CN111848377B - Preparation method of ethyl vanillin - Google Patents
Preparation method of ethyl vanillin Download PDFInfo
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- CN111848377B CN111848377B CN202010832296.9A CN202010832296A CN111848377B CN 111848377 B CN111848377 B CN 111848377B CN 202010832296 A CN202010832296 A CN 202010832296A CN 111848377 B CN111848377 B CN 111848377B
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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
- C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
Abstract
The invention relates to a preparation method of ethyl vanillin. The preparation method of the ethyl vanillin comprises the following steps: firstly, preparing an inorganic oxide supported copper oxide-tungsten oxide catalyst, then sequentially introducing 3-ethoxy-4-hydroxyglycolic acid, the inorganic oxide supported copper oxide-tungsten oxide catalyst and tetrahydrofuran into a reaction kettle, sealing, then purging with nitrogen, purging with oxygen, and charging oxygen to 0.5-1MPa, and reacting for 4-6h at 80-90 ℃ and 0.7-1.2 MPa. The method for preparing the ethyl vanillin has the advantages that the conversion rate of the 3-ethoxy-4-hydroxyglycolic acid can reach more than 99%, and the selectivity of the ethyl vanillin can reach more than 95%.
Description
Technical Field
The invention relates to a preparation method of ethyl vanillin.
Background
The ethyl vanillin is also called ethyl vanillin, has a chemical name of 3-ethoxy-4-hydroxybenzaldehyde, is white to light yellow needle crystal or crystalline powder, is slightly soluble in water and ethanol, and has strong vanilla fragrance and sweet taste. The aroma intensity of the ethyl vanillin is 3-4 times of that of the methyl vanillin, and the ethyl vanillin is widely applied to the fields of candies, chocolates, seasonings, soft drinks, alcoholic drinks, baked foods, tobaccos, daily necessities, medical intermediates, cosmetics, detergents and the like ("ethyl vanillin synthesis method and research new progress", zhangshan et al, chemical science and technology, vol.13, no. 5, page 59, left column, no. 1, lines 1-7, published Japanese 12/31, research on phase transfer catalysis method for synthesizing ethyl vanillin ", caozoong et al, chemical world 1995, no. 1, page 31, left column, lines 1-6, published Japanese 1995, no. 12/31, research progress on ethyl vanillin synthesis method, zhang Josetron, yunnan chemical industry, vol.35, no. 5, page 62, left column, lines 1, lines 2008-6, and published Japanese 10/31).
Ethyl vanillin is a non-natural synthetic flavor ("research progress on ethyl vanillin synthesis method", zhanli qiong, yunnan chemical, vol.35, no. 5, page 62, left column, no. 1, lines 1-2, published 2008, month 10, 31). Industrially, ethyl vanillin is generally synthesized by the following steps: firstly, using pyrocatechol and bromoethane as raw materials to synthesize ethyl guaiacol, then using ethyl guaiacol and glyoxylic acid as raw materials to synthesize 3-ethoxy-4-hydroxyphenylglycolic acid, and then using 3-ethoxy-4-hydroxyphenylglycolic acid as raw materials to prepare ethyl vanillin through oxidation reaction.
However, in the synthesis of ethyl vanillin, there are the following problems: in the process of preparing the ethyl vanillin by the oxidation reaction of the 3-ethoxy-4-hydroxyphenylglycolic acid, because the reaction is selective oxidation, the catalyst used in the industry at present can not oxidize only the alcoholic hydroxyl group of the 3-ethoxy-4-hydroxyphenylglycolic acid with high selectivity and can not oxidize the phenolic hydroxyl group, thereby causing a certain amount of byproducts and causing great difficulty for subsequent treatment. The development of a high-selectivity catalyst with a specific structure and size for catalyzing 3-ethoxy-4-hydroxy mandelic acid to synthesize ethyl vanillin is urgently needed.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing ethyl vanillin.
