JP2002201010A - Hydrogen peroxide production equipment - Google Patents
Hydrogen peroxide production equipmentInfo
- Publication number
- JP2002201010A JP2002201010A JP2000402382A JP2000402382A JP2002201010A JP 2002201010 A JP2002201010 A JP 2002201010A JP 2000402382 A JP2000402382 A JP 2000402382A JP 2000402382 A JP2000402382 A JP 2000402382A JP 2002201010 A JP2002201010 A JP 2002201010A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- hydrogen peroxide
- membrane
- oxygen
- reactor
- 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.)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
(57)【要約】
【課題】 工程が複雑で、電力を必要とする電気分解法
を用いることなく、水素と酸素とを反応させるだけで過
酸化水素を製造し得る装置を提供する。
【解決手段】 水素を解離させて膜内を透過させ得る水
素選択透過膜および酸素源供給手段を反応器に設け、反
応器内で水素と酸素とを反応せしめるようにした過酸化
水素製造装置。水素選択透過膜としては、一般に多孔質
支持体上に水素を選択的に透過させる分離機能膜が設け
られたものが用いられる。PROBLEM TO BE SOLVED: To provide an apparatus capable of producing hydrogen peroxide simply by reacting hydrogen and oxygen without using an electrolysis method which requires complicated processes and requires electric power. SOLUTION: A hydrogen peroxide producing apparatus in which a hydrogen selective permeable membrane and an oxygen source supply means capable of dissociating hydrogen and permeating the inside of the membrane is provided in a reactor so that hydrogen and oxygen react in the reactor. As the hydrogen permselective membrane, generally used is a porous support provided with a separation functional membrane for selectively permeating hydrogen.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、過酸化水素製造装
置に関する。更に詳しくは、水素と酸素とを反応させて
過酸化水素を製造する装置に関する。[0001] The present invention relates to an apparatus for producing hydrogen peroxide. More specifically, the present invention relates to an apparatus for producing hydrogen peroxide by reacting hydrogen and oxygen.
【０００２】[0002]
【従来の技術】過酸化水素の工業的製法としては、有機
過酸化物経由法と電気分解法とがあり、我が国において
は殆んど前者の方法で過酸化水素が製造されている。有
機過酸化物経由法は、α-エチルアントラキノンをベン
ゼン等の水不溶性溶媒に溶解し、これを還元してα-エ
チルハイドロアントラキノンとし、これを酸化するとα
-エチルアントラキノンと過酸化水素とになるので、生
成した過酸化水素を水で抽出して循環的に得るという方
法である。また、電気分解法は、電解液として硫酸溶液
中にアンモニアガスを吹き込み酸性硫酸アンモニウムと
した後、白金電極を用いて電気分解を行って過硫酸アン
モニウムを発生させ、この液を真空蒸留して生成過酸化
水素を水に吸収させる方法である。2. Description of the Related Art Industrial methods for producing hydrogen peroxide include an organic peroxide method and an electrolysis method. In Japan, hydrogen peroxide is almost always produced by the former method. In the method using an organic peroxide, α-ethylanthraquinone is dissolved in a water-insoluble solvent such as benzene, and this is reduced to α-ethylhydroanthraquinone.
-Because ethylanthraquinone and hydrogen peroxide are formed, the produced hydrogen peroxide is extracted with water and obtained cyclically. In the electrolysis method, ammonia gas is blown into a sulfuric acid solution as an electrolytic solution to form acidic ammonium sulfate, and then electrolysis is performed using a platinum electrode to generate ammonium persulfate. This is a method of absorbing hydrogen into water.
【０００３】前者の有機過酸化物経由法は、工程が多段
になるばかりではなく、最終工程でアントラキノンを含
む溶媒と過酸化水素とを分離しなければならず、またア
ントラキノンの劣化という問題もある。一方、後者の電
気分解法も、工程が多段になるばかりではなく、複数の
装置を組み合せて使用する必要がある。The former method involving the use of an organic peroxide requires not only a multi-step process but also a separation of a solvent containing anthraquinone and hydrogen peroxide in a final step, and also has a problem of deterioration of anthraquinone. . On the other hand, the latter electrolysis method requires not only a multi-step process but also a combination of a plurality of devices.
【０００４】このような電気分解法を改良した方法とし
て、電解質水溶液と水素吸蔵合金とからなる電極(陰極)
を用い、電極間に直流電流を流すことで陰極に水素を吸
蔵させ、その後電解質溶液に空気を封入して過酸化水素
を発生させる方法が提案されている(特開平4-13882号公
報)。しかしながら、この方法では過酸化水素を電解質
水溶液から分離しなければならないばかりではなく、連
続的な製造ができないという欠点を有している。また、
電気分解法では、当然のことながら電力を必要としてい
る。[0004] As an improved method of such an electrolysis method, an electrode (cathode) comprising an aqueous electrolyte solution and a hydrogen storage alloy has been proposed.
