CN112500286A - Preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid - Google Patents
Preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid Download PDFInfo
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- CN112500286A CN112500286A CN202011585846.8A CN202011585846A CN112500286A CN 112500286 A CN112500286 A CN 112500286A CN 202011585846 A CN202011585846 A CN 202011585846A CN 112500286 A CN112500286 A CN 112500286A
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The invention provides a preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid, which belongs to the field of chemical production. The invention adds the cocatalyst composite solid acid catalytic oxidation solution, thus improving the yield of the glyoxylic acid; the operating environment is improved, the defects of easy environmental pollution and easy corrosion of equipment are avoided, the product quality is stable, and the method is suitable for industrial production; the invention can ensure the production efficiency of the glyoxylic acid and the production purity of the glyoxylic acid by multi-layer filtration, improves the use effect, and has simple storage and easy mastering.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid.
Background
Glyoxylic acid (OHCOOH) has the properties of aldehyde and carboxylic acid and is an important intermediate and biochemical reagent of organic chemical raw materials. Dozens of fine chemical products can be derived from the glyoxylic acid and widely applied to the fields of medicines, spices, pesticides, paints, papermaking, food additives and the like; the application of glyoxylic acid to leather, electronics and electroplating is in the development stage. In the last decade, as the application field of downstream products of glyoxylic acid is continuously expanded, the market demand of glyoxylic acid is continuously increased and the yield is rapidly increased.
The preparation method of glyoxylic acid in the prior art is widely applied.
However, the existing preparation method of glyoxylic acid has the problems of laggard preparation process, poor preparation effect, no filtering function and poor catalytic effect.
Therefore, the invention provides a preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid, which aims to solve the problems of laggard preparation process, poor preparation effect, no filtering function and poor catalytic effect of the existing preparation method for glyoxylic acid, and the preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid specifically comprises the following steps:
the method comprises the following steps: preparing raw materials, namely preparing glyoxal, hydrogen peroxide and a catalyst, mixing and stirring glyoxal solution at the temperature of 12-15 ℃, continuously carrying out mixing reaction, and simultaneously adding a catalyst ferrous sulfide and a catalyst to react to generate an oxide;
step two: the oxidation extraction treatment specifically comprises the following steps:
the first step is as follows: filtering with a screen, namely placing the oxide on a stainless steel screen, continuously performing vibration screening to remove larger particles, leaving the filtered oxide, and storing impurity particles;
the second step is that: grinding the oxide, namely grinding the oxide in a grinder, grinding the oxide into powder, filtering and screening the powder again to remove non-uniformly ground particles, and preparing and forming oxidized extract powder;
step three: the preparation and processing operation of the oxidized extract powder specifically comprises the following steps:
the first step is as follows: performing oxide extraction reaction, namely performing esterification reaction on the oxidation extraction powder and absolute ethyl alcohol at the temperature of 140 ℃ for 2-4 hours in the presence of sulfuric acid, collecting an esterification product from a reaction liquid, placing the esterification product in a storage tank, avoiding hand contact, stirring the esterification product, and fishing out impurities;
the second step is that: performing reaction treatment on the esterification product, performing hydrolysis reaction on the esterification product and sulfuric acid at the temperature of 110-120 ℃ for 2-3 hours, collecting a target product glyoxylic acid from the reaction liquid, and storing the glyoxylic acid for later use;
step four: the glyoxylate processing and filtering treatment specifically comprises the following steps:
the first step is as follows: processing glyoxylic acid, namely putting the glyoxylic acid into a stainless steel tank, oscillating and stirring, visually checking whether macroscopic impurities are mixed or not, fishing out the glyoxylic acid through a stainless steel net, continuously oscillating and stirring, and then preparing for storage;
the second step is that: filtering glyoxylic acid, namely placing the treated glyoxylic acid on a stainless steel mesh sieve for direct filtration, performing secondary filtration, collecting filtered liquid, and taking out residual impurities and particles;
the third step: storing glyoxylic acid, namely storing the glyoxylic acid at a temperature within a reasonable range, canning, keeping a distance between cans, and checking in time during storage to ensure no leakage;
step five: transportation, use, in the transportation, avoid sunshine to penetrate directly, avoid high temperature simultaneously, in the use, avoid the hand contact to wear the gauze mask, after finishing using at every turn, the lid is good.
