CN111848377A - Preparation method of ethyl vanillin - Google Patents
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- CN111848377A CN111848377A CN202010832296.9A CN202010832296A CN111848377A CN 111848377 A CN111848377 A CN 111848377A CN 202010832296 A CN202010832296 A CN 202010832296A CN 111848377 A CN111848377 A CN 111848377A
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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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- 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
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Abstract
The invention relates to a preparation method of ethyl vanillin. 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-hydroxyglycolic 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. 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 percent, and the selectivity of the ethyl vanillin can reach more than 95 percent.
Description
Technical Field
The invention relates to a preparation method of ethyl vanillin.
Background
Ethyl vanillin is also known as 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, is easily soluble in ethanol, and has strong vanilla fragrance and sweet taste. The fragrance intensity of the ethyl vanillin is 3-4 times of that of the methyl vanillin, and the ethyl vanillin is widely applied to candies, chocolates, seasonings, soft drinks, wine drinks and baked foods, tobacco, daily necessities, pharmaceutical 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, p.59, left column, lines 1, 7, published day 12, month 31, "research on Synthesis of Ethyl vanillin by phase transfer catalysis", Caozoan et al, chemical world, No. 1, p.31, left column, lines 1, 6, published day 1995, line 12, month 31; "research progress on Ethyl vanillin Synthesis method", Zhang Liqiong, Yunnan chemical industry, Vol.35, No. 5, p.62, left column, lines 1, 6, published day 2008, month 10, month 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-hydroxyglycollic acid, then using 3-ethoxy-4-hydroxyglycollic acid as raw material and making them undergo the process of oxidation reaction so as to obtain the ethyl vanillin
However, in the synthesis of ethyl vanillin, there are the following problems: in the process of preparing ethyl vanillin by oxidation reaction of 3-ethoxy-4-hydroxyglycolic acid, because the reaction is selective oxidation, the catalyst used in industry at present can not oxidize only alcoholic hydroxyl of 3-ethoxy-4-hydroxyglycolic acid with high selectivity and does not oxidize phenolic hydroxyl, thereby causing a certain amount of by-products 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-hydroxyglycolic 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 achieve 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-hydroxyglycolic 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.
Furthermore, 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; 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 12-24 h.
Further, in the step B, the drying temperature is 120 ℃, and the drying time is 4-6 h.
Further, in the step B, the reduction temperature is 400 ℃, and the time is 3-6 h.
Further, in the step C, the drying temperature is 120 ℃, and the drying time is 4-6 h.
Further, in the step C, the roasting temperature is 450-580 ℃, and the roasting time is 3-8 h.
Further, in the step C, the reduction temperature is 400 ℃, and the time is 3-6 h.
Further, in the step D, the drying temperature is 120 ℃, and the drying time is 4-6 h.
Further, in the step D, the roasting temperature is 450-580 ℃, and the roasting time is 3-8 h.
Further, in the step D, the temperature of reduction in the carbon monoxide atmosphere is 400 ℃, and the time is 3-6 h. .
Further, in the step G, the temperature of the reduction in the air atmosphere is 450-580 ℃, and the time is 3-8 h.
Further, the mass ratio of the copper nitrate to the phosphotungstic acid is 1.9-5.7: 0.2-0.4.
The invention also aims to protect a catalyst for catalyzing 3-ethoxy-4-hydroxyglycolic 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.
Furthermore, 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-hydroxyglycolic acid can reach more than 99 percent.
