WO2006131040A1 - Procede de preparation de l'acide glyoxalique par oxydation du glyoxal avec l'ozonide de l'acide maleique - Google Patents

Procede de preparation de l'acide glyoxalique par oxydation du glyoxal avec l'ozonide de l'acide maleique Download PDF

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Publication number
WO2006131040A1
WO2006131040A1 PCT/CN2006/000487 CN2006000487W WO2006131040A1 WO 2006131040 A1 WO2006131040 A1 WO 2006131040A1 CN 2006000487 W CN2006000487 W CN 2006000487W WO 2006131040 A1 WO2006131040 A1 WO 2006131040A1
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WIPO (PCT)
Prior art keywords
acid
glyoxal
reaction
ozonide
maleic acid
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PCT/CN2006/000487
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English (en)
Chinese (zh)
Inventor
Wumanjiang Aili
Zicai Sun
Yagang Zhang
Xin Dong
Tongyu Xu
Shuming Hu
Nuer Maimaiti
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The Xinjiang Technical Institute Of Physics & Chemistry Chinese Academy Of Sciences
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Application filed by The Xinjiang Technical Institute Of Physics & Chemistry Chinese Academy Of Sciences filed Critical The Xinjiang Technical Institute Of Physics & Chemistry Chinese Academy Of Sciences
Publication of WO2006131040A1 publication Critical patent/WO2006131040A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides

