JPH0769604A - Production of hydrogen peroxide - Google Patents
Production of hydrogen peroxideInfo
- Publication number
- JPH0769604A JPH0769604A JP21743993A JP21743993A JPH0769604A JP H0769604 A JPH0769604 A JP H0769604A JP 21743993 A JP21743993 A JP 21743993A JP 21743993 A JP21743993 A JP 21743993A JP H0769604 A JPH0769604 A JP H0769604A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- catalyst
- group metal
- platinum group
- reaction medium
- 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.)
- Pending
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- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は反応媒体中で酸素と水素
を接触的に反応させ、過酸化水素を製造する改良された
方法に関するものである。さらに詳しくは、本発明はハ
ロゲンイオン等の助触媒を含まない反応媒体中で、酸素
と水素を白金族触媒の存在下に反応させることにより過
酸化水素を製造する方法に関するものである。FIELD OF THE INVENTION The present invention relates to an improved process for catalytically reacting oxygen and hydrogen in a reaction medium to produce hydrogen peroxide. More specifically, the present invention relates to a method for producing hydrogen peroxide by reacting oxygen and hydrogen in the presence of a platinum group catalyst in a reaction medium containing no cocatalyst such as halogen ions.
【０００２】[0002]
【従来の技術】現在、工業的に行われている過酸化水素
の主な製造方法は、アルキルアンスラキノンを媒体とす
る自動酸化法である。この方法の問題点としては、アル
キルアンスラキノンの還元、酸化、生成した過酸化水素
の抽出分離及び精製そして濃縮等の多くの工程が必要で
ありプロセスが複雑となるために、装置費、運転費が大
きいという事が挙げられる。更には、アルキルアンスラ
キノンの劣化による損失、還元用触媒の活性の劣化等の
問題もある。これらの問題点を改善するために、上記製
造法以外の製造方法が試みられているが、その一つに、
反応媒体中で触媒を用いて、酸素と水素から直接的に過
酸化水素を製造する方法がある。例えば、白金族金属を
触媒として用い、酸素と水素から過酸化水素を製造する
方法が提案されており、かなりの濃度の過酸化水素が生
成する事が知られている（例えば、特公昭56-47121号、
特公昭55-18646号、特公平1-23401号、特開昭63-156005
号）。これらでは、いずれも反応媒体として酸や無機塩
を溶存させた水溶液を用いている。特に反応媒体中にハ
ロゲンイオンを含むことにより触媒の活性が抑制されて
過酸化水素生成反応の選択性が大幅に向上し、取得過酸
化水素の濃度が高くなることが示されている。特開昭63
-156005号公報には、白金族金属触媒を用い、硫酸酸性
水溶液中で加圧下酸素及び水素から過酸化水素を製造す
る方法に於いて、水溶液中に臭化物イオン等のハロゲン
イオンを共存させる事によって、選択的に高濃度の過酸
化水素を製造出来る事を示している。即ち従来の技術
は、酸素と水素を反応媒体中で接触的に反応させて過酸
化水素を高い選択率で取得するために、ハロゲンイオン
等の助触媒を用いて酸性水溶液中で反応を行うものであ
った。2. Description of the Related Art Currently, the main method of industrially producing hydrogen peroxide is an autoxidation method using alkylanthraquinone as a medium. The problem with this method is that it requires many steps such as reduction of alkylanthraquinone, oxidation, extraction and separation of the produced hydrogen peroxide, purification and concentration, which complicates the process, resulting in equipment costs and operating costs. Is large. Further, there are problems such as loss due to deterioration of alkyl anthraquinone and deterioration of activity of the reduction catalyst. In order to improve these problems, a manufacturing method other than the above manufacturing method has been attempted, and one of them is
There is a method of producing hydrogen peroxide directly from oxygen and hydrogen using a catalyst in a reaction medium. For example, a method of producing hydrogen peroxide from oxygen and hydrogen using a platinum group metal as a catalyst has been proposed, and it is known that a considerable concentration of hydrogen peroxide is produced (for example, Japanese Patent Publication No. 56- No. 47121,
JP-B-55-18646, JP-B-1-23401, JP-A-63-156005
issue). In each of these, an aqueous solution in which an acid or an inorganic salt is dissolved is used as a reaction medium. In particular, it has been shown that by including a halogen ion in the reaction medium, the activity of the catalyst is suppressed, the selectivity of the hydrogen peroxide generation reaction is significantly improved, and the concentration of hydrogen peroxide obtained is increased. JP 63
JP-A-156005, in a method for producing hydrogen peroxide from oxygen and hydrogen under pressure in a sulfuric acid acidic aqueous solution using a platinum group metal catalyst, a halogen ion such as bromide ion is allowed to coexist in the aqueous solution. , Shows that high concentration hydrogen peroxide can be selectively produced. That is, the conventional technique is to carry out a reaction in an acidic aqueous solution using a cocatalyst such as a halogen ion in order to catalytically react oxygen and hydrogen in a reaction medium to obtain hydrogen peroxide with a high selectivity. Met.
