CN111454140B - Method for preparing acetic acid by photocatalytic oxidation of lactic acid - Google Patents
Method for preparing acetic acid by photocatalytic oxidation of lactic acid Download PDFInfo
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- CN111454140B CN111454140B CN202010498315.9A CN202010498315A CN111454140B CN 111454140 B CN111454140 B CN 111454140B CN 202010498315 A CN202010498315 A CN 202010498315A CN 111454140 B CN111454140 B CN 111454140B
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- acetic acid
- lactic acid
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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
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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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
Abstract
The invention relates to a method for preparing acetic acid by photocatalytic oxidation of lactic acid. The preparation method comprises the following steps: in the presence of catalyst and oxygen, lactic acid reacts in solvent at certain temperature, time and pressure to obtain acetic acid. The method has the advantages of high selectivity, environmental protection, high efficiency, simple process and potential industrial application prospect.
Description
Technical Field
The invention relates to the field of chemical substance preparation, in particular to a method for preparing acetic acid by photocatalytic oxidation of lactic acid.
Background
The global demand and the rapid increase in production capacity of acetic acid, an important organic chemical raw material, make it a focus of industrial attention to reduce its production cost. In industry, acetic acid is mainly used as a raw material at present and is converted into a downstream product. The downstream products mainly comprise acetate, cellulose acetate, acetic anhydride, chloroacetic acid and the like, and the downstream products are widely used in industrial solvents, coatings, adhesives, medicines, spice raw materials, medicine intermediates, plastic products, edible glacial acetic acid and the like, and have very wide application prospects. At present, about 80% of the production capacity in the world acetic acid production comes from the methanol carbonylation method, and the acetic acid production plants in China have reached more than 50. The methanol carbonylation method is further classified into a methanol high-pressure carbonylation method and a methanol low-pressure carbonylation method (menthane method). The methanol high-pressure carbonylation method uses a carbonyl cobalt or carbonyl hydrogen cobalt catalyst and iodine as a cocatalyst. The method for producing acetic acid by methanol carbonylation at 250 ℃ and 63.74MPa has the advantages of more acetic acid by-products, complex separation process and harsh reaction conditions, wherein the yield of acetic acid is 90% by methanol and 70% by CO. The methanol low-pressure carbonylation method uses rhodium trichloride as a catalyst and methyl iodide as a cocatalyst, and performs carbonylation to synthesize acetic acid under milder reaction conditions (150 ℃, 2.94MPa), so that the method has higher catalytic activity and selectivity. Almost no by-product is generated in the process, and the yield of acetic acid is 90 percent calculated by methanol and 90 percent calculated by CO. However, the method adopts expensive rhodium catalysts, the reaction equipment needs to use a hastelloy pressure kettle with a mechanical stirring function, the used equipment is made of zirconium 702, and the production cost is high.
Disclosure of Invention
The raw material used in the invention is lactic acid (lactic acid is a biomass product with wide sources), oxygen is used as an oxidant, and the lactic acid can be converted into acetic acid under the action of a catalyst and under the illumination condition. The reaction has high selectivity, high conversion rate, high efficiency, low power consumption, simple preparation process and low cost. Therefore, the method has important application prospect in industry.
Specifically, the invention provides a preparation method for converting lactic acid into acetic acid. The preparation method comprises the following steps: in the presence of catalyst, oxygen and light, lactic acid reacts in solvent at certain temperature, pressure and time to obtain acetic acid.
The purpose of the invention is realized by the following technical scheme:
the invention provides a method for preparing acetic acid by using lactic acid as a raw material and reacting in a solvent in the presence of a catalyst, oxygen and light.
In some embodiments, the solvent comprises dichloromethane, acetonitrile, methanol, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, gamma valerolactone, and water.
In some embodiments, the catalyst is selected from one or more of iron oxide, aluminum oxide, tin dioxide, titanium dioxide, tungsten trioxide, molybdenum sulfide, cadmium sulfide, and carbon nitride.
In some embodiments, the reaction time is from 1 to 24h, preferably from 18 to 20 h.
In some embodiments, the reaction temperature is from 0 to 50 ℃, preferably from 20 to 30 ℃.
In some embodiments, the mass ratio of lactic acid to catalyst is from 1:100 to 100:1, preferably from 10:1 to 50: 1.
In some embodiments, the mass to volume ratio of lactic acid to solvent (g/mL) is from 1:100 to 1:1, preferably from 1:10 to 1: 2.
In some embodiments, the oxygen pressure is from 0.1 to 10MPa, preferably from 3 to 5 MPa.
In some embodiments, the wavelength of light ranges from 256 to 780 nm.