Preferably, in the step one, the catalyst adopts a composite solid acid catalytic oxidation solution.
Preferably, in the second step, the stainless steel screen mesh in the first step adopts a double-layer fine stainless steel screen mesh, and the vibration frequency is set to be 5-8 times.
Preferably, in the second step, the grinding speed in the second step is set to be 100r/min-150 r/min.
Preferably, in the third step, the stirring speed in the first step is set to be 150r/min-200 r/min.
Preferably, in step three, the storage temperature of the glyoxylic acid in the second step is set to be 20-25 ℃.
Preferably, in step four, the oscillation speed in the first step is set to 200-.
Preferably, in step four, the distance in the third step is set to 10-15 cm.
Compared with the prior art, the invention has the following beneficial effects: the preparation method for producing the glyoxylic acid by catalytic oxidation of the composite solid acid is widely applied to the technical field of chemical production. The invention adds the cocatalyst composite solid acid catalytic oxidation solution, thus improving the yield of the glyoxylic acid; the operating environment is improved, the defects of easy environmental pollution and easy corrosion of equipment are avoided, the product quality is stable, and the method is suitable for industrial production; the invention can ensure the production efficiency of the glyoxylic acid and the production purity of the glyoxylic acid by multi-layer filtration, improves the use effect, and has simple storage and easy mastering.
Drawings
FIG. 1 is a flow chart of a preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid.
FIG. 2 is a flow chart of the oxidative extraction process.
FIG. 3 is a flow chart of the oxidative extraction powder preparation process operation.
FIG. 4 is a flow chart of the filtration process for glyoxylate processing.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
in the figure:
as shown in figure 1
The preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid specifically comprises the following steps:
s101: preparing raw materials, namely preparing glyoxal, hydrogen peroxide and a catalyst, mixing and stirring glyoxal solution at the temperature of 12-15 ℃, continuously carrying out mixing reaction, and simultaneously adding a catalyst ferrous sulfide and a catalyst to react to generate an oxide;
s102: the oxidation extraction treatment, as shown in the attached figure 2, specifically comprises the following steps:
s201: filtering with a screen, namely placing the oxide on a stainless steel screen, continuously performing vibration screening to remove larger particles, leaving the filtered oxide, and storing impurity particles;
s202: grinding the oxide, namely grinding the oxide in a grinder, grinding the oxide into powder, filtering and screening the powder again to remove non-uniformly ground particles, and preparing and forming oxidized extract powder;
s103: the preparation and processing operation of the oxidized extract powder is shown in the attached figure 3, and specifically comprises the following steps:
s301: performing oxide extraction reaction, namely performing esterification reaction on the oxidation extraction powder and absolute ethyl alcohol at the temperature of 140 ℃ for 2-4 hours in the presence of sulfuric acid, collecting an esterification product from a reaction liquid, placing the esterification product in a storage tank, avoiding hand contact, stirring the esterification product, and fishing out impurities;
s302: performing reaction treatment on the esterification product, performing hydrolysis reaction on the esterification product and sulfuric acid at the temperature of 110-120 ℃ for 2-3 hours, collecting a target product glyoxylic acid from the reaction liquid, and storing the glyoxylic acid for later use;
s104: the glyoxylate processing and filtering treatment specifically comprises the following steps as shown in the attached figure 4:
s401: processing glyoxylic acid, namely putting the glyoxylic acid into a stainless steel tank, oscillating and stirring, visually checking whether macroscopic impurities are mixed or not, fishing out the glyoxylic acid through a stainless steel net, continuously oscillating and stirring, and then preparing for storage;
s402: filtering glyoxylic acid, namely placing the treated glyoxylic acid on a stainless steel mesh sieve for direct filtration, performing secondary filtration, collecting filtered liquid, and taking out residual impurities and particles;
s403: storing glyoxylic acid, namely storing the glyoxylic acid at a temperature within a reasonable range, canning, keeping a distance between cans, and checking in time during storage to ensure no leakage;
s105: transportation, use, in the transportation, avoid sunshine to penetrate directly, avoid high temperature simultaneously, in the use, avoid the hand contact to wear the gauze mask, after finishing using at every turn, the lid is good.
Preferably, in S101, the catalyst is a composite solid acid catalytic oxidation solution.
