CN114591170B - Method for preparing glyoxylate by oxidizing glycolate - Google Patents
Method for preparing glyoxylate by oxidizing glycolate Download PDFInfo
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- CN114591170B CN114591170B CN202011439027.2A CN202011439027A CN114591170B CN 114591170 B CN114591170 B CN 114591170B CN 202011439027 A CN202011439027 A CN 202011439027A CN 114591170 B CN114591170 B CN 114591170B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The application discloses a method for preparing glyoxylate by oxidizing glycolate. The method comprises the following steps: the material containing glycollate and solvent is contacted with an oxidation catalyst in the presence of an oxygen source to react to obtain glycollate; wherein, air and/or oxygen is used as oxygen source; the oxidation catalyst comprises a component I, a component II and a component III; wherein the component I is cupric salt, the component II is tetravalent vanadium salt and/or pentavalent vanadium salt, and the component III is at least one of nitric acid, nitrate or nitrite. The method has the advantages of low raw material cost, high conversion rate and product selectivity, mild reaction conditions and the like.
Description
Technical Field
The application relates to a method for preparing glyoxylate by oxidizing glycolate, belonging to the field of organic chemical industry.
Background
Glyoxylate is an important organic chemical raw material. Glyoxylate can be hydrolyzed to obtain glyoxylate. The glyoxylic acid can be made into ethyl vanillin, and can be used as flavoring agent for daily chemicals such as cosmetics. Allantoin prepared from glyoxylate has effects of protecting from light, sterilizing, preventing corrosion, relieving pain, resisting oxidation, hydrophilizing and preventing water emission, and can be used as cosmetic additive, plant growth regulator, skin wound healing agent and antiulcer agent. Glyoxylic acid is also used for preparing medicines such as cefamam penicillin, amoxicillin, atenolol, p-hydroxyphenylacetic acid, p-hydroxyphenylhydantoin, etc.
The traditional preparation method of glyoxylic acid comprises the following steps: (1) oxalic acid electrolysis. The oxalic acid solution is electrolyzed to obtain glyoxylic acid solution, and then the glyoxylic acid solution is evaporated, concentrated, frozen, filtered, concentrated and the like to obtain glyoxylic acid. The method has high energy consumption. (2) ozone oxidation reduction method of maleic anhydride. Dissolving maleic anhydride in formic acid, oxidizing with ozone, and reducing with zinc powder to obtain glyoxylic acid. The method is a metering reaction, and has the advantages of high raw material consumption, high cost and poor operation safety. (3) Condensing dichloroacetic acid with sodium methoxide to obtain sodium dimethoxy acetate, and hydrolyzing with hydrochloric acid to obtain glyoxylic acid. The method has the advantages of high raw material cost, serious equipment corrosion, large amount of acid wastewater generation and complex post-treatment. (4) oxidizing glyoxal under the action of catalyst to prepare glyoxalic acid. The method has the advantages of difficult control of selectivity, easy generation of by-products such as oxalic acid by excessive oxidation, and low product selectivity.
In recent years, coal-derived ethylene glycol has been greatly advanced. The glycolate is an intermediate product and a byproduct in the process of preparing the ethylene glycol from the coal, and has great significance for increasing economic benefit and promoting the development of the industry of preparing the ethylene glycol from the coal. Patent CN107445827A, CN107445833A discloses a method for preparing glyoxylate by oxidizing glycolate, but the reaction conditions are severe, and the reaction temperature is up to 200-500 ℃ or 230-400 ℃. Patent CN110627645a discloses a method for preparing glyoxylate by dehydrogenation of glycolate, the reaction temperature is 160-240 ℃, and the preparation of the catalyst is complex. Patent CN107445830A, CN107445832A discloses a method for preparing glyoxylate by oxidizing glycolate, wherein the reaction temperature is 50-180 ℃ or 80-250 ℃, and a large amount of NO and N are consumed in the reaction process 2 O 3 、NO 2 Equinitrogen oxides, molar ratio of nitrogen oxides to oxygen up to (4-50): 1.
disclosure of Invention
In order to solve the problems of harsh reaction conditions, high energy consumption, high raw material consumption, high cost, poor safety, low product selectivity and the like in the conventional glyoxylate preparation method, the application provides a method for preparing glyoxylate by oxidizing glycolate, and the method has the advantages of low raw material cost, high conversion rate, high product selectivity, mild reaction conditions and the like.
