JPS6256450A - Production of oxalic acid - Google Patents
Production of oxalic acidInfo
- Publication number
- JPS6256450A JPS6256450A JP60196069A JP19606985A JPS6256450A JP S6256450 A JPS6256450 A JP S6256450A JP 60196069 A JP60196069 A JP 60196069A JP 19606985 A JP19606985 A JP 19606985A JP S6256450 A JPS6256450 A JP S6256450A
- Authority
- JP
- Japan
- Prior art keywords
- osmium tetroxide
- oxalic acid
- catalyst
- propylene
- copper halide
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は気相接触酸化反応によりプロピレンから直接シ
ュウ酸を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing oxalic acid directly from propylene by a gas phase catalytic oxidation reaction.
〔従来技術及び発明が解決しようとする問題点〕化学薬
品等として有用なシュウ酸は主としてギ酸ソーダ法によ
り製造されており、その他の製法としてエチレングリコ
ール法、ジブチルエステル法などが知られている。しか
しながら、これらは工程が長（、副産物も多いという欠
点や原料を安価に入手できない等の欠点もある。[Prior Art and Problems to be Solved by the Invention] Oxalic acid, which is useful as a chemical agent, is mainly produced by the sodium formate method, and other known production methods include the ethylene glycol method and the dibutyl ester method. However, these methods have drawbacks such as long processes (and many by-products), and the inability to obtain raw materials at low prices.
一方、四酸化オスミウム（ＯｓＯ４）はオレフィンを酸
化してグリコールを製造する際の触媒として用いられて
いる。この酸化反応は水と塩基の共存下に過酸化物を酸
化剤として用いて行なわれる。On the other hand, osmium tetroxide (OsO4) is used as a catalyst when oxidizing olefins to produce glycols. This oxidation reaction is carried out in the presence of water and a base using peroxide as an oxidizing agent.
これまでに四酸化オスミウム触媒を不均一系接触酸化反
応に使用した例がない。本発明者らはプロピレンの酸化
反応に対する四酸化オスミウムの触媒作用について検討
したところ、酸素ガスによる気相接触酸化反応に利用す
ると、プロピレンから直接シュウ酸が製造できることを
見出し、かかる知見に基いて本発明を完成した。Until now, there is no example of using an osmium tetroxide catalyst in a heterogeneous catalytic oxidation reaction. The present inventors investigated the catalytic effect of osmium tetroxide on the oxidation reaction of propylene and found that oxalic acid can be produced directly from propylene when used in a gas phase catalytic oxidation reaction using oxygen gas. Completed the invention.
すなわち本発明は、四酸化オスミウムまたは四酸化オス
ミウムとハロゲン化銅を触媒としてプロピレンを酸素と
反応させることを特徴とするシュウ酸の製造方法である
。That is, the present invention is a method for producing oxalic acid characterized by reacting propylene with oxygen using osmium tetroxide or osmium tetroxide and copper halide as a catalyst.
この反応は以下の式によって表わされる。This reaction is expressed by the following formula.
プロピレンの酸化反応に用いる触媒は四酸化オスミウム
または四酸化オスミウムとハロゲン化銅であり、ハロゲ
ン化銅としては臭化銅（ＣｕＢｒ２）が好ましい。触媒
は上記触媒成分を担体に担持して用いることが好ましく
、担体としてはアルミナ。The catalyst used for the propylene oxidation reaction is osmium tetroxide or osmium tetroxide and copper halide, and copper bromide (CuBr2) is preferable as the copper halide. The catalyst is preferably used by supporting the above catalyst components on a carrier, and the carrier is alumina.
活性炭、ケイソウ土、シリカゲル等の各種のものを使用
できるが、活性炭を用いると四酸化オスミウムが流失し
ないので好都合である。担持率は四酸化オスミウムの場
合、０．１〜２０重量％、望ましくは１〜５重量％が適
当である。また、ハロゲン化銅を併用する場合も同時に
担体に担持することが好ましい。ハロゲン化銅の使用量
は四酸化オスミウム１に対して０．１〜１０ （重量比
）、好ましくは０．５〜５（重量比）が適当である。Various materials such as activated carbon, diatomaceous earth, and silica gel can be used, but activated carbon is advantageous because it prevents osmium tetroxide from being washed away. In the case of osmium tetroxide, the supporting ratio is suitably 0.1 to 20% by weight, preferably 1 to 5% by weight. Also, when copper halide is used in combination, it is preferable to support it on the carrier at the same time. The appropriate amount of copper halide to be used is 0.1 to 10 (weight ratio), preferably 0.5 to 5 (weight ratio) to 1 part of osmium tetroxide.
