from the results in Table 1, the molybdic acid solution of the present invention can be made into a fluid solution up to a high concentration, and has excellent solution stability even at a high concentration. .
また、この本発明のモリブデン酸溶液の濃縮品Ｎｏ、
４を、還流器を備えた容器内で攪拌を行ないながら９０
６Ｃで２時間加熱処理を行ない、白色の沈殿を得た。In addition, concentrated product No. of the molybdic acid solution of the present invention,
4 while stirring in a container equipped with a reflux device.
A white precipitate was obtained by heat treatment at 6C for 2 hours.
これを濾別後乾燥し、得られた粉末のＸ線回折の測定を
行なった。This was filtered and dried, and the resulting powder was subjected to X-ray diffraction measurements.
Ｘ線回折の測定結果は、第３図に示したＸａ回折ピーク
と同一であり、その生成物は三酸化モリブデンであり、
本発明のモリブデン酸溶液はこのように濃縮を行っても
、何らその特性に変化は生じない。The measurement results of X-ray diffraction are the same as the Xa diffraction peak shown in Figure 3, and the product is molybdenum trioxide,
Even when the molybdic acid solution of the present invention is concentrated in this manner, its properties do not change at all.
第１図は、実施例１で得た本発明のモリブデン酸溶液を
３５℃で乾燥した粉末のＸ線回折図である。
第２図は、オル）（リブデン酸粉末のＸ線回折図である
。
第３図は、実施例１で得た本発明のモリブデン酸溶液を
９０℃で２時間熱処理して得た沈殿物の乾燥粉末のＸ線
回折図である。
特許出願人 多木化学株式会社
２０ｏ。
鳴
ＰＳFIG. 1 is an X-ray diffraction diagram of a powder obtained by drying the molybdic acid solution of the present invention obtained in Example 1 at 35°C. Fig. 2 is an X-ray diffraction pattern of ol)(lybdic acid powder). Fig. 3 is an X-ray diffraction diagram of the precipitate obtained by heat-treating the molybdic acid solution of the present invention obtained in Example 1 at 90°C for 2 hours. It is an X-ray diffraction diagram of dry powder. Patent applicant: Taki Chemical Co., Ltd. 20o. Naru PS
Claims (1)
デンを生成することを特徴とする新規なモリブデン酸溶
液。A novel molybdic acid solution characterized in that it produces molybdenum trioxide under heat treatment conditions at 90°C for 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1108588A JP2766990B2 (en) | 1989-04-26 | 1989-04-26 | New molybdic acid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1108588A JP2766990B2 (en) | 1989-04-26 | 1989-04-26 | New molybdic acid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02289428A true JPH02289428A (en) | 1990-11-29 |
| JP2766990B2 JP2766990B2 (en) | 1998-06-18 |
Family
ID=14488614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1108588A Expired - Fee Related JP2766990B2 (en) | 1989-04-26 | 1989-04-26 | New molybdic acid solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2766990B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002134108A (en) * | 2000-10-24 | 2002-05-10 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery |
| CN102583542A (en) * | 2012-02-28 | 2012-07-18 | 洛阳栾川钼业集团股份有限公司 | Preparation method of beta type ammonium tetramolybdate |
| JP2013023414A (en) * | 2011-07-21 | 2013-02-04 | Sumitomo Metal Mining Co Ltd | Easily soluble molybdenum trioxide |
| JPWO2023013244A1 (en) * | 2021-08-04 | 2023-02-09 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730758B (en) * | 2012-07-14 | 2013-11-27 | 河南科技大学 | Method for reducing and removing metal impurities from ammonium molybdate solution by using ion exchange resin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5581823U (en) * | 1978-12-01 | 1980-06-05 | ||
| JPS6278662A (en) * | 1985-10-02 | 1987-04-10 | Chino Corp | Input-output device |
| JPS62172439A (en) * | 1986-01-24 | 1987-07-29 | Fuji Electric Co Ltd | Detecting system for unmounted printed board |
| JPS62162755U (en) * | 1986-04-01 | 1987-10-16 | ||
| JPS6327927U (en) * | 1986-08-04 | 1988-02-24 | ||
| JPS63307121A (en) * | 1987-06-09 | 1988-12-14 | Hisao Fujita | Production of high-purity molybdenum oxide |
-
1989
- 1989-04-26 JP JP1108588A patent/JP2766990B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5581823U (en) * | 1978-12-01 | 1980-06-05 | ||
| JPS6278662A (en) * | 1985-10-02 | 1987-04-10 | Chino Corp | Input-output device |
| JPS62172439A (en) * | 1986-01-24 | 1987-07-29 | Fuji Electric Co Ltd | Detecting system for unmounted printed board |
| JPS62162755U (en) * | 1986-04-01 | 1987-10-16 | ||
| JPS6327927U (en) * | 1986-08-04 | 1988-02-24 | ||
| JPS63307121A (en) * | 1987-06-09 | 1988-12-14 | Hisao Fujita | Production of high-purity molybdenum oxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002134108A (en) * | 2000-10-24 | 2002-05-10 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery |
| JP2013023414A (en) * | 2011-07-21 | 2013-02-04 | Sumitomo Metal Mining Co Ltd | Easily soluble molybdenum trioxide |
| CN102583542A (en) * | 2012-02-28 | 2012-07-18 | 洛阳栾川钼业集团股份有限公司 | Preparation method of beta type ammonium tetramolybdate |
| JPWO2023013244A1 (en) * | 2021-08-04 | 2023-02-09 | ||
| WO2023013244A1 (en) | 2021-08-04 | 2023-02-09 | 三井金属鉱業株式会社 | Molybdic acid solution and method for producing same, molybdenum oxide powder and method for producing same |
| KR20240039170A (en) | 2021-08-04 | 2024-03-26 | 미쓰이금속광업주식회사 | Molybdic acid solution and its production method, molybdenum oxide powder and its production method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2766990B2 (en) | 1998-06-18 |
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