CN116143605A - Preparation method of hexuronic acid - Google Patents
Preparation method of hexuronic acid Download PDFInfo
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- CN116143605A CN116143605A CN202111395285.XA CN202111395285A CN116143605A CN 116143605 A CN116143605 A CN 116143605A CN 202111395285 A CN202111395285 A CN 202111395285A CN 116143605 A CN116143605 A CN 116143605A
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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
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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Abstract
The application discloses a preparation method of hexuronic acid, which comprises the following steps: carrying out oxidation reaction I on a solution containing hexose and a catalyst, and then adding water to carry out oxidation reaction II to obtain the hexuronic acid; wherein the catalyst comprises a metal catalyst; the solvent in the solution comprises an organic solvent; the reaction temperature of the oxidation reaction II is higher than that of the oxidation reaction I. The invention has high selectivity and is environment-friendly, and provides a novel method for preparing uronic acid with high selectivity.
Description
Technical Field
The application relates to a preparation method of hexuronic acid, and belongs to the technical field of biomass chemical industry.
Background
Uronic acid is widely present in nature, among which the most common uronic acids are glucuronic acid, mannuronic acid, galacturonic acid, iduronic acid, guluronic acid, etc., which are the main components of cell walls or mucus substances such as pectin, hemicellulose, alginic acid, bacterial polysaccharides, etc. The uronic acid, such as glucuronic acid, has important biological functions, and can be combined with toxic substances such as hydroxyl, amino, sulfhydryl and the like to discharge the toxic substances out of the body, thereby achieving the detoxification effect. Glucuronic acid can be used as intermediate for synthesizing D-calcium glucarate, D-glucarate 1, 4-lactone and L-ascorbic acid with anticancer effects, and can also be used as food additive for functional beverage and health food. With the increasing health concept and the increasing quality of life requirements of people, the requirements for glucuronic acid are larger and larger, and great potential economic benefits are achieved.
Uronic acid is easily decarboxylated during intensive water treatment, and thus uronic acid is mainly prepared by biological and chemical methods. Biological processes mainly obtain uronic acid by fermentation, but there are problems in that the substrate concentration is low and purification is complicated, and thus the yield is limited. At present, oxidized starch is mainly obtained by oxidizing starch with nitric acid, then glucuronic acid is obtained by hydrolysis, CN 105198940B firstly uses ferric sulfate as a catalyst, hydrogen peroxide is used as an oxygen source to oxidize the starch, and the glucuronic acid is obtained by hydrolysis, but the process is complicated, the reaction time is long, a large amount of wastewater is generated, and the method is not suitable for industrial production. Therefore, in order to meet the increasing demand of human beings for uronic acid, a process for preparing uronic acid with high selectivity and environmental protection needs to be developed.
Disclosure of Invention
According to one aspect of the present application, there is provided a method for preparing hexuronic acid by a two-step oxidation process in an organic acid system, wherein first, halide and/or nitrate of metal ion is used to catalyze nitrogen oxide to generate nitroxide free radical, and the generated nitroxide free radical can oxidize hydroxymethyl in hexose to aldehyde group with high selectivity under medium and low temperature condition; and then adding a certain amount of water to prevent the combustion of the substrate and the solvent, wherein the water also participates in the reaction of oxidizing the aldehyde groups into carboxyl groups, and under the condition of medium and high temperature, the nitroxide free radical further oxidizes one of the aldehyde groups into the carboxyl groups, so that the generated hexuronic acid is separated out from the organic acid solution, and the excessive oxidization and decarboxylation of the hexuronic acid are prevented.
A process for the preparation of hexuronic acid as described herein, characterized in that the process comprises:
carrying out oxidation reaction I on a solution containing hexose and a catalyst, and then adding water to carry out oxidation reaction II to obtain the hexuronic acid;
wherein the catalyst comprises a metal catalyst;
the solvent in the solution comprises an organic solvent;
the reaction temperature of the oxidation reaction II is higher than that of the oxidation reaction I.
Optionally, the oxidation reaction I is a low temperature reaction, and the oxidation reaction II is a medium temperature reaction.
