CN112642455B - Aluminum nitride supported metal oxide catalyst for synthesizing guaiacol and preparation method and application thereof - Google Patents

Aluminum nitride supported metal oxide catalyst for synthesizing guaiacol and preparation method and application thereof Download PDF

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CN112642455B
CN112642455B CN201910956991.3A CN201910956991A CN112642455B CN 112642455 B CN112642455 B CN 112642455B CN 201910956991 A CN201910956991 A CN 201910956991A CN 112642455 B CN112642455 B CN 112642455B
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catechol
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林建东
丛振霞
李俊平
王锐
付松
丁大康
王勤隆
黎源
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Wanhua Chemical Group Nutrition Technology Co.,Ltd.
Wanhua Chemical Group Co Ltd
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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Abstract

The invention provides an aluminum nitride supported metal oxide catalyst, wherein the loading amount of metal oxide in the catalyst is 10-40 wt%, and the metal is selected from one or more of iron, zinc, manganese, cerium and lanthanum. The preparation method of the catalyst comprises the following steps: (1) respectively adding a nitrogen source, an aluminum source and a nano silicon dioxide solution into alcohol, stirring and mixing uniformly, and evaporating to dryness to obtain blocks; (2) calcining the blocks at high temperature, placing the calcined blocks in an ammonium bifluoride aqueous solution, stirring the demoulding plate, and filtering, washing and drying the obtained product to obtain a carrier; (3) and adding the carrier and the metal source into water, and impregnating, evaporating and calcining to obtain the catalyst. The catalyst can efficiently and selectively catalyze the mono-etherification of catechol to prepare the guaiacol at a lower temperature, the conversion rate can reach 80 percent, the selectivity can reach 97 percent, the stability is good after the catalyst is continuously operated for 1000 hours, and the problem of carbon deposition inactivation of the catalyst in a gas phase fixed bed process is solved.

Description

Aluminum nitride supported metal oxide catalyst for synthesizing guaiacol and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to an aluminum nitride supported metal oxide catalyst for synthesizing guaiacol, and a preparation method and application thereof.
Background
Guaiacol (guaiacol), also known as o-hydroxyanisole, o-i b hydroxyanisole, and methylcatechol, are important fine chemical intermediates in the industries of perfumery, medicine, agriculture, and dyes. The guaiacol is used for producing vanillin which is a precious high-grade perfume in a broad spectrum and can be used as a fixative, a flavoring agent and a flavoring agent to be widely applied to industries such as cosmetics, perfumed soaps, cakes, candies, beverages, tobaccos, baked foods and the like. Guaiacol is used as important organic synthesis intermediate, and may be used in producing potassium guaiacol sulfonate as expectorant and antitussive and 5-nitroguaiacol sodium as efficient plant growth regulator. In addition, guaiacol is used as an antioxidant in polymerization reactions and in the food industry; it can also be used for the quantitative detection of copper, hydrocyanic acid and nitrite.
At present, the synthetic methods of guaiacol mainly comprise a diazonium salt catalytic oxidation method, a liquid-phase catalytic synthesis method, a phase transfer catalytic synthesis method, a gas-solid phase catalytic synthesis method and the like, wherein the first three methods are all carried out by adopting a liquid-phase batch method, and although the synthetic steps are simple, the problems of complex post-treatment, equipment corrosion, extremely toxic materials, environmental pollution and the like exist. In contrast, the gas-solid phase catalytic synthesis method uses catechol as a raw material, and the catechol and a methylating agent selected from methanol, dimethyl carbonate and the like are used for preparing guaiacol under the action of a catalyst, and the methanol route has more advantages (the reaction formula is shown as formula I) in consideration of cost factors.
Figure BDA0002227665690000021
The process has the advantages of continuous production, high atom utilization rate and less three wastes, the used raw materials have low toxicity and corrosivity and are cheap and easy to obtain, the process route is the most advanced and competitive process route in the world at present, the process is worthy of deep research from the economic perspective and the environmental protection perspective, and the process technology has the greatest difficulty in developing the high-efficiency and high-stability catalyst. Common catalysts include kaolin, oxides and mixed oxides, phosphates, supported catalysts, and the like, depending on the constituent components. The phosphate catalyst has weak acid and weak base centers as catalytic sites, so that the catalytic performance is more excellent compared with other systems.
