JP3313217B2 - Method for producing glyoxylic acid - Google Patents
Method for producing glyoxylic acidInfo
- Publication number
- JP3313217B2 JP3313217B2 JP31781293A JP31781293A JP3313217B2 JP 3313217 B2 JP3313217 B2 JP 3313217B2 JP 31781293 A JP31781293 A JP 31781293A JP 31781293 A JP31781293 A JP 31781293A JP 3313217 B2 JP3313217 B2 JP 3313217B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- platinum
- aqueous
- solution
- acid
- 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.)
- Expired - Fee Related
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
Description
【０００１】[0001]
【産業上の利用分野】本発明はグリオキシル酸の新規な
製造方法に関する。さらにくわしくは触媒量の白金とパ
ラジウム、鉛、錫、ビスマスからなる群から選んだ一種
以上の元素、またはその元素の化合物の存在下、グリオ
キサール水溶液を酸素により触媒酸化してグリオキシル
酸を製造する方法に関する。The present invention relates to a novel process for producing glyoxylic acid. More specifically, a method for producing glyoxylic acid by catalytically oxidizing an aqueous glyoxal solution with oxygen in the presence of a catalytic amount of one or more elements selected from the group consisting of platinum, palladium, lead, tin, and bismuth, or a compound of those elements. About.
【０００２】[0002]
【従来の技術】グリオキシル酸はアモキシリンやバニリ
ンなどを合成する中間体として非常に有用な化合物であ
る。グリオキシル酸を製造する方法については種々の提
案がある。例えば、グリオキサールの硝酸酸化にる方法
が現在行われている。この酸化を塩素、過酸化水素によ
って行うこともできる。また、グリオキサールの酸化は
電解の陽極部における電気化学的手段によっても行うこ
とができる。2. Description of the Related Art Glyoxylic acid is a very useful compound as an intermediate for synthesizing amoxicillin and vanillin. There are various proposals for a method for producing glyoxylic acid. For example, a method based on nitric acid oxidation of glyoxal is currently used. This oxidation can be carried out with chlorine or hydrogen peroxide. Glyoxal can also be oxidized by electrochemical means at the anode part of the electrolysis.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これらの方法
はグリオキサール、蓚酸の分離精製を必要とし、連続作
業に適しないという問題があった。又、マレイン酸のオ
ゾン酸化や蓚酸の電解還元による製造方法も公知である
が、高価な試薬や装置を使用したり選択性が良好でない
などの欠点があった。However, these methods have a problem that they require separation and purification of glyoxal and oxalic acid and are not suitable for continuous operation. Although methods for producing maleic acid by ozone oxidation and oxalic acid by electrolytic reduction are also known, they have drawbacks such as the use of expensive reagents and equipment and poor selectivity.
【０００４】一方、貴金属を触媒としてアルコールを酸
化してカルボン酸を得ることは公知である。例えば、パ
ラジウム系多元触媒によるアルコールの接触酸化につい
て、「触媒」誌 vol.33 No.2 p111(1991) にはパラジウ
ム−カーボン触媒（収率８６％）だけよりも鉛、錫、ビ
スマス、テルル、セリウム、ランタンと複合化すること
によりカルボン酸収率（９６％）が上がることが記載さ
れていたり、特開昭５４−１３８８８６では白金または
パラジウム系多元触媒（助触媒パラジウム、錫、インジ
ウム、テルル）による１−プロパノールからプロピオン
酸ソーダ、グルコースからグルコン酸ソーダ、ジエチレ
ングリコールからジソジウムオキシジアセテートの製造
方法が記載されている。On the other hand, it is known to oxidize an alcohol using a noble metal as a catalyst to obtain a carboxylic acid. For example, regarding the catalytic oxidation of alcohol using a palladium-based multi-way catalyst, “Catalyst” vol. 33 No. 2 p111 (1991) shows that lead, tin, bismuth, tellurium, It is described that the carboxylic acid yield (96%) is increased by complexing with cerium and lanthanum, and Japanese Patent Application Laid-Open No. 54-138886 discloses a platinum or palladium-based multi-way catalyst (promoter palladium, tin, indium, tellurium). Describes a method for producing sodium propionate from 1-propanol, sodium gluconate from glucose, and disodium oxydiacetate from diethylene glycol.