Alternatively, the oxidation reaction I is to oxidize hydroxymethyl groups in the hexacarbaldehyde to aldehyde groups.
Optionally, the oxidation reaction II is to oxidize one of aldehyde groups into carboxyl under the condition of medium and high temperature on the basis of the first-step oxidation to obtain the hexuronic acid.
Optionally, the organic solvent comprises an organic acid solvent.
Alternatively, the organic acid solvent is a monocarboxylic acid.
Optionally, the organic acid solvent is a C1-C8 monocarboxylic acid.
Optionally, the monocarboxylic acid includes at least one of acetic acid, propionic acid, butyric acid.
Optionally, the organic acid solvent is acetic acid.
Optionally, the solvent is an organic acid solvent or a mixture of an organic acid solvent and water;
the water content in the organic solvent is 0-5% of the total system mass.
Optionally, the solvent is a mixture of an organic acid solvent and water; the water content in the raw materials is 0-5% of the mass of the whole system.
Alternatively, the solvent is a mixture of an organic acid solvent and water, and the upper limit of the amount of water added (based on the mass of the whole system) in the raw material is selected from 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 5%. The lower limit is selected from 0.1, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%.
Optionally, the content of the hexose is 4-30% of the mass of the whole system;
the addition amount of the metal catalyst is 50-1000 ppm; the addition amount of the metal catalyst is calculated as the addition amount of the metal ion.
Alternatively, the upper limit of the content of hexose in the feedstock is selected from 4.8wt%, 5wt%, 10wt%, 13 wt%, 14.3wt%, 15wt%, 20wt%, 28.5wt% or 30wt%; the lower limit is selected from 4wt%, 4.8wt%, 5wt%, 10wt%, 13 wt%, 14.3wt%, 15wt%, 20wt% or 28.5wt%.
Alternatively, the upper limit of the addition amount of the metal catalyst is selected from 100ppm, 190ppm, 200ppm, 600ppm or 1000ppm; the lower limit is selected from 50ppm, 100ppm, 190ppm, 200ppm, 600ppm or 800ppm.
Optionally, the six-carbon sugar comprises at least one of glucose, mannose and galactose.
Optionally, the catalyst is a metal catalyst or a mixture of a metal catalyst and nitrogen oxides;
the addition amount of the nitrogen oxide is 0-500 ppm.
Optionally, the adding amount of the nitrogen oxide is 90-500 ppm.
Optionally, the upper limit of the adding amount of the nitrogen oxide is selected from 50ppm, 90ppm, 95ppm, 100ppm, 190ppm, 200ppm, 285ppm, 300ppm or 500ppm; the lower limit is selected from 10ppm, 50ppm, 90ppm, 95ppm, 100ppm, 190ppm, 200ppm, 285ppm or 300ppm.
Optionally, the metal catalyst includes at least one of ruthenium-based catalyst, zirconium-based catalyst, cobalt-based catalyst, cerium-based catalyst, titanium-based catalyst, manganese-based catalyst, iron-based catalyst, vanadium-based catalyst, copper-based catalyst.
Alternatively, the metal catalyst includes at least two of ruthenium-based catalyst, zirconium-based catalyst, cobalt-based catalyst, cerium-based catalyst, titanium-based catalyst, manganese-based catalyst, iron-based catalyst, vanadium-based catalyst, copper-based catalyst.
Alternatively, the metal catalyst includes at least two of ruthenium-based catalyst, cobalt-based catalyst, cerium-based catalyst, manganese-based catalyst, iron-based catalyst, copper-based catalyst.
Optionally, the nitroxide comprises at least one of N-hydroxyphthalimide, 2, 6-tetramethylpiperidine nitroxide, 5-dimethyl-1-pyrroline-nitroxide, 4-hydroxy-2, 6-tetramethylpiperidine nitroxide.
Optionally, the metal catalyst is selected from at least one of metal halides, metal acetates, metal nitrates, metal nitrites.
Optionally, the metal catalyst is added to the organic acid in the form of a halide, acetate, nitrate and/or nitrite, preferably a halide and/or nitrate.
