JPH04285003A - Production of hydrogen peroxide - Google Patents
Production of hydrogen peroxideInfo
- Publication number
- JPH04285003A JPH04285003A JP7435491A JP7435491A JPH04285003A JP H04285003 A JPH04285003 A JP H04285003A JP 7435491 A JP7435491 A JP 7435491A JP 7435491 A JP7435491 A JP 7435491A JP H04285003 A JPH04285003 A JP H04285003A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- hydrogen peroxide
- hydrogen
- catalyst
- 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
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 150000003016 phosphoric acids Chemical class 0.000 claims abstract description 6
- 239000012429 reaction media Substances 0.000 claims description 24
- -1 chlorine ions Chemical class 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000012431 aqueous reaction media Substances 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 45
- 239000007864 aqueous solution Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000581652 Hagenia abyssinica Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
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
を触媒と接触的に反応させ、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。FIELD OF THE INVENTION This invention relates to an improved process for producing hydrogen peroxide by catalytically reacting oxygen and hydrogen with a catalyst in a reaction medium.
【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、還元、
酸化、水抽出分離、精製、濃縮等のプロセスが複雑であ
り、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、水素
添加触媒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、上記製造方法以外の製造方法が試みられて
いるが、その一つに、反応媒体中で直接酸素と水素から
接触的に過酸化水素を製造する方法がある。既に、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示されている（特公昭５６−４７１
２１、特公昭５５−１８６４６、特公平１−２３４０１
、特開昭６３−１５６００５ ）。
これらでは、いずれも反応媒体として水溶液を用いてい
る。しかも、水溶液である反応媒体中に酸や無機塩を溶
存させている。特に反応媒体中にハロゲンイオンを含む
ことにより、反応の選択性が大幅に向上し、生成過酸化
水素の濃度を高めている。特開昭６３−１５６００５
号公報には、白金族触媒を用い、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、
水溶液中に臭素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できる
事が示されている。BACKGROUND OF THE INVENTION The main method for producing hydrogen peroxide currently practiced industrially is an autoxidation method using an alkylanthraquinone as a medium. The problem with this method is that reduction,
Processes such as oxidation, water extraction separation, purification, and concentration are complicated, and equipment costs and operating costs are high. Furthermore, there are also problems such as loss due to deterioration of alkylanthraquinone and deterioration of the hydrogenation catalyst. In order to improve these problems, production methods other than those described above have been attempted, one of which is a method of producing hydrogen peroxide catalytically from oxygen and hydrogen directly in a reaction medium. . A method for producing hydrogen peroxide from oxygen and hydrogen using a platinum group metal as a catalyst has already been proposed, and it has been shown that hydrogen peroxide can be produced at a considerable concentration (Japanese Patent Publication No. 56-471).
21, Special Publication No. 55-18646, Special Publication No. 1-23401
, Japanese Patent Publication No. 63-156005). In all of these, an aqueous solution is used as the reaction medium. Furthermore, an acid or an inorganic salt is dissolved in the reaction medium which is an aqueous solution. In particular, the inclusion of halogen ions in the reaction medium greatly improves the selectivity of the reaction and increases the concentration of hydrogen peroxide produced. Japanese Patent Publication No. 63-156005
The publication describes a method for producing hydrogen peroxide from oxygen and hydrogen under pressure in an acidic aqueous solution using a platinum group catalyst.
It has been shown that high concentration hydrogen peroxide can be selectively produced by coexisting halogen ions such as bromide ions in an aqueous solution.
【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
素を触媒の存在下で直接反応させて過酸化水素を製造す
る方法に於いて、高濃度の過酸化水素を選択性高く得る
ためには、反応媒体を酸性に保ち、しかも一定量以上の
ハロゲンイオンを存在させる必要がある。この場合、反
応媒体中に存在するハロゲンイオンは、一般に反応の選
択性を高める効果を示すが、同時に白金族触媒の触媒活
性を低下させるという問題が知られている。触媒活性の
低下は、取得される過酸化水素の濃度を低下させると共
に、より高い圧力での反応が必要となり、経済上大きな
問題となる。[Problem to be solved by the invention] In a method for producing hydrogen peroxide by directly reacting oxygen and hydrogen in the presence of a catalyst in a reaction medium, in order to obtain highly concentrated hydrogen peroxide with high selectivity. It is necessary to keep the reaction medium acidic and to have a certain amount or more of halogen ions present. In this case, the halogen ions present in the reaction medium generally have the effect of increasing the selectivity of the reaction, but are known to have the problem of simultaneously reducing the catalytic activity of the platinum group catalyst. A decrease in catalytic activity reduces the concentration of hydrogen peroxide obtained and requires a reaction at a higher pressure, which poses a major economic problem.