【０００５】貴金属触媒を用いてジオールの一方だけの
ＯＨ基を酸化し、α−ヒドロキシカルボン酸を得ること
は特公昭６０−１００１６（白金−カーボン触媒、収率
〜８４％）、特公昭６０−３９０６３（白金触媒、パラ
ジウム、ロジウム、ルテニウム、オスニウム助触媒、収
率８７％）に開示されている。又、α−ヒドロキシカル
ボン酸あるいはα−ヒドロキシカルボン酸エステルのＯ
Ｈ基を酸化してα−ケトカルボン酸あるいはα−ケトカ
ルボン酸エステルを得ることは特公昭６１−１６２６３
において白金叉は／及びパラジウムとビスマスを触媒と
して乳酸を液相酸化してピルビン酸を製造する方法（転
化率９０％以上）、特公平１−１１０１１においてタン
グステンオキシドを触媒として乳酸エステルを液相酸化
してピルビン酸エステルを製造する方法（収率３０
％）、および特開平５−２５５１８９においてγ−二酸
化マンガンを触媒として液相酸化により乳酸メチルから
ピルビン酸（収率５２．１％）、グリコール酸エチルか
らグリオキシル酸エチル（収率４５．４％）の製造方法
などが開示されている。[0005] Oxidation of only one OH group of a diol by using a noble metal catalyst to obtain an α-hydroxycarboxylic acid is disclosed in JP-B-60-10016 (platinum-carbon catalyst, yield ~ 84%) and JP-B-60-160. 39063 (platinum catalyst, palladium, rhodium, ruthenium, osnium cocatalyst, 87% yield). O-hydroxycarboxylic acid or α-hydroxycarboxylic acid ester
Oxidation of the H group to obtain α-ketocarboxylic acid or α-ketocarboxylic acid ester is disclosed in JP-B-61-16263.
A method of producing pyruvic acid by subjecting lactic acid to liquid phase oxidation using platinum or / and palladium and bismuth as catalysts (conversion rate of 90% or more), and a liquid phase oxidation of lactate ester using tungsten oxide as catalyst in Japanese Patent Publication No. 1-11011 To produce pyruvic acid ester (yield 30
%) And JP-A-5-255189, and liquid phase oxidation using γ-manganese dioxide as a catalyst to convert methyl lactate to pyruvate (yield 52.1%) and ethyl glycolate to ethyl glyoxylate (yield 45.4%). Are disclosed.
【０００６】しかし、驚いたことにはジアルデヒドにお
いて一方だけのアルデヒド基を酸化してα−ケトカルボ
ン酸を得る例は唯一 Jornal of Catarlysis,133,479-48
5(1992) （特公平４−３５２７４３）だけであるが、原
料のグリオキサール濃度（０．５７３wt％）が低いこと
と、グリオキサール転化率（９２．５％）、グリオキシ
ル酸選択率（７９．３％）ともに低いことが満足できな
い。[0006] Surprisingly, however, the only example of oxidizing only one aldehyde group in dialdehyde to obtain α-ketocarboxylic acid is Journal of Catarlysis, 133, 479-48.
5 (1992) (Japanese Patent Publication No. 4-352743), but the glyoxal concentration (0.573 wt%) of the raw material is low, the conversion of glyoxal (92.5%), and the selectivity of glyoxylic acid (79.3%) ) I am not satisfied that both are low.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、α−ヒド
ロキシカルボン酸あるいはα−ヒドロキシカルボン酸エ
ステルを酸化してα−ケトカルボン酸あるいはα−ケト
カルボン酸エステルを製造する方法を鋭意検討を重ねた
結果、グリオキサールのグリオキシル酸への分子酸素に
よる直接触媒酸化の製造方法において、白金の活性を更
に向上できる本発明を完成したものである。Means for Solving the Problems The present inventors have intensively studied a method for producing α-ketocarboxylic acid or α-ketocarboxylic acid ester by oxidizing α-hydroxycarboxylic acid or α-hydroxycarboxylic acid ester. As a result, in the production method of direct catalytic oxidation of glyoxal to glyoxylic acid with molecular oxygen, the present invention in which the activity of platinum can be further improved has been completed.
【０００８】即ち本発明のグリオキシル酸の製造方法
は、触媒量の白金と、パラジウム、鉛、錫、ビスマスか
らなる群から選んだ一種以上の元素叉はその元素の化合
物の存在下、グリオキサール水溶液を酸素により触媒酸
化する方法である。That is, the method for producing glyoxylic acid of the present invention comprises the steps of: preparing a glyoxal aqueous solution in the presence of a catalytic amount of platinum and one or more elements selected from the group consisting of palladium, lead, tin and bismuth or a compound of the elements; This is a method of catalytic oxidation with oxygen.