Optionally, the conditions of the oxidation reaction I include: in the presence of oxygen source, the reaction temperature is 50-120 deg.c and the reaction pressure is 0.1-1 Mpa.
Optionally, the upper limit of the reaction temperature of the oxidation reaction I is selected from 80 ℃, 90 ℃, 100 ℃ or 120 ℃; the lower limit is selected from 50 ℃, 80 ℃, 90 ℃ or 100 ℃.
Optionally, the upper limit of the reaction pressure of the oxidation reaction I is selected from 0.5Mpa, 0.8Mpa or 1Mpa; the lower limit is selected from 0.1Mpa, 0.5Mpa or 0.8Mpa.
Optionally, the reaction time of the oxidation reaction I is 30-90 min.
Optionally, the oxygen source includes molecular oxygen.
Optionally, the oxygen source comprises air (air), pure oxygen, oxygen enriched or a mixture of oxygen and an inactive gas.
Optionally, the inactive gas is at least one selected from nitrogen and inert gas.
Optionally, the water content in the oxidation reaction II solvent is 5-15% of the mass of the whole system; the mass of the raw materials is calculated as the sum of the raw materials I and water.
Alternatively, the upper limit of the water content in the feedstock is selected from 6%, 9%, 9.5%, 10%, 13%, 13.1%, 14% or 15%; the lower limit is selected from 5%, 6%, 9%, 9.5%, 10%, 13%, 13.1% or 14%.
Optionally, the conditions of oxidation reaction II include: in the presence of oxygen source, the reaction temperature is 130-180 deg.c and the reaction pressure is 2-5 Mpa.
Optionally, the upper limit of the reaction temperature of the oxidation reaction II is 160 ℃, 170 ℃ or 180 ℃; the lower limit is selected from 130 ℃, 160 ℃ or 170 ℃.
Optionally, the upper limit of the reaction pressure of the oxidation reaction II is selected from 3Mpa, 4Mpa or 5Mpa; the lower limit is selected from 2Mpa, 3Mpa or 4Mpa.
Optionally, the reaction time of the oxidation reaction II is 60-120 min.
Optionally, the oxygen source includes molecular oxygen.
Optionally, the oxygen source comprises air, pure oxygen, oxygen enriched or a mixture of oxygen and an inactive gas.
Optionally, the preparation method comprises the following steps: performing oxidation reaction I on a mixture containing hexose, a solvent and a catalyst in the presence of molecular oxygen, and then adding water to perform oxidation reaction II to obtain the hexuronic acid;
the solvent is an organic acid solvent or a mixture of an organic acid solvent and water.
As a specific embodiment thereof, the preparation method comprises: the raw materials of hexose, a metal catalyst, (nitrogen oxide) and water are subjected to low-temperature oxidation reaction under the oxygen source condition, water is added after the reaction is finished, the temperature is raised, and medium-temperature oxidation reaction is carried out, so that the hexuronic acid is obtained.
The preparation method comprises the steps of taking molecular oxygen as an oxygen source, obtaining hexuronic acid by a two-step oxidation method under the synergistic catalysis of metal ions and nitrogen oxides in an organic acid solvent, and oxidizing hydroxymethyl in hexose to aldehyde groups under the condition of medium and low temperature in the first step of oxidation; and oxidizing one of aldehyde groups into carboxyl under the condition of medium and high temperature to obtain hexuronic acid. The invention has high selectivity and is environment-friendly, and provides a novel method for preparing uronic acid with high selectivity.
The beneficial effects that this application can produce include:
1) The method adopts a two-step oxidation method, reduces the reaction of side reaction and improves the selectivity of hexuronic acid;
2) The method uses organic acid as solvent, and can effectively prevent peroxidation and decarboxylation of the hexuronic acid due to the fact that the hexuronic acid is low in solubility;
3) The metal catalyst is added into an oxidation system in the form of halide and/or nitrites, wherein the halide and the nitrites can generate free radicals so as to accelerate the oxidation rate;
4) The method uses the nitrogen oxide as a cocatalyst, and the generated nitroxide free radical can selectively oxidize the hydroxymethyl, so that the possibility of oxidization of the hydroxyl at the 2-5 position is reduced, and the oxidization selectivity is improved;
5) The solvent and the metal catalyst for the reaction in the method can be recycled, so that the oxidation cost is reduced, three wastes are not generated, the process is environment-friendly, and a novel method is provided for the preparation of the hexuronic acid.