The embodiment of the invention takes lactic acid as raw material, and the lactic acid reacts with oxygen in a solvent under the catalysis of a catalyst and under certain temperature, pressure, time and illumination to obtain acetic acid. The reaction process is simple and has great application prospect.
Brief Description of Drawings
Figure 1 shows a gas phase diagram of the product acetic acid of example 1.
Figure 2 shows the hydrogen spectrum of the product acetic acid of example 1.
Detailed Description
The embodiment of the invention takes lactic acid as raw material, and the lactic acid reacts with oxygen in a solvent under the catalysis of a catalyst and under certain temperature, pressure, time and illumination to obtain acetic acid.
More specifically, the invention provides a method for preparing acetic acid by reacting lactic acid raw material in a solvent in the presence of a catalyst, oxygen and light.
Solvents used in the process include dichloromethane, acetonitrile, methanol, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, gamma valerolactone and water.
The catalyst used in the method is selected from one or more of iron oxide, aluminum oxide, tin dioxide, titanium dioxide, tungsten trioxide, molybdenum sulfide, cadmium sulfide and carbon nitride.
The reaction time in the process is from 1 to 24h, preferably from 18 to 20 h.
The reaction temperature in the process is from 0 to 50 ℃, preferably from 20 to 30 ℃.
The mass ratio of lactic acid to catalyst in the process is from 1:100 to 100:1, preferably from 10:1 to 50: 1.
The mass-to-volume ratio (g/mL) of lactic acid to solvent in the method is 1:100 to 1:1, preferably 1:10 to 1: 2.
The oxygen pressure in the process is from 0.1 to 10MPa, preferably from 3 to 5 MPa.
The wavelength of the light in the method is in the range of 256 to 780 nm.
The following examples are provided to further illustrate the practice of the present invention. The following description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto.
Example 1
Adding 0.1g of lactic acid (traditional Chinese medicine), 10mg of graphite-phase carbon nitride and 5mL of dichloromethane (traditional Chinese medicine) solvent into a 25mL high-pressure reaction kettle with a high-light-transmission pressure-resistant quartz lens, closing the kettle after the addition is finished, filling oxygen into the kettle under 1MPa, irradiating the kettle with blue light with the wavelength of 400nm, heating the reaction kettle to 30 ℃ by magnetic stirring, and reacting for 18 hours at the stirring speed of 600 r/min. After the reaction is finished, the kettle is disassembled, the reaction liquid is transferred to a sample bottle, biphenyl (national medicine) is added as an internal standard, the sample is sent to a gas chromatograph after centrifugation, and the gas phase conditions are as follows: detector temperature: the temperature of the column is programmed to 100 ℃ and kept for 5min at 250 ℃ and 250 ℃ in a gasification chamber, then the temperature is increased to 240 ℃ at the speed of 10 ℃/min and kept for 5min, and the split ratio is as follows: 50, the yield of the product acetic acid by gas phase detection is 98.5%. Fig. 1 and 2 show the gas phase diagram and the hydrogen spectrum, respectively, of the product acetic acid of example 1.
Example 2
The specific reaction process and detection method are the same as those in example 1, except that carbon nitride is changed into molybdenum sulfide (national medicine), the obtained product is acetic acid, and the yield is 97.8%.
Example 3
The specific reaction process and detection method are the same as those in example 1, except that the catalyst carbon nitride is changed into titanium dioxide (national medicine), the obtained product is acetic acid, and the yield is 98.2%.
Example 4
The specific reaction process and detection method are the same as those in example 1, except that the catalyst carbon nitride is changed into cadmium sulfide (national medicine), the obtained product is acetic acid, and the yield is 97.3%.
Example 5
The specific reaction process and detection method are the same as those in example 1, except that the solvent dichloromethane is changed to acetonitrile (national medicine), the obtained product is acetic acid, and the yield is 97.9%.
Example 6
The specific reaction process and detection method are the same as those in example 1, except that the solvent dichloromethane is changed to methanol (national medicine), the obtained product is acetic acid, and the yield is 96.9%.
Example 7
The specific reaction process and detection method are the same as those in example 1, except that the solvent dichloromethane is changed to tetrahydrofuran (national medicine), the obtained product is acetic acid, and the yield is 96.1%.
Example 8
The specific reaction process and detection method were the same as in example 1 except that the amount of lactic acid was changed from 0.1g to 0.2g, the obtained product was acetic acid, and the yield was 97.5%.
Example 9
The specific reaction process was the same as in example 1 except that the amount of lactic acid was changed from 0.1g to 0.5g, and the obtained product was acetic acid. And the yield was 97.2%.