【０００９】本発明は白金のみを担持した触媒を使用す
る場合よりも白金の活性を大巾に向上させ、単位時間、
単位触媒あたりの反応処理量を増加する事できる触媒組
成物である。すなわち、白金を主触媒としてパラジウ
ム、鉛、錫、ビスマスからなる群から選んだ一種以上の
元素叉はその元素の化合物のを助触媒として添加した触
媒組成物である。According to the present invention, the activity of platinum is greatly improved as compared with the case where a catalyst supporting only platinum is used.
It is a catalyst composition that can increase the amount of reaction treatment per unit catalyst. That is, it is a catalyst composition in which at least one element selected from the group consisting of palladium, lead, tin and bismuth or a compound of the element is added as a promoter with platinum as a main catalyst.
【００１０】従来、これらの助触媒成分はいずれも白金
に対して触媒毒となる事が広く知られている。ところ
が、グリオキサール水溶液を酸素により酸化してグリオ
キシル酸にする反応においては意外にも反応が効率良く
進行し、選択率のみか転化率も大巾に上昇する事を見い
出した。本発明の触媒は白金を主触媒としてパラジウ
ム、鉛、錫、ビスマスからなる群から選んだ一種以上の
元素叉はその元素の化合物を助触媒として用いる。Heretofore, it has been widely known that all of these promoter components are poisonous to platinum. However, in the reaction of oxidizing a glyoxal aqueous solution with oxygen to produce glyoxylic acid, it was surprisingly found that the reaction proceeded efficiently, and that only the selectivity or the conversion increased significantly. The catalyst of the present invention uses one or more elements selected from the group consisting of palladium, lead, tin and bismuth or a compound of the elements as a cocatalyst with platinum as a main catalyst.
【００１１】本発明の方法の触媒は前述の元素叉は化合
物を組み合わせたものを担体に担持して用いるのが有利
である。担体としては、反応に対して不活性な固体、ア
ルミナ、シリカ、マグネシア、炭酸カルシウムなどやグ
ラファイト、カーボンブラック及び活性炭などが用いら
れる。触媒を高分散付着させるために担体の表面積は大
きいことが好ましく、１００m2/g以上、好ましくは５０
０m2/g以上、更に好ましくは１０００m2/g以上の担体が
用いられる。担体への白金の担持量は元素に換算して
０．１〜２０wt％、好ましくは０．５〜１０wt％、更に
好ましくは１．０〜６wt％である。又、パラジウム、
鉛、錫、ビスマスからなる群から選んだ一種以上の元素
叉はその元素の化合物の担持量は元素に換算して０．１
〜１０wt％、好ましくは０．５〜８wt％、更に好ましく
は１．０〜５．０wt％である。The catalyst used in the process of the present invention is advantageously a combination of the aforementioned elements or compounds supported on a carrier. As the carrier, a solid inert to the reaction, alumina, silica, magnesia, calcium carbonate or the like, graphite, carbon black, activated carbon or the like is used. The surface area of the carrier is preferably large in order to highly disperse and attach the catalyst, and is preferably 100 m 2 / g or more, preferably 50 m 2 / g or more.
A carrier of 0 m 2 / g or more, more preferably 1000 m 2 / g or more is used. The amount of platinum carried on the carrier is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 1.0 to 6% by weight in terms of element. Also, palladium,
The amount of one or more elements selected from the group consisting of lead, tin, and bismuth or a compound of the element is 0.10
The content is 10 to 10% by weight, preferably 0.5 to 8% by weight, and more preferably 1.0 to 5.0% by weight.
【００１２】本発明の方法の触媒は、常法、例えば触媒
担体を塩化白金酸水溶液あるいは塩化テトラアンミン白
金酸水溶液に懸濁し、ホルマリン、ヒドラジン叉は水素
で還元処理を行った後、パラジウム、鉛、錫、ビスマス
からなる群から選んだ一種以上の元素の化合物水溶液を
含浸する方法で調製できる。また、白金化合物溶液とパ
ラジウム、鉛、錫、ビスマスからなる群から選んだ一種
以上の元素の化合物水溶液に担体を浸漬し、そのまま乾
燥し焼成、還元処理を行ったり、あるいは浸漬後、中和
加水分解し担体に沈着させて調製することができる。あ
るいは白金担持触媒をグリオキサール水溶液に懸濁し、
助触媒成分の水溶性化合物を水に溶解させた水溶液を添
加しても調製できる。The catalyst used in the method of the present invention can be prepared by a conventional method, for example, by suspending a catalyst support in an aqueous solution of chloroplatinic acid or tetraammineplatinic acid chloride, reducing the suspension with formalin, hydrazine or hydrogen, and then palladium, lead, or the like. It can be prepared by a method of impregnating an aqueous solution of a compound of one or more elements selected from the group consisting of tin and bismuth. Further, the carrier is immersed in a platinum compound solution and an aqueous solution of a compound of one or more elements selected from the group consisting of palladium, lead, tin, and bismuth, and dried and calcined or reduced as it is, or after immersion, neutralized and hydrolyzed. It can be prepared by decomposition and deposition on a carrier. Alternatively, a platinum-supported catalyst is suspended in an aqueous glyoxal solution,
It can also be prepared by adding an aqueous solution in which a water-soluble compound of a promoter component is dissolved in water.