【０００４】0004
【課題を解決するための手段】本発明者らは、酸性の水
性反応媒体中で、酸素及び水素から接触的に過酸化水素
を製造する方法に於いて、白金族触媒の活性を低下させ
ることなく、ハロゲンイオンの助触媒効果を有効に利用
し、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、ハロゲンイオンとして塩素イオンを用い、かつ触
媒として酸化ランタン担持白金族触媒を用いることによ
り、この目的を達成できることを見いだした。この場合
、反応媒体を酸性に保つために、塩酸、硝酸、硫酸のご
とき一般の酸を用いた場合でも高濃度の過酸化水素が得
られるが、これら一般の酸は酸化ランタンを溶かすもの
が多く、反応後に酸化ランタンは反応媒体中に完全に溶
解消失する。そこで本発明者らは、さらに工業的に有利
な製造方法を検討した結果、酸として、オルト燐酸、亜
燐酸またはピロ燐酸のごとき燐酸類を用いることにより
、酸化ランタンの反応媒体への溶解消失を防ぎ得る事を
見いだした。即ち、本発明は、反応媒体中で酸素及び水
素を触媒の存在下で直接反応させて過酸化水素を製造す
る方法に於いて、燐酸類で酸性に保った水性反応媒体を
使用し、かつ酸化ランタン担持白金族触媒と塩素イオン
助触媒を組み合わせて用いることにより高活性・高選択
性を同時に達成せしめ、高濃度の過酸化水素を取得する
事を特徴とする過酸化水素の製造方法である。Means for Solving the Problems The present inventors have proposed a method for catalytically producing hydrogen peroxide from oxygen and hydrogen in an acidic aqueous reaction medium by reducing the activity of a platinum group catalyst. As a result of continuing to study a production method that effectively utilizes the cocatalytic effect of halogen ions to obtain high-concentration hydrogen peroxide, we found that we used chlorine ions as the halogen ions and a platinum group catalyst supported on lanthanum oxide as the catalyst. We found that this purpose could be achieved by doing so. In this case, high concentrations of hydrogen peroxide can be obtained even if common acids such as hydrochloric acid, nitric acid, or sulfuric acid are used to keep the reaction medium acidic, but these common acids often dissolve lanthanum oxide. After the reaction, the lanthanum oxide completely dissolves and disappears in the reaction medium. Therefore, the present inventors further investigated an industrially advantageous production method, and found that by using phosphoric acids such as orthophosphoric acid, phosphorous acid, or pyrophosphoric acid as the acid, dissolution and disappearance of lanthanum oxide in the reaction medium can be reduced. I found something that could be prevented. That is, the present invention uses an aqueous reaction medium kept acidic with phosphoric acids in a method for producing hydrogen peroxide by directly reacting oxygen and hydrogen in the presence of a catalyst in a reaction medium, and This method of producing hydrogen peroxide is characterized by simultaneously achieving high activity and high selectivity by using a combination of a lanthanum-supported platinum group catalyst and a chloride ion co-catalyst, and obtaining high-concentration hydrogen peroxide.
【０００５】本発明に於いて触媒として用いられる白金
族金属は具体的にはルテニウム、オスミウム、ロジウム
、イリジウム、パラジウム、白金などであり、これらを
単独またはそれらの２種以上の混合物もしくは合金とし
て用いることができる。通常、パラジウムまたは白金が
用いられることが多いが、特にパラジウムが好ましい。
これらの白金族金属は通常酸化ランタン担体上に１〜５
重量％の割合で担持されて触媒として使用されるが、触
媒の使用量としては反応媒体１リットル当たり１ｇ〜１
００ｇ、好ましくは５ｇ〜５０ｇ が使用される。本発
明に於いて、酸化ランタンを担体として用いることによ
り、塩化パラジウムや硝酸パラジウム等の白金族金属塩
の吸着が極めて容易に起こり、触媒調製が効率的に行わ
れると共に高活性の触媒の調製を容易にするメリットが
ある。担体として用いられる酸化ランタンの形状は微粉
、粒、ペレット等任意に選択される。[0005] Platinum group metals used as catalysts in the present invention are specifically ruthenium, osmium, rhodium, iridium, palladium, platinum, etc., and these may be used alone or as a mixture or alloy of two or more thereof. be able to. Usually, palladium or platinum is often used, and palladium is particularly preferred. These platinum group metals are usually 1-5 on a lanthanum oxide support.