【０００３】[0003]
【発明が解決しようとする課題】反応媒体中で酸素と水
素を接触的に反応させ過酸化水素を製造する方法に於い
て、従来の公知技術では、実用的な濃度の過酸化水素を
得るためには反応媒体中に酸とハロゲンイオンを共存さ
せる必要があった。しかしながら、酸性反応媒体中に高
濃度のハロゲンイオンが存在する場合には、その取り扱
いにおいて使用できる装置の材質が制限され、その結
果、高価な耐蝕性の反応容器が必要となり経済的な問題
がある。更に、このような反応系においては触媒の活性
成分である白金族金属が反応媒体中に溶出するという問
題も生じる。特に、白金族金属の溶出量はハロゲンイオ
ンの濃度に対して比例的に増加する。この白金族金属成
分の溶出は触媒活性の低下及び触媒寿命の低減の原因と
なり、工業的な連続操作により過酸化水素を製造する場
合には、経済的に大きな問題となる。また、ハロゲンイ
オンの存在下で反応を行う方法は、製造された過酸化水
素からハロゲンイオンを除去するための精製工程が必要
である。この様に、従来の技術には種々の問題があっ
た。DISCLOSURE OF THE INVENTION In a method for producing hydrogen peroxide by catalytically reacting oxygen and hydrogen in a reaction medium, the conventional known technique is to obtain a practical concentration of hydrogen peroxide. It was necessary to coexist an acid and a halogen ion in the reaction medium. However, when a high concentration of halogen ions is present in the acidic reaction medium, the material of the apparatus that can be used for handling the same is limited, and as a result, an expensive corrosion-resistant reaction container is required, which is an economical problem. . Furthermore, in such a reaction system, there is a problem that the platinum group metal, which is an active component of the catalyst, is eluted into the reaction medium. In particular, the amount of platinum group metal eluted increases in proportion to the concentration of halogen ions. The elution of the platinum group metal component causes a decrease in catalyst activity and a decrease in catalyst life, and becomes a serious economic problem when hydrogen peroxide is produced by an industrial continuous operation. Further, the method of carrying out the reaction in the presence of halogen ions requires a purification step for removing the halogen ions from the produced hydrogen peroxide. As described above, the conventional technique has various problems.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、反応に悪
影響を及ぼさない窒素などの不活性ガスの存在下または
不存在下に白金族触媒を用いて反応媒体中で酸素と水素
を接触的に反応させて過酸化水素を製造する方法に於い
て、ハロゲンイオンを含まない反応媒体中で高濃度の過
酸化水素を得る製造方法の検討を続けた結果、ジルコニ
ウム及びアルミニウムのうち一種以上の元素で修飾した
白金族金属触媒を用いることにより、ハロゲンイオンを
含まない酸性水溶液を反応媒体として高濃度の過酸化水
素が得られることを見いだした。本発明は、酸素と水素
を反応媒体中で接触的に反応させて過酸化水素を製造す
る方法に於いて、触媒として、ジルコニウム及びアルミ
ニウムのうち少なくとも一種以上の元素と白金族金属と
を担体上に同時に担持することにより調製された修飾白
金族金属触媒を用いることを特徴とする過酸化水素の製
造方法である。本発明においては、ハロゲンイオンを含
まない酸性水溶液を反応媒体として使用することができ
る。The present inventors have contacted oxygen and hydrogen in a reaction medium using a platinum group catalyst in the presence or absence of an inert gas such as nitrogen which does not adversely affect the reaction. In the method for producing hydrogen peroxide by reacting with hydrogen, a study on a production method for obtaining a high concentration of hydrogen peroxide in a reaction medium containing no halogen ion was conducted. It was found that high concentration hydrogen peroxide can be obtained by using an acidic aqueous solution containing no halogen ion as a reaction medium by using a platinum group metal catalyst modified with an element. The present invention relates to a method for producing hydrogen peroxide by catalytically reacting oxygen and hydrogen in a reaction medium, wherein at least one element of zirconium and aluminum and a platinum group metal are used as a catalyst on a carrier. A method for producing hydrogen peroxide, characterized in that a modified platinum group metal catalyst prepared by simultaneously supporting the same on a substrate is used. In the present invention, an acidic aqueous solution containing no halogen ion can be used as the reaction medium.