【００１３】本発明のグリオキサール水溶液の酸素酸化
反応は中性付近、好ましくはｐＨ５．０〜９．０、更に
好ましくはｐＨ６．０〜８．０で行う。ｐＨが低いとグ
リオキサールの酸化反応が進行しにくく、またｐＨが高
いとグリコール酸の生成などの副反応が起こり好ましく
ない。反応が進行してグリオキシル酸が生成するとｐＨ
は低下するので、水酸化ナトリウム、水酸化カリウム、
アンモニア水などのアルカリを添加してｐＨを中性付近
に制御することが望ましい。The oxygen oxidation reaction of the aqueous glyoxal solution of the present invention is carried out at around neutral pH, preferably at pH 5.0 to 9.0, more preferably at pH 6.0 to 8.0. If the pH is low, the oxidation reaction of glyoxal hardly proceeds, and if the pH is high, side reactions such as formation of glycolic acid occur, which is not preferable. When the reaction proceeds and glyoxylic acid is generated, pH
Decrease, sodium hydroxide, potassium hydroxide,
It is desirable to control the pH to around neutral by adding an alkali such as aqueous ammonia.
【００１４】本発明のグリオキサール水溶液の酸素酸化
反応は温度が１０〜８０℃、好ましくは２０〜７０℃更
に好ましくは３０〜６０℃で行う。反応温度が低いと反
応の転化率を上げるのに長時間を要し、又反応温度が高
いと蓚酸の生成が多くなったり、触媒に高沸点有機物が
付着して触媒ライフが短くなるので好ましくない。The oxygen oxidation reaction of the aqueous glyoxal solution of the present invention is carried out at a temperature of 10 to 80 ° C, preferably 20 to 70 ° C, more preferably 30 to 60 ° C. When the reaction temperature is low, it takes a long time to increase the conversion of the reaction, and when the reaction temperature is high, the generation of oxalic acid increases, or the high-boiling organic substances adhere to the catalyst, which shortens the catalyst life, which is not preferable. .
【００１５】[0015]
【実施例】以下に本発明を実施例によって具体的に例示
するが、本発明はこれらの実施例に限定されるものでは
ない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００１６】比較例１ テトラクロロ白金酸カリウム水溶液に比表面積５８０m2
/gのシリカを浸漬し、ホルマリンで還元し、５．０wt％
の白金担持シリカ触媒を調製した。１wt％グリオキサー
ル水溶液２００mlに５．０wt％の白金担持シリカ触媒３
grを懸濁させ、２０wt％水酸化ナトリウム水溶液でｐＨ
７．５に調整した。５００rpm で撹拌し、温度４０℃、
空気１００ml／min を供給し、２０wt％水酸化ナトリウ
ム水溶液でｐＨ７．５に制御し、反応を２時間行った。
反応の結果は、グリオキサール転化率９０％、グリオキ
シル酸選択率７１％、蓚酸選択率１８％、グリコール酸
選択率３％、蟻酸選択率３％であった。Comparative Example 1 A specific surface area of 580 m 2 was added to an aqueous solution of potassium tetrachloroplatinate.
/ g of silica and reduced with formalin, 5.0 wt%
Was prepared. 5.0 wt% of a platinum-supported silica catalyst 3 in 200 ml of a 1 wt% aqueous glyoxal solution 3
gr and suspend with 20wt% sodium hydroxide aqueous solution.
Adjusted to 7.5. Stir at 500 rpm, temperature 40 ° C,
The reaction was carried out for 2 hours while supplying 100 ml / min of air and controlling the pH to 7.5 with a 20 wt% aqueous sodium hydroxide solution.
As a result of the reaction, glyoxal conversion was 90%, glyoxylic acid selectivity was 71%, oxalic acid selectivity was 18%, glycolic acid selectivity was 3%, and formic acid selectivity was 3%.