The technical scheme for preparing glyoxylate by oxidizing glycolate comprises the following steps: the material containing glycollate and solvent is contacted with an oxidation catalyst in the presence of an oxygen source to react to obtain glycollate; wherein air and/or oxygen is used as oxygen source.
The oxidation catalyst comprises a component I, a component II and a component III;
wherein the component I is cupric salt, the component II is tetravalent vanadium salt and/or pentavalent vanadium salt, and the component III is at least one of nitric acid, nitrate or nitrite.
According to the invention, the catalyst is extremely important. Without catalyst or with low catalyst activity, glycolate conversion is very low. When the catalyst activity and selectivity are high, a high conversion of glycolate and a high selectivity of glyoxylate can be obtained.
According to the invention, the active component for catalyzing the oxidation of glycolate to prepare glyoxylate is pentavalent vanadium salt, and the pentavalent vanadium is reduced into tetravalent vanadium in the catalytic reaction process.
According to the invention, the function of the cupric is to catalyze the oxidation of tetravalent vanadium to pentavalent vanadium, realizing the redox cycle of tetravalent vanadium and pentavalent vanadium, while the cupric is reduced to monovalent copper.
According to the invention, nitric acid, nitrate or nitrite and other catalyst components can generate NO in the catalytic reaction process 2 Or NO, NO being oxidized by oxygen to NO 2 ，NO 2 Catalyzing oxidation of monovalent copper to divalent copper, realizing redox cycle of monovalent copper and divalent copper, and simultaneously NO 2 Is reduced to NO, realize NO 2 And NO redox cycle.
Optionally, the divalent copper salt is Cu (NO 3 ) 2 、CuSO 4 、CuCl 2 At least one of them.
Optionally, the tetravalent vanadium salt is VOSO 4 、VOCl 2 At least one of them.
Optionally, the pentavalent vanadium salt is VOPO 4 、VOCl 3 At least one of them.
Optionally, the nitrate is NaNO 3 、KNO 3 At least one of them.
Optionally, the nitrite is NaNO 2 、KNO 2 At least one of them.
Alternatively, the glycolate is methyl glycolate or ethyl glycolate.
Optionally, the glyoxylate is methyl glyoxylate or ethyl glyoxylate.
Optionally, the solvent is selected from at least one of methanol, ethanol, acetonitrile.
Optionally, the amount of the oxidation catalyst component I is 0.1-1.0% of the mass of the glycolate.
Optionally, the amount of the oxidation catalyst component II is 0.1-1.0% of the mass of the glycolate.
Optionally, the amount of the oxidation catalyst component III is 0.1-1.0% of the mass of the glycolate.
Alternatively, the oxidation catalyst component I is used in a proportion by mass of glycolate independently selected from any of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% or a range of values between any two.
Alternatively, the oxidation catalyst component II is used in an amount such that the ratio of the mass of glycolate is independently selected from any of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% or a range of values between any two.
Alternatively, the ratio of the amount of the oxidation catalyst component III to the mass of the glycolate is independently selected from any value or range of values between any two of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.
Optionally, the mass percentage concentration of the glycolate in the reaction system is 10-50%, wherein the reaction system comprises glycolate, a solvent and an oxidation catalyst.
Alternatively, the mass percent concentration of the glycolate in the reaction system is independently selected from any value or range of values between any two of 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%.
Alternatively, the reaction conditions are:
the reaction temperature is 25-80 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 1-5 h.
Alternatively, the reaction temperature is independently selected from any value or range of values between any two of 25 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃.
Alternatively, the reaction pressure is independently selected from any value or range of values between any two of 0.1MPa, 0.12MPa, 0.14MPa, 0.16MPa, 0.18MPa, 0.2 MPa.
Alternatively, the reaction time is independently selected from any value or range of values between any two of 1h, 2h, 3h, 4h, 5h.