【０００５】本発明における修飾白金族金属触媒の製造
法においては、ジルコニウム及びアルミニウムのうち少
なくとも一種以上の元素と白金族金属とを担体上に同時
に担持することが重要であり、たとえば、ジルコニウム
及びアルミニウムのうち一種以上の元素を含む化合物と
白金族金属の塩を同一の溶媒中に溶解させる等の方法に
より十分均一になるよう混合し、この混合物を担体上に
担持した後、これを焼成、還元処理することにより触媒
を調製する方法が採用される。なお、白金族元素金属を
予め担持した触媒にジルコニウムまたはアルミニウムを
担持させる方法、または、ジルコニウムまたはアルミニ
ウムを予め担持した触媒に白金族元素金属を担持させる
方法により得られる修飾白金族金属触媒は効果が出な
い。In the method for producing a modified platinum group metal catalyst of the present invention, it is important to simultaneously support at least one element of zirconium and aluminum and a platinum group metal on a carrier. For example, zirconium and aluminum. Of the compound containing at least one element and a platinum group metal salt are mixed in a solvent so as to be sufficiently homogeneous, and the mixture is supported on a carrier, and then calcined and reduced. A method of preparing a catalyst by treating is adopted. The modified platinum group metal catalyst obtained by the method of supporting zirconium or aluminum on the catalyst preliminarily supporting the platinum group metal, or the method of supporting the platinum group metal on the catalyst preliminarily supporting zirconium or aluminum is effective. Does not appear.
【０００６】用いられる白金族金属の塩としては、具体
的には、パラジウム、白金、ルテニウム、オスミウム、
ロジウム、イリジウムまたは金の塩、好ましくはパラジ
ウムまたは白金の硝酸塩、塩酸塩または酢酸塩などの
塩、パラジウムまたは白金のテトラアンミン錯体等の錯
体が挙げられる。前記白金族金属の担持量としては担体
に対して０．１〜１０重量％、好ましくは、０．５〜５
重量％である。Specific examples of the platinum group metal salt used include palladium, platinum, ruthenium, osmium,
Mention may be made of rhodium, iridium or gold salts, preferably palladium or platinum nitrates, salts such as hydrochlorides or acetates, complexes of palladium or platinum tetraammine complexes and the like. The amount of the platinum group metal supported on the carrier is 0.1 to 10% by weight, preferably 0.5 to 5%.
% By weight.
【０００７】ジルコニウム化合物あるいはアルミニウム
化合物としては、例えば、ジルコニウムまたはアルミニ
ウムの硝酸塩、塩酸塩、硫酸塩または酢酸塩が挙げられ
る。本発明に於いて用いられる修飾白金族金属触媒中の
ジルコニウム及びアルミニウムの量としては重量比で白
金族金属の１／２倍量以上、好ましくは１０倍量以上で
ある。本発明の触媒調製に用いる担体としては特別な制
限はなく、任意の触媒担体に対して前述の方法により白
金族金属とジルコニウム及びアルミニウムの化合物を担
持することが可能ではあるが、触媒の機械的強度あるい
は比表面積の点から、酸化アルミニウム、酸化珪素、酸
化ジルコニウム、酸化チタン、ゼオライト、シリカ−ア
ルミナ、活性炭、イオン交換樹脂または吸着樹脂等の担
体を使用することが、本発明の効果が十分発揮されるの
で好ましい。Examples of the zirconium compound or aluminum compound include zirconium or aluminum nitrate, hydrochloride, sulfate or acetate. The amount of zirconium and aluminum in the modified platinum group metal catalyst used in the present invention is at least 1/2 times the weight of the platinum group metal, preferably at least 10 times the weight of the platinum group metal. The carrier used for preparing the catalyst of the present invention is not particularly limited, and it is possible to support the platinum group metal and the compound of zirconium and aluminum on any catalyst carrier by the above-mentioned method. From the standpoint of strength or specific surface area, the use of a carrier such as aluminum oxide, silicon oxide, zirconium oxide, titanium oxide, zeolite, silica-alumina, activated carbon, an ion exchange resin or an adsorption resin exerts the effect of the present invention sufficiently. Therefore, it is preferable.