【００１７】実施例１ テトラクロロ白金酸カリウム水溶液に比表面積５８０m2
/gのシリカを浸漬し、ホルマリンで還元し、５wt％の白
金担持シリカ触媒を調製した。ろ過、水洗後、この担持
触媒を鉛に換算して１wt％になるように硝酸鉛を水に溶
解した水溶液に懸濁し、水酸化ナトリウム溶液で中和
し、白金−鉛担持シリカ触媒を調製した。１wt％グリオ
キサール水溶液２００mlにこの白金（５wt％）−鉛（１
wt％）の担持シリカ触媒３grを懸濁させ、２０wt％水酸
化ナトリウム水溶液でｐＨ７．５にに調整した。４００
rpm で撹拌し、温度４０℃、空気１００ml／min を供給
し、２０wt％水酸化ナトリウム水溶液でｐＨ７．５に制
御し、反応を２時間行った。反応の結果はグリオキサー
ル転化率９７％、グリオキシル酸選択率８２％、蓚酸選
択率１３％、グリコール酸選択率１％以下、蟻酸選択率
１％以下であった。Example 1 A specific surface area of 580 m 2 was added to an aqueous solution of potassium tetrachloroplatinate.
/ g of silica was immersed and reduced with formalin to prepare a 5 wt% platinum-supported silica catalyst. After filtration and washing with water, the supported catalyst was suspended in an aqueous solution of lead nitrate dissolved in water so as to be 1 wt% in terms of lead, and neutralized with a sodium hydroxide solution to prepare a platinum-lead-supported silica catalyst. . This platinum (5 wt%)-lead (1) was added to 200 ml of a 1 wt% aqueous glyoxal solution.
(wt%) of a supported silica catalyst was suspended in 3 gr, and the pH was adjusted to 7.5 with a 20 wt% aqueous sodium hydroxide solution. 400
The mixture was stirred at rpm, supplied at a temperature of 40 ° C. and 100 ml / min of air, and adjusted to pH 7.5 with a 20 wt% aqueous sodium hydroxide solution, and the reaction was carried out for 2 hours. As a result of the reaction, the conversion of glyoxal was 97%, the selectivity of glyoxylic acid was 82%, the selectivity of oxalic acid was 13%, the selectivity of glycolic acid was 1% or less, and the selectivity of formic acid was 1% or less.
【００１８】比較例２ テトラクロロ白金酸カリウム水溶液に比表面積１２００
m2/gの活性炭を浸漬し、ホルマリンで還元し、５wt％の
白金担持活性炭触媒を調製した。５wt％グリオキサール
水溶液２００mlに５wt％白金・カーボン粉末１０grを懸
濁させ、２０wt％水酸化ナトリウム水溶液でｐＨ８．５
にした。５００rpm で撹拌し、温度３５℃、空気０．３
リットル／min を供給し、２０wt％水酸化ナトリウム水
溶液でｐＨ８．５に制御し、反応を２時間行った。反応
の結果は、グリオキサール転化率８５％、グリオキシル
酸選択率６８％、蓚酸選択率１４％、グリコール酸選択
率１％、蟻酸選択率１以下％であった。Comparative Example 2 Specific surface area of 1200 aqueous potassium tetrachloroplatinate solution
m 2 / g activated carbon was immersed and reduced with formalin to prepare a 5 wt% platinum-supported activated carbon catalyst. 10 gr of 5 wt% platinum-carbon powder is suspended in 200 ml of 5 wt% glyoxal aqueous solution, and pH 8.5 is added with 20 wt% sodium hydroxide aqueous solution.
I made it. Stir at 500 rpm, temperature 35 ° C, air 0.3
The reaction was carried out for 2 hours by supplying liter / min and controlling the pH to 8.5 with a 20 wt% aqueous sodium hydroxide solution. As a result of the reaction, glyoxal conversion was 85%, glyoxylic acid selectivity was 68%, oxalic acid selectivity was 14%, glycolic acid selectivity was 1%, and formic acid selectivity was 1% or less.
【００１９】実施例２ テトラクロロ白金酸カリウム水溶液に比表面積１２００
m2/gの活性炭を浸漬し、ホルマリンで還元し、４wt％の
白金担持活性炭触媒を調製した。ろ過、水洗後この担持
触媒を鉛に換算して２wt％になるように硝酸鉛を水に溶
解した水溶液に懸濁し、水酸化ナトリウム溶液で中和
し、白金−鉛担持活性炭触媒を調製した。５wt％グリオ
キサール水溶液２００mlに４wt％白金−２wt％鉛カーボ
ン粉末１０grを懸濁させ、２０wt％水酸化ナトリウム水
溶液でｐＨ８．５にした。５００rpm で撹拌し、温度３
５℃、空気０．３リットル／min を供給し、２０wt％水
酸化ナトリウム水溶液でｐＨ８．５に制御し、反応を２
時間行った。反応の結果は、グリオキサール転化率９４
％、グリオキシル酸選択率８１％、蓚酸選択率１４％、
グリコール酸選択率１％以下、蟻酸選択率１以下％であ
った。EXAMPLE 2 A specific surface area of 1200 aqueous potassium tetrachloroplatinate solution was added.