触媒の調製記担持法により行なう場合、四酸化オスミウ
ム（およびハロゲン化銅）と水、担体（特に活性炭）を
混合し、空気流通下Ｏ℃程度にて水を蒸発させることに
より目的とする触媒が得られる。触媒として四酸化オス
ミウムと共にハロゲン化銅を用いることにより、シュウ
酸の選択率は向上する。Preparation of catalyst When using the supported method, the desired catalyst is prepared by mixing osmium tetroxide (and copper halide), water, and a carrier (especially activated carbon), and evaporating the water at about 0°C under air circulation. can get. By using copper halide with osmium tetroxide as a catalyst, the selectivity of oxalic acid is improved.
次に、反応条件について述べると、プロピレンと酸素の
混合ガス組成（容量比）を前者：後者＝１：０．０１〜
１０、好ましくは１：０．１〜５とし、さらにＮｚ、Ｆ
ｌｅ、Ａｒなどの不活性ガスとｉｔの水蒸気を存在させ
て反応を行なうことが望ましい。Next, regarding the reaction conditions, the mixed gas composition (volume ratio) of propylene and oxygen is the former: latter = 1: 0.01 ~
10, preferably 1:0.1 to 5, and further Nz, F
It is desirable to carry out the reaction in the presence of an inert gas such as Le, Ar, etc. and water vapor.
この場合、プロピレン／不活性ガス／Ｈ，Ｏ＝１／１〜
１００１０．０１〜１０ （容量比）の割合で用いる。In this case, propylene/inert gas/H,O=1/1~
Used at a ratio of 10010.01 to 10 (capacity ratio).
反応温度は５０〜２００℃、好ましくは８０〜１５０℃
が適当であり、触媒と原料ガスの接触時間Ｗ／Ｆ （触
媒量／流量）は１０〜１０’ｇＣａｔ、 ・ｈｒ／ｍｏ
１ 、、好ましくは１０”〜３ Ｘ １０’ｇＣａｔ
、 −ｈｒ／ｍｏ １ 、である。また、反応圧力は０
．１〜１０気圧の範囲であり、常圧が好ましい。Reaction temperature is 50-200°C, preferably 80-150°C
is appropriate, and the contact time W/F (catalyst amount/flow rate) between catalyst and raw material gas is 10 to 10'gCat, hr/mo
1, preferably 10"~3 x 10'gCat
, -hr/mo 1 . Also, the reaction pressure is 0
．． The pressure is in the range of 1 to 10 atm, preferably normal pressure.
本発明の方法によるシュウ酸の生成機構については、触
媒上に分子状に固定化されている四酸化オスミウムにプ
ロピレンが吸着して安定なサイクリックエステルを形成
し、次いで酸素との１次反応によりシュウ酸が生成する
ものと推定される。The production mechanism of oxalic acid by the method of the present invention is that propylene is adsorbed to osmium tetroxide, which is molecularly immobilized on the catalyst, to form a stable cyclic ester, and then through a primary reaction with oxygen. It is estimated that oxalic acid is produced.
したがって、該サイクリックエステルの加水分解を促進
させ、生成物の脱離を促す助触媒を共存させることによ
ってシュウ酸の生成効率を著しく向上させることができ
る。Therefore, the production efficiency of oxalic acid can be significantly improved by coexisting with a co-catalyst that promotes the hydrolysis of the cyclic ester and the elimination of the product.
次に、本発明を実施例により詳しく説明する。 Next, the present invention will be explained in detail with reference to examples.
実施例１
１００ｍ７！容のフラスコに四酸化オスミウム０、０４
ｇをとり、水１０ｍ６を加えて溶解させた。Example 1 100m7! Osmium tetroxide in a flask with a volume of 0.04
g was taken, and 10 m6 of water was added to dissolve it.