CN1274418C discloses a preparation method of an aluminum phosphate catalyst and an application of the aluminum phosphate catalyst in preparing a polyhydroxy benzene monoalkyl ether system. The catalyst has a particle size of 50-100 m2Specific surface area per gram, at 190 ℃The device is used for continuously operating for 1300 hours to catalyze catechol and methanol to prepare guaiacol, but the reaction activity is low, the conversion rate of catechol is only 23%, and the selectivity is 99%. The catalytic system disclosed in US4025566 is based on a mixed oxide system of boron, aluminum and phosphorus, which has a high initial catalytic activity, but the boron component is gradually lost as the reaction proceeds, resulting in a gradual decrease in the catalytic activity. EP0509927 discloses a method for preparing mixed oxides of aluminum, phosphorus, titanium and silicon, which is used for preparing guaiacol by catechol etherification, after the reaction temperature is raised to 280 ℃, the conversion rate of diphenol can reach 64 percent, the selectivity of guaiacol is 98 percent, but the specific surface area of the catalyst is small and is only 30-50 m2The catalyst is rapidly deactivated by carbon deposition caused by high temperature.
Therefore, although some of the reported traditional phosphate series catalysts have good initial activity and selectivity, the disadvantages of low efficiency at low temperature and easy deactivation at high temperature still need to be improved. It is hoped to develop a catalyst which can efficiently and selectively catalyze the mono-etherification of catechol to prepare guaiacol under mild conditions.
Disclosure of Invention
An object of the present invention is to provide an aluminum nitride supported Metal Oxide (MO)xAlN) catalyst, the catalyst can efficiently and selectively catalyze catechol to prepare guaiacol through monoetherification under mild conditions, and has long service life and good stability.
The invention also aims to provide a preparation method of the catalyst.
It is a further object of the present invention to provide the use of such a catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
aluminum nitride loaded Metal Oxide (MO) for synthesizing guaiacolx/AlN) catalyst, wherein the metal is selected from one or more of iron, zinc, manganese, cerium, lanthanum, preferably one or more of iron, zinc, lanthanum; the loading of the metal oxide in the catalyst is 10 to 40 wt%, preferably 20 to 30 wt%.
In the invention, the preparation method of the catalyst comprises the following steps:
(1) respectively adding a nitrogen source, an aluminum source and a nano silicon dioxide solution into alcohol, stirring and mixing uniformly, and evaporating the solution to obtain blocks;
(2) calcining the blocks at high temperature, placing the calcined blocks in an ammonium bifluoride aqueous solution, stirring the demoulding plate, and filtering, washing and drying the obtained product to obtain a carrier;
(3) and adding the carrier and the metal source into water, and impregnating, evaporating and calcining to obtain the catalyst.
In the preparation method of the catalyst, the alcohol in the step (1) is preferably ethanol; the nitrogen source is one or more of cyanamide, urea and dicyandiamide, preferably cyanamide; the aluminum source is one or more of aluminum trichloride, aluminum nitrate and aluminum hydroxide, and preferably the aluminum trichloride.
In the preparation method of the catalyst, in the step (1), the molar ratio of the aluminum source to the nitrogen source is (0.8-1.2) to 1; the molar ratio of the nano silicon dioxide to the nitrogen source is (0.2-0.4) to 1; the mass ratio of the ethanol to the nitrogen source is (3-7) to 1. The concentration of the nano silicon dioxide solution is 20-40 wt%, the solvent is water, and the nano silicon dioxide solution is used as a pore-forming template agent.
In the preparation method of the catalyst, the raw materials are added in the step (1) and then stirred for 6-12h at the temperature of 20-40 ℃, preferably for 8-10h at the temperature of 25-35 ℃ to be uniformly mixed; the solution is evaporated to dryness at 90-120 deg.C, preferably at 100-110 deg.C.
In the preparation method of the catalyst, the calcination atmosphere in the step (2) is nitrogen, the calcination temperature is 500-1000 ℃, preferably 700-800 ℃, the heating rate is 1-6 ℃/min, preferably 2-4 ℃/min, and the calcination time is 4-8h, preferably 5-7 h.