m 2 / g of activated carbon was immersed and reduced with formalin to prepare a 4 wt% platinum-supported activated carbon catalyst. After filtration and washing with water, the supported catalyst was suspended in an aqueous solution in which lead nitrate was dissolved in water so as to be 2% by weight in terms of lead, and neutralized with a sodium hydroxide solution to prepare a platinum-lead supported activated carbon catalyst. 10 gr of 4 wt% platinum-2 wt% lead carbon powder was suspended in 200 ml of 5 wt% aqueous glyoxal solution, and the pH was adjusted to 8.5 with a 20 wt% aqueous sodium hydroxide solution. Stir at 500 rpm, temperature 3
At a temperature of 5 ° C., air was supplied at a rate of 0.3 liter / min.
Time went. The result of the reaction was a glyoxal conversion of 94.
%, Glyoxylic acid selectivity 81%, oxalic acid selectivity 14%,
The selectivity of glycolic acid was 1% or less, and the selectivity of formic acid was 1% or less.
【００２０】実施例３ テトラクロロ白金酸カリウム水溶液に比表面積１５００
m2/gの活性炭を浸漬し、ホルマリンで還元し、５wt％の
白金担持活性炭触媒を調製した。この担持触媒をビスマ
スに換算して２wt％になるように硝酸ビスマスを水に溶
解した水溶液に懸濁し、水酸化ナトリウム溶液で中和
し、白金−ビスマス担持活性炭触媒を調製した。５wt％
グリオキサール水溶液２００mlに５wt％白金−２wt％ビ
スマス・カーボン粉末１０grを懸濁させ、２０wt％水酸
化ナトリウム水溶液でｐＨ８．０にした。５００rpm で
撹拌し、温度５５℃、空気０．３リットル／min.を供給
し、２０wt％水酸化ナトリウム水溶液でｐＨ８．０に制
御し、反応を１時間行った。反応の結果は、グリオキサ
ール転化率９３％、グリオキシル酸選択率８１％、蓚酸
選択率１５％、グリコール酸選択率２％、蟻酸選択率１
以下％であった。EXAMPLE 3 A specific surface area of 1500 aqueous potassium tetrachloroplatinate solution was added.
m 2 / g activated carbon was immersed and reduced with formalin to prepare a 5 wt% platinum-supported activated carbon catalyst. This supported catalyst was suspended in an aqueous solution of bismuth nitrate dissolved in water so as to be 2% by weight in terms of bismuth, and neutralized with a sodium hydroxide solution to prepare a platinum-bismuth-supported activated carbon catalyst. 5wt%
10 gr of 5 wt% platinum-2 wt% bismuth carbon powder was suspended in 200 ml of an aqueous glyoxal solution, and the pH was adjusted to 8.0 with a 20 wt% aqueous sodium hydroxide solution. The mixture was stirred at 500 rpm, the temperature was 55 ° C., air was supplied at 0.3 liter / min., The pH was controlled at 8.0 with a 20 wt% aqueous sodium hydroxide solution, and the reaction was carried out for 1 hour. The results of the reaction were: glyoxal conversion 93%, glyoxylic acid selectivity 81%, oxalic acid selectivity 15%, glycolic acid selectivity 2%, formic acid selectivity 1
%.
【００２１】実施例４ テトラクロロ白金酸カリウム水溶液に比表面積１５００
m2/gの活性炭を浸漬し、ホルマリンで還元し、４wt％の
白金担持活性炭触媒を調製した。この担持触媒を錫に換
算して３wt％になるように塩化第２錫を水に溶解した水
溶液に懸濁し、水酸化ナトリウム溶液で中和し、白金−
錫担持活性炭触媒を調製した。５wt％グリオキサール水
溶液２００mlにこの白金（４wt％）−錫（３wt％）の担
持活性炭触媒１０grを懸濁させ、２０wt％水酸化ナトリ
ウム水溶液でｐＨ８．０にした。４００rpm.で撹拌し、
温度２５℃、空気０．２リットル／min.を供給し、２０
wt％水酸化ナトリウム水溶液でｐＨ８．０に制御し、反
応を４時間行った。反応の結果は、グリオキサール転化
率９５％、グリオキシル酸選択率８１％、蓚酸選択率１
６％、グリコール酸選択率１％以下、蟻酸選択率１％以
下であった。Example 4 A specific surface area of 1500 aqueous potassium tetrachloroplatinate solution
m 2 / g of activated carbon was immersed and reduced with formalin to prepare a 4 wt% platinum-supported activated carbon catalyst. This supported catalyst was suspended in an aqueous solution of stannic chloride dissolved in water so as to be 3% by weight in terms of tin, neutralized with a sodium hydroxide solution, and treated with platinum.