In order to realize the purpose, the technical scheme of the invention is as follows:
the preparation method of the ethyl vanillin comprises the following steps:
firstly, preparing a copper oxide-tungsten oxide catalyst supported by an inorganic oxide, then sequentially introducing 3-ethoxy-4-hydroxyphenylglycolic acid, the copper oxide-tungsten oxide catalyst supported by the inorganic oxide and tetrahydrofuran into a reaction kettle, sealing, then purging with nitrogen, purging with oxygen, and charging oxygen to 0.5-1MPa, and then reacting for 4-6h at 80-90 ℃ and 0.7-1.2 MPa.
Further, the inorganic oxide includes silica or alumina.
Furthermore, the loading amount of the copper oxide accounts for 2.34-6.72% of the total mass of the catalyst.
Further, the loading amount of the tungsten oxide accounts for 0.15-0.3% of the total mass of the catalyst.
Further, the preparation of the catalyst comprises the following steps:
A. roasting inorganic oxide in nitrogen atmosphere, and cooling to room temperature to obtain a carrier;
B. dissolving copper nitrate and phosphotungstic acid in water to obtain a mixed solution; b, adding the carrier obtained in the step A into the mixed solution, standing, drying, roasting, and then reducing in a carbon monoxide atmosphere;
C. dissolving copper nitrate and phosphotungstic acid in water to obtain a mixed solution; adding the solid obtained by reduction in the step B into the mixed solution, standing, drying, roasting, and then reducing in a hydrogen atmosphere;
D. dissolving copper nitrate and phosphotungstic acid in water to obtain a mixed solution; and D, adding the solid obtained by reduction in the step C into the mixed solution, standing, drying, roasting, reducing in a carbon monoxide atmosphere, and reducing in an air atmosphere to obtain the catalyst.
Further, in the step A, the roasting temperature is 600 ℃ and the roasting time is 12-24h.
Further, in the step B, the drying temperature is 120 ℃, and the drying time is 4-6h.
Further, in the step B, the reduction temperature is 400 ℃, and the time is 3-6h.
Further, in the step C, the drying temperature is 120 ℃, and the drying time is 4-6h.
Furthermore, in the step C, the roasting temperature is 450-580 ℃, and the roasting time is 3-8h.
Further, in the step C, the reduction temperature is 400 ℃, and the time is 3-6h.
Further, in the step D, the drying temperature is 120 ℃, and the drying time is 4-6h.
Further, in the step D, the roasting temperature is 450-580 ℃ and the roasting time is 3-8h.
Further, in the step D, the temperature of reduction in the carbon monoxide atmosphere is 400 ℃, and the time is 3-6h.
Further, in the step G, the reduction temperature in the air atmosphere is 450-580 ℃ and the time is 3-8h.
Further, the mass ratio of the copper nitrate to the phosphotungstic acid is 1.9-5.7.
The invention also aims to protect a catalyst for catalyzing 3-ethoxy-4-hydroxyphenylglycolic acid to synthesize ethyl vanillin, which comprises copper oxide-tungsten oxide supported by inorganic tungsten oxide.
Further, the inorganic oxide includes silica or alumina.
Furthermore, the loading amount of the copper oxide accounts for 2.34-6.72% of the total mass of the catalyst.
Further, the loading amount of the tungsten oxide accounts for 0.15-0.3% of the total mass of the catalyst.
The invention has the beneficial effects that:
the catalyst of the invention has high reaction selectivity, and the selectivity of the ethyl vanillin can reach more than 95%.
The catalyst of the invention has high catalytic activity, and the conversion rate of the 3-ethoxy-4-hydroxyphenylglycolic acid can reach more than 99 percent.
The catalyst and the reaction system are easy to separate and can be repeatedly used, thereby being beneficial to realizing industrial production.
The preparation method of the invention has relatively mild reaction conditions and short reaction time.
The preparation method of the invention has high reaction selectivity, and the selectivity of the ethyl vanillin can reach more than 95%.
The preparation method of the invention has high catalytic activity, and the conversion rate of the 3-ethoxy-4-hydroxyphenylglycolic acid can reach more than 99 percent.