In the preparation method of the catalyst, the concentration of the ammonium bifluoride aqueous solution in the step (2) is 2-10 wt%, preferably 3-6 wt%, and preferably, the ratio of the amount of the ammonium bifluoride aqueous solution to the mass of the calcined block is (10-20): 1; the time for stirring the stripping plate is 12 to 60 hours, preferably 24 to 48 hours; the drying condition is 100-150 ℃ for 12-60h, preferably 110-130 ℃ for 24-48 h.
In the preparation method of the catalyst of the present invention, the metal source in the step (3) is preferably a nitrate of the corresponding metal.
In the preparation method of the catalyst, the mass ratio of the carrier to the water in the step (3) is 1: (4-6); the impregnation is carried out for 12 to 48 hours at the temperature of 20 to 50 ℃, preferably for 24 to 36 hours at the temperature of 30 to 40 ℃; the condition of evaporation to dryness is evaporation to dryness at 90-120 ℃, preferably at 100-110 ℃; the calcining atmosphere is air, the calcining temperature is 300-500 ℃, preferably 350-450 ℃, the heating rate is 1-6 ℃/min, preferably 2-4 ℃/min, and the calcining time is 3-7h, preferably 4-6 h.
In the preparation method of the catalyst, the catalyst obtained after calcination is prepared into strips, pills or granules according to a known technical forming process, preferably the catalyst is prepared into strips through extrusion forming, and the particle size is preferably 40-60 meshes.
The invention also relates to the use of said catalyst: the catalyst prepared by the preparation method is used for synthesizing guaiacol by gas-phase catechol-methanol etherification, and the preferable steps are as follows: filling the catalyst into a fixed bed reactor, heating to reaction temperature, adding catechol and methanol reaction solution into the reactor, and condensing the product in a collecting tank.
In the invention, preferably, when the guaiacol is synthesized, the reaction temperature is 180-240 ℃, and preferably 200-220 ℃; the molar ratio of catechol to methanol is (0.1-1) to 1, preferably (0.2-0.4) to 1; the mass airspeed of the catechol feeding is 0.05-0.7 h-1Preferably 0.1 to 0.3 hour-1。
The invention adopts aluminum nitride loaded metal oxide MOxThe catalyst/AlN is used for catechol etherification reaction, and compared with the traditional kaolin, oxide and mixed oxide, phosphate and a supported catalyst system, the catalyst has the following advantages: MO (metal oxide semiconductor)xthe/AlN reserves a Lewis weak acid-base catalytic center, and the specific surface area can reach 200-500 m2The catalytic reaction can be carried out under mild conditions, the conversion rate of catechol can reach about 80 percent, and the selectivity of guaiacol is about 97 percent.
The invention has the positive effects that:
(1) the invention adopts aluminum nitride loaded metal oxide MOxAlN as catalyst and can catalyze the reaction under mild condition, and the conversion rate of catechol can reach about80%, guaiacol selectivity about 97%;
(2) in the preparation process of the catalyst, proper preparation parameters such as a nitrogen source, an aluminum source, a metal source, a calcination temperature and the like are selected, so that the active sites of the loaded metal oxide are fully exposed and uniformly dispersed, the C-alkylation side reaction can be reduced, the selectivity of the guaiacol product is improved, and the service life of the catalyst is prolonged. The addition of the template agent enables the catalyst to have a larger pore diameter, is beneficial to mass transfer of reaction molecules and delays carbon deposition, and the catalyst can be continuously used for 1000 hours and has good stability.
Drawings
FIG. 1: example 4 life test curve of ZnO/AlN.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
BET test method: the dynamic method specific surface area tester F-Sorb2400, the minimum measurement range: 0.01m2(ii)/g; testing precision: the measurement repeatability error is less than or equal to 1.5 percent; testing gas: the carrier gas is high-purity He gas (99.99%); and (3) testing time: the average time for adsorption and desorption per point P/P0 was 5 minutes per sample.