A tin-supported activated carbon catalyst was prepared. 10 g of the platinum (4 wt%)-tin (3 wt%) supported activated carbon catalyst was suspended in 200 ml of a 5 wt% aqueous glyoxal solution, and the pH was adjusted to 8.0 with a 20 wt% aqueous sodium hydroxide solution. Stir at 400 rpm.
Supply the air at a temperature of 25 ° C and air at 0.2 l / min.
The pH was controlled at 8.0 with a wt% aqueous sodium hydroxide solution, and the reaction was carried out for 4 hours. The results of the reaction were as follows: glyoxal conversion 95%, glyoxylic acid selectivity 81%, oxalic acid selectivity 1
6%, glycolic acid selectivity 1% or less, formic acid selectivity 1% or less.
【００２２】比較例３ テトラクロロパラジウム酸アンモニウム水溶液に比表面
積１５００m2/gの活性炭を浸漬しホルマリンで還元し、
５．０wt％のパラジウム活性炭触媒を調製した。５wt％
グリオキサール水溶液２００mlに５．０wt％のパラジウ
ム担持活性炭触媒１０grを懸濁させ、２０wt％水酸化ナ
トリウム水溶液でｐＨ７．５にした。５００rpm で撹拌
し、温度４５℃、空気０．３リットル／min.を供給し、
２０wt％水酸化ナトリウム水溶液でｐＨ７．５に制御
し、反応を２時間行った。反応の結果は、グリオキサー
ル転化率６６％、グリオキシル酸選択率３０％、蓚酸選
択率１８％、グリコール酸選択率３％、蟻酸選択率３％
であった。Comparative Example 3 Activated carbon having a specific surface area of 1500 m 2 / g was immersed in an aqueous solution of ammonium tetrachloropalladate and reduced with formalin.
A 5.0 wt% palladium activated carbon catalyst was prepared. 5wt%
10 g of a 5.0 wt% palladium-supported activated carbon catalyst was suspended in 200 ml of an aqueous glyoxal solution, and the pH was adjusted to 7.5 with a 20 wt% aqueous sodium hydroxide solution. Stir at 500 rpm, supply temperature 45 ° C, air 0.3 liter / min.
The pH was controlled to 7.5 with a 20 wt% aqueous sodium hydroxide solution, and the reaction was carried out for 2 hours. The results of the reaction were as follows: glyoxal conversion 66%, glyoxylic acid selectivity 30%, oxalic acid selectivity 18%, glycolic acid selectivity 3%, formic acid selectivity 3%
Met.
【００２３】実施例５ テトラクロロ白金酸アンモニウム水溶液に比表面積１５
００m2/gの活性炭を浸漬し、ホルマリンで還元し、２wt
％の白金担持活性炭触媒を調製した。この担持触媒をパ
ラジウムに換算して４wt％になるようにテトラクロロパ
ラジウム酸アンモニウム水溶液を浸漬しホルマリンで還
元し、白金−パラジウム担持触媒を調製した。５wt％グ
リオキサール水溶液２００mlにこの白金（２wt％）−バ
ラジウム（４wt％）の担持活性炭触媒１０grを懸濁さ
せ、２０wt％水酸化ナトリウム水溶液でｐＨ６．５にし
た。４００rpm で撹拌し、温度５０℃、空気０．４リッ
トル／min を供給し、２０wt％水酸化ナトリウム水溶液
でｐＨ６．５に制御し、反応を１時間行った。反応の結
果は、グリオキサール転化率９６％、グリオキシル酸選
択率８２％、蓚酸選択率１２％、グリコール酸選択率２
％、蟻酸選択率１％であった。Example 5 An aqueous solution of ammonium tetrachloroplatinate having a specific surface area of 15
Immersed in activated carbon of 00m 2 / g, reduced with formalin,
% Of a platinum-supported activated carbon catalyst was prepared. This supported catalyst was immersed in an aqueous solution of ammonium tetrachloropalladate so as to be 4% by weight in terms of palladium, and reduced with formalin to prepare a platinum-palladium supported catalyst. 10 g of the platinum (2 wt%)-palladium (4 wt%) supported activated carbon catalyst was suspended in 200 ml of a 5 wt% aqueous glyoxal solution, and the pH was adjusted to 6.5 with a 20 wt% aqueous sodium hydroxide solution. The mixture was stirred at 400 rpm, supplied at a temperature of 50 ° C. and air at a rate of 0.4 L / min, and adjusted to pH 6.5 with a 20 wt% aqueous solution of sodium hydroxide to carry out the reaction for 1 hour. The results of the reaction were as follows: glyoxal conversion 96%, glyoxylic acid selectivity 82%, oxalic acid selectivity 12%, glycolic acid selectivity 2
% And formic acid selectivity was 1%.