Detailed Description
The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
The following detection method for the copper oxide loading capacity comprises the following steps: after being dissolved in aqua regia, ICP-AES atomic emission spectrum is adopted: (ThermoElemental Company, USA) directly;
the following method for detecting the loading capacity of tungsten oxide comprises the following steps: after being dissolved in aqua regia, ICP-AES atomic emission spectrum is adopted: (ThermoElemental Company, USA) directly;
the following detection method for the conversion rate of the 3-ethoxy-4-hydroxyphenylglycolic acid comprises the following steps: determining the quality of 3-ethoxy-4-hydroxyphenylglycolic acid by adopting gas chromatography detection, wherein the adopted detector is a hydrogen flame ion detector, the chromatography conditions are that a sample inlet is 200 ℃, the detector is 200 ℃, the sample injection amount is 0.5ul, a chromatographic column HP-5 is adopted, the initial temperature of the column temperature is 80 ℃, the temperature is raised to 200 ℃ by a program of 10 ℃/min, and the temperature is kept for 10min; then, an external standard curve is prepared by using 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L and 1.0 mol/L3-ethoxy-4-hydroxyphenylglycolic acid solution (external standard method), and the prepared standard curve is a straight line (the concentration of the 3-ethoxy-4-hydroxyphenylglycolic acid is used as a horizontal coordinate, and the area of a chromatographic peak is used as a vertical coordinate); after the reaction is finished, measuring the peak area of the reacted 3-ethoxy-4-hydroxyphenylglycolic acid corresponding to the concentration c of the 3-ethoxy-4-hydroxyphenylglycolic acid on a standard curve, then obtaining the amount n2 of the reacted 3-ethoxy-4-hydroxyphenylglycolic acid according to the formula n2= cxv (wherein n2 is the amount of the reacted 3-ethoxy-4-hydroxyphenylglycolic acid and is expressed in mol; c is the amount of the reacted 3-ethoxy-4-hydroxyphenylglycolic acid and is expressed in mol/L; V is the volume of the reacted solution and is expressed in L) and obtaining the amount n2 of the reacted 3-ethoxy-4-hydroxyphenylglycolic acid, and then obtaining the amount n2 of the reacted 3-ethoxy-4-hydroxyphenylglycolic acid according to the formula
(wherein n1 represents the amount of the 3-ethoxy-4-hydroxyphenylglycolic acid added before the reactionThe unit is mol; n2 is the amount of the reacted 3-ethoxy-4-hydroxyphenylglycolic acid, and the unit is mol) calculating the conversion rate of the 3-ethoxy-4-hydroxyphenylglycolic acid;
the following detection method for the yield and selectivity of ethyl vanillin is as follows: determining the quality of the ethyl vanillin by adopting gas chromatography detection, wherein the adopted detector is a hydrogen flame ion detector, the chromatographic conditions are that a sample inlet is 200 ℃, the detector is 200 ℃, the sample injection amount is 0.5ul, a chromatographic column HP-5 is adopted, the initial temperature of the column is 80 ℃, the temperature is raised to 200 ℃ by a program of 10 ℃/min, and the temperature is kept for 10min; then, using ethyl vanillin solutions of 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L and 1.0mol/L to prepare external standard curves (external standard method), wherein the prepared standard curves are straight lines (using the concentration of ethyl vanillin as an abscissa and the area of chromatographic peaks as an ordinate); after the reaction is finished, measuring the area of the ethyl vanillin corresponding to the concentration c1 of the ethyl vanillin on a standard curve, obtaining the amount n3 of the reacted ethyl vanillin according to a formula n3= c1 xV (in the formula, n3 is the amount of the ethyl vanillin material and is expressed in mol; c1 is the amount concentration of the ethyl vanillin material measured according to the standard curve and is expressed in mol/L; V is the volume of the solution after the reaction and is expressed in L), and obtaining the amount n3 of the reacted ethyl vanillin material according to a formula
(wherein n1 is the amount of 3-ethoxy-4-hydroxyphenylglycolic acid added before the reaction in mol; n2 is the amount of 3-ethoxy-4-hydroxyphenylglycolic acid added after the reaction in mol, and n3 is the amount of ethyl vanillin), and the yield of ethyl vanillin was calculated according to the formula y = con self (wherein y is the yield, con is the conversion of 3-ethoxy-4-hydroxyphenylglycolic acid, and sel is the selectivity of ethyl vanillin).