The beneficial effects that this application can produce include:
the method for preparing glyoxylate by oxidizing glycolate provided by the application has the advantages of low catalyst consumption, environment friendliness, safety, low raw material cost, high conversion rate and product selectivity, mild reaction conditions and the like, adopts molecular oxygen as an oxidant, and has a good industrial application prospect.
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. Unless otherwise indicated, the test methods were all conventional.
In the embodiment of the application, conversion rate and selectivity are calculated as follows:
example 1
10g methyl glycolate and 20g acetonitrile were mixed and 0.05g CuSO was added 4 、0.05g VOSO 4 、0.05g NaNO 2 Stirring, heating to 80 ℃, charging oxygen to the pressure of 0.1MPa, reacting for 2 hours, and carrying out qualitative and quantitative analysis on the reaction product by gas chromatography-mass spectrometry, wherein the conversion rate of methyl glycolate is 99%, and the selectivity of methyl glyoxylate is 99%.
Example 2
Example 2 is similar to example 1, except that: the ethyl glycolate is oxidized to prepare ethyl glyoxylate, the solvent is ethanol, air is used as an oxygen source, the air pressure is 0.2MPa, the conversion rate of the ethyl glycolate is 98% as a result of the reaction, and the selectivity of the ethyl glyoxylate is 99%.
Examples 3 to 12
Examples 3-12 examined the effect of different catalysts on the reaction, in a manner similar to example 1, except that different catalyst components were used, and the other reaction conditions were the same as in example 1, with the results shown in Table 1.
Example 3 differs from example 1 in that: the oxidation catalyst component I is Cu (NO) 3 ) 2 Component II is VOPO 4 Component III is KNO 2 。
Example 4 differs from example 1 in that: the oxidation catalyst component I is CuCl 2 Component II is VOCl 2 Component III is NaNO 3 。
Example 5 differs from example 1 in that: the oxidation catalyst component II is VOCl 3 Component III is KNO 3 。
Example 6 differs from example 1 in that: the oxidation catalyst component I is CuCl 2 Component III is HNO with the mass concentration of 68 percent 3 。
Example 7 differs from example 1 in that: the oxidation catalyst component I is Fe 2 (SO 4 ) 3 。
Example 8 differs from example 1 in that: the oxidation catalyst component I is CoSO 4 。
Example 9 differs from example 1 in that: the oxidation catalyst component I is NiSO 4 。
Example 10 differs from example 1 in that: the oxidation catalyst component I is blank.
Example 11 differs from example 1 in that: the oxidation catalyst component II is blank.
Example 12 differs from example 1 in that: the oxidation catalyst component III is blank.
The oxidation catalyst component I in examples 3 to 6 was Cu (NO) 3 ) 2 、CuCl 2 、CuSO 4 At least one of which, component II is VOPO 4 、VOCl 2 、VOCl 3 、VOSO 4 Component III is KNO respectively 2 、NaNO 3 、KNO 3 、HNO 3 The conversion rate of methyl glycolate reaches more than 95%, and the selectivity of methyl glyoxylate reaches more than 95%.
Examples 7 to 9 were each prepared with Fe 2 (SO 4 ) 3 、CoSO 4 、NiSO 4 Instead of CuSO 4 Examples 10 to 12 are blank experiments of oxidation catalyst component I, component II and component III, respectively, with methyl glycolate conversion not exceeding 50%.
TABLE 1 catalytic Effect of different catalysts on methyl glycolate oxidation to methyl glyoxylate
Examples 13 to 20
Examples 13 to 20 examined the effect of different reaction conditions, similar to example 1, except that the solvent, the amount of the catalyst component, the substrate concentration, the reaction temperature, the reaction pressure, and the reaction time were different, and the response to the catalytic effect was examined, and the other reaction conditions were the same as in example 1, and the results are shown in Table 2. In solvents such as methanol and acetonitrile, cuSO 4 /VOSO 4 /NaNO 2 The catalyst is prepared from three components of methyl glycolate, wherein the dosage of the three components of the catalyst is 0.1-1.0% of the mass of the methyl glycolate, the mass percentage concentration of a methyl glycolate reaction substrate is 10-50%, the reaction temperature is 25-80 ℃, the reaction pressure is 0.1-0.2 MPa, the reaction time is 1-5 h, the methyl glycolate conversion rate can reach more than 90%, and the methyl glyoxylate selectivity can reach more than 95%.
