CN1709849A - Method for synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide - Google Patents
Method for synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide Download PDFInfo
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- C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides
Abstract
This invention has disclosed a kind of method to use maleic acid ozonide to oxidize glyoxal in order to gain glyoxylic acid. This method succeeds in combining maleic acid ozonide oxidizing method with other glyoxal catalyzed oxidizing method, devised a new way of to use maleic acid ozonide to oxidize glyoxal in order to gain glyoxylic acid, it has high concentration and purity with the simple step. This method craft is simple, the whole course reflects mild condition, the supplies are saved, and pollution-free to the environment, help industrialization to cosmically produce.
Description
Technical field
The present invention relates to a kind of method of using synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide.
Background technology
Oxoethanoic acid (OHCCOOH) has the character of aldehyde and carboxylic acid concurrently, is a kind of important Organic Chemicals intermediate and biochemical reagents.Can derive tens kinds of fine chemical products by oxoethanoic acid, be widely used in fields such as medicine, spices, agricultural chemicals, paint, papermaking, foodstuff additive; Oxoethanoic acid is in the development phase in the application aspect leather and electronics, the plating.Over past ten years, because the Application Areas of oxoethanoic acid derived product constantly enlarges, the market requirement of oxoethanoic acid constantly increases, the output rapid growth.The production status of China's oxoethanoic acid is backward relatively, and imbalance between supply and demand is very outstanding, and high-end product is mainly from Europe and Japanese import.(referring to US 6225334; The chemical industry progress, 2001,20 (8): 53-55; Sichuan chemical industry and corrosion control, 2000,6 (3): 38-47; Chemical research and application, 2000,12 (2): 125-131; The Jiangsu chemical industry, 2000,28 (11): 28; The Hunan chemical industry, 2000,30 (2): 1-3).
At present, realized that the production method of industrialized oxoethanoic acid mainly contains the oxalic dialdehyde nitric acid oxidation method, acid by electrolytic reduction of oxalic method, and toxilic acid ozonize-shortening method.Wherein the oxalic dialdehyde nitric acid oxidation method is to realize industrialized method the earliest, but this method cost of material height, byproduct oxalic acid amount is big, and equipment corrosion is serious, and environmental pollution is big, and product purity is lower, is eliminated gradually (referring to US 4146731; The Hunan chemical industry, 1989,2:31-32; The Jiangsu Petrochemical Engineering College journal, 2000,12 (2): 12-14; The Jilin Institute of Chemical Technology journal, 2002,19 (3): 10-12).Electrolytic process is the main method of the current production oxoethanoic acid of China, and domestic research worker has done a large amount of work to this method, and this method has developed into oxalic acid catholyte reduction method at present, the two three kinds of technologies of chamber electrolytic process of oxalic dialdehyde anonizing and both bonded.Summary is got up, and this method raw material is easy to get, and technology is simple, and by product is few, pollutes for a short time, but product purity is low, the quality instability, and the solution evaporation amount is big, the energy consumption height, facility investment and production cost are higher, and the abundant area of only suitable electric power resource produces.And because electrode materials is undesirable, the ion-exchange membrane poor performance, the poisoning of easily breaking, anodic corrosion, the negative electrode inactivation, reason such as mass transfer is inhomogeneous, and space-time yield is low, and electrolytic solution is contaminated all fails to realize continuous ordinary production both at home and abroad.(referring to US 5474658; CN 1322860; CN 1281063; CN 1560326; CN 1369575; CN 1064111; CN 1322859; CN 1219611; CN 1318653; Fine chemistry industry, 2001,18 (8): 37-39; Chemical science and technology, 2001,9 (4): 35～37; The chemical industry journal, 2001,52 (2): 135-140; Or the like).Outside the deozonize oxidation style, other is mainly contained dichloro acetic acid and methyl esters hydrolysis method thereof (referring to Hebei Normal University's journal: the natural version .2003 of section, 27 (5): 490-492 by the method for primary study; CN 1070184), oxalic dialdehyde metal catalytic oxidation method is (referring to EP 438948; DE 4324442; US 5395965; Fine chemistry industry, 2002,19 (8): 479-481 etc.) oxalic dialdehyde or oxyacetic acid enzymatic oxidation method (referring to J.Org.Chem.1993,58:2253-2259. and J.Org.Chem.1995,60:3957-3963.), (CN 1167751 for the oxalic dialdehyde hydrogen peroxide oxidation method; Chemistry world, 2004,9:479-480.) this method nearly all has its points of course, but some unavoidable shortcomings are also all arranged, perhaps at present technology that is that all right is ripe, still can't realize industrialization.