It is used as a catalyst supported in a proportion of 1% by weight, but the amount of catalyst used is 1g to 1% per liter of reaction medium.
00g, preferably 5g to 50g. In the present invention, by using lanthanum oxide as a carrier, adsorption of platinum group metal salts such as palladium chloride and palladium nitrate occurs extremely easily, making it possible to efficiently prepare a catalyst and to prepare a highly active catalyst. It has the advantage of making it easier. The shape of the lanthanum oxide used as a carrier is arbitrarily selected such as fine powder, grains, pellets, etc.
【０００６】本発明に於いて、塩素イオンを助触媒とし
て用いた場合には触媒活性の低下は認められず、しかも
高選択性を示し高濃度の過酸化水素が生成する。しかし
臭素イオンを助触媒として用いた場合には、高い選択性
は得られるが、著しい触媒活性の低下が認められ、本発
明と同等の好結果を得ることは出来ない。つまり本発明
が示すごとく、塩素イオンと酸化ランタン担持白金族触
媒の組合せが極めて有利であることが理解される。本発
明に於いて、必要な塩素イオンの量は使用する触媒の量
にもよるが、一般的には反応媒体１リットル当たり０．
００１ミリモル以上、好ましくは０．１ミリモル以上で
ある。塩素イオンの上限量は特に規定されるものではな
いが、使用する触媒に担持された金属の反応媒体中での
濃度が１ミリグラム／リットルに対し０．０２モル／リ
ットル以上の塩素イオンを加えても添加量増加に見合う
効果は得られない。また塩酸のごとき酸の形態で塩素イ
オンを添加する場合には、塩酸の添加量を大幅に増やす
と酸化ランタンの溶出が起こるため好ましくない。しか
し本発明者らは、酸化ランタンが塩基性であり、一定量
以上の塩酸を添加しない限り反応媒体は酸性を示すに至
らず、その結果酸化ランタンの溶出は全く起こらず、し
かもこの範囲の塩素イオン濃度の存在で充分な助触媒効
果が発揮されることを見いだした。In the present invention, when chlorine ions are used as a cocatalyst, no decrease in catalytic activity is observed, and moreover, high selectivity is exhibited and hydrogen peroxide is produced at a high concentration. However, when bromide ions are used as a co-catalyst, although high selectivity can be obtained, a significant decrease in catalytic activity is observed, and good results equivalent to those of the present invention cannot be obtained. In other words, as shown in the present invention, it is understood that the combination of chloride ions and platinum group catalyst supported on lanthanum oxide is extremely advantageous. In the present invention, the amount of chlorine ions required depends on the amount of catalyst used, but is generally 0.000 chloride per liter of reaction medium.
0.001 mmol or more, preferably 0.1 mmol or more. The upper limit of the amount of chlorine ions is not particularly specified, but if the concentration of chlorine ions in the reaction medium of the metal supported on the catalyst used is 1 milligram/liter, 0.02 mol/liter or more of chlorine ions should be added. However, the effect commensurate with the increase in the amount added cannot be obtained. Further, when adding chlorine ions in the form of an acid such as hydrochloric acid, it is not preferable because lanthanum oxide will elute if the amount of added hydrochloric acid is significantly increased. However, the present inventors discovered that lanthanum oxide is basic and that the reaction medium does not become acidic unless a certain amount of hydrochloric acid is added. It has been found that the presence of ion concentration provides a sufficient cocatalytic effect.