Preferably, in S102, the stainless steel screen mesh in S201 adopts a double-layer fine stainless steel screen mesh, and the vibration frequency is set to 5-8 times.
Preferably, in S102, the grinding speed in S202 is set to be 100r/min-150 r/min.
Preferably, in S103, the stirring speed in S301 is set to be 150r/min-200 r/min.
Preferably, in S103, the storage temperature of glyoxylic acid in S302 is set to be 20-25 ℃.
Preferably, in S104, the oscillation speed in S401 is set to 200-.
Preferably, in S104, the distance in S403 is set to 10-15 cm.
Detailed description of the preferred embodiment example 1
Adding 300ml (3.55mol) of 50% glyoxal solution into a 3500ml reactor provided with a reflux condenser tube, a stirrer and a thermometer, stirring and cooling, controlling the temperature to be 7 +/-2 ℃, slowly dropping 300ml (3.55mol) of 35% hydrogen peroxide solution, 280ml (0.355mol) of 17% ferrous sulfate solution and 120ml (0.75mol) of 15% ammonia water solution within 3 hours, keeping the temperature at 8 +/-2 ℃ for reaction for 3 hours, standing overnight, filtering reaction liquid to remove solid by-products, adding 350ml of water-carrying agent toluene into reaction mother liquid, heating and refluxing, removing water, distilling out the water-carrying agent toluene, and obtaining an oxidation product.
Respectively adding 120ml of concentrated sulfuric acid and 700ml of absolute ethyl alcohol into the oxidation product, carrying out esterification reaction at 140 ℃ for 3 hours, then carrying out reduced pressure distillation, and collecting the esterification product at 185 ℃ under 0.02 Mpa.
Adding 120ml of 18 percent sulfuric acid into the esterification product, heating the mixture under stirring, and carrying out hydrolysis reaction for 2 hours at the temperature of 95-98 ℃; cooling the hydrolysate to room temperature, filtering to separate out white solid product, washing with 120ml toluene for 4 times, and drying to obtain 180g target product glyoxylic acid with purity of 99.5% (HPLC), yield of 88% and melting point of 98.1-98.6 ℃.
Detailed description of the preferred embodiment example 2
Adding 900ml (3.55mol) of 50% glyoxal solution into a 3500ml reactor provided with a reflux condenser tube, a stirrer and a thermometer, stirring and cooling, controlling the temperature to be 9 +/-2 ℃, slowly dropping 600ml (3.55mol) of 45% hydrogen peroxide solution, 300ml (0.355mol) of 17% ferrous sulfate solution and 140ml (0.75mol) of 20% ammonia water solution within 3 hours, keeping the temperature to be 10 +/-2 ℃ for reaction for 3 hours, standing overnight, filtering reaction liquid to remove solid by-products, adding 400ml of water-carrying agent toluene into reaction mother liquid, heating and refluxing, removing water, and distilling out the water-carrying agent toluene to obtain an oxidation product.
Adding 140ml of concentrated sulfuric acid and 800ml of absolute ethyl alcohol into the oxidation product respectively, carrying out esterification reaction at 160 ℃ for 3 hours, then carrying out reduced pressure distillation, and collecting the esterification product at 195 ℃ under 0.02 Mpa.
Adding 140ml of 20 percent sulfuric acid into the esterification product, heating the mixture under stirring, and carrying out hydrolysis reaction for 2 hours at the temperature of 98-99 ℃; cooling the hydrolysate to room temperature, filtering to separate out white solid product, washing with 140ml toluene for 4 times, and drying to obtain 190g of target product glyoxylic acid with purity of 99.5% (HPLC), yield of 88% and melting point of 98.6-99.1 ℃.
The invention adds the cocatalyst composite solid acid catalytic oxidation solution, thus improving the yield of the glyoxylic acid; the operating environment is improved, the defects of easy environmental pollution and easy corrosion of equipment are avoided, the product quality is stable, and the method is suitable for industrial production; the invention can ensure the production efficiency of the glyoxylic acid and the production purity of the glyoxylic acid by multi-layer filtration, improves the use effect, and has simple storage and easy mastering.
The technical solutions of the present invention or similar technical solutions designed by those skilled in the art based on the teachings of the technical solutions of the present invention are all within the scope of the present invention.