Drawings
FIG. 1 is a detection chart of the liquid phase after the completion of the reaction in example 2.
FIG. 2 is a reaction scheme of one embodiment of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, both the starting materials and the catalysts in the examples of the present application were purchased commercially.
The analytical methods and selectivity calculation formulas in the embodiments of the present application are as follows:
hexoses and hexuronic acids were detected using HPLC.
Hexuronic acid selectivity = molar amount of hexuronic acid/(molar amount of six carbon sugars before reaction-molar amount of six carbon sugars after reaction) ×100%.
According to one embodiment of the present application, in the preparation method of the high-selectivity hexuronic acid, in the condition that molecular oxygen is used as an oxygen source, a two-step oxidation method is used for oxidizing hexoses into hexuronic acid, and in the first step of oxidation, hydroxymethyl in the hexoses is oxidized into aldehyde groups under the synergistic catalytic oxidation of metal ions and nitrogen oxides in an organic acid solvent at a medium-low temperature; the second step of oxidation is to add a certain amount of water based on the first step of oxidation, and oxidize one of aldehyde groups into carboxyl under the condition of medium and high temperature to obtain the hexuronic acid.
As one specific embodiment, the molecular oxygen is air oxygen, pure oxygen, oxygen-enriched oxygen, and the like.
As one specific embodiment, the six-carbon aldose comprises at least one of glucose, mannose and galactose, and the addition amount of the six-carbon aldose is 5-30wt%.
As one specific embodiment, the low temperature condition in the first oxidation step is 50-120 ℃ and the reaction pressure is 0.1-1 Mpa.
As one embodiment, the organic acid is a monocarboxylic acid including, but not limited to, acetic acid, propionic acid, butyric acid, etc., preferably acetic acid.
As one embodiment, the metal catalyst includes at least one of ruthenium (Ru), zirconium (Zr), cobalt (Co), cerium (Ce), titanium (Ti), manganese (Mn), iron (Fe), vanadium (V), and copper (Cu).
As one specific embodiment, the metal catalyst is added to the organic acid in the form of halide, acetate, nitrate and/or nitrite, preferably the halide and/or nitrate, and the addition amount of the metal catalyst is 50-1000 ppm.
As one specific embodiment, the nitrogen oxides include, but are not limited to, N-hydroxyphthalimide, tetramethylpiperidine nitrogen oxides, 5-dimethyl-1-pyrroline-nitrogen oxides, 4-hydroxy-2, 6-tetramethylpiperidine nitrogen oxides, etc., and the addition amount of the nitrogen oxides is 0 to 500ppm.
As one specific embodiment, the water content is 0-15 wt%, further, the water content in the first oxidation process is 0-5 wt%, and the water content in the second oxidation process is 5-15 wt%.
As one specific embodiment, the high temperature condition in the second oxidation step is 130-180 ℃ and the reaction pressure is 2-5 Mpa.
Example 1
5g of galactose, 90g of acetic acid, 0.01g of ferric nitrate nonahydrate, 0.01g of cobalt chloride and 0.02g of 2, 6-tetramethylpiperidine nitrogen oxide are weighed into a reaction kettle, heated to 100 ℃, air is introduced into the reaction kettle to react for 50min, then 10g of water is pumped into the reaction kettle by using a high-pressure pump, the temperature is raised to 180 ℃, the pressure is regulated to 4Mpa, after the reaction is carried out for 60min, the ventilation is stopped, the temperature is reduced, the content of galacturonic acid and galactose in solid and liquid is detected, and the selectivity of galacturonic acid is calculated to be 94.6%.