The ozone oxidation method also is one of process for production of glyoxalic acid that is studied the earliest abroad, but China has not yet to see the correlative study bibliographical information.1966, Black etc. were (referring to I﹠amp; EC.Product Research and Development, 1966, the toxilic acid aqueous solution that 5:350.) will about 40wt% is at the O of 15～25 ℃ of logical 4wt%
3/ O
2Carry out ozonize to reacting completely, then under 50 ℃, underpressure distillation removes formic acid and the most of aqueous solvent that dereaction generates, then raffinate is carried out crystallization under 20 ℃, obtain the monohydrate of oxoethanoic acid, productive rate is near 50% (generating the 2mol oxoethanoic acid in theory with the 1mol toxilic acid calculates), and product purity reaches more than 97%.1964, after-40 ℃ of following ozonize, low temperature was used the phosphinate fast restore down to Thompson etc. (referring to US 3145232), obtains the oxoethanoic acid butyl ester with the toxilic acid butyl ester, and productive rate is 78%.1966, Pappas etc. (referring to GB 1092615) were solvent with methyl alcohol, with the toxilic acid ozonize, reduced with dimethyl sulphide under 2 ℃ under-50 ℃ again, and the yield of oxoethanoic acid is 91% (being measured by 2,4 dinitrophenyl hydrazine).They also attempt to be raw material, to obtain corresponding glyoxylic ester obtain oxoethanoic acid after the hydrolysis, but productive rate not to have obvious raising with ethyl maleate and dimethyl maleate in addition.Because dimethyl sulphide and phosphorous acid ester all are expensive reductive agents, and all with the oxoethanoic acid separation difficulty, therefore can't be used for scale operation.Subsequently, Pryde and Moore etc. (referring to US 3112329 and US 3349106) improve solvent respectively, the former adopts methyl alcohol-ethyl acetate to mix solvent (volume ratio is 1: 4), and add a spot of pyridine, the latter is further enhanced the productive rate of aldehyde with the Fatty Alcohol(C12-C14 and C12-C18) of equivalent and the mixed solvent of lipid acid.But product separation and solvent recuperation are still very difficult.1972, Callghan etc. (referring to US 3644508) led to the O of 4wt% with toxilic acid and acetone or ethyl acetate wiring solution-forming about 5 ℃
3/ O
2Carry out ozonize to reacting completely, the logical excessive ozone of oxygen flush away maintains the temperature at below 30 ℃ then, logical SO
2Superoxide is reduced.After reacting completely, add quantitative CaO, with the SO that generates
3Precipitate and separate adds less water then, and below 50 ℃, underpressure distillation removes and desolvates, and obtains oxoethanoic acid one hydrate crystal, and productive rate is up to more than 95%.This method is simple and practical, but SO
2And SO
3Serious to equipment corrosion, and can cause environmental pollution.As seen, laboratory stage can only be rested on, industrialization can't be realized for the research at ozone oxidation method initial stage.After the appearance of ozone oxidation-shortening technology, this method is just progressively realized suitability for industrialized production.1972, Callighan etc. (referring to US3705922) adopted ozone oxidation-shortening method synthesizing glyoxalic acid first, and they are solvent with methyl alcohol, under-50 ℃ with toxilic acid with ozone oxidation after, blow out remaining ozone with nitrogen, maintain the temperature at then below 15 ℃, use 5wt%Pd/Al
2O