【０００７】更に、本発明では反応媒体として水溶液（
水性反応媒体）が使用されるが、水性反応媒体を酸性に
保つための酸としてオルト燐酸、亜燐酸またはピロ燐酸
のごとき燐酸類を用いることにより酸化ランタンの溶出
が完全に抑制され、本発明が極めて有利に実施されるこ
とが見いだされた。本発明ではオルト燐酸やピロ燐酸な
どが好適に使用されるが、これらの燐酸類の使用量は反
応媒体１リットル当たり０．０１モル〜１モルが使用さ
れる。本発明を実施する場合に用いられる反応槽は固定
床でも撹拌槽でも使用できる。また、本発明の過酸化水
素の製造反応は通常、反応圧力３ｋｇ／ｃｍ２ ・Ｇ〜
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。Furthermore, in the present invention, an aqueous solution (
However, by using phosphoric acids such as orthophosphoric acid, phosphorous acid, or pyrophosphoric acid as an acid to keep the aqueous reaction medium acidic, the elution of lanthanum oxide is completely suppressed, and the present invention It has been found that this can be carried out with great advantage. In the present invention, orthophosphoric acid, pyrophosphoric acid, etc. are preferably used, and the amount of these phosphoric acids used is 0.01 mol to 1 mol per liter of reaction medium. The reaction vessel used in carrying out the present invention can be either a fixed bed or a stirred vessel. In addition, the hydrogen peroxide production reaction of the present invention is usually carried out at a reaction pressure of 3 kg/cm2 ・G~
The reaction is carried out under the following conditions: 150 kg/cm 2 ·G, reaction temperature 0 to 50°C, and reaction time 30 minutes to 6 hours.
【０００８】[0008]
【実施例】次に、実施例及び比較例で本発明を更に具体
的に説明する。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。溶液中の
過酸化水素濃度の測定は、硫酸酸性ー過マンガン酸カリ
ウムによる滴定法により行った。また、溶液中の金属イ
オン濃度の測定は、誘導結合型プラズマ発光分析法〔セ
イコー電子工業株式会社製の１２００ＶＲ型分析計使用
。〕により行った。[Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The analytical values of gas composition used in the examples are values determined by gas chromatography. The concentration of hydrogen peroxide in the solution was measured by titration using sulfuric acid and potassium permanganate. In addition, the metal ion concentration in the solution was measured by inductively coupled plasma emission spectrometry [using a 1200VR model analyzer manufactured by Seiko Electronics Industries, Ltd.]. ].
【０００９】実施例１
塩化パラジウム（小宗化学社製）を、市販の酸化ランタ
ン（関東化学社製）に含浸法により担持させた。活性成
分であるパラジウムの重量が、酸化ランタンの重量に対
して１％となるように塩化パラジウムの水溶液の添加量
を調整した。含浸操作後、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。乾
燥後４００℃にて空気気流中で２時間焼成し、その後２
００℃にて水素気流中で１時間還元することにより触媒
を調製した。内容積６５ｍｌのガラス容器に、反応媒体
として塩酸０．０１ｍｏｌ／ｌ、オルト燐酸０．１ｍｏ
ｌ／ｌとなるように調製した水溶液１０ｇを入れた。こ
の水溶液に、上記の方法で調製した触媒を５０ｍｇ加え
、このガラス容器を１００ｍｌの容積のオートクレーブ
に入れた。水素ガス４容量％、酸素ガス４０容量％、窒
素ガス５６容量％からなる混合ガスにてオートクレーブ
内を置換後、この混合ガスにて５０ｋｇ／ｃｍ２ ・Ｇ
まで加圧した後、全体を１０℃に保ち、撹拌回転数２０
００ｒｐｍにて１時間反応させた。反応中ガスの補給は
行わなかった。反応後の水溶液中の過酸化水素濃度は０
．８９重量％であり、この時の水素選択率は８２％、転
化率は４２％であった。反応後の反応液中のランタンイ
オンの濃度は、１ｐｐｍ以下であった。尚、水素選択率
及び水素転化率は次式によって計算した。Example 1 Palladium chloride (manufactured by Koso Kagaku Co., Ltd.) was supported on commercially available lanthanum oxide (manufactured by Kanto Kagaku Co., Ltd.) by an impregnation method. The amount of the palladium chloride aqueous solution added was adjusted so that the weight of palladium, which is an active ingredient, was 1% based on the weight of lanthanum oxide. After the impregnation operation, it was evaporated to dryness on a hot plate, and further dried in a dryer at 110° C. all day and night. After drying, it was baked at 400℃ for 2 hours in an air stream, and then 2 hours.
The catalyst was prepared by reduction in a hydrogen stream at 00°C for 1 hour. In a glass container with an internal volume of 65 ml, 0.01 mol/l of hydrochloric acid and 0.1 mol of orthophosphoric acid were added as reaction media.