Example 2
10g of glucose, 75g of propionic acid, 0.01g of cobalt acetate tetrahydrate, 0.05g of manganese nitrate tetrahydrate and 0.01. 0.01g N-hydroxyphthalimide are weighed into a reaction kettle, heated to 50 ℃, introduced with pure oxygen to 0.1Mpa, reacted for 60min, then 15g of water is pumped into the kettle by using a high-pressure pump, the temperature is raised to 130 ℃, the pressure is regulated to 2Mpa, after the reaction is carried out for 90min, ventilation is stopped, the temperature is reduced, the glucuronic acid and the glucose content in solid and liquid are detected, and the glucuronic acid selectivity is calculated to be 96.6%.
After the reaction, the reaction solution was subjected to liquid phase detection analysis (Agilent 1260), and the result is shown in fig. 1, wherein the presence of a trace of glucose dialdehyde in the liquid phase can be seen, which indicates that the route for oxidizing glucose to form gluconic acid in the system is the route a in fig. 2, not the route b.
Example 3
20g of glucose, 70g of acetic acid, 0.01g of ruthenium nitrate aqueous solution (ruthenium content is 1.5%), 0.1g of cerium acetate tetrahydrate and 0.05g of 4-hydroxy-2, 6-tetramethylpiperidine nitrogen oxide are weighed into a reaction kettle, heated to 80 ℃, air is introduced to 0.5Mpa for reaction for 60min, then 10g of water is pumped into the reaction kettle by using a high-pressure pump, the temperature is raised to 170 ℃, the pressure is regulated to 4Mpa, after the reaction is carried out for 100min, ventilation is stopped, the temperature is reduced, the content of glucuronic acid and glucose in solid and liquid is detected, and the glucuronic acid selectivity is calculated to be 95.8%.
Example 4
30g of mannose, 65g of acetic acid, 0.02g of copper nitrate trihydrate, 0.15g of ferric chloride and 0.03. 0.03g N-hydroxyphthalimide are weighed into a reaction kettle, heated to 120 ℃, introduced into 1Mpa according to the ratio of air to nitrogen, reacted for 30min, then 10g of water is pumped into the reaction kettle by using a high-pressure pump, the temperature is raised to 160 ℃, the pressure is regulated to 5Mpa, after the reaction is carried out for 120min, the ventilation is stopped, the temperature is reduced, the mannuronic acid and mannose content in solid and liquid are detected, and the mannuronic acid selectivity is calculated to be 95.6%.
Example 5
15g of glucose, 80g of acetic acid, 0.02g of cerium nitrate hexahydrate, 0.15g of manganese acetate tetrahydrate and 0.01g of 2, 6-tetramethylpiperidine nitrogen oxide are weighed into a reaction kettle, heated to 80 ℃, air is introduced into the reaction kettle to 0.8Mpa, the reaction is carried out for 50min, then 10g of water is pumped into the reaction kettle by using a high-pressure pump, the temperature is raised to 180 ℃, the pressure is regulated to 3Mpa, after the reaction is carried out for 60min, the ventilation is stopped, the temperature is reduced, the content of glucuronic acid and glucose in solid and liquid is detected, and the glucuronic acid selectivity is calculated to be 96.8%.
Example 6
10g of galactose, 80g of acetic acid, 0.02g of cobalt acetate tetrahydrate and 0.1g of manganese acetate tetrahydrate are weighed into a reaction kettle, heated to 80 ℃, air is introduced to 1Mpa for reaction for 60min, then 10g of water is pumped into the reaction kettle by using a high-pressure pump, the temperature is raised to 170 ℃, the pressure is regulated to 4Mpa, after the reaction is carried out for 80min, ventilation and cooling are stopped, the content of galacturonic acid and galactose in solid and liquid is detected, and the selectivity of galacturonic acid is calculated to be 94.7%.