A method has been proposed in which a direct current is passed between electrodes to absorb hydrogen in the cathode, and then air is sealed in the electrolyte solution to generate hydrogen peroxide (Japanese Patent Application Laid-Open No. H4-13882). However, this method has the disadvantage that not only must hydrogen peroxide be separated from the aqueous electrolyte solution, but also it cannot be manufactured continuously. Also,
The electrolysis method naturally requires electric power.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、工程
が複雑で、電力を必要とする電気分解法を用いることな
く、水素と酸素とを反応させるだけで過酸化水素を製造
し得る装置を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an apparatus capable of producing hydrogen peroxide simply by reacting hydrogen and oxygen without using an electrolysis method requiring a complicated process and requiring electric power. Is to provide.
【０００６】[0006]
【課題を解決するための手段】かかる本発明の目的は、
水素を解離させて膜内を透過させ得る水素選択透過膜お
よび酸素源供給手段を反応器に設け、反応器内で水素と
酸素とを反応せしめるようにした過酸化水素製造装置に
よって達成される。SUMMARY OF THE INVENTION The object of the present invention is as follows.
This is achieved by a hydrogen peroxide production apparatus in which a hydrogen selective permeable membrane capable of dissociating hydrogen and permeating the inside of the membrane and an oxygen source supply means are provided in the reactor, and hydrogen and oxygen are reacted in the reactor.
【０００７】[0007]
【発明の実施の形態】水素を解離させて膜内を透過させ
得る水素選択透過膜としては、多孔質支持体上に水素を
選択的に透過させる分離機能層を設けたものが一般に用
いられる。多孔質支持体としては、例えばアルミナ、シ
リカ、ゼオライト、チタニア、シリカアルミナ等のセラ
ミックスの管状体、平板状体等が用いられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS As a hydrogen selective permeable membrane capable of dissociating hydrogen and permeating the inside of the membrane, a membrane provided with a separation functional layer for selectively permeating hydrogen on a porous support is generally used. As the porous support, for example, a tubular body or a flat body of ceramics such as alumina, silica, zeolite, titania, and silica-alumina are used.
【０００８】これらの多孔質支持体上への分離機能層の
形成は、PdまたはそれとAg、Au、Pt、Rh、Ru、Sn、Se、
Te、Si、Zn、Ir、Ta、Nb、V、Ni、Zr等の少くとも一種
との合金、VまたはそれとNi、Co、Mo等との合金等を用
い、CVD法、電気メッキ法、無電解メッキ法等によって
行われ、CVD法の一例が特開平11-300182号公報に記載さ
れている。なお、分離機能層が形成されない多孔質支持
体表面には、そこからのガスの透過を防止するために、
ガラス材、耐熱性ロウ材等による被覆が行われる。ま
た、分離機能層を多孔質支持体全面に形成させ、これを
非ガス透過性水素ガス導入管と接続して使用することも
できる。[0008] The separation functional layer is formed on these porous supports by forming Pd or Ag, Au, Pt, Rh, Ru, Sn, Se, and Ag.
Using an alloy with at least one of Te, Si, Zn, Ir, Ta, Nb, V, Ni, Zr, etc., and V or an alloy thereof with Ni, Co, Mo, etc., using a CVD method, an electroplating method, It is performed by an electrolytic plating method or the like, and an example of the CVD method is described in JP-A-11-300182. In addition, on the surface of the porous support on which the separation function layer is not formed, in order to prevent gas permeation therefrom,
Coating with a glass material, a heat-resistant brazing material, or the like is performed. Alternatively, a separation functional layer may be formed on the entire surface of the porous support, and this may be used by connecting to a non-gas-permeable hydrogen gas introducing pipe.
【０００９】常圧下または加圧下で行われるこの反応で
生成する過酸化水素は、高温程分解し易いので、装置の
運転温度は約-20〜120℃が好ましいものの、本発明で用
いられる水素選択透過膜では、一般的にその水素透過機
構から高温程水素透過速度は増大するが、上記の運転温
度では水素透過速度が著しく低下するため、必要な水素
透過量を確保するために水素選択透過膜の膜厚は薄い方
がよく、特に水素選択透過性を示す分離機能層の厚みは
10μm以下であることが好ましく、一般には約0.5〜5μm
程度に設定される。The operating temperature of the apparatus is preferably about -20 to 120 ° C., since the hydrogen peroxide produced by this reaction carried out under normal pressure or under pressure is more likely to decompose at higher temperatures. In a permeable membrane, the hydrogen permeation rate generally increases as the temperature rises due to its hydrogen permeation mechanism. However, the hydrogen permeation rate decreases significantly at the operating temperature described above. The thinner the better, the more particularly the thickness of the separation functional layer showing hydrogen selective permeability is
Preferably not more than 10 μm, generally about 0.5-5 μm
Set to about.