Inductively coupled plasma emission spectroscopy (ICP): instrument brand: agilent (usa) model: 720-OES. The operating conditions of the apparatus are as follows: power (KW): 1.30; plasma gas flow (L/min): 15.0 of the total weight of the mixture; auxiliary gas flow (L/min): 1.50; atomization gas flow rate (L/min): 0.80; one reading time (S): 5.00; instrument stability delay (S): 15; sample introduction delay (S): 60, adding a solvent to the mixture; pump speed (rpm): 15; cleaning time (S): 30, of a nitrogen-containing gas; the number of readings: 3; the slope deviation is 10%; correlation coefficient limit value: 0.995000.
gas chromatography: the composition of the catechol-methanol reaction solution is analyzed by gas chromatography, and the operation conditions are as follows: DB-5MS UI (30m × 0.25mm × 0.25 μm) chromatographic column, acetonitrile as solvent, vaporization chamber temperature of 280 deg.C, column flow of 1.00mL/min, and sample injection amount of 0.2 μ L are adopted. Temperature programming of a chromatographic column: firstly heating to 80 ℃ at the heating rate of 5 ℃/min at 50 ℃, and finally heating to 280 ℃ at the heating rate of 15 ℃/min.
The reactors used in the examples: the guaiacol is prepared by the etherification of catechol by adopting a stainless steel fixed bed reactor, the model of a reaction tube is DN15 x 606, and two ends of the catalyst are filled with alpha-Al with the diameter of 2mm2O3And (4) porcelain balls.
The raw materials used were derived as follows:
feedstock or apparatus Specification/model Manufacturer(s)
Anhydrous methanol AR Xilong Chemical Co., Ltd.
Catechol AR Aladdin reagent
Anhydrous ethanol AR Xilong Chemical Co., Ltd.
Urea AR Aladdin reagent
Cyanamide AR Aladdin reagent
Dicyandiamide AR Aladdin reagent
Aluminium trichloride Anhydrous, AR Aladdin reagent
Aluminium nitrate AR Aladdin reagent
Aluminum hydroxide AR Aladdin reagent
Ferric nitrate Nine water, AR Aladdin reagent
Zinc nitrate Hexahydrate of AR Aladdin reagent
Lanthanum nitrate Hexahydrate of AR Aladdin reagent
Ludox SiO2 40nm, 30 wt% aqueous solution Sigma-Aldrich
Example 1
The aluminum nitride supported zinc oxide catalyst is marked as ZnO/AlN, and the preparation method comprises the following steps:
(1) adding 180g of Ludox silicon dioxide solution, 126g of cyanamide and 400g of aluminum trichloride into 630g of ethanol, fully stirring for 12 hours at 40 ℃, and evaporating to dryness at 120 ℃ to obtain a block;
(2) and calcining 300g of the block at 1000 ℃ for 8h in a nitrogen atmosphere, heating at the rate of 5 ℃/min, placing the calcined block in 4500g of ammonium bifluoride aqueous solution (5 wt%), stirring for 36h to remove the silicon oxide template, filtering, washing with distilled water, and drying at 120 ℃ for 36h to obtain the AlN carrier. The specific surface area of the carrier was 355m2G, pore diameter of about 22 nm.
(3)250g of water were added with 50g of AlN carrier and 61g of zinc nitrate (Zn (NO)3)2·6H2Theoretical load of O and ZnO is 25wt percent), soaking for 48 hours at 50 ℃, and evaporating to dryness at 120 ℃. And then calcining the catalyst for 5 hours at 500 ℃ in the air atmosphere at the heating rate of 3 ℃/min to obtain the catalyst after calcining. The ZnO loading was 23.9 wt% by ICP.
The ZnO/AlN catalyst prepared by the method is used for preparing guaiacol by gas-phase monoetherification of catechol and methanol. The method comprises the following specific steps: and (3) filling 10g of 40-60-mesh extrusion forming catalyst into a fixed bed reactor, heating to the reaction temperature, and taking catechol-methanol reaction raw material liquid to the reactor by a feed pump. The reaction conditions are as follows: the reaction temperature is 210 ℃, the molar ratio of catechol to methanol is 0.3:1, and the space velocity of catechol feeding is 0.2h-1. The reaction solution was analyzed by gas chromatography in a collection tank, wherein the conversion of catechol was 80.3% and the selectivity of guaiacol was 97.1%.