Example 10
The specific reaction process and detection method are the same as those in example 1, except that the reaction time is changed from 18h to 15h, the obtained product is acetic acid, and the yield is 96.6%.
Example 11
The specific reaction process and detection method are the same as those in example 1, except that the reaction time is changed from 18h to 20h, the obtained product is acetic acid, and the yield is 99.1%.
Example 12
The specific reaction process and detection method are the same as those in example 1, except that the reaction temperature is changed from 30 ℃ to 20 ℃, the obtained product is acetic acid, and the yield is 90.5%.
Example 13
The specific reaction process and detection method are the same as those in example 1, except that the reaction temperature is changed from 30 ℃ to 40 ℃, the obtained product is acetic acid, and the yield is 95.5%.
Example 14
The specific reaction process and detection method are the same as those in example 1, except that the volume of the solvent is changed to 7mL, the obtained product is acetic acid, and the yield is 98.2%.
Example 15
The specific reaction process and detection method are the same as those in example 1, except that the volume of the solvent is 3mL, the obtained product is acetic acid, and the yield is 98.4%.
Example 16
The specific reaction process and detection method are the same as those in example 1, except that the oxygen pressure is changed to 0.1MPa, the obtained product is acetic acid, and the yield is 98.9%.
Example 17
The specific reaction process and detection method are the same as those in example 1, except that the oxygen pressure is changed to 5MPa, the obtained product is acetic acid, and the yield is 99.1%.
Example 18
The specific reaction process and detection method are the same as those of example 1, except that the wavelength of light is changed to 390nm, the obtained product is acetic acid, and the yield is 99.6%.
Example 19
The specific reaction process and detection method are the same as those of example 1, except that the wavelength of light is changed to 440nm, the obtained product is acetic acid, and the yield is 99.4%.
Example 20
The specific reaction process and detection method are the same as example 1, except that the wavelength of light is changed to 467nm, the obtained product is acetic acid, and the yield is 99.3%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (13)
1. A method of producing acetic acid from lactic acid, the method comprising: in the presence of a photosensitive semiconductor catalyst, oxygen and light, reacting lactic acid in a solvent to obtain acetic acid, wherein the photosensitive semiconductor catalyst is one or more of molybdenum sulfide, cadmium sulfide and carbon nitride.
2. The method of claim 1, wherein the solvent comprises dichloromethane, acetonitrile, methanol, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, gamma valerolactone, and water.
3. The method according to claim 1, wherein the mass ratio of the lactic acid to the catalyst is 1:100 to 100: 1.
4. The method according to claim 3, wherein the mass ratio of the lactic acid to the catalyst is 10:1 to 50: 1.
5. The method according to claim 1, wherein the mass-to-volume ratio g/mL of the lactic acid to the solvent is 1:100 to 1: 1.
6. The method according to claim 5, wherein the mass-to-volume ratio g/mL of the lactic acid to the solvent is 1:10 to 1: 2.
7. The process according to claim 1, wherein the reaction temperature is from 0 to 50 ℃.
8. The process according to claim 7, characterized in that the reaction temperature is 20 to 30 ℃.
9. The process according to claim 1, wherein the reaction time is from 1 to 24 h.
10. The process according to claim 9, characterized in that the reaction time is 18 to 20 h.
11. The method of claim 1, wherein the oxygen pressure is from 0.1 to 10 MPa.
12. The method of claim 11, wherein the oxygen pressure is 3 to 5 MPa.
13. The method of claim 1, wherein the light has a wavelength in the range of 256 to 780 nm.
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| CN102770403A (en) * | 2009-12-04 | 2012-11-07 | 巴斯夫欧洲公司 | Producing acetaldehyde and/or acetic acid from bioethanol |
| CN102198403A (en) * | 2011-04-06 | 2011-09-28 | 西北师范大学 | Pore structure supported catalyst Al2O3-AlBrx and preparation and application thereof |
| CN103086866B (en) * | 2013-02-19 | 2015-01-21 | 中国科学院化学研究所 | Method for synthesizing acid by oxidizing aldehyde in photocatalytic selective mode |
| CN104923278A (en) * | 2015-05-22 | 2015-09-23 | 宁夏大学 | Novel graphene-based Mo2N-Mo2C/CdS composite photocatalyst, and preparation and application thereof |
| KR102062893B1 (en) * | 2017-11-15 | 2020-01-06 | 한국화학연구원 | Novel visible light active carbon nanodot-silica composite photocatalyst, method for production of formic acid from carbon dioxide by applying the same to a photocatalyst-enzyme integrated system |
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