【００１０】水素選択透過膜は、水素のみを選択的に透
過させるので、一方の原料となる水素源は純粋なもので
ある必要はなく、工業用水素や各種の水素含有ガスが使
用可能である。また、他方の原料である酸素源も、空気
や各種酸素含有ガスを使用することもできる。Since the hydrogen selective permeable membrane selectively permeates only hydrogen, the hydrogen source as one raw material does not need to be pure, and industrial hydrogen and various hydrogen-containing gases can be used. . In addition, air and various oxygen-containing gases can also be used as the other source, the oxygen source.
【００１１】水素選択透過膜を透過した水素は、分離機
能層を形成する金属膜の結晶格子内をH2の形ではなくH
の形で拡散し、透過する。このように、水素を解離させ
て膜内を透過するため、透過側の膜表面には解離し、反
応性に富んだ状態の水素が存在し、そのような水素と酸
素とが低温でも容易に反応して過酸化水素を生成させ
る。また、酸素を含むガスは、水素選択透過膜の表面を
スイープする効果を有しており、生成した過酸化水素を
速やかに水素選択透過膜表面から脱離させるので、効率
的に連続して過酸化水素を製造することができる。Hydrogen that has passed through the hydrogen selective permeable membrane causes H 2 instead of H 2 in the crystal lattice of the metal film forming the separation function layer.
Diffuse and transmit in the form of As described above, since hydrogen is dissociated and permeates the membrane, hydrogen is dissociated on the membrane surface on the permeation side, and hydrogen in a highly reactive state exists. Reacts to produce hydrogen peroxide. In addition, the gas containing oxygen has an effect of sweeping the surface of the hydrogen selective permeable membrane, and the generated hydrogen peroxide is quickly desorbed from the surface of the hydrogen selective permeable membrane, so that it is efficiently and continuously removed. Hydrogen oxide can be produced.
【００１２】水素透過膜を透過した水素と酸素との反応
は、液相または気相で行われる。液相での反応は、水素
選択透過膜および酸素源供給手段を過酸化水素捕集用溶
媒中に浸せきした状態で行われ、この捕集用溶媒は酸素
源供給側(水素透過側)に存在させて用いられる。捕集用
溶媒として水を用いた場合には、生成した過酸化水素は
水に吸収され過酸化水素水となるため、従来の有機酸化
物経由法や電気分解法での如く最終工程で過酸化水素を
溶媒や電気液から分離する必要がない。この場合には、
その運転温度は約0〜100℃である。この際、生成した過
酸化水素の分解を抑制し、安定化するために、過酸化水
素水溶液の場合には酸、アルカリ、有機安定化剤等の安
定化剤を適宜添加され、好ましくは塩酸、硝酸、硫酸等
の無機酸またはギ酸、酢酸等の有機酸が用いられる。The reaction between hydrogen and oxygen permeating the hydrogen permeable membrane is performed in a liquid phase or a gas phase. The reaction in the liquid phase is performed in a state where the hydrogen selective permeable membrane and the oxygen source supply means are immersed in a hydrogen peroxide collecting solvent, and the collecting solvent is present on the oxygen source supplying side (hydrogen permeable side). Used. When water is used as the trapping solvent, the generated hydrogen peroxide is absorbed by the water and becomes aqueous hydrogen peroxide. There is no need to separate the hydrogen from the solvent or the electric liquid. In this case,
Its operating temperature is about 0-100 ° C. At this time, in order to suppress and stabilize the decomposition of the generated hydrogen peroxide, in the case of an aqueous hydrogen peroxide solution, a stabilizer such as an acid, an alkali, or an organic stabilizer is appropriately added, and preferably hydrochloric acid, Inorganic acids such as nitric acid and sulfuric acid and organic acids such as formic acid and acetic acid are used.
【００１３】水素選択透過膜は、管状、平板状等本発明
の目的を達成し得る限り任意の形状で用いることができ
る。図1〜2では管状として、また図3では平板状で用い
られた液相反応の態様が示されている。The hydrogen selective permeable membrane can be used in any shape such as a tubular shape and a flat shape as long as the object of the present invention can be achieved. FIGS. 1 and 2 show an embodiment of a liquid phase reaction used as a tube, and FIG.