3Make catalyzer, to the ozonation products shortening, filter to isolate catalyzer under normal pressure, underpressure distillation obtains the hemiacetal of oxoethanoic acid, and productive rate is up to 95%.To distill out methyl alcohol after the hemiacetal hydrolysis, promptly obtain the acetaldehyde aqueous acid.In this technology, productive rate is very strong according to patience to catalyst levels, and the 1mol toxilic acid needs the 0.5g catalyzer approximately, if reduce catalyst consumption, then productive rate can reduce rapidly, and does not propose the recoverying and utilizing method of catalyzer in the technology.1988, Arashiba etc. (referring to EP 0293127) improved this technology, mainly were to add some antioxidants in this step of shortening, thereby had improved the selectivity and the productive rate of reaction significantly.These antioxidants comprise some benzoquinones classes, phenols and aromatic amine compounds and some organosulfurs and organic phosphine compound.The technology for this reason that Japan's strain formula chemistry can adopt.1991, Alexander etc. (referring to US 5015760) have carried out further improvement to technology, with cation exchange resin as catalyst, earlier maleic anhydride is used esterifications such as ethanol, propyl carbinol or nonylcarbinol, ozonize under the condition that excessive methanol exists then, then blow out remaining ozone with nitrogen after, add the reduction of Pt or Pd/C catalytic hydrogenation, obtain the hemiacetal of glyoxylic ester, the hydrolysis distillation promptly gets glyoxylic acid solution then.Because earlier with the toxilic acid esterification, make the ozonize temperature bring up to 0～4 ℃, reduction temperature is brought up to 30～40 ℃, life of catalyst obtains prolonging, and operational condition obtains bigger improvement, and productive rate still maintains more than 95%.What Austria Linz company adopted is exactly this technology.As seen ozonize-this technology of shortening technology has that raw material is cheap and easy to get, environmental pollution is little, good product quality, advantage such as scale operation easily.But will use expensive hydrogenation catalyst in the production process, the catalyzer solvent is poisoned and is difficult to reclaim and reuses, thereby makes complex manufacturing, and production cost is higher.
Synthesizing glyoxalic acid of the present invention is based on the toxilic acid ozonation technology, but all be essentially different with above-mentioned existing technology, because the present invention successfully combines toxilic acid ozone oxidation method and oxalic dialdehyde catalytic oxidation, developed the brand-new method of synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide, synthesized high density, highly purified oxoethanoic acid with the simple steps high productivity.This law is utilized the further oxidation oxalic dialdehyde of toxilic acid ozonide, has successfully avoided the shortcoming that catalyzer is poisoned easily in ozonize-shortening technology, has also saved materials such as hydrogen.Simultaneously, it is low successfully to have solved the existing transformation efficiency of other various oxidation of glyoxal, problems such as poor product quality.Because this law technology is simple, whole process reaction mild condition, material is saved, and environmentally safe, very helps large-scale industrial production, is a new breakthrough of oxoethanoic acid industry.
Summary of the invention
The object of the invention is, proposed the toxilic acid ozonide and can be further used as oxygenant oxidation oxalic dialdehyde and prepare oxoethanoic acid.The noble metal catalyst of industrialized ozonize at present-shortening Technology Need costliness, the shortcoming that catalyzer is poisoned and is difficult to reclaim have easily successfully been avoided in the invention of this originality.Moreover, in the technological line that the present invention adopts, when being the raw material complete reaction with the toxilic acid (acid anhydride) of equimolar amount and oxalic dialdehyde, can synthesize oxoethanoic acid, do not need to use hydrogen and the employed nitric acid of other oxidation of glyoxal, potassium permanganate etc. to add material, thereby saved material and energy widely, and avoided the introducing tramp material, improved the quality of product.