10 g of an aqueous solution prepared at a ratio of 1/1 was added. 50 mg of the catalyst prepared by the above method was added to this aqueous solution, and the glass container was placed in a 100 ml autoclave. After replacing the inside of the autoclave with a mixed gas consisting of 4% by volume of hydrogen gas, 40% by volume of oxygen gas, and 56% by volume of nitrogen gas, this mixed gas produced 50kg/cm2・G
After pressurizing to
The reaction was carried out at 00 rpm for 1 hour. Gas was not replenished during the reaction. The hydrogen peroxide concentration in the aqueous solution after the reaction is 0.
．． The hydrogen selectivity at this time was 82% and the conversion rate was 42%. The concentration of lanthanum ions in the reaction solution after the reaction was 1 ppm or less. Note that the hydrogen selectivity and hydrogen conversion rate were calculated using the following formula.
【００１０】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）〕×１
００Hydrogen selectivity (%) = [(amount of hydrogen peroxide produced by reaction, mol) ÷ (theoretical production amount of hydrogen peroxide, mol calculated from the amount of hydrogen consumed)]×1
00
【００１１】水素転化率（％）＝｛〔（反応前の容
器内の水素ガス量 ｍｏｌ）−（反応後の容器内の水
素ガス量 ｍｏｌ）〕÷（反応前の容器内の水素ガス
量ｍｏｌ）｝×１００Hydrogen conversion rate (%) = {[(amount of hydrogen gas in the container before reaction, mol) - (amount of hydrogen gas in the container after reaction, mol)] ÷ (amount of hydrogen gas in the container before reaction, mol) )}×100
【００１２】比較例１
反応媒体として臭素酸ナトリウム０．５ｍｍｏｌ／ｌ、
オルト燐酸０．１ｍｏｌ／ｌとなるように調製した水溶
液を用いたことを除き、実施例１と同様の反応方法によ
る操作を行った。反応後の水溶液中の過酸化水素濃度は
０．２０重量％であり、この時の水素選択率は８０％、
水素転化率は８％であった。また、反応後の反応液中の
ランタンイオンの濃度は、１ｐｐｍ以下であった。Comparative Example 1 Sodium bromate 0.5 mmol/l as reaction medium;
The same reaction method as in Example 1 was carried out except that an aqueous solution prepared to have an orthophosphoric acid concentration of 0.1 mol/l was used. The hydrogen peroxide concentration in the aqueous solution after the reaction was 0.20% by weight, and the hydrogen selectivity at this time was 80%.
The hydrogen conversion rate was 8%. Further, the concentration of lanthanum ions in the reaction solution after the reaction was 1 ppm or less.
【００１３】比較例２
反応媒体として、塩酸０．０１ｍｏｌ／ｌ、硫酸０．１
ｍｏｌ／ｌとなるように調製した水溶液を用いたことを
除き、実施例１と同様の反応方法による操作を行った。
反応後の水溶液中の過酸化水素濃度は０．４１重量％で
あり、この時の水素選択率は８０％、水素転化率は２３
％であった。反応後、酸化ランタンは完全に溶解消失し
、金属パラジウムが微粉となって残った。Comparative Example 2 Hydrochloric acid 0.01 mol/l and sulfuric acid 0.1 mol/l were used as the reaction medium.
The same reaction method as in Example 1 was performed except that an aqueous solution prepared to have a mol/l ratio was used. The hydrogen peroxide concentration in the aqueous solution after the reaction was 0.41% by weight, the hydrogen selectivity at this time was 80%, and the hydrogen conversion rate was 23%.
%Met. After the reaction, the lanthanum oxide completely dissolved and disappeared, leaving metallic palladium as a fine powder.
【００１４】比較例３
反応媒体として、塩酸０．１ｍｏｌ／ｌとなるように調
製した水溶液を用いたことを除き、実施例１と同様の反
応方法による操作を行った。反応後の水溶液中の過酸化
水素濃度は０．５２重量％であり、この時の水素選択率
は８３％、水素転化率は２８％であった。反応後、酸化
ランタンは完全に溶解消失し、金属パラジウムが微粉と
なって残った。Comparative Example 3 The same reaction method as in Example 1 was carried out except that an aqueous solution of hydrochloric acid prepared to have a concentration of 0.1 mol/l was used as the reaction medium. The hydrogen peroxide concentration in the aqueous solution after the reaction was 0.52% by weight, the hydrogen selectivity at this time was 83%, and the hydrogen conversion rate was 28%. After the reaction, the lanthanum oxide completely dissolved and disappeared, leaving metallic palladium as a fine powder.