【００１４】図1に示された態様では、反応器1の上方か
らは管状水素選択透過膜2が、また下方からは酸素源供
給口としての酸素供給パイプ3がそれぞれ挿入されてい
る。管状水素選択膜2は、多孔質支持体4上に水素を選択
的に透過させる分離機能層5が設けられており、また分
離機能層が設けられていない多孔質支持体表面はガラス
によりシールされており、多孔質支持体先端部は接着剤
等により閉塞6されており、分離機能層5の部分は過酸化
水素捕集用溶媒7中に浸せきされている。また、酸素供
給パイプ3の先端部には、焼結金属等の多孔質体8が設け
られており、酸素は微細な気泡状となって水素選択透過
膜2の分離機能層5部分を覆うように過酸化水素捕集用溶
媒7中を浮上していく様にしている。なお、過酸化水素
捕集用溶媒7のレベリングは、バルブを備えた水供給口9
からの水の供給によって水準器10により調整され、加水
と回収とを連続的に加減して連続運転を可能とさせてお
り、余分のガスはその排出口11から排出され、生成した
過酸化水素溶液はバルブの操作により抜取口9から取り
出される。In the embodiment shown in FIG. 1, a tubular hydrogen selective permeable membrane 2 is inserted from above the reactor 1, and an oxygen supply pipe 3 as an oxygen source supply port is inserted from below the reactor 1. The tubular hydrogen selective membrane 2 is provided with a separation functional layer 5 for selectively permeating hydrogen on the porous support 4, and the surface of the porous support having no separation functional layer is sealed with glass. The tip of the porous support is closed 6 with an adhesive or the like, and the portion of the separation function layer 5 is immersed in a solvent 7 for collecting hydrogen peroxide. In addition, a porous body 8 such as a sintered metal is provided at the tip of the oxygen supply pipe 3 so that oxygen becomes fine bubbles and covers the separation function layer 5 of the hydrogen selective permeable membrane 2. In the solvent 7 for trapping hydrogen peroxide. The level of the hydrogen peroxide trapping solvent 7 is determined by the water supply port 9 equipped with a valve.
Is adjusted by the level 10 by the supply of water from the furnace, and the water and the recovery are continuously adjusted to enable continuous operation.Excess gas is discharged from the discharge port 11 and generated hydrogen peroxide. The solution is taken out of the outlet 9 by operating the valve.
【００１５】図2に示された態様では、図1で用いられた
管状水素選択透過膜2が分離機能層5の部分においてU字
形として用いられており、閉塞部は設けられていない。
他の部分は図1と同じであり、余分のガスは排出口11か
ら排出される。また、水素はU字管の供給口12から供給
され、余剰の水素含有ガスは排出口13から排出される。In the embodiment shown in FIG. 2, the tubular hydrogen permselective membrane 2 used in FIG. 1 is used as a U-shape in the portion of the separation function layer 5, and no closing portion is provided.
Other parts are the same as those in FIG. 1, and the excess gas is discharged from the outlet 11. Further, hydrogen is supplied from the supply port 12 of the U-shaped tube, and excess hydrogen-containing gas is discharged from the discharge port 13.
【００１６】また、図3に示された態様では、多孔質支
持体14の過酸化水素捕集用溶媒7側の片面に分離機能層1
5を設けた平板状水素選択膜22が反応器1中に傾けて設置
されており、水素含有ガスは供給口12から供給され、余
分の水素含有ガスは排出口13から排出される。In the embodiment shown in FIG. 3, the separation support layer 1 is provided on one side of the porous support 14 on the side of the solvent 7 for trapping hydrogen peroxide.
The plate-shaped hydrogen selective membrane 22 provided with 5 is installed in the reactor 1 at an angle, and the hydrogen-containing gas is supplied from the supply port 12, and the excess hydrogen-containing gas is discharged from the discharge port 13.