A kind of method with toxilic acid ozonide oxidation oxalic dialdehyde reduction synthesizing glyoxalic acid of the present invention follows these steps to carry out:
A, with toxilic acid or with the water of maleic anhydride and equimolar amount, be made into the solution of toxilic acid quality percentage composition with methyl alcohol and acetic acid at 4%-15%, be cooled to-5-5 ℃ the O of violent stirring and logical 2-6wt%
3/ O
2After mixed gas reaction is complete, get rid of remaining ozone, make the ozonide of toxilic acid with nitrogen;
B, take by weighing oxalic dialdehyde and acetic acid and water with the toxilic acid equimolar amount, be made into oxalic dialdehyde the quality percentage composition behind the solution of 10-30%, add catalyzer or do not add catalyzer, controlled temperature is at 30-40 ℃;
C, with toxilic acid ozonide oxidation oxalic dialdehyde: stir and in glyoxal solution, drip ozonation products down, continue to drip 2 hours, continue to be stirred to reaction and finish, with starch/potassium iodide starch paper detection reaction terminal point to finishing;
D, 50 ℃ of underpressure distillation remove and desolvate, and the strength of solution that obtains oxoethanoic acid is at 70-90%, and the productive rate of entire reaction is at 90-99%.
In the toxilic acid ozonization, solvent adopts the mixed solvent of methyl alcohol and acetic acid, and wherein the massfraction of acetic acid accounts for the 5-95% of whole solvent; The oxidation oxalic dialdehyde in the reaction, adopt acetic acid and water to make solvent in the time of the dilution oxalic dialdehyde, wherein the massfraction of water accounts for the 4-60% of whole solvent.
In the time of toxilic acid ozonide oxidation oxalic dialdehyde, the catalyzer of employing is manganese acetate or ferrous sulfate or cupric chloride or plumbic acetate or argent or carries the load metal Pd or carry load metal Pt, or do not adopt catalyzer.
At present, smellyization of ozone method is produced the solvent overwhelming majority that oxoethanoic acid adopted and is methyl alcohol, but, in the present invention, if merely use methyl alcohol to be solvent, in the reaction of second step, methyl alcohol will generate hemiacetal or acetal with oxalic dialdehyde, the ozonide of toxilic acid can't be up hill and dale with oxalic dialdehyde hemiacetal or acetal be oxidized to oxoethanoic acid, thereby the transformation efficiency and the selectivity of reaction are lower.In the present invention simultaneously, also can't merely use acetic acid to be solvent, solid-state because pure acetic acid will condense at 16 ℃, ozonization can't be carried out smoothly.So ozonization of the present invention adopts the mixed solvent of methyl alcohol and acetic acid, and in second step, oxalic dialdehyde is dissolved in acetic acid-aqueous solution, so just successfully having hindered oxalic dialdehyde is transformed into hemiacetal or acetal form, the existence of water and acetic acid simultaneously, help the stable of oxoethanoic acid, and suppressed the generation of glyoxalic acid methylester.Moreover, acetic acid can also generate Peracetic Acid with toxilic acid ozonide reaction, and Peracetic Acid is a kind of good common agents, it can make reaction not even according to Baeyer-Villiger mechanism (referring to Chem.Listy, 1952,46:567. with C.H.Hassailin Organic Reactions, Vol.9, Wiley, New York, 1957, p.84), expeditiously formoxy-is changed into carboxylic acid.Experiment showed, that in the present invention even do not adopt any catalyzer, the productive rate of oxoethanoic acid can be greater than 90%.Simultaneously, methyl alcohol and acetic acid all are low-boiling point materials, methyl alcohol, acetic acid and water separate with oxoethanoic acid by the decompression component distillation just being easy to below 50 ℃, thereby can obtain concentration easily greater than 70% aqueous glyoxylic acid product, and this is that other method is difficult to realize at present.