【０００８】本発明の過酸化水素の製造における本発明
の触媒の使用量は通常、反応媒体１リットル当たり１グ
ラム以上が使用され、スラリー状で使用することもでき
る。反応媒体としては、水溶液が好ましく、特にハロゲ
ンイオンを含まない水溶液が使用でき、硫酸、硝酸また
は燐酸等のハロゲンイオンを含まない無機酸を添加した
水溶液が最も好適に使用される。また、過酸化水素分解
防止のための公知の安定剤、例えば、アミノトリ（メチ
レンホスホン酸）、１−ヒドロキシエチリデン−１，１
−ジホスホン酸、エチレンジアミンテトラ（メチレンホ
スホン酸）、ピロリン酸またはこれらの塩等を反応媒体
に添加することは好ましい。本発明の修飾白金族触媒を
使用した場合の過酸化水素製造の反応条件としては、通
常、反応圧力３〜１５０ｋｇ／ｃｍ2 ・Ｇ、反応温度０
〜５０℃、反応時間３０分〜６時間の条件で実施され
る。The amount of the catalyst of the present invention used in the production of hydrogen peroxide of the present invention is usually 1 gram or more per liter of the reaction medium, and it may be used in the form of a slurry. As the reaction medium, an aqueous solution is preferable, and an aqueous solution containing no halogen ion can be used, and an aqueous solution containing an inorganic acid containing no halogen ion such as sulfuric acid, nitric acid or phosphoric acid is most preferably used. Further, known stabilizers for preventing decomposition of hydrogen peroxide, such as aminotri (methylenephosphonic acid) and 1-hydroxyethylidene-1,1.
-It is preferable to add diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), pyrophosphoric acid or salts thereof to the reaction medium. The reaction conditions for hydrogen peroxide production using the modified platinum group catalyst of the present invention are usually a reaction pressure of 3 to 150 kg / cm 2 · G and a reaction temperature of 0.
It is carried out under the conditions of -50 ° C and a reaction time of 30 minutes to 6 hours.
【０００９】[0009]
【実施例】以下、実施例及び比較例によって本発明を更
に詳細に説明する。実施例中で用いられているガス組成
の分析値は、ガスクロマトグラフによる値である。ま
た、溶液中の過酸化水素濃度の測定は、硫酸酸性−過マ
ンガン酸カリウム溶液による滴定法により行った。 実施例１ 修飾白金族触媒の調製を以下の方法により行った。即
ち、市販の二酸化チタン（ＴＡＹＣＡ（株）製、アナタ
ーゼ型）１０ｇを１００ｍｌの水に懸濁させた懸濁液中
に、市販の硝酸ジルコニウム（小宗化学薬品（株）製）
４．３７ｇを５０ｍｌの水に溶解した水溶液と硝酸パラ
ジウム溶液の希釈液（石福金属興業社製、１ｇ−Ｐｄ／
リットル）５０ｍｌの混合溶液を滴下した。滴下終了
後、この懸濁液をホットプレート上で蒸発・乾固し、さ
らに乾燥器中で１１０℃にて一昼夜乾燥した。その後、
空気気流中で５００℃にて２時間焼成し、次いで水素気
流中で１２０℃にて１時間還元して触媒を得た。酸素と
水素より直接的に過酸化水素を製造する反応方法として
以下の操作を行った。内容積６５ｍｌのガラス容器に、
硫酸０．１ｍｏｌ／リットルとなるように調製した水溶
液１０ｇを入れた。この水溶液に前述の方法で調製した
修飾白金族触媒５０ｍｇを加え、ガラス容器を１００ｍ
ｌの容積のオートクレーブに入れ、水素ガスが３．５容
積％、酸素ガスが３５容積％、窒素ガスが６１．５容積
％の組成からなる混合ガスで圧力テストを行った後、同
じ組成のガスで５０ｋｇ／ｃｍ2 ・Ｇ迄加圧した。温度
を１０℃に保ちながら２，０００ｒｐｍで１時間攪拌し
た。攪拌終了後、水溶液中の過酸化水素濃度は０．２８
重量％、水素選択率は４４％であった。水素選択率は次
式によって計算した。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The analysis value of the gas composition used in the examples is a value obtained by gas chromatography. The concentration of hydrogen peroxide in the solution was measured by a titration method using a sulfuric acid-potassium permanganate solution. Example 1 A modified platinum group catalyst was prepared by the following method. That is, in a suspension obtained by suspending 10 g of commercially available titanium dioxide (TAYCA Corporation, anatase type) in 100 ml of water, commercially available zirconium nitrate (manufactured by Komune Chemical Co., Ltd.)