【００２４】[0024]
【発明の効果】本発明の方法によれば、白金触媒にパラ
ジウム、鉛、錫、ビスマスからなる群から選んだ一種以
上の元素、またはその元素の化合物を助触媒として、グ
リオキサール水溶液を酸素により酸化してグリオキシル
酸を製造するに当たり、高収率でしかも副生成物の生成
を抑えることができて、産業に利するところ極めて大で
ある。According to the method of the present invention, an aqueous glyoxal solution is oxidized with oxygen using at least one element selected from the group consisting of palladium, lead, tin, and bismuth or a compound of the element as a cocatalyst as a platinum catalyst. In the production of glyoxylic acid, the production of by-products can be suppressed in a high yield, which is extremely useful for industry.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｃ０７Ｂ 61/00 ３００ Ｂ０１Ｊ 23/64 １０１Ｘ (72)発明者 岩根 伸久 大阪府高石市高砂１丁目６番地 三井東 圧化学株式会社内 審査官 藤森 知郎 (56)参考文献 特開 平４−352743（ＪＰ，Ａ) 特開 平７−51567（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 51/235 C07C 59/153 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI // C07B 61/00 300 B01J 23/64 101X (72) Inventor Nobuhisa Iwane 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui East Pressure Chemical Examiner Tomoro Fujimori (56) References JP-A-4-352743 (JP, A) JP-A-7-51567 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 51/235 C07C 59/153
Claims (4)
から選んだ一種以上の元素、またはその元素の化合物と
白金とを触媒として、グリオキサール水溶液を酸素によ
り酸化する事を特徴とするグリオキシル酸の製造方法。1. A method for preparing glyoxylic acid, comprising oxidizing an aqueous glyoxal solution with oxygen using at least one element selected from the group consisting of palladium, lead, tin and bismuth, or a compound of the elements, and platinum as a catalyst. Production method.
し、元素として０．１〜２０wt％、及びパラジウム、
鉛、錫、ビスマスからなる群から選んだ一種以上の元素
またはその化合物を不活性担体に対し、元素として０．
１〜１０wt％含有させたものを触媒として、グリオキサ
ール水溶液を酸素により酸化する請求項１記載のグリオ
キシル酸の製造方法。2. An inert carrier comprising platinum or a platinum compound in an amount of 0.1 to 20% by weight as an element, and palladium,
One or more elements or compounds thereof selected from the group consisting of lead, tin, and bismuth are added to the inert carrier in an amount of 0.1%.
The method for producing glyoxylic acid according to claim 1, wherein the glyoxal aqueous solution is oxidized with oxygen using a catalyst containing 1 to 10% by weight as a catalyst.
際の温度が、１０〜８０℃の範囲である請求項１記載の
グリオキシル酸の製造方法。3. The method for producing glyoxylic acid according to claim 1, wherein the temperature at which the aqueous glyoxal solution is reacted with oxygen is in the range of 10 to 80 ° C.
際のｐＨが、５．０〜９．０の範囲である請求項１記載
のグリオキシル酸の製造方法。4. The method for producing glyoxylic acid according to claim 1, wherein the pH at the time of reacting the aqueous glyoxal solution with oxygen is in the range of 5.0 to 9.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31781293A JP3313217B2 (en) | 1993-12-17 | 1993-12-17 | Method for producing glyoxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31781293A JP3313217B2 (en) | 1993-12-17 | 1993-12-17 | Method for producing glyoxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07173099A JPH07173099A (en) | 1995-07-11 |
| JP3313217B2 true JP3313217B2 (en) | 2002-08-12 |
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ID=18092324
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| JP31781293A Expired - Fee Related JP3313217B2 (en) | 1993-12-17 | 1993-12-17 | Method for producing glyoxylic acid |
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