TABLE 2 reaction conditions vs. CuSO 4 /VOSO 4 /NaNO 2 Influence of catalyzing methyl glycolate to prepare ethyl glyoxylate by oxidation
In the present application, "substrate concentration" refers to the mass percent concentration of glycolate in a reaction system, which is composed of glycolate, a solvent, and a catalyst.
In summary, air or oxygen is taken as an oxygen source, and under the condition of the existence of an oxidation catalyst, the oxidation catalyst comprises a component I, a component II and a component III, wherein the component I is a cupric salt, the component II is at least one of tetravalent vanadium salt or pentavalent vanadium salt, the component III is at least one of nitric acid, nitrate or nitrite, the glycolate is oxidized to prepare glyoxylate, and the maximum conversion rate of the glycolate and the selectivity of the glyoxylate can reach 99%. The method has the advantages of low raw material cost, high conversion rate and product selectivity, mild reaction conditions and the like.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (5)
1. A method for preparing glyoxylate by oxidizing glycolate is characterized in that a material containing glycolate and a solvent is contacted with an oxidation catalyst in the presence of an oxygen source to react to obtain glyoxylate;
wherein, air and/or oxygen is used as oxygen source;
the oxidation catalyst comprises a component I, a component II and a component III;
wherein the component I is cupric salt, the component II is tetravalent vanadium salt and/or pentavalent vanadium salt, and the component III is at least one of nitric acid, nitrate or nitrite; the cupric salt is Cu (NO) 3 ) 2 、CuSO 4 、CuCl 2 At least one of (a) and (b); the tetravalent vanadium salt is VOSO 4 、VOCl 2 At least one of (a) and (b);
the pentavalent vanadium salt is VOPO 4 、VOCl 3 At least one of (a) and (b);
the nitrate is NaNO 3 、KNO 3 At least one of (a) and (b);
the nitrite is NaNO 2 、KNO 2 At least one of them.
2. The method of claim 1, wherein the glycolate is methyl glycolate or ethyl glycolate.
3. The method of claim 1, wherein the glyoxylate is methyl glyoxylate or ethyl glyoxylate.
4. The method according to claim 1, wherein the solvent is selected from at least one of methanol, ethanol, acetonitrile.
5. The method according to claim 1, wherein the amount of the oxidation catalyst component I is 0.1-1.0% of the mass of glycolate;
the dosage of the oxidation catalyst component II is 0.1-1.0% of the mass of glycolate;
the consumption of the oxidation catalyst component III is 0.1-1.0% of the mass of the glycolate;
the mass percentage concentration of the glycolate in the reaction system is 10-50 percent, wherein,
the reaction system comprises glycolate, a solvent and an oxidation catalyst;
the reaction conditions are as follows: the reaction temperature is 25-80 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 1-5 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900864A (en) * | 1988-08-09 | 1990-02-13 | Anantaneni Prakasa R | Manufacture of alkyl glyoxylates with ferric phosphate catalyst |
| CN107445830A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | The method that ethyl glycolate oxidative dehydrogenation produces glyoxylic ester |
| CN107445831A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | The production method of glyoxylic ester |
| CN108084012A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method that peroxyester prepares adipic acid |
| CN109574834A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of glyoxylic ester |
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2020
- 2020-12-07 CN CN202011439027.2A patent/CN114591170B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4900864A (en) * | 1988-08-09 | 1990-02-13 | Anantaneni Prakasa R | Manufacture of alkyl glyoxylates with ferric phosphate catalyst |
| CN107445830A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | The method that ethyl glycolate oxidative dehydrogenation produces glyoxylic ester |
| CN107445831A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | The production method of glyoxylic ester |
| CN108084012A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method that peroxyester prepares adipic acid |
| CN109574834A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of glyoxylic ester |
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