An aqueous solution of 4.37 g dissolved in 50 ml of water and a diluted solution of a palladium nitrate solution (manufactured by Ishifuku Metal Industry Co., Ltd., 1 g-Pd /
Liter) 50 ml of the mixed solution was added dropwise. After the completion of dropping, the suspension was evaporated to dryness on a hot plate and further dried in a dryer at 110 ° C. for 24 hours. afterwards,
It was calcined in an air stream at 500 ° C for 2 hours and then reduced in a hydrogen stream at 120 ° C for 1 hour to obtain a catalyst. The following operation was performed as a reaction method for directly producing hydrogen peroxide from oxygen and hydrogen. In a glass container with an internal volume of 65 ml,
10 g of an aqueous solution prepared to have a sulfuric acid content of 0.1 mol / liter was added. To this aqueous solution was added 50 mg of the modified platinum group catalyst prepared by the above method, and the glass container was placed at 100 m.
The mixture was put in an autoclave having a volume of 1 l, and a pressure test was performed using a mixed gas having a composition of 3.5% by volume of hydrogen gas, 35% by volume of oxygen gas and 61.5% by volume of nitrogen gas, and then a gas of the same composition. The pressure was increased to 50 kg / cm 2 · G. The mixture was stirred at 2,000 rpm for 1 hour while maintaining the temperature at 10 ° C. After stirring, the hydrogen peroxide concentration in the aqueous solution is 0.28
The weight percentage and hydrogen selectivity were 44%. The hydrogen selectivity was calculated by the following formula.
【数１】水素選択率（％）＝［（反応により生成した過
酸化水素の量 mol ）÷（消費された水素量から算出し
た過酸化水素の理論生成量 mol ）］×100[Equation 1] Hydrogen selectivity (%) = [(amount of hydrogen peroxide produced by the reaction) / (theoretical amount of hydrogen peroxide calculated from the amount of hydrogen consumed)] x 100
【００１０】実施例２ 修飾白金族触媒調製に際して、市販の二酸化チタン（Ｔ
ＡＹＣＡ（株）製、アナターゼ型）１０ｇの代わりに市
販の酸化アルミニウム（水沢化学（株）製、活性アルミ
ナ）１０ｇを用いたことを除き、実施例１と同様の操作
を行い触媒調製および反応を行った。１時間の攪拌終了
後、水溶液中の過酸化水素濃度は０．２９重量％であ
り、水素選択率は４１％であった。Example 2 In preparing a modified platinum group catalyst, commercially available titanium dioxide (T
Catalyst preparation and reaction were performed in the same manner as in Example 1 except that 10 g of commercially available aluminum oxide (manufactured by Mizusawa Chemical Co., Ltd., activated alumina) was used in place of 10 g of AYCA, anatase type. went. After completion of stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.29% by weight, and the hydrogen selectivity was 41%.
【００１１】実施例３ 修飾白金族触媒調製に際して、市販の硝酸ジルコニウム
４．３７ｇの代わりに市販の硝酸アルミニウム（小宗化
学薬品（株）製）２０．８５ｇを用いたことを除き、実
施例１と同様の操作を行い触媒調製および反応を行っ
た。１時間の攪拌終了後、水溶液中の過酸化水素濃度は
０．２３重量％であり、水素選択率は２０％であった。Example 3 Example 1 was repeated except that 20.85 g of commercially available aluminum nitrate (manufactured by Komune Chemical Co., Ltd.) was used in place of 4.37 g of commercially available zirconium nitrate in preparing the modified platinum group catalyst. The same operation was performed to prepare a catalyst and carry out a reaction. After completion of stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.23% by weight, and the hydrogen selectivity was 20%.