Example 7
15g of glucose, 4g of water, 80g of acetic acid, 0.1g of cobalt acetate tetrahydrate, 0.2g of manganese chloride tetrahydrate and 0.1g of cerium nitrate hexahydrate are weighed into a reaction kettle, heated to 90 ℃, air is introduced into the reaction kettle to 0.8Mpa, the reaction is carried out for 90min, then 15g of water is pumped into the reaction kettle by using a high-pressure pump, the temperature is raised to 160 ℃, the pressure is regulated to 3Mpa, after the reaction is carried out for 100min, the ventilation and the cooling are stopped, the glucuronic acid and the glucose content in solid and liquid are detected, and the glucuronic acid selectivity is calculated to be 91.8%.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A process for the preparation of hexuronic acid, the process comprising:
carrying out oxidation reaction I on a solution containing hexose and a catalyst, and then adding water to carry out oxidation reaction II to obtain the hexuronic acid;
wherein the catalyst comprises a metal catalyst;
the solvent in the solution comprises an organic solvent;
the reaction temperature of the oxidation reaction II is higher than that of the oxidation reaction I.
2. The method of producing according to claim 1, wherein the organic solvent comprises an organic acid solvent;
preferably, the organic acid solvent is a monocarboxylic acid;
further preferably, the monocarboxylic acid includes at least one of acetic acid, propionic acid, butyric acid.
3. The production method according to claim 1 or 2, wherein the solvent is an organic acid solvent or a mixture of an organic acid solvent and water;
the water content in the solvent in the oxidation reaction I is 0-5% of the mass of the whole system.
4. The preparation method according to claim 1, wherein the content of the hexose is 4-30% of the mass of the whole system;
the addition amount of the metal catalyst is 50-1000 ppm;
the addition amount of the metal catalyst is calculated by the addition amount of metal ions;
preferably, the six-carbon sugar comprises at least one of glucose, mannose and galactose.
5. The method according to claim 1 or 4, wherein the catalyst is a metal catalyst or a mixture of a metal catalyst and nitrogen oxides;
the addition amount of the nitrogen oxide is 0-500 ppm;
preferably, the addition amount of the nitrogen oxide is 90-500 ppm.
6. The method according to claim 5, wherein the metal catalyst comprises at least one of ruthenium-based catalyst, zirconium-based catalyst, cobalt-based catalyst, cerium-based catalyst, titanium-based catalyst, manganese-based catalyst, iron-based catalyst, vanadium-based catalyst, copper-based catalyst;
the nitrogen oxide comprises at least one of N-hydroxyphthalimide, 2, 6-tetramethylpiperidine nitrogen oxide, 5-dimethyl-1-pyrroline-nitrogen oxide and 4-hydroxy-2, 6-tetramethylpiperidine nitrogen oxide;
preferably, the metal catalyst is selected from at least one of metal halides, metal acetates, metal nitrates, metal nitrites.
7. The method according to claim 1, wherein the conditions of the oxidation reaction I include: in the presence of oxygen source, the reaction temperature is 50-120 ℃, the reaction pressure is 0.1-1 Mpa, and the reaction time is 30-90 min;
the oxygen source includes molecular oxygen.
8. The preparation method according to claim 1, wherein the water content in the solvent in the oxidation reaction II is 5-15% of the mass of the whole system.
9. The process of claim 1, wherein the conditions of oxidation reaction II comprise: in the presence of oxygen source, the reaction temperature is 130-180 ℃, the reaction pressure is 2-5 Mpa, and the reaction time is 60-120 min;
the oxygen source includes molecular oxygen.
10. The preparation method according to claim 1, characterized in that the preparation method comprises: performing oxidation reaction I on a mixture containing hexose, a solvent and a catalyst in the presence of molecular oxygen, and then adding water to perform oxidation reaction II to obtain the hexuronic acid;
the solvent is an organic acid solvent or a mixture of an organic acid solvent and water.
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| CN116217743A (en) * | 2021-12-03 | 2023-06-06 | 中国科学院宁波材料技术与工程研究所 | Method for oxidizing carbohydrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116217743A (en) * | 2021-12-03 | 2023-06-06 | 中国科学院宁波材料技术与工程研究所 | Method for oxidizing carbohydrate |
| CN116217743B (en) * | 2021-12-03 | 2024-04-12 | 中国科学院宁波材料技术与工程研究所 | Method for oxidizing carbohydrate |
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