【００１７】さらに、水素選択透過膜を透過した水素と
酸素との反応が気相で行われる場合には、酸素源を供給
した反応器内に水素選択透過膜を設置し、気相で生成し
た過酸化水素を過酸化水素捕集用溶媒中に捕集せしめる
捕集管を反応器外に設けた製造装置、例えば図4に示さ
れた態様の装置を用いて行われる。この場合には、酸素
源供給口33を備えた反応器1内に、多孔質支持体34上に
水素を選択的に透過させる分離機能層35が設けられた管
状水素選択透過膜32が設置されており、水素供給口12か
ら供給され、分離機能層35を透過した水素は酸素と反応
して過酸化水素を形成し、酸素ガスあるいはキャリアー
ガスによって過酸化水素捕集用溶媒7を入れた捕集管36
中に捕集され、余分の水素含有ガスは排出口13から排出
される。この気相法による反応は、約-20〜800℃、好ま
しくは約0〜500℃の温度および約0.001〜300Kgf/cm2(約
98Pa〜29.4MPa)、好ましくは約1〜100Kgf/cm2(約0.098
〜9.8MPa)の圧力条件下で行われる。Further, when the reaction between hydrogen and oxygen permeated through the hydrogen permselective membrane is performed in the gas phase, the hydrogen permselective membrane is installed in a reactor to which an oxygen source is supplied, and the hydrogen is generated in the gas phase. The production is carried out using a manufacturing apparatus provided with a collecting tube for collecting hydrogen peroxide in a hydrogen peroxide collecting solvent outside the reactor, for example, the apparatus shown in FIG. In this case, in the reactor 1 provided with the oxygen source supply port 33, a tubular hydrogen selectively permeable membrane 32 provided with a separation functional layer 35 for selectively transmitting hydrogen on a porous support 34 is provided. The hydrogen supplied from the hydrogen supply port 12 and permeating the separation function layer 35 reacts with oxygen to form hydrogen peroxide, and the hydrogen peroxide-collecting solvent 7 is charged with oxygen gas or carrier gas. Collecting pipe 36
The excess hydrogen-containing gas is collected in the exhaust port 13 and discharged. The reaction by the gas phase method is carried out at a temperature of about -20 to 800 ° C, preferably about 0 to 500 ° C and about 0.001 to 300 Kgf / cm 2 (about
98Pa~29.4MPa), preferably from about 1~100Kgf / cm 2 (about 0.098
9.89.8 MPa).
【００１８】[0018]
【発明の効果】本発明装置によれば、従来法と比べて簡
素な構成で、連続的に効率良く過酸化水素溶液を製造す
ることができる。また、その製造時の工程数も少なく、
電気分解法のように電力を必要とはしないため、低コス
トでの製造を可能とする。According to the apparatus of the present invention, a hydrogen peroxide solution can be continuously and efficiently produced with a simple structure as compared with the conventional method. In addition, the number of manufacturing processes is small,
Since power is not required unlike the electrolysis method, it enables low-cost production.
【００１９】[0019]
【実施例】次に、実施例について本発明を説明する。Next, the present invention will be described by way of examples.
【００２０】実施例１ 多孔質支持体として多孔質α-アルミナ管(外径2mm、内
径1.7mm、平均細孔径0.15μm、気孔率43%、有効膜面積
6.4cm2)を用い、接着剤で閉塞された先端部から10cmの
部分に、厚さ約1μmのPd膜よりなる分離機能層を形成さ
せた。Pd膜の形成は、Pd源として酢酸パラジウムを用
い、特開平11-300182号公報記載の方法に従ってCVD法に
よって行われた。なお、分離機能層非形成部分の多孔質
支持体表面は、ガラスによって被覆されている。Example 1 A porous α-alumina tube (outer diameter 2 mm, inner diameter 1.7 mm, average pore diameter 0.15 μm, porosity 43%, effective membrane area as a porous support)
Using 6.4 cm 2 ), a separation functional layer consisting of a Pd film having a thickness of about 1 μm was formed at a portion 10 cm from the tip end closed with the adhesive. The Pd film was formed by CVD using palladium acetate as a Pd source according to the method described in JP-A-11-300182. Note that the surface of the porous support in the portion where the separation function layer is not formed is covered with glass.
【００２１】このようにして得られた管状水素選択性透
過膜を用い、図1に示される装置を用いて、過酸化水素
溶液の製造が行われた。過酸化水素捕集用溶媒としては
25mlの水が用いられ、Pd膜よりなる分離機能層をその中
に十分に浸せきした。多孔質α-アルミナ管内には圧力3
Kg/cm2(0.294MPa)の純水素が、また酸素供給パイプには
5L/hの供給量で純酸素がそれぞれ供給され、生成過酸化
水素水抜取口を閉じたまま、装置全体を20℃に24時間保
持した。その結果、約130μモルの過酸化水素が得られ
た。Using the tubular hydrogen-selective permeable membrane thus obtained, a hydrogen peroxide solution was produced using the apparatus shown in FIG. As a solvent for collecting hydrogen peroxide,
25 ml of water was used, and a separation function layer composed of a Pd membrane was sufficiently immersed therein. Pressure 3 inside porous α-alumina tube
Pure hydrogen of Kg / cm 2 (0.294MPa) and oxygen supply pipe
Pure oxygen was supplied at a supply rate of 5 L / h, and the entire apparatus was kept at 20 ° C. for 24 hours with the generated hydrogen peroxide aqueous solution outlet closed. As a result, about 130 μmol of hydrogen peroxide was obtained.