Toxilic acid ozonide oxidation oxalic dialdehyde in this step, do not use catalyzer can successfully carry out thoroughly yet, but suitably adopt the catalyzer can fast reaction speed, the selectivity that can also improve oxoethanoic acid that has.We have mainly studied the catalytic effect of several conventional redox catalysts, as manganese acetate, ferrous sulfate, cupric chloride, plumbic acetate, argent, single supported noble metal such as Pd/Al
2O
3Catalytic effect with Pt/C etc.Experiment showed, that speed of response is the fastest when making catalyzer with ferrous salt and mantoquita, but reaction preference is poor.With manganese acetate or plumbic acetate is catalyzer, and speed of response is moderate, and selectivity is also better.But the best catalyzer of effect is a noble metal catalyst, and under precious metal catalyst, not only Fan Ying speed is moderate, and the selectivity of generation oxoethanoic acid is very high.
Embodiment
The present invention will be further described below by embodiment.
Embodiment 1
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 500ml acetic acid, add 50ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃, the O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone, and the ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 100ml acetic acid of 43.5g40%, stirs and heat to make temperature remain on 35 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to react about 4 hours until detect no longer variable color with starch/potassium iodide starch paper, learns that superoxide reacts completely;
Remove methyl alcohol, acetic acid and portion water 50 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 102.9g, concentration is 55.79%, and the yield of oxoethanoic acid is 86.2%.
Embodiment 2
Take by weighing 29.6g toxilic acid (0.30mol), be dissolved in the 400ml acetic acid, add 100ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature between-3 ℃, the O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out 2.5 hours stopped reaction (the ozone consumption is about 0.34mol) of ozonization, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone, and the ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 100ml acetic acid of 43.5g40%, stirs and heat to make temperature remain on 35 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to react about 4 hours until detect no longer variable color with starch/potassium iodide starch paper, learns that superoxide reacts completely;
Add 250ml distilled water in reaction product, remove methyl alcohol, acetic acid and portion water 45 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 294.3g, concentration is 20.07%, and the yield of oxoethanoic acid is 88.7%.
Embodiment 3
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 350ml acetic acid, add 150ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature between 3 ℃, the O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone, and the ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 100ml acetic acid of 43.5g40%, stirs and heat to make temperature remain on 35 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to react about 4 hours until detect no longer variable color with starch/potassium iodide starch paper, learns that superoxide reacts completely;
Remove methyl alcohol, acetic acid and portion water 50 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 95.9g, concentration is 63.34%, and the yield of oxoethanoic acid is 91.2%.
Embodiment 4
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 300ml acetic acid, add 200ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at 5 ℃, the O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone, and the ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 100ml acetic acid of 43.5g40%, stirs and heat to make temperature remain on 30 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to react about 4 hours until detect no longer variable color with starch/potassium iodide starch paper, learns that superoxide reacts completely;
Add 250ml distilled water in reaction product, remove methyl alcohol, acetic acid and portion water 50 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 309.1g, concentration is 20.25%, and the yield of oxoethanoic acid is 93.9%.
Embodiment 5
Take by weighing 29.6g toxilic acid (0.30mol), be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at 4 ℃, the O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone, and the ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 100ml acetic acid of 43.5g40%, stirs and heat to make temperature remain on 40 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to react about 4 hours until detect no longer variable color with starch/potassium iodide starch paper, learns that superoxide reacts completely;
Add 250ml distilled water in reaction product, remove methyl alcohol, acetic acid and portion water 50 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 275.5g, concentration is 22.90%, and the yield of oxoethanoic acid is 94.72%.
Embodiment 6
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 100ml acetic acid, add 400ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at 0 ℃, the O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone, and the ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 100ml acetic acid of 43.5g40%, stirs and heat to make temperature remain on 36 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to react about 4 hours until detect no longer variable color with starch/potassium iodide starch paper, learns that superoxide reacts completely;
Add 250ml distilled water in reaction product, remove methyl alcohol, acetic acid and portion water 50 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 262.2g, concentration is 24.82%, and the yield of oxoethanoic acid is 97.7%.