Example 2
Aluminum nitride supported iron catalyst, noted Fe3O4AlN, the preparation method is as follows:
(1) adding 120g of Ludox silicon oxide solution, 180g of urea and 511g of aluminum nitrate (with the molecular weight of 213) into 540g of ethanol, fully stirring for 9 hours at the temperature of 30 ℃, and evaporating to dryness at the temperature of 105 ℃ to obtain a block;
(2) and calcining 300g of the block at 750 ℃ for 4h in a nitrogen atmosphere, heating at a rate of 3 ℃/min, placing the calcined block in 3000g of ammonium bifluoride aqueous solution (2 wt%), stirring for 60h, removing the silicon oxide template, filtering, washing with distilled water, and drying for 60h at 100 ℃ to obtain the AlN carrier. Carrier ratio tableArea is 492m2G, pore diameter about 35 nm.
(3) 50g of AlN carrier and 29g of ferric nitrate nonahydrate (theoretical loading amount: 10 wt%) were added to 200g of water, and the mixture was immersed at 35 ℃ for 30 hours and evaporated to dryness at 105 ℃. And calcining at 400 ℃ for 3h in an air atmosphere at the heating rate of 1 ℃/min to obtain the catalyst. ICP determination of Fe3O4The loading was 8.7 wt%.
Fe prepared as above3O4AlN catalyst is used for preparing guaiacol by gas-phase monoetherification of catechol and methanol. The method comprises the following specific steps: and (3) filling 10g of 40-60-mesh extrusion forming catalyst into a fixed bed reactor, heating to the reaction temperature, and taking catechol-methanol reaction raw material liquid to the reactor by a feed pump. The reaction conditions are as follows: the reaction temperature is 180 ℃, the molar ratio of catechol to methanol is 0.1:1, and the feeding airspeed is 0.05h-1. The reaction solution was analyzed by gas chromatography in a collection tank, wherein the conversion of catechol was 61.4% and the selectivity of guaiacol was 98.2%.
Example 3
Aluminum nitride supported lanthanum oxide catalyst, denoted as La2O3AlN, the preparation method is as follows:
(1)1764g of ethanol is added with 240g of Ludox silicon oxide solution, 252g of dicyandiamide and 281g of aluminum hydroxide, fully stirred for 6h at 20 ℃, and evaporated to dryness at 90 ℃ to obtain a block;
(2) and calcining 300g of the block at 500 ℃ for 6h in a nitrogen atmosphere, heating at the rate of 6 ℃/min, placing the calcined block in 6000g of ammonium bifluoride aqueous solution (10 wt%), stirring for 12h to remove the silicon oxide template, filtering, washing with distilled water, and drying at 150 ℃ for 12h to obtain the AlN carrier. The specific surface area of the carrier was 237m2G, pore diameter is about 18 nm.
(3)300g of water were added with 50g of AlN carrier and 89g of lanthanum nitrate (La (NO)3)3·6H2O, theoretical loading 40 wt%), soaking at 20 deg.C for 12 hr, and evaporating at 90 deg.C. And calcining for 7h at 350 ℃ in the air atmosphere at the heating rate of 6 ℃/min to obtain the catalyst after calcining. ICP measurement of La2O3The loading was 38.3 wt%.
La prepared as above2O3Use of AlN catalysts for o-benzeneThe gas phase monoetherification of diphenol and methanol is used to prepare guaiacol. The method comprises the following specific steps: and (3) filling 10g of 40-60-mesh extrusion forming catalyst into a fixed bed reactor, heating to the reaction temperature, and taking catechol-methanol reaction raw material liquid to the reactor by a feed pump. The reaction conditions are as follows: the reaction temperature is 240 ℃, the molar ratio of catechol to methanol is 1:1, and the feeding airspeed is 0.7h-1. The reaction solution was analyzed by gas chromatography in a collection tank, wherein the conversion of catechol was 49.3% and the selectivity of guaiacol was 98.5%.
Comparative example 1
The aluminium phosphate disclosed in the document CN1274418C is used as a catalyst for preparing guaiacol by gas phase monoetherification of catechol and methanol. The method comprises the following specific steps: after 10g of 40-60 mesh extrusion forming catalyst is filled in a fixed bed reactor, nitrogen is blown and the temperature is raised to the reaction temperature, and catechol-methanol reaction liquid is brought to the reactor by a feed pump. The reaction conditions are as follows: the reaction temperature is 210 ℃, the molar ratio of catechol to methanol is 0.3:1, and the feed space velocity is 0.2h-1. The reaction solution was analyzed by gas chromatography in a collection tank, wherein the conversion of catechol was 41.2% and the selectivity of guaiacol was 96.0%.