【００１２】実施例４ 修飾白金族触媒調製に際して、担体として市販の二酸化
チタンの代わりに市販の酸化ジルコニウム（小宗化学薬
品（株）製）を用いたことを除き、実施例３と同様の操
作を行い触媒調製および反応を行った。１時間の攪拌終
了後、水溶液中の過酸化水素濃度は０．２０重量％であ
り、水素選択率は２０％であった。Example 4 The same procedure as in Example 3 except that a commercially available zirconium oxide (manufactured by Komune Chemical Co., Ltd.) was used as a carrier in the preparation of the modified platinum group catalyst, instead of the commercially available titanium dioxide. Then, catalyst preparation and reaction were performed. After completion of stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.20% by weight, and the hydrogen selectivity was 20%.
【００１３】実施例５ 修飾白金族触媒調製に際して、市販の硝酸ジルコニウム
４．３７ｇを溶解した水溶液の代わりに市販の硝酸ジル
コニウム２．１９ｇと市販の硝酸アルミニウム１０．４
３ｇを溶解した水溶液を用いたことを除き、実施例１と
同様の操作を行い触媒調製および反応を行った。１時間
の攪拌終了後、水溶液中の過酸化水素濃度は０．２５重
量％であり、水素選択率は３２％であった。Example 5 In preparing the modified platinum group catalyst, 2.19 g of commercially available zirconium nitrate and 10.4 of commercially available aluminum nitrate were used instead of the aqueous solution in which 4.37 g of commercially available zirconium nitrate was dissolved.
Catalyst preparation and reaction were carried out in the same manner as in Example 1 except that an aqueous solution in which 3 g was dissolved was used. After completion of stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.25% by weight, and the hydrogen selectivity was 32%.
【００１４】実施例６ 反応溶液として、硫酸０．１ｍｏｌ／リットルとなるよ
うに調製した水溶液１０ｇの代わりに５０ｐｐｍのエチ
レンジアミンテトラ（メチレンホスホン酸）および０．
１ｍｏｌ／リットルの硫酸を含む水溶液１０ｇを用いた
ことを除き、実施例１と同様の操作を行い触媒調製およ
び反応を行った。１時間の攪拌終了後、水溶液中の過酸
化水素濃度は０．３２重量％であり、水素選択率は５０
％であった。Example 6 As a reaction solution, 50 ppm of ethylenediaminetetra (methylenephosphonic acid) and 0.1% of an aqueous solution was prepared in place of 10 g of an aqueous solution prepared so that sulfuric acid was 0.1 mol / liter.
A catalyst was prepared and reacted in the same manner as in Example 1 except that 10 g of an aqueous solution containing 1 mol / liter of sulfuric acid was used. After stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.32% by weight, and the hydrogen selectivity was 50.
%Met.
【００１５】 比較例１（実施例１、３、５、６に対する） 白金族触媒調製に際して、市販の硝酸ジルコニウムを用
いずに二酸化チタン担体にパラジウムのみを担持したこ
とを除き、実施例１と同様の操作を行い触媒調製および
反応を行った。１時間の攪拌終了後水溶液中の過酸化水
素濃度は０．００重量％であり、水素選択率は０％であ
った。Comparative Example 1 (Compared to Examples 1, 3, 5, and 6) Similar to Example 1 except that when a platinum group catalyst was prepared, only titanium was supported on a titanium dioxide carrier without using commercially available zirconium nitrate. Then, the catalyst preparation and reaction were carried out. After completion of stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.00% by weight, and the hydrogen selectivity was 0%.
【００１６】比較例２（実施例２に対する） 白金族触媒調製に際して、二酸化チタンの代わりに酸化
アルミニウムを用いたことを除き、比較例１と同様の操
作を行い触媒調製および反応を行った。１時間の攪拌終
了後水溶液中の過酸化水素濃度は０．００重量％であ
り、水素選択率は０％であった。Comparative Example 2 (Comparative to Example 2) The catalyst preparation and reaction were carried out in the same manner as in Comparative Example 1 except that aluminum oxide was used in place of titanium dioxide when preparing the platinum group catalyst. After completion of stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.00% by weight, and the hydrogen selectivity was 0%.