Embodiment 7
Take by weighing 29.4g maleic anhydride (0.30mol), add and to mix in the 5ml water and, add 500ml methyl alcohol then, mix and be transferred in the four-hole bottle, at-5 ℃, stir and the O of logical 3wt% with icy salt solution mixture hierarchy of control temperature at 40 ℃ of reaction 10min down
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone, and the ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 100ml methyl alcohol of 43.5g40%, stirs and heat to make temperature remain on 34 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues reaction and detects no longer variable color with starch/potassium iodide starch paper after about 6 hours, learns that superoxide reacts completely;
Add 250ml distilled water in reaction product, remove methyl alcohol and portion water in underpressure distillation below 50 ℃, obtain aqueous glyoxylic acid 274.6g, concentration is 16.84%, and the yield of oxoethanoic acid is 69.5%.
Embodiment 8
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 100ml acetic acid, add 100ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃, the O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds glyoxal water solution and the 50ml acetic acid of 43.5g40%, stirs and heat to make temperature remain on 38 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to react about 4 hours until detect no longer variable color with starch/potassium iodide starch paper, learns that superoxide reacts completely;
Add 250ml distilled water in reaction product, remove methyl alcohol, acetic acid and portion water 50 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 176.0g, concentration is 27.39%, and the yield of oxoethanoic acid is 72.4%.
Embodiment 9
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃.The O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds the glyoxal water solution of 43.5g40%, 100ml acetic acid and 0.50g manganese acetate (Mn (OAc)
24H
2O), stirring and heating make temperature remain on 35 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continue to detect i.e. no longer variable color with starch/potassium iodide starch paper behind the about 1h15min of reaction, learn that superoxide reacts completely (promptly the reaction times that needs altogether is about 3h15min);
After reaction finished, mn ion changed manganese dioxide precipitate into, after the filtration, in reaction product, add 250ml distilled water, remove methyl alcohol, acetic acid and portion water, obtain aqueous glyoxylic acid 274.7g 50 ℃ of underpressure distillation, concentration is 21.60%, and the yield of oxoethanoic acid is 89.1%.
Embodiment 10
Take by weighing 29.6g toxilic acid (0.30mol), be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃.The O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds the glyoxal water solution of 43.5g40%, 100ml acetic acid and 0.5g ferrous sulfate (FeSO
47H
2O), stirring and heating make temperature remain on 35 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to detect i.e. no longer variable color with starch/potassium iodide starch paper behind the about 50min of reaction, learns that superoxide reacts completely;
Reaction back Fe
2+Be converted into sorrel Fe
3+, to remove with Zeo-karb, the yield that obtains oxoethanoic acid is 74.5%.
Embodiment 11
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃.The O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds the glyoxal water solution of 43.5g40%, 100ml acetic acid and 0.5g cupric chloride (CuCl
22H
2O), stirring and heating make temperature remain on 35 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to detect i.e. no longer variable color with starch/potassium iodide starch paper behind the about 55min of reaction, learns that superoxide reacts completely;
After reaction finishes, portion C u
2+Be converted into the precipitation perforated, remaining Cu
2+Remove with Zeo-karb, the yield that obtains oxoethanoic acid is 79.3%.
Embodiment 12
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃.The O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds the glyoxal water solution of 43.5g40%, 100ml acetic acid and 0.5g plumbic acetate (Pb (OAc)
23H
2O), stirring and heating make temperature remain on 36 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to detect i.e. no longer variable color with starch/potassium iodide starch paper behind the about 1h20min of reaction, learns that superoxide reacts completely;
After reaction finishes, reaction back Pb
2+Being converted into plumbous oxide precipitation can remove by filter, and the yield that obtains oxoethanoic acid is 87.7%.