Example 4
The ZnO/AlN catalyst obtained in example 1 was used for the life test of guaiacol prepared by gas phase monoetherification of catechol with methanol. The reaction was carried out as in example 1, continuously for 1000 h. The reaction solution was analyzed by gas chromatography, wherein the conversion of catechol and the selectivity of guaiacol are shown in FIG. 1.

Claims (16)

1. The catalyst for synthesizing guaiacol is characterized in that the catalyst is aluminum nitride loaded metal oxide, and the loading amount of the metal oxide in the catalyst is 10-40 wt%; the metal is selected from one or more of iron, zinc, manganese, cerium and lanthanum; the preparation method of the catalyst comprises the following steps:
(1) respectively adding a nitrogen source, an aluminum source and a nano silicon dioxide solution into alcohol, uniformly mixing, and evaporating to obtain blocks;
(2) calcining the blocks at high temperature, placing the calcined blocks in an ammonium bifluoride aqueous solution, stirring a stripper plate, filtering, washing and drying to obtain a carrier;
(3) and adding the carrier and the metal source into water, and impregnating, evaporating and calcining to obtain the catalyst.
2. The catalyst of claim 1, wherein the loading of metal oxide in the catalyst is 20 to 30 wt%; the metal is selected from one or more of iron, zinc and lanthanum.
3. The catalyst according to claim 1, wherein the nitrogen source in step (1) is one or more selected from the group consisting of cyanamide, urea, and dicyandiamide; the aluminum source is one or more of aluminum trichloride, aluminum nitrate and aluminum hydroxide; the molar ratio of the aluminum source to the nitrogen source is (0.8-1.2): 1.
4. The catalyst of claim 3, wherein the nitrogen source in step (1) is cyanamide; the aluminum source is aluminum trichloride.
5. The catalyst according to any one of claims 1 to 3, wherein the alcohol in the step (1) is ethanol, and the mass ratio of the ethanol to the nitrogen source is (3-7): 1; the molar ratio of the nano silicon dioxide to the nitrogen source is (0.2-0.4) to 1.
6. The catalyst according to claim 1, wherein the calcining atmosphere in the step (2) is nitrogen, the calcining temperature is 500-1000 ℃, and the calcining time is 4-8 h.
7. The catalyst of claim 6, wherein the calcining temperature in the step (2) is 700-800 ℃, and the calcining time is 5-7 h.
8. The catalyst according to claim 1, wherein the concentration of the aqueous ammonium acid fluoride solution in the step (2) is 2 to 10 wt%; the mass ratio of the ammonium bifluoride aqueous solution to the calcined block is (10-20): 1.
9. The catalyst according to claim 8, wherein the concentration of the aqueous ammonium acid fluoride solution in the step (2) is 3 to 6 wt%.
10. The catalyst of claim 1, wherein the carrier to water mass ratio in step (3) is 1: (4-6); the impregnation is carried out at 20-50 ℃ for 12-48 h.
11. The catalyst of claim 10, wherein the impregnation in step (3) is carried out at 30-40 ℃ for 24-36 h.
12. The catalyst according to claim 1, wherein the condition of evaporation to dryness in step (3) is evaporation to dryness at 90-120 ℃; the calcining atmosphere is air, the calcining temperature is 300-500 ℃, and the calcining time is 3-7 h.
13. The catalyst as claimed in claim 12, wherein the conditions of evaporation in step (3) are 100-110 ℃; the calcining temperature is 350-450 ℃, and the calcining time is 4-6 h.
14. Use of a catalyst according to any one of claims 1 to 13 for the synthesis of guaiacol by gas phase catechol-methanol etherification.
15. The use according to claim 14, wherein the reaction temperature is 180 to 240 ℃; the molar ratio of catechol to methanol is (0.1-1) to 1; the mass airspeed of the catechol feeding is 0.05-0.7 h-1。
16. The use according to claim 15, characterized in that the reaction temperature is 200 to 220 ℃; the molar ratio of catechol to methanol is (0.2-0.4) to 1; the mass airspeed of the catechol feeding is 0.1-0.3 h-1。
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