Definitions

  • the present invention relates to a method for synthesizing glyoxylic acid by oxidizing glyoxal using maleic acid ozonide.
  • Glyoxylic acid (0HCC00H) combines the properties of aldehydes and carboxylic acids and is an important organic chemical raw material intermediate and biochemical reagent. Glyoxylic acid can be used to extract dozens of fine chemical products. It is widely used in medicine, spices, pesticides, paints, paper, food additives, etc.
  • the application of glyoxylic acid in leather and electronics, electroplating is in the development stage. In the past ten years, as the application field of glyoxylic acid downstream products has been expanding, the market demand for glyoxylic acid has been increasing, and the output has grown rapidly. The production of glyoxylic acid in China is relatively backward, and the contradiction between supply and demand is very prominent. High-end products mainly gargle from Europe and Japan.
  • the production methods of industrialized glyoxylic acid mainly include glyoxal nitric acid oxidation method, oxalic acid electrolysis reduction method, and maleic acid ozonation-catalytic hydrogenation method.
  • the glyoxal nitric acid oxidation method is the earliest method to realize industrialization, but the method has high raw material price, large amount of by-product oxalic acid, serious equipment corrosion, large environmental pollution, low product purity, and is gradually being eliminated (see US 4146731; Hunan Chemical Industry Co., Ltd.
  • Electrolysis is currently produced in China.
  • the main method of aldehyde acid, domestic researchers have done a lot of work on this method, the method has been developed into three processes: oxalic acid cathodic electrolysis reduction method, glyoxy acid anodic oxidation method and two-chamber electrolysis method.
  • the method is easy to obtain, the process is simple, the by-products are small, the dyeing is small, but the product purity is low, the quality is unstable, the solution evaporation is large, the energy consumption is low, the equipment investment and production cost are relatively low, and it is only suitable for abundant power resources. Regional production. Moreover, due to the unsatisfactory electrode material, poor performance of ion exchange membrane, easy cracking and poisoning, anodic corrosion, cathode deactivation, uneven mass transfer, low space-time yield, and contamination of the electrolyte, continuous normal production has not been achieved at home and abroad. .
  • Ozone oxidation is one of the earliest studied methods for the production of glyoxylic acid in foreign countries. However, there is no relevant research report in China.
  • Black et al. (see I&EC. Product Research and Development, 1966, 5: 350.) ozonized about 40% by weight of an aqueous maleic acid solution at 15-25 °C to 4 wt% of 0 3 /0 2 to the reaction.
  • the residual ozone is blown off with nitrogen, and then the temperature is kept below 15 ° C, and the ozonation product is catalytically hydrogenated under normal pressure with 5 wt% Pd/Al 2 O 3 as a catalyst, and the catalyst is separated by filtration.
  • the hemiacetal acid hemiacetal is obtained by steaming, and the yield is as high as 95%.
  • methanol is distilled off to obtain an aqueous solution of glyoxylic acid. In the process, the yield is highly resistant to the amount of the catalyst, and the lraol maleic acid needs about 0.5 g of the catalyst.
  • the ozonation-catalytic hydrogenation technology has the advantages of cheap and easy raw materials, low environmental pollution, good product quality and easy mass production.
  • an expensive hydrogenation catalyst is used in the production process, the catalyst solvent is poisoned and it is difficult to recycle and reuse, thereby making the production process complicated and the production cost high.
  • the synthetic glyoxylic acid of the present invention is based on the maleic acid ozonation technology, but is substantially different from the above-mentioned prior art, because the present invention successfully combines the maleic acid ozone oxidation method and the glyoxal catalytic oxidation method.
  • a new method for synthesizing acetic acid by maleic acid ozonide oxidation of glyoxal was developed, and high-concentration, high-purity glyoxylic acid was synthesized in a high yield by a simple procedure.
  • the method further utilizes maleic acid ozonide to further oxidize glyoxal, thereby successfully avoiding the disadvantage of easy poisoning of the catalyst in the ozonation-catalytic hydrogenation technology, and saving materials such as hydrogen.
  • the problems of low conversion rate and poor product quality of various other glyoxal oxidation methods have been successfully solved.
  • the modification method is simple in process, the reaction process is mild in the whole process, the material is saved, and the environment is not polluted, which is very beneficial to large-scale industrial production, and is a new breakthrough in the glyoxylic acid industry. Summary of the invention
  • An object of the present invention is to provide a process for producing a glyoxylic acid by further oxidizing glyoxal as an oxidizing agent.
  • This method successfully avoids the disadvantage that the currently industrialized ozonation-catalytic hydrogenation technology requires expensive precious metal catalysts, which are easily poisoned and difficult to recycle.
  • glyoxylic acid can be synthesized by completely reacting an equimolar amount of maleic acid (anhydride) and glyoxal as a raw material, without using hydrogen gas and other glyoxal oxidation methods.
  • the added materials such as nitric acid and potassium permanganate greatly save material and energy, and avoid introduction of foreign impurities, thereby improving the quality of the product.
  • the method for reducing glyoxylic acid by oxidation of ethylenedialdehyde with maleic acid ozonide is carried out according to the following steps: - a, maleic acid or maleic anhydride and an equimolar amount of water, and methanol And acetic acid is formulated into a maleic acid mass percentage of 4% - 15% solution, cooled to - 5 ° C ⁇ 5 ° C, vigorously stirred and passed through 2-6 wt% of the 0 3 / 0 2 mixed gas reaction completely Thereafter, the residual ozone is removed by nitrogen to obtain an ozonide of maleic acid;