Example 1
The preparation method of the inorganic oxide supported copper oxide-tungsten oxide catalyst comprises the following specific steps:
A. placing 100g of silicon dioxide in a muffle furnace, roasting for 24 hours at 600 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain a carrier;
B. dissolving 1.9g of copper nitrate and 0.2g of phosphotungstic acid in 100g of distilled water to obtain a mixed solution; adding 100g of carrier into the mixed solution, standing at room temperature for 4h, drying at 120 ℃ for 6h, roasting at 450 ℃ for 8h, and reducing at 400 ℃ in a carbon monoxide atmosphere for 6h;
C. 1.9g of copper nitrate and 0.2g of phosphotungstic acid are put into 100g of distilled water to obtain a mixed solution; adding the solid obtained by reduction in the step B into the mixed solution, standing at room temperature for 4h, drying at 120 ℃ for 6h, roasting at 580 ℃ for 3h, and then reducing at 400 ℃ in a hydrogen atmosphere for 6h;
D. 1.9g of copper nitrate and 0.2g of phosphotungstic acid are put into 100g of distilled water to obtain a mixed solution; and D, adding the solid obtained by reduction in the step C into the mixed solution, standing at room temperature for 4h, drying at 120 ℃ for 6h, roasting at 580 ℃ for 3h, reducing at 400 ℃ for 6h in a carbon monoxide atmosphere, and reducing at 580 ℃ for 3h in an air atmosphere to obtain the catalyst.
Example 2
The preparation method of the ethyl vanillin comprises the following specific steps:
100g of 3-ethoxy-4-hydroxyphenylglycolic acid, 3g of the catalyst obtained in example 1 and 300ml of tetrahydrofuran are introduced into a 1000ml high-pressure reaction vessel in this order, sealed, purged 3 times with nitrogen, 3 times with oxygen and charged to 0.5MPa, and reacted at 90 ℃ under 0.7MPa for 6 hours.
Example 3
The preparation method of the inorganic oxide supported copper oxide-tungsten oxide catalyst comprises the following specific steps:
A. placing 100g of alumina in a muffle furnace, roasting at 600 ℃ for 12h in a nitrogen atmosphere, and cooling to room temperature to obtain a carrier;
B. dissolving 5.7g of copper nitrate and 0.4g of phosphotungstic acid in 100g of distilled water to obtain a mixed solution; adding 100g of carrier into the mixed solution, standing at room temperature for 6h, drying at 120 ℃ for 4h, roasting at 580 ℃ for 3h, and then reducing at 400 ℃ in a carbon monoxide atmosphere for 3h;
C. adding 5.7g of copper nitrate and 0.4g of phosphotungstic acid into 100g of distilled water to obtain a mixed solution; adding the solid obtained by reduction in the step B into the mixed solution, standing at room temperature for 4h, drying at 120 ℃ for 4h, roasting at 450 ℃ for 8h, and then reducing at 400 ℃ in a hydrogen atmosphere for 3h;
D. adding 5.7g of copper nitrate and 0.4g of phosphotungstic acid into 100g of distilled water to obtain a mixed solution; and D, adding the solid obtained by reduction in the step C into the mixed solution, standing at room temperature for 4h, drying at 120 ℃ for 4h, roasting at 450 ℃ for 8h, reducing at 400 ℃ for 3h in a carbon monoxide atmosphere, and reducing at 580 ℃ for 3h in an air atmosphere to obtain the catalyst.
Example 4
The preparation method of the ethyl vanillin comprises the following specific steps:
100g of 3-ethoxy-4-hydroxyphenylglycolic acid, 3g of the catalyst obtained in example 1 and 300ml of tetrahydrofuran are introduced into a 1000ml high-pressure reaction vessel in this order, sealed, purged 3 times with nitrogen, 3 times with oxygen and charged to 1.0MPa, and reacted at 80 ℃ under 1.2MPa for 4 hours.
Performance detection
The loading amount of copper oxide and the loading amount of tungsten oxide in the catalysts prepared in the examples 1 and 3 are detected; meanwhile, the conversion rate of 3-ethoxy-4-hydroxyphenylglycolic acid and the yield and selectivity of ethyl vanillin in example 2 and example 4 were measured, and the results are shown in tables 1 and 2.