Embodiment 13
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃.The O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds the glyoxal water solution of 43.5g40%, and the active silver powder of 100ml acetic acid and 0.5g (by silver ammino solution and oxalic dialdehyde preparation) stirs and heating makes temperature remain on 33 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to detect i.e. no longer variable color with starch/potassium iodide starch paper behind the about 2h25min of reaction, learns that superoxide reacts completely;
After reaction finishes, after the silver powder filtration, add 250ml distilled water in reaction product, remove methyl alcohol, acetic acid and portion water 50 ℃ of underpressure distillation, obtain aqueous glyoxylic acid 291.4g, concentration is 22.40%, and the yield of oxoethanoic acid is 98.9%.
Embodiment 14
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃.The O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds the glyoxal water solution of 43.5g40%, 100ml acetic acid and 1.0g5%Pd/Al
2O
3Be catalyzer, stirring and heating make temperature remain on 38 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to detect i.e. no longer variable color with starch/potassium iodide starch paper behind the about 2h10min of reaction, learns that superoxide reacts completely;
After reaction finishes, can use repeatedly behind the catalyzer filtering drying, the yield that obtains oxoethanoic acid is 98.2%.
Embodiment 15
Take by weighing 29.4g maleic anhydride (0.30mol) and 5ml water, be dissolved in the 200ml acetic acid, add 300ml methyl alcohol then, after mixing, use icy salt solution mixture hierarchy of control temperature at-5 ℃.The O of stirring and logical 3wt%
3/ O
2Mixed gas 0.1m
3/ h carries out ozonization stopped reaction (the ozone consumption is about 0.34mol) after 2.5 hours, logical nitrogen 0.2m
3/ h1-2min gets rid of ozone.The ozonide that obtains detects with starch/potassium iodide starch paper and becomes blue;
Other gets four-hole bottle, adds the glyoxal water solution of 43.5g40%, and 100ml acetic acid and 1.0g5%Pt/C are catalyzer, stirs and heat to make temperature remain on 40 ℃;
Drip the ozonide (frozen water protection) that the first step reaction makes then, the control flow velocity makes it to dropwise at 2 hours, continues to detect i.e. no longer variable color with starch/potassium iodide starch paper behind the about 2h15min of reaction, learns that superoxide reacts completely;
After reaction finishes, can use repeatedly behind the catalyzer filtering drying, the yield that obtains oxoethanoic acid is 96.4%.
Claims (3)
1, a kind of method of synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide is characterized in that following these steps to carrying out:
A, with toxilic acid or with the water of maleic anhydride and equimolar amount, be made into the solution of toxilic acid quality percentage composition with methyl alcohol and acetic acid at 4%-15%, be cooled to-5-5 ℃ the O of violent stirring and logical 2-6wt%
3/ O
2After mixed gas reaction is complete, get rid of remaining ozone, make the ozonide of toxilic acid with nitrogen;
B, take by weighing oxalic dialdehyde and acetic acid and water with the toxilic acid equimolar amount, be made into oxalic dialdehyde the quality percentage composition behind the solution of 10-30%, add catalyzer or do not add catalyzer, controlled temperature is at 30-40 ℃;
C, with toxilic acid ozonide oxidation oxalic dialdehyde: stir and in glyoxal solution, drip ozonation products down, continue to drip 2 hours, continue to be stirred to reaction and finish, with starch/potassium iodide starch paper detection reaction terminal point to finishing;
D, 50 ℃ of underpressure distillation remove and desolvate, and the strength of solution that obtains oxoethanoic acid is at 70-90%, and the productive rate of entire reaction is at 90-99%.
2. a kind of method of using synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide according to claim 1, it is characterized in that, in the toxilic acid ozonization, solvent adopts the mixed solvent of methyl alcohol and acetic acid, and wherein the massfraction of acetic acid accounts for the 5-95% of whole solvent; The oxidation oxalic dialdehyde in the reaction, adopt acetic acid and water to make solvent in the time of the dilution oxalic dialdehyde, wherein the massfraction of water accounts for the 4-60% of whole solvent.