【００１７】比較例３（実施例４に対する） 白金族触媒調製に際して、二酸化チタンの代わりに酸化
ジルコニウムを用いたことを除き、比較例１と同様の操
作を行い触媒調製および反応を行った。１時間の攪拌終
了後水溶液中の過酸化水素濃度は０．００重量％であ
り、水素選択率は０％であった。Comparative Example 3 (Comparative to Example 4) The catalyst was prepared and reacted in the same manner as in Comparative Example 1 except that zirconium oxide was used instead of titanium dioxide in the preparation of the platinum group catalyst. After completion of stirring for 1 hour, the hydrogen peroxide concentration in the aqueous solution was 0.00% by weight, and the hydrogen selectivity was 0%.
【００１８】[0018]
【発明の効果】本発明により、反応媒体である水溶液中
にハロゲンイオンを存在させなくとも選択的に高濃度の
過酸化水素が製造できる。よって、本発明により従来法
のような反応媒体中に高濃度のハロゲンイオンが共存す
ることにより生ずる、反応容器の材質の問題やハロゲン
イオンの共存による触媒活性の低下等の種々の問題点が
解決される。According to the present invention, a high concentration of hydrogen peroxide can be selectively produced without the presence of halogen ions in the aqueous solution which is the reaction medium. Therefore, according to the present invention, various problems such as the problem of the material of the reaction vessel and the decrease of the catalytic activity due to the coexistence of halogen ions, which are caused by the coexistence of high concentration of halogen ions in the reaction medium as in the conventional method, are solved. To be done.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河上 道也 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michiya Kawakami 6-1-1, Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory
Claims (6)
させて過酸化水素を製造する方法に於いて、触媒とし
て、ジルコニウム及びアルミニウムのうち少なくとも一
種以上の元素と白金族金属とを担体上に同時に担持する
ことにより調製された修飾白金族金属触媒を用いること
を特徴とする過酸化水素の製造方法。1. A method for producing hydrogen peroxide by catalytically reacting oxygen and hydrogen in a reaction medium, wherein as a catalyst, at least one element of zirconium and aluminum and a platinum group metal are used as a carrier. A method for producing hydrogen peroxide, which comprises using a modified platinum group metal catalyst prepared by simultaneously supporting the same on the above.
記載の過酸化水素の製造方法。2. The platinum group metal is palladium.
The method for producing hydrogen peroxide described above.
性水溶液である請求項１記載の過酸化水素の製造方法。3. The method for producing hydrogen peroxide according to claim 1, wherein the reaction medium is an acidic aqueous solution containing no halogen ions.
性水溶液である請求項１記載の過酸化水素の製造方法。4. The method for producing hydrogen peroxide according to claim 1, wherein the reaction medium is an acidic aqueous solution containing a stabilizer for hydrogen peroxide.
レンホスホン酸）、１−ヒドロキシエチリデン−１，１
−ジホスホン酸、エチレンジアミンテトラ（メチレンホ
スホン酸）、ピロリン酸、およびこれらの塩からなる群
から選ばれた少なくとも一種である請求項４記載の過酸
化水素の製造方法。5. A stabilizer of hydrogen peroxide is aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1.
The method for producing hydrogen peroxide according to claim 4, wherein the hydrogen peroxide is at least one selected from the group consisting of diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), pyrophosphoric acid, and salts thereof.
酸化ジルコニウム、酸化チタン、ゼオライト、シリカ−
アルミナ、活性炭、イオン交換樹脂および吸着樹脂から
なる群から選ばれた少なくとも１種である請求項１記載
の過酸化水素の製造方法。6. The carrier is aluminum oxide, silicon oxide,
Zirconium oxide, titanium oxide, zeolite, silica-
The method for producing hydrogen peroxide according to claim 1, which is at least one selected from the group consisting of alumina, activated carbon, an ion exchange resin, and an adsorption resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21743993A JPH0769604A (en) | 1993-09-01 | 1993-09-01 | Production of hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21743993A JPH0769604A (en) | 1993-09-01 | 1993-09-01 | Production of hydrogen peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0769604A true JPH0769604A (en) | 1995-03-14 |
Family
ID=16704252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21743993A Pending JPH0769604A (en) | 1993-09-01 | 1993-09-01 | Production of hydrogen peroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0769604A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3511295A1 (en) | 2018-01-15 | 2019-07-17 | Univerza V Ljubljani | Method for preparation of isotopically labeled hydrogen peroxide |
-
1993
- 1993-09-01 JP JP21743993A patent/JPH0769604A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3511295A1 (en) | 2018-01-15 | 2019-07-17 | Univerza V Ljubljani | Method for preparation of isotopically labeled hydrogen peroxide |
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