  • Oxidizing glyoxal with maleic acid ozonide adding ozonation product to the glyoxal solution under stirring, continuously adding dropwise for 2 hours until completion, stirring is continued until the end of the reaction, and the reaction end point is detected by using a starch/potassium iodide test paper; d.
  • the solvent is distilled off under reduced pressure at 50 ° C to obtain a solution concentration of glyoxylic acid of 70-90%, and the yield of the whole reaction is 90-99%.
  • the solvent is a mixed solvent of methanol and acetic acid, wherein the mass fraction of acetic acid accounts for 5-95% of the total solvent; in the reaction of oxidizing glyoxal, acetic acid and water are used as solvents when diluting glyoxal. , wherein the mass fraction of water accounts for 4 to 60% of the total solvent.
  • the catalyst used is manganese acetate or ferrous sulfate or copper chloride or lead acetate or metallic silver or carrier metal Pd or carrier metal Pt, or no catalyst.
  • the ozonation reaction of the present invention uses a mixed solvent of methanol and acetic acid, and in the second step, glyoxal is dissolved in an aqueous solution of acetic acid, which successfully hinders the conversion of glyoxal to a form of hemiacetal or acetal.
  • acetic acid can also react with maleic acid ozonide to form peroxyacetic acid, which is a good reagent commonly used to make the reaction not even follow the Baeyer-Villiger mechanism (see Chem.
  • the catalyst In the step of oxidizing the glyoxal of the maleic acid ozonide, the catalyst can be smoothly carried out without using a catalyst, but the catalyst can be used to accelerate the reaction rate, and some can also increase the glyoxylic acid selectivity.
  • the invention mainly studies the catalytic effects of several conventional redox catalysts, such as manganese acetate, ferrous sulfate, copper chloride, lead acetate, metallic silver, single-load precious metals such as Pd/Al 2 0 ⁇ B Pt/C. . Practice has proved that the reaction rate is the fastest when using ferrous salt and copper salt as catalyst, but the reaction selectivity is poor.
  • the reaction rate is moderate and the selectivity is also good.
  • the most effective catalyst is a noble metal catalyst. Under the catalysis of noble metals, not only the reaction rate is moderate, but also the selectivity to glyoxylic acid is high. detailed description
  • Another four-necked bottle was added, and 43. 5g of 40% aqueous solution of oxalic acid and 100 ml of acetic acid were added, stirred and heated to maintain the temperature at 35 ° C;
  • Another four-necked bottle was added, 43.5 g of 40% aqueous oxalic acid solution and 100 ml of acetic acid were added, stirred and heated to maintain the temperature at 35 ° C ;
  • Another four-necked bottle was added, and 43. 5g of 40% aqueous solution of glyoxal and 100 ml of acetic acid were added, stirred and heated to maintain the temperature at 35 ° C;
  • Another four-necked bottle was added, and 43. 5g of 40% aqueous solution of glyoxal and 100 ml of acetic acid were added, stirred and heated to maintain the temperature at 3 CTC;
  • the yield of the glyoxylic acid was 94.72%.
  • the yield of the glyoxylic acid was 94.72%.
  • the aqueous solution of the glyoxylic acid was 275. 5 g, the concentration was 22.90%, and the yield of glyoxylic acid was 94.72%.
  • Another four-necked bottle was added, and 43.5 g of a 40% aqueous solution of glyoxal and 100 ml of acetic acid were added, stirred and heated to maintain the temperature at 36 ° C ;
  • the yield of the glyoxylic acid was 97.7%.
  • the yield of the glyoxylic acid was 97.7%.
  • the concentration of the glyoxylic acid was 97.7%.
  • the yield of glyoxylic acid is 72.4%.
  • the yield of glyoxylic acid is 72.4%.
  • the yield of glyoxylic acid is 72.4%. .
  • the manganese ion is converted into a manganese dioxide precipitate, and after filtration, 250 ml of distilled water is added to the reaction mixture, and methanol, acetic acid and a part of water are distilled off under reduced pressure to obtain a glyoxylic acid aqueous solution (274. 7 g, a concentration of 21. 60% ⁇ The yield of glyoxylic acid was 89. 1%.
  • the obtained ozonide is detected with starch / potassium iodide test paper Blue; another four bottles, add 43.5 g 40% aqueous solution of glyoxal, 100 ml of acetic acid and 0.5 g of ferrous sulfate (FeS0 4 . 7H 2 0), stir and heat to keep the temperature at 35 ° C ; then drip Add the ozonide obtained by the first step reaction (ice water protection), control the flow rate to complete the addition in 2 hours, continue the reaction for about 50 minutes, then use the starch/potassium iodide test paper to detect no change of color, and know that the peroxide has reacted. complete;
  • Another four-necked bottle was added, 43. 5g of 40% aqueous solution of glyoxal, 100 ml of acetic acid and 0.5 g of active silver powder (prepared from silver ammonia solution and glyoxal), stirred and heated to maintain the temperature at 33 Torr;
  • the silver powder is filtered, the reaction product is added with 250 ml of distilled water, and the methanol, acetic acid and a part of water are distilled off under reduced pressure at 50 ° C to obtain a glyoxylic acid aqueous solution 291. 4 g, a concentration of 22.40%, acetaldehyde 9% ⁇ The acid yield was 98.9%.
  • Another four-necked bottle adding 43.5 g of 40% aqueous glyoxal solution, 100 ml of acetic acid and 1.0 g of 5% Pd / Al 2 O 3 as a catalyst, stirring and heating to maintain the temperature at 38 C;
  • Another four-necked bottle was added, 43. 5g of 40% aqueous solution of glyoxal, 100ml of acetic acid and 1.0g of 5% Pt/C as catalyst, stirred and heated to keep the temperature at 40 ⁇ ;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de préparation de l'acide glyoxalique par oxydation du glyoxal avec l'ozonide de l'acide maléique. L'invention combine avec succès l'ozonisation de l'acide maléique et l'oxydation catalytique du glyoxal pour développer un nouveau procédé de préparation de l'acide glyoxalique par oxydation catalytique du glyoxal avec l'ozonide de l'acide maléique. Le procédé peut permettre de préparer l'acide glyoxalique avec une concentration élevée et une grande pureté dans des étapes simples et avec un rendement élevé. En raison du procédé simple, des conditions de réaction modérées, d'une économie des matériaux et de l'absence de pollution de l'environnement, le procédé favorise une production industrielle à grande échelle.
PCT/CN2006/000487 2005-06-07 2006-03-24 Procede de preparation de l'acide glyoxalique par oxydation du glyoxal avec l'ozonide de l'acide maleique WO2006131040A1 (fr)