3. a kind of method of using synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide according to claim 1, it is characterized in that, in the time of toxilic acid ozonide oxidation oxalic dialdehyde, the catalyzer that adopts is manganese acetate or ferrous sulfate or cupric chloride or plumbic acetate or argent or carries the load metal Pd or carry load metal Pt, or do not adopt catalyzer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100782599A CN1312100C (en) | 2005-06-07 | 2005-06-07 | Method for synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide |
| PCT/CN2006/000487 WO2006131040A1 (en) | 2005-06-07 | 2006-03-24 | A method for preparation of glyoxalic acid by oxidating glyoxal with ozonide of maleic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100782599A CN1312100C (en) | 2005-06-07 | 2005-06-07 | Method for synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1709849A true CN1709849A (en) | 2005-12-21 |
| CN1312100C CN1312100C (en) | 2007-04-25 |
Family
ID=35706145
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|---|---|---|---|
| CNB2005100782599A Expired - Fee Related CN1312100C (en) | 2005-06-07 | 2005-06-07 | Method for synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide |
Country Status (2)
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| CN (1) | CN1312100C (en) |
| WO (1) | WO2006131040A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006131040A1 (en) * | 2005-06-07 | 2006-12-14 | The Xinjiang Technical Institute Of Physics & Chemistry Chinese Academy Of Sciences | A method for preparation of glyoxalic acid by oxidating glyoxal with ozonide of maleic acid |
| CN101462946A (en) * | 2008-12-30 | 2009-06-24 | 上海华谊（集团）公司 | Method for preparing ethanol acid by catalytic oxidation of biformyl |
| CN101559927B (en) * | 2009-06-02 | 2011-07-20 | 天津市职业大学 | Green technology for synchronously producing chlorine dioxide and glyoxalic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009014431A1 (en) * | 2007-07-23 | 2009-01-29 | Pluim, Henk | Selective production of sulphoxides |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644508A (en) * | 1969-07-23 | 1972-02-22 | United States Steel Corp | Process for the recovery of glyoxylic acid |
| DE3224795A1 (en) * | 1982-07-02 | 1984-01-05 | Lentia GmbH Chem. u. pharm. Erzeugnisse - Industriebedarf, 8000 München | METHOD FOR PRODUCING GLYOXYL ACID AND GLYOXYL ACID DERIVATIVES |
| JPH0830026B2 (en) * | 1987-05-27 | 1996-03-27 | 三井東圧化学株式会社 | Method for producing glyoxylic acids |
| CN1312100C (en) * | 2005-06-07 | 2007-04-25 | 中国科学院新疆理化技术研究所 | Method for synthesizing glyoxalic acid by oxidation of glyoxal with maleuric ozonide |
-
2005
- 2005-06-07 CN CNB2005100782599A patent/CN1312100C/en not_active Expired - Fee Related
-
2006
- 2006-03-24 WO PCT/CN2006/000487 patent/WO2006131040A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006131040A1 (en) * | 2005-06-07 | 2006-12-14 | The Xinjiang Technical Institute Of Physics & Chemistry Chinese Academy Of Sciences | A method for preparation of glyoxalic acid by oxidating glyoxal with ozonide of maleic acid |
| CN101462946A (en) * | 2008-12-30 | 2009-06-24 | 上海华谊（集团）公司 | Method for preparing ethanol acid by catalytic oxidation of biformyl |
| CN101462946B (en) * | 2008-12-30 | 2012-11-07 | 上海华谊（集团）公司 | Method for preparing ethanol acid by catalytic oxidation of biformyl |
| CN101559927B (en) * | 2009-06-02 | 2011-07-20 | 天津市职业大学 | Green technology for synchronously producing chlorine dioxide and glyoxalic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1312100C (en) | 2007-04-25 |
| WO2006131040A1 (en) | 2006-12-14 |
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