The catalyst and the reaction system of the invention are easy to separate and can be repeatedly used, thus 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-hydroxyglycolic 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 tungsten 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 conversion rate of the 3-ethoxy-4-hydroxyglycolic acid comprises the following steps: determining the quality of 3-ethoxy-4-hydroxyglycolic acid by gas chromatography detection, wherein the detector is a hydrogen flame ion detector, the chromatography conditions are that the sample inlet is 200 ℃, the detector is 200 ℃, the sample injection amount is 0.5ul, the chromatographic column is an HP-5 column, 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 10 min; then, using 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L and 1.0 mol/L3-ethoxy-4-hydroxyglycolic acid solution to prepare an external standard curve (external standard method), wherein the prepared standard curve is a straight line (the concentration of 3-ethoxy-4-hydroxyglycolic acid is used as an abscissa, and the area of a chromatographic peak is used as an ordinate); after the reaction is finished, the peak area of the reacted 3-ethoxy-4-hydroxyglycolic acid is determined to correspond to the concentration c of the 3-ethoxy-4-hydroxyglycolic acid on a standard curve, then the amount n2 of the reacted 3-ethoxy-4-hydroxyglycolic acid is obtained according to the formula n2 ═ cxv (where n2 is the amount of the reacted 3-ethoxy-4-hydroxyglycolic acid in mol; c is the amount of the reacted 3-ethoxy-4-hydroxyglycolic acid in mol/L; V is the volume of the reacted solution in L) and the formula n2 is obtained
(wherein n1 represents the amount of the 3-ethoxy-4-hydroxyglycolic acid added before the reaction in mol; n2 represents the amount of the 3-ethoxy-4-hydroxyglycolic acid added after the reaction in mol.)Calculating the conversion rate of 3-ethoxy-4-hydroxyglycolic acid;
the following detection method for the yield and selectivity of ethyl vanillin is as follows: determining the quality of the ethyl vanillin by 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 temperature is 80 ℃, the temperature is raised to 200 ℃ by a program of 10 ℃/min, and the temperature is kept for 10 min; 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, the measured area of the ethyl vanillin corresponds to the concentration c1 of the ethyl vanillin on the standard curve, then the amount n3 of the reacted ethyl vanillin can be obtained according to the formula n3 ═ c1 xV (in the formula, n3 is the amount of the ethyl vanillin material and is in mol; c1 is the amount concentration of the ethyl vanillin material and is in mol/L, and V is the volume of the solution after the reaction and is in L), and then the amount n3 of the reacted ethyl vanillin material can be obtained according to the formula
(wherein n1 represents the amount of 3-ethoxy-4-hydroxyglycolic acid added before the reaction in mol; n2 represents the amount of 3-ethoxy-4-hydroxyglycolic acid added after the reaction in mol; n3 represents the amount of ethyl vanillin in mol.) the ethyl vanillin selectivity was calculated, and then the ethyl vanillin yield was calculated according to the formula y ═ con self (wherein y represents the yield, con represents the conversion of 3-ethoxy-4-hydroxyglycolic acid, and sel represents the ethyl vanillin selectivity).
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 then reducing at 400 ℃ for 6h in a carbon monoxide atmosphere;
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 h, and then reducing at 400 ℃ for 6h in a hydrogen atmosphere;
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-hydroxyglycolic acid, 3g of the catalyst prepared in example 1 and 300ml of tetrahydrofuran were 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 ℃ for 3h in a carbon monoxide atmosphere;
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 ℃ for 3h in a hydrogen atmosphere;
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-hydroxyglycolic acid, 3g of the catalyst prepared in example 1 and 300ml of tetrahydrofuran were 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 example 1 and example 3 were measured; meanwhile, the conversion rate of 3-ethoxy-4-hydroxyglycolic acid and the yield and selectivity of ethyl vanillin in examples 2 and 4 were measured, and the results are shown in tables 1 and 2.
TABLE 1 Performance test results
| Origin of origin | Copper oxide loading/%) | Tungsten oxide loading/%) |
| Example 1 | 2.34 | 0.15％ |
| Example 3 | 6.72％ | 0.3 |
TABLE 2 Performance test results
As shown in Table 2, in examples 2 and 4, the conversion of 3-ethoxy-4-hydroxyglycolic 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 (10)
1. The preparation method of the ethyl vanillin is characterized by comprising the following steps:
firstly, preparing a copper oxide-tungsten oxide catalyst supported by an inorganic oxide, then sequentially introducing 3-ethoxy-4-hydroxyglycolic 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.
2. The method of claim 1, wherein the inorganic oxide comprises silica or alumina.
3. The preparation method according to claim 1 or 2, wherein the loading amount of the copper oxide is 2.34-6.72% of the total mass of the catalyst.
4. The process according to any one of claims 1 to 3, wherein the tungsten oxide is supported in an amount of 0.15 to 0.3% by mass based on the total mass of the catalyst.
5. The process according to any one of claims 1 to 4, wherein the preparation of the catalyst comprises the steps of:
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; 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.
6. The preparation method of claim 5, wherein in the step A, the roasting temperature is 600 ℃ and the roasting time is 12-24 h.
7. The preparation method according to claim 5 or 6, wherein in the step B, the drying temperature is 120 ℃ and the drying time is 4-6 h.
8. The process according to any one of claims 5 to 7, wherein in step B, the temperature of the reduction is 400 ℃ and the time is 3 to 6 hours.
9. The method as claimed in any one of claims 5 to 8, wherein the temperature of the calcination in step D is 450-580 ℃ for 3-8 h.
10. The catalyst for catalyzing 3-ethoxy-4-hydroxyglycolic acid to synthesize ethyl vanillin is characterized by comprising copper oxide-tungsten oxide supported by inorganic tungsten oxide.
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Cited By (1)
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| CN112973725A (en) * | 2021-03-08 | 2021-06-18 | 重庆化工职业学院 | Catalyst for synthesizing sclareolide by oxidizing sclareol |
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