【００２２】実施例２ 実施例1において、24時間反応後の水相を新規に取り換
え、水溶媒25mlを用いて同様の反応を行った結果、約10
0μモルの過酸化水素が得られた。Example 2 The same reaction as in Example 1 was carried out except that the aqueous phase after the reaction for 24 hours was newly replaced, and the same reaction was carried out using 25 ml of an aqueous solvent.
0 μmol of hydrogen peroxide was obtained.
【００２３】実施例３ 実施例1において、25mlの水に酢酸を加え、pHを4として
同様の反応を3時間行った結果、約68μモルの過酸化水
素が得られた。Example 3 In Example 1, acetic acid was added to 25 ml of water to adjust the pH to 4, and the same reaction was carried out for 3 hours. As a result, about 68 μmol of hydrogen peroxide was obtained.
【００２４】実施例４ 実施例1において、25mlの水に硝酸を加え、pHを4として
同様の反応を3時間行った結果、約45μモルの過酸化水
素が得られた。Example 4 In Example 1, nitric acid was added to 25 ml of water to adjust the pH to 4, and the same reaction was carried out for 3 hours. As a result, about 45 μmol of hydrogen peroxide was obtained.
【００２５】実施例５ 実施例1において、反応温度を40℃にして同様の反応を
行った結果、約60μモルの過酸化水素が得られた。Example 5 The same reaction as in Example 1 was carried out except that the reaction temperature was 40 ° C., and as a result, about 60 μmol of hydrogen peroxide was obtained.
【００２６】実施例６ 実施例1において、反応温度を60℃にして同様の反応を
行った結果、約13μモルの過酸化水素が得られた。Example 6 The same reaction as in Example 1 was carried out except that the reaction temperature was 60 ° C., and as a result, about 13 μmol of hydrogen peroxide was obtained.
【００２７】実施例７ 多孔質支持体として多孔質α-アルミナU字管(外径2mm、
内径1.7mm、平均細孔径0.15μm、気孔率43%、有効膜面
積12.5cm2)を用い、実施例1と同様にして、厚さ約1μm
のPd膜よりなる分離機能膜を20cmにわたりU字状に形成
させた。なお、分離機能層非形成部分の多孔質支持体表
面は、ガラスによって被覆されている。Example 7 As a porous support, a porous α-alumina U-shaped tube (outer diameter 2 mm,
Using an inner diameter of 1.7 mm, an average pore diameter of 0.15 μm, a porosity of 43%, and an effective membrane area of 12.5 cm 2 ) in the same manner as in Example 1 and a thickness of about 1 μm
Was formed in a U-shape over 20 cm. Note that the surface of the porous support in the portion where the separation function layer is not formed is covered with glass.
【００２８】このようにして得られた管状水素選択透過
膜を用い、図2に示される装置を用いて、過酸化水素溶
液の製造が行われた。過酸化水素捕集用溶媒としては50
mlの水が用いられ、Pd膜よりなる分離機能層をその中に
十分に浸せきさせた。多孔質α-アルミナ管内には圧力3
Kg/cm2(0.294MPa)の純酸素が、また酸素供給パイプには
10L/hの供給量で純酸素がそれぞれ供給され、生成過酸
化水素水抜取口を閉じたまま、装置全体を40℃に24時間
保持した。その結果、約120μモルの過酸化水素が得ら
れた。Using the tubular hydrogen permselective membrane thus obtained, a hydrogen peroxide solution was produced using the apparatus shown in FIG. 50 as a solvent for collecting hydrogen peroxide
Using water of ml, the separation function layer composed of a Pd membrane was sufficiently immersed therein. Pressure 3 inside porous α-alumina tube
Pure oxygen of Kg / cm 2 (0.294MPa) and oxygen supply pipe
Pure oxygen was supplied at a supply rate of 10 L / h, and the entire apparatus was kept at 40 ° C. for 24 hours with the generated hydrogen peroxide aqueous solution outlet closed. As a result, about 120 μmol of hydrogen peroxide was obtained.
【００２９】実施例８ 多孔質支持体として多孔質α-アルミナ平板(厚さ1.6m
m、平均細孔径2μm、気孔率47%、有効膜面積25cm2)を用
い、その片面に特開平3-135424号公報記載の方法に従っ
て、無電解メッキ法により厚さ5μmのPd膜よりなる分離
機能層を形成させた。Example 8 A porous α-alumina flat plate (having a thickness of 1.6 m) was used as a porous support.
m, average pore diameter of 2 μm, porosity of 47%, effective membrane area of 25 cm 2 ), using a method described in JP-A-3-135424 on one side thereof, separation of a 5 μm thick Pd film by electroless plating. A functional layer was formed.