TABLE 1 Performance test results
| Source | Copper oxide loading/% | Tungsten oxide loading/%) |
| Example 1 | 2.34 | 0.15％ |
| Practice ofExample 3 | 6.72％ | 0.3 |
TABLE 2 Performance test results
As can be seen from Table 2, in examples 2 and 4, the conversion of 3-ethoxy-4-hydroxyphenylglycolic acid was 99%, and the selectivity of ethyl vanillin was 95% to 96.8%. Therefore, the catalyst has high reaction selectivity and high reaction activity.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (17)
1. The preparation method of the ethyl vanillin is characterized by comprising the following steps:
firstly, preparing an inorganic oxide supported copper oxide-tungsten oxide catalyst, then sequentially introducing 3-ethoxy-4-hydroxyphenylglycolic acid, the inorganic oxide supported copper oxide-tungsten oxide catalyst and tetrahydrofuran into a reaction kettle, sealing, then purging with nitrogen, purging with oxygen, and charging oxygen to 0.5-1MPa, and reacting for 4-6h at 80-90 ℃ under the condition of 0.7-1.2 MPa; the preparation of the catalyst comprises the following steps:
A. roasting inorganic oxide in nitrogen atmosphere, and cooling to room temperature to obtain a carrier;
B. dissolving copper nitrate and phosphotungstic acid in water to obtain a mixed solution; adding the carrier obtained in the step A into the mixed solution, standing, drying, roasting, and then reducing in a carbon monoxide atmosphere;
C. dissolving copper nitrate and phosphotungstic acid in water to obtain a mixed solution; adding the solid obtained by reduction in the step B into the mixed solution, standing, drying, roasting, and then reducing in a hydrogen atmosphere;
D. dissolving copper nitrate and phosphotungstic acid in water to obtain a mixed solution; c, adding the solid obtained by reduction in the step C into the mixed solution, standing, drying, roasting, reducing in a carbon monoxide atmosphere, and reducing in an air atmosphere to obtain the catalyst; the inorganic oxide includes silica or alumina.
2. The preparation method according to claim 1, wherein the loading amount of the copper oxide is 2.34-6.72% of the total mass of the catalyst.
3. The preparation method according to claim 1 or 2, wherein the loading amount of the tungsten oxide is 0.15 to 0.3 percent of the total mass of the catalyst.
4. The method according to claim 1 or 2, wherein in the step A, the roasting temperature is 600 ℃ and the roasting time is 12-24h.
5. The preparation method according to claim 3, wherein in the step A, the roasting temperature is 600 ℃ and the roasting time is 12-24h.
6. The preparation method according to claim 1, 2 or 5, wherein in the step B, the drying temperature is 120 ℃ and the drying time is 4-6h.
7. The preparation method according to claim 3, wherein in the step B, the drying temperature is 120 ℃ and the drying time is 4-6h.
8. The preparation method according to claim 4, wherein in the step B, the drying temperature is 120 ℃ and the drying time is 4-6h.
9. The method according to claim 1, 2, 5, 7 or 8, wherein in the step B, the temperature of the reduction is 400 ℃ and the time is 3-6h.
10. The method according to claim 3, wherein in the step B, the temperature of the reduction is 400 ℃ and the time is 3-6h.
11. The method according to claim 4, wherein in the step B, the temperature of the reduction is 400 ℃ and the time is 3-6h.
12. The method according to claim 6, wherein in the step B, the temperature of the reduction is 400 ℃ and the time is 3-6h.
13. The method of claim 1, 2, 5, 7, 8, 10, 11 or 12, wherein in step D, the temperature of the calcination is 450-580 ℃ for 3-8h.
14. The method according to claim 3, wherein the roasting temperature is 450-580 ℃ for 3-8h in step D.
15. The method according to claim 4, wherein in step D, the roasting temperature is 450-580 ℃ and the roasting time is 3-8h.
16. The preparation method of claim 6, wherein in the step D, the roasting temperature is 450-580 ℃ and the roasting time is 3-8h.
17. The preparation method of claim 9, wherein in the step D, the roasting temperature is 450-580 ℃ and the roasting time is 3-8h.
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