次に、フラスコを０℃に冷却して活性炭４ｇを加え、０
℃に冷却したまま空気を流して水を蒸発せしめ、１重量
％の四酸化オスミウムが担持された活性炭触媒を調製し
た。Next, cool the flask to 0°C, add 4g of activated carbon, and
Water was evaporated by flowing air while cooling to 0.degree. C. to prepare an activated carbon catalyst on which 1% by weight of osmium tetroxide was supported.
この触媒２ｇを内径Ｌｏｗのガラス製反応管に入れ、ガ
ス組成プロピレン／酸素／ヘリウム／Ｈ２０＝１１０．
３／１．２１０．０１５ （容量比）の混合ガスをＷ／
Ｆ＝１５００ｇＣａｔ、−ｈｒ／ｍｏ１．にて流して１
００℃で反応させた。2 g of this catalyst was placed in a glass reaction tube with a low inner diameter, and the gas composition was propylene/oxygen/helium/H20=110.
3/1.210.015 (volume ratio) mixed gas W/
F=1500gCat, -hr/mo1. 1
The reaction was carried out at 00°C.
反応ガスをガスクロマトグラフィーにて分析したところ
、プロピレン転化率１．７％、シュウ酸選択率４４．２
％、シュウ酸収率０．７５％であった。When the reaction gas was analyzed by gas chromatography, the propylene conversion rate was 1.7% and the oxalic acid selectivity was 44.2.
%, and the oxalic acid yield was 0.75%.
実施例２
実施例１において、四酸化オスミウム０．０４ｇと共に
臭化銅０．０４ ｇを用いて触媒を調製し、四酸化オス
ミウム１重量％および臭化銅１重量％が担持された活性
炭触媒を得た。Example 2 In Example 1, a catalyst was prepared using 0.04 g of osmium tetroxide and 0.04 g of copper bromide, and an activated carbon catalyst supported with 1% by weight of osmium tetroxide and 1% by weight of copper bromide was prepared. Obtained.
この触媒２ｇを用いて実施例１と同様に反応を行なった
。反応ガスを分析した結果、プロピレン転化率４．０％
、シュウ酸選択率９７．５％、シュウ酸収率３，９％で
あった。A reaction was carried out in the same manner as in Example 1 using 2 g of this catalyst. As a result of analyzing the reaction gas, the propylene conversion rate was 4.0%.
, oxalic acid selectivity was 97.5%, and oxalic acid yield was 3.9%.
本発明によれば、プロピレンから直接シュウ酸を製造す
ることができる。特に、触媒として四酸化オスミウムと
共にハロゲン化銅を用いると、シュウ酸選択率は著しく
高くなる。According to the present invention, oxalic acid can be produced directly from propylene. In particular, when copper halide is used together with osmium tetroxide as a catalyst, the oxalic acid selectivity is significantly increased.
得られたシュウ酸は化学薬品、染料、染色助剤。The resulting oxalic acid is used as a chemical, dye, and dyeing aid.
分析試薬等としてを用である。It is used as an analytical reagent, etc.
Claims (3)
ゲン化銅を触媒としてプロピレンを酸素と反応させるこ
とを特徴とするシュウ酸の製造方法。(1) A method for producing oxalic acid, which comprises reacting propylene with oxygen using osmium tetroxide or osmium tetroxide and copper halide as a catalyst.
第１項記載の方法。(2) The method according to claim 1, wherein the catalyst component is supported on activated carbon.
範囲第１項記載の方法。(3) The method according to claim 1, wherein the reaction is carried out at a temperature of 50 to 200°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60196069A JPS6256450A (en) | 1985-09-06 | 1985-09-06 | Production of oxalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60196069A JPS6256450A (en) | 1985-09-06 | 1985-09-06 | Production of oxalic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6256450A true JPS6256450A (en) | 1987-03-12 |
Family
ID=16351678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60196069A Pending JPS6256450A (en) | 1985-09-06 | 1985-09-06 | Production of oxalic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6256450A (en) |
-
1985
- 1985-09-06 JP JP60196069A patent/JPS6256450A/en active Pending
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