【００３０】このようにして得られた平板状水素選択膜
を用い、図3に示される装置を用いて、過酸化水素溶液
の製造が行われた。過酸化水素捕集用溶媒としては100m
lの水が用いられ、水素ガス供給口からは圧力3Kg/cm
2(0.294MPa)の純水素が、また酸素供給パイプからは20L
/hの供給量で純酸素がそれぞれ供給され、生成過酸化水
素水抜取口を閉じたまま、装置全体を60℃に24時間保持
した。その結果、約8μモルの過酸化水素が得られた。Using the plate-like hydrogen selective membrane thus obtained, a hydrogen peroxide solution was produced using the apparatus shown in FIG. 100m as a solvent for collecting hydrogen peroxide
l of water is used and the pressure is 3 kg / cm from the hydrogen gas supply port.
2 (0.294MPa) pure hydrogen and 20L from oxygen supply pipe
Pure oxygen was supplied at a supply rate of / h, and the entire apparatus was kept at 60 ° C for 24 hours with the generated hydrogen peroxide aqueous solution outlet closed. As a result, about 8 μmol of hydrogen peroxide was obtained.
【００３１】実施例９ 多孔質支持体として多孔質α-アルミナ管(外径2mm、内
径1.6mm、平均細孔径0.15μm、気孔率43%、有効膜面積
6.4cm2)を用い、長さ10cmの部分に、Pd源として酢酸パ
ラジウムを用いCVD法により、厚さ1μmのPd膜よりなる
分離機能層を形成させた。なお、分離機能層非形成部分
の多孔質支持体表面は、ガラスによって被覆されてい
る。Example 9 A porous α-alumina tube (outer diameter 2 mm, inner diameter 1.6 mm, average pore diameter 0.15 μm, porosity 43%, effective membrane area as a porous support)
Using 6.4 cm 2 ), a separation function layer consisting of a 1 μm-thick Pd film was formed on a portion having a length of 10 cm by a CVD method using palladium acetate as a Pd source. Note that the surface of the porous support in the portion where the separation function layer is not formed is covered with glass.
【００３２】このようにして得られた管状水素選択膜を
用い、図4に示される装置を用いて、過酸化水素溶液の
製造が行われた。水素含有ガス供給口よりヘリウムで希
釈した5%濃度の水素を、また酸素ガス供給口よりヘリウ
ムガスで希釈した酸素をそれぞれ25ml/hの流速で導入
し、250℃で24時間反応させると、25mlのトラップ水中
に約56μモルの過酸化水素が得られた。Using the tubular hydrogen selective membrane thus obtained, a hydrogen peroxide solution was produced using the apparatus shown in FIG. 5% concentration hydrogen diluted with helium from the hydrogen-containing gas supply port, and oxygen diluted with helium gas from the oxygen gas supply port were introduced at a flow rate of 25 ml / h, and reacted at 250 ° C. for 24 hours to obtain 25 ml. About 56 μmol of hydrogen peroxide was obtained in the trap water.
【図１】管状の水素選択透過膜を用いた液相法による本
発明装置の一態様の概略断面図である。FIG. 1 is a schematic cross-sectional view of one embodiment of the apparatus of the present invention by a liquid phase method using a tubular hydrogen permselective membrane.
【図２】管状の水素選択透過膜を用いた液相法による本
発明装置の他の態様の概略断面図である。FIG. 2 is a schematic sectional view of another embodiment of the apparatus of the present invention by a liquid phase method using a tubular hydrogen permselective membrane.
【図３】平板状の水素選択透過膜を用いた液相法による
本発明装置の一態様の概略断面図である。FIG. 3 is a schematic cross-sectional view of one embodiment of the apparatus of the present invention by a liquid phase method using a flat hydrogen selective permeable membrane.
【図４】管状の水素選択透過膜を用いた気相法による本
発明装置の一態様の概略断面図である。FIG. 4 is a schematic sectional view of one embodiment of the apparatus of the present invention by a gas phase method using a tubular hydrogen permselective membrane.