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CN200510078259.9 2005-06-07
CNB2005100782599A CN1312100C (zh) 2005-06-07 2005-06-07 马来酸臭氧化物氧化乙二醛合成乙醛酸的方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009014431A1 (fr) * 2007-07-23 2009-01-29 Pluim, Henk Production sélective de sulfoxydes

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* Cited by examiner, † Cited by third party
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CN1312100C (zh) * 2005-06-07 2007-04-25 中国科学院新疆理化技术研究所 马来酸臭氧化物氧化乙二醛合成乙醛酸的方法
CN101462946B (zh) * 2008-12-30 2012-11-07 上海华谊（集团）公司 乙二醛催化氧化制备乙醛酸的方法
CN101559927B (zh) * 2009-06-02 2011-07-20 天津市职业大学 一种同时生产二氧化氯和乙醛酸绿色工艺

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EP0293127A1 (fr) * 1987-05-27 1988-11-30 MITSUI TOATSU CHEMICALS, Inc. Procédé de préparation de l'acide glyoxylique
US5015760A (en) * 1982-07-02 1991-05-14 Chemie Linz Aktiengesellschaft Process for the preparation of glyoxylic acid and glyoxylic acid derivatives
CN1709849A (zh) * 2005-06-07 2005-12-21 中国科学院新疆理化技术研究所 马来酸臭氧化物氧化乙二醛合成乙醛酸的方法

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US5015760A (en) * 1982-07-02 1991-05-14 Chemie Linz Aktiengesellschaft Process for the preparation of glyoxylic acid and glyoxylic acid derivatives
EP0293127A1 (fr) * 1987-05-27 1988-11-30 MITSUI TOATSU CHEMICALS, Inc. Procédé de préparation de l'acide glyoxylique
CN1709849A (zh) * 2005-06-07 2005-12-21 中国科学院新疆理化技术研究所 马来酸臭氧化物氧化乙二醛合成乙醛酸的方法

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WO2009014431A1 (fr) * 2007-07-23 2009-01-29 Pluim, Henk Production sélective de sulfoxydes

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