Claims (10)
1. The preparation method for producing the glyoxylic acid by catalytic oxidation of the composite solid acid is characterized by comprising the following steps of:
the method comprises the following steps: preparing raw materials, namely preparing glyoxal, hydrogen peroxide and a catalyst, mixing and stirring glyoxal solution at the temperature of 12-15 ℃, continuously carrying out mixing reaction, and simultaneously adding a catalyst ferrous sulfide and a catalyst to react to generate an oxide;
step two: oxidation extraction treatment;
step three: oxidation extraction powder preparation processing operation;
step four: processing and filtering glyoxylic acid;
step five: transportation, use, in the transportation, avoid sunshine to penetrate directly, avoid high temperature simultaneously, in the use, avoid the hand contact to wear the gauze mask, after finishing using at every turn, the lid is good.
2. The preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid according to claim 1, wherein in step two, the oxidation extraction treatment specifically comprises the following steps:
the first step is as follows: filtering with a screen, namely placing the oxide on a stainless steel screen, continuously performing vibration screening to remove larger particles, leaving the filtered oxide, and storing impurity particles;
the second step is that: and (3) grinding the oxide, namely, grinding the oxide in a grinder, grinding the oxide into powder, filtering and screening the powder again to remove non-uniformly ground particles, and preparing the oxide extract powder.
3. The preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid according to claim 1, wherein in step three, the preparation and processing operation of the oxidized extract powder specifically comprises the following steps:
the first step is as follows: performing oxide extraction reaction, namely performing esterification reaction on the oxidation extraction powder and absolute ethyl alcohol at the temperature of 140 ℃ for 2-4 hours in the presence of sulfuric acid, collecting an esterification product from a reaction liquid, placing the esterification product in a storage tank, avoiding hand contact, stirring the esterification product, and fishing out impurities;
the second step is that: and (3) carrying out reaction treatment on the esterification product, carrying out hydrolysis reaction on the esterification product and sulfuric acid at the temperature of 110-120 ℃ for 2-3 hours, collecting a target product glyoxylic acid from the reaction liquid, and storing the glyoxylic acid for later use.
4. The method for preparing glyoxylic acid by catalytic oxidation of composite solid acid according to claim 1, wherein in step four, the glyoxylic acid processing and filtering treatment specifically comprises the following steps:
the first step is as follows: processing glyoxylic acid, namely putting the glyoxylic acid into a stainless steel tank, oscillating and stirring, visually checking whether macroscopic impurities are mixed or not, fishing out the glyoxylic acid through a stainless steel net, continuously oscillating and stirring, and then preparing for storage;
the second step is that: filtering glyoxylic acid, namely placing the treated glyoxylic acid on a stainless steel mesh sieve for direct filtration, performing secondary filtration, collecting filtered liquid, and taking out residual impurities and particles;
the third step: and (3) storing the glyoxylic acid, storing the glyoxylic acid at a temperature within a reasonable range, canning, keeping a distance between cans, and timely checking during storage to ensure no leakage.
5. The method for preparing glyoxylic acid by catalytic oxidation of composite solid acid according to claim 1, wherein in step one, the catalyst is a composite solid acid catalytic oxidation solution.
6. The method for preparing glyoxylic acid by catalytic oxidation of composite solid acid according to claim 2, wherein in step two, the stainless steel mesh in the first step is a double-layer fine stainless steel mesh, and the vibration frequency is set to 5-8 times.
7. The method for preparing glyoxylic acid by catalytic oxidation of a composite solid acid according to claim 2 wherein in step two, the milling rate in step two is set to 100 to 150 r/min.
8. The method for preparing glyoxylic acid by catalytic oxidation of composite solid acid according to claim 3 wherein in step three, the stirring speed in the first step is set to 150-200 r/min.
9. The method for preparing glyoxylic acid by catalytic oxidation of a composite solid acid according to claim 3 wherein in step three, the storage temperature of glyoxylic acid in step two is set to 20 to 25 ℃.
10. The method as claimed in claim 4, wherein in step four, the oscillation speed in the first step is set to 200-260 r/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115745774A (en) * | 2022-12-07 | 2023-03-07 | 临沂市金沂蒙生物科技有限公司 | Preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115745774A (en) * | 2022-12-07 | 2023-03-07 | 临沂市金沂蒙生物科技有限公司 | Preparation method for producing glyoxylic acid by catalytic oxidation of composite solid acid |
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