１ 反応器 ２,32 管状水素選択透過膜 ３ 酸素供給パイプ(酸素源供給口) ４,14,34 多孔質支持体 ５,15,35 分離機能層 ７ 過酸化水素捕集用溶媒 ８ 焼結金属多孔質体 ９ 水供給口、過酸化水素溶液抜取口 10 水準器 11 ガス排出口 12 水素供給口 13 余剰水素含有ガス排出口 22 平板状水素選択透過膜 33 酸素源供給口 36 捕集管 DESCRIPTION OF SYMBOLS 1 Reactor 2, 32 Tubular hydrogen selective permeable membrane 3 Oxygen supply pipe (Oxygen source supply port) 4, 14, 34 Porous support 5, 15, 35 Separation function layer 7 Solvent for collecting hydrogen peroxide 8 Sintered metal Porous material 9 Water supply port, Hydrogen peroxide solution discharge port 10 Level 11 Gas outlet 12 Hydrogen supply port 13 Excess hydrogen-containing gas discharge port 22 Flat hydrogen selective permeable membrane 33 Oxygen source supply port 36 Collection tube
───────────────────────────────────────────────────── フロントページの続き (74)上記１名の代理人 100066005 弁理士 吉田 俊夫 (72)発明者 難波 竹巳 茨城県つくば市和台25番地 エヌオーケー 株式会社内 (72)発明者 齋藤 知成 茨城県つくば市和台25番地 エヌオーケー 株式会社内 (72)発明者 水上 富士夫 茨城県つくば市東１丁目１番地 工業技術 院物質工学工業技術研究所内 (72)発明者 丹羽 修一 茨城県つくば市東１丁目１番地 工業技術 院物質工学工業技術研究所内 (72)発明者 鳥羽 誠 茨城県つくば市東１丁目１番地 工業技術 院物質工学工業技術研究所内 (72)発明者 伊東 直次 茨城県つくば市東１丁目１番地 工業技術 院物質工学工業技術研究所内 (72)発明者 庄司 宏 千葉県市原市島野551−10 (72)発明者 羽場 一彦 千葉県市原市根田３−10−８ ──────────────────────────────────────────────────続 き Continuing on the front page (74) One of the above agents 100066005 Patent Attorney Toshio Yoshida (72) Inventor Takemi Namba 25 Wadai, Tsukuba, Ibaraki Prefecture NOK Co., Ltd. (72) Inventor Tomonari Saito Ibaraki 25, Wadai, Tsukuba, Japan NOK Co., Ltd. (72) Inventor Fujio 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Institute of Industrial Science and Technology (72) Inventor Shuichi Niwa 1-1-1, Higashi, Tsukuba, Ibaraki Address Industrial Technology Institute, National Institute of Materials Science and Technology (72) Inventor Makoto Toba 1-1, Higashi, Tsukuba, Ibaraki Pref.National Institute of Advanced Industrial Science and Technology (72) (72) Inventor Hiroshi Shoji 55 Shimano, Ichihara, Chiba 1-10 (72) Inventor Kazuhiko Haba 3-10-8 Neda, Ichihara-shi, Chiba
Claims (6)
素選択透過膜および酸素源供給手段を反応器に設け、反
応器内で水素と酸素とを反応せしめるようにした過酸化
水素製造装置。1. A hydrogen peroxide producing apparatus in which a hydrogen selective permeable membrane and an oxygen source supply means capable of dissociating hydrogen and permeating the inside of the membrane are provided in a reactor so that hydrogen and oxygen react in the reactor. .
せる分離機能膜が設けられた水素選択透過膜が用いられ
た請求項１記載の過酸化水素製造装置。2. The hydrogen peroxide production apparatus according to claim 1, wherein a hydrogen selective permeable membrane provided with a separation function membrane for selectively permeating hydrogen on the porous support is used.
項１または２記載の過酸化水素製造装置。3. The hydrogen peroxide production apparatus according to claim 1, wherein a tubular hydrogen permselective membrane is used.
求項１または２記載の過酸化水素製造装置。4. The hydrogen peroxide production apparatus according to claim 1, wherein a flat hydrogen selective permeable membrane is used.
過酸化水素捕集用溶媒中に浸せきして用いた請求項１ま
たは２記載の過酸化水素製造装置。5. The hydrogen peroxide production apparatus according to claim 1, wherein the hydrogen selective permeable membrane and the oxygen source supply means are used by being immersed in a solvent for collecting hydrogen peroxide.
過膜を設置し、気相で生成した過酸化水素を過酸化水素
捕集用溶媒中に捕集せしめる捕集管を反応器外に設けた
請求項１または２記載の過酸化水素製造装置。6. A hydrogen selective permeable membrane is provided in a reactor for supplying an oxygen source, and a collecting tube for collecting hydrogen peroxide generated in a gas phase in a hydrogen peroxide collecting solvent is provided outside the reactor. The hydrogen peroxide production apparatus according to claim 1 or 2, wherein the apparatus is provided.
Priority Applications (1)
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| JP2000402382A JP2002201010A (en) | 2000-12-28 | 2000-12-28 | Hydrogen peroxide production equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000402382A JP2002201010A (en) | 2000-12-28 | 2000-12-28 | Hydrogen peroxide production equipment |
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| JP2002201010A true JP2002201010A (en) | 2002-07-16 |
Family
ID=18866689
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014142324A1 (en) * | 2013-03-15 | 2014-09-18 | 独立行政法人産業技術総合研究所 | Continuous direct synthesis/recovery method for hydrogen peroxide using catalyst-coated reaction tube, and device therefor |
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