【００１５】実施例２
反応媒体として、塩酸０．０１ｍｏｌ／ｌ、ピロ燐酸０
．１ｍｏｌ／ｌとなるように調製した水溶液を用いたこ
とを除き、実施例１と同様の反応方法による操作を行っ
た。反応後の水溶液中の過酸化水素濃度は０．７７重量
％であり、この時の水素選択率は７１％、水素転化率は
４２％であった。反応後の反応液中のランタンイオン濃
度は１ｐｐｍ以下であった。Example 2 As reaction medium, hydrochloric acid 0.01 mol/l, pyrophosphoric acid 0
．． The same reaction method as in Example 1 was performed except that an aqueous solution prepared to have a concentration of 1 mol/l was used. The hydrogen peroxide concentration in the aqueous solution after the reaction was 0.77% by weight, the hydrogen selectivity at this time was 71%, and the hydrogen conversion rate was 42%. The lanthanum ion concentration in the reaction solution after the reaction was 1 ppm or less.
【００１６】実施例３
反応媒体として塩化カリウム０．０５ｍｏｌ／ｌ、オル
ト燐酸０．１ｍｏｌ／ｌとなるように調製した水溶液を
用いたことを除き、実施例１と同様の反応方法による操
作を行った。反応後の水溶液中の過酸化水素濃度は０．
７６重量％であり、この時の水素選択率は８１％、水素
転化率は３６％であった。また、反応後の反応液中のラ
ンタンイオンの濃度は１ｐｐｍ以下であった。Example 3 The same reaction method as in Example 1 was carried out, except that an aqueous solution prepared to contain potassium chloride 0.05 mol/l and orthophosphoric acid 0.1 mol/l was used as the reaction medium. Ta. The hydrogen peroxide concentration in the aqueous solution after the reaction is 0.
The hydrogen selectivity at this time was 81% and the hydrogen conversion rate was 36%. Further, the concentration of lanthanum ions in the reaction solution after the reaction was 1 ppm or less.
【００１７】[0017]
【発明の効果】比較例に対して本発明の実施例では、高
い水素選択率が得られており、同時に水素転化率が高く
取得過酸化水素の濃度が高くなっている。さらに、酸化
ランタンの溶出は完全に抑制されている。このように本
発明の製造方法によれば、効率よく高濃度の過酸化水素
を製造することができる。Effects of the Invention: Compared to the comparative example, in the example of the present invention, a high hydrogen selectivity was obtained, and at the same time, the hydrogen conversion rate was high and the concentration of obtained hydrogen peroxide was high. Furthermore, the elution of lanthanum oxide is completely suppressed. As described above, according to the production method of the present invention, highly concentrated hydrogen peroxide can be produced efficiently.
Claims (1)
と接触的に反応させ、過酸化水素を製造する方法に於い
て、（１）酸化ランタンを担体とする担持白金族触媒を
使用し、（２）燐酸類の添加により、酸性に保った水性
反応媒体を使用し、（３）塩素イオンを助触媒として共
存させることを特徴とする過酸化水素の製造方法。Claim 1: A method for producing hydrogen peroxide by catalytically reacting oxygen and hydrogen with a platinum group catalyst in a reaction medium, comprising: (1) using a supported platinum group catalyst using lanthanum oxide as a carrier; , (2) using an aqueous reaction medium kept acidic by adding phosphoric acids, and (3) allowing chlorine ions to coexist as a co-catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7435491A JPH04285003A (en) | 1991-03-15 | 1991-03-15 | Production of hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7435491A JPH04285003A (en) | 1991-03-15 | 1991-03-15 | Production of hydrogen peroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04285003A true JPH04285003A (en) | 1992-10-09 |
Family
ID=13544707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7435491A Pending JPH04285003A (en) | 1991-03-15 | 1991-03-15 | Production of hydrogen peroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04285003A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378450A (en) * | 1993-04-19 | 1995-01-03 | Mitsubishi Gas Chemical Company, Inc. | Process for producing hydrogen peroxide |
| US5496532A (en) * | 1992-11-20 | 1996-03-05 | Showa Denko K. K. | Process for producing hydrogen peroxide |
-
1991
- 1991-03-15 JP JP7435491A patent/JPH04285003A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496532A (en) * | 1992-11-20 | 1996-03-05 | Showa Denko K. K. | Process for producing hydrogen peroxide |
| US5378450A (en) * | 1993-04-19 | 1995-01-03 | Mitsubishi Gas Chemical Company, Inc. | Process for producing hydrogen peroxide |
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