Preparation of modified catalyst and application of modified catalyst in hydroxylation of anisole

Abstract

The invention provides preparation of a modified catalyst and application of the modified catalyst in hydroxylation of anisole. The modified catalyst is a modified TS-1 raw powder catalyst, the modified TS-1 raw powder catalyst is obtained by modifying a naphthylamine phosphine ligand compound, the structure of the naphthylamine phosphine ligand compound is that the modified TS-1 raw powder catalyst is applied to an anisole hydroxylation reaction, and the modified TS-1 raw powder catalyst has the remarkable advantages of high product selectivity, high catalyst activity and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of chemical synthesis process, and particularly relates to a modified catalyst preparation and application thereof in anisole hydroxylation. BACKGROUND

[0002] Guaiacol, i.e. ortho-hydroxy anisole, ortho-methoxy phenol, is an important fine chemical product in the fields of medicine, perfume, agriculture, etc., and can also be used to synthesize vanillin, guaiacol glyceryl ether, potassium guaiacol sulfonate and other high-value-added products. The current annual demand for guaiacol is more than 3 wt%, and is still growing, and its application prospect is very promising. p-Hydroxyanisole, also known as 4-methoxyphenol, is also an important organic chemical product; it is mainly used as a polymerization inhibitor for olefin monomers, a dye intermediate, a pharmaceutical intermediate and an antioxidant, and has a very wide application field.

[0003] The synthesis process of ortho-hydroxy anisole and p-hydroxyanisole is very similar, mainly including an ortho / p-phenol methylation process and an anisole hydroxylation process. Among them, the ortho / p-phenol methylation process is mostly used, i.e. using ortho / p-phenol as a raw material to react with dimethyl sulfate, dimethyl carbonate, methanol and other methylation reagents to obtain an etherization product. However, this process is often limited by high raw material cost, high toxicity of the methylation reagent, and a large amount of waste, etc. In comparison, the anisole hydroxylation process can synthesize the two products under mild conditions, and therefore is increasingly attracting attention from the relevant industry.

[0004] CN105985226A discloses a method for anisole hydroxylation, mainly adding an appropriate amount of C1-C5 carboxylic acid to anisole and hydrogen peroxide raw materials, and the active component of the catalyst is a titanium silicalite molecular sieve with a hollow structure crystal grain, which can obtain a higher anisole conversion rate in a short time under the reaction conditions described in the patent. CN115490579B uses a microspherical titanium silicalite molecular sieve modified by a base, and then a microspherical titanium silicalite molecular sieve catalyst loaded with copper and cadmium is prepared by an equal-volume impregnation method, which is used to catalyze the reaction of anisole and hydrogen peroxide. The hydroxyanisole obtained by this method has excellent yield and selectivity.

[0005] Therefore, the anisole hydroxylation process has important industrial application prospects, and the hydroxylation of anisole can be achieved by using different methods and different catalysts, the key is how to improve the activity and life of the catalyst, so as to achieve high conversion rate of anisole and high selectivity of the product. SUMMARY

[0006] One of the purposes of the present application is to provide a modified naphthylamine phosphine ligand compound, the TS-1 raw catalyst modified by the compound has the characteristics of high activity and long service life, and the method has the advantages of high product selectivity and high hydrogen peroxide utilization rate.

[0007] To achieve the above-mentioned purposes, the technical scheme adopted by the present application comprises the following:

[0008] A naphthylamine phosphine ligand compound, the structure of the compound is as follows:

[0009]

[0010] Another purpose of the present application is to provide a preparation method of a naphthylamine phosphine ligand compound.

[0011] A preparation method of a naphthylamine phosphine ligand compound, the ligand compound is the naphthylamine phosphine ligand compound described above, the preparation method adopts the reaction of 4-bromo-1-naphthylamine, butyllithium and dichloro(diethylamino) phosphine, and the preparation method comprises the following steps:

[0012] S1: 4-bromo-1-naphthylamine is mixed with a solvent M;

[0013] S2: butyllithium solution is added, then dichloro(diethylamino) phosphine is added, and the reaction is warmed;

[0014] S3: the reaction is quenched, extraction and separation are carried out, and the crude product is obtained;

[0015] Optionally, S4: the pure product is obtained by recrystallization.

[0016] In an embodiment of the present application, the solvent M in S1 is a polar solvent, preferably one or more of acetone, dichloromethane, tetrahydrofuran, N,N-dimethylformamide and N,N-dimethylacetamide, more preferably tetrahydrofuran and / or N,N-dimethylformamide; preferably, the mass ratio of 4-bromo-1-naphthylamine to the solvent M is 1:(2-20), preferably 1:(5-10). The solvent in this step of the present application is a commonly used solvent for this type of step.

[0017] In an embodiment of the present application, in S2, butyllithium is added dropwise in the 4-bromo-1-naphthylamine solution, the dropwise temperature is controlled to be-100℃ to-60℃, and the dropwise temperature is preferably-78℃; preferably, the molar ratio of 4-bromo-1-naphthylamine to butyllithium is 1:(0.6-1.8), preferably 1:(1-1.2).

[0018] In an embodiment of the present application, in S2, the molar ratio of 4-bromo-1-naphthylamine to dichloro(diethylamino) phosphine is 1:(0.4-1.2), preferably 1:(0.5-1).

[0019] In an embodiment of the present application, the reaction temperature in S2 is 30-90°C, preferably 40-55°C; and the reaction time is 5-15h, preferably 8-12h.

[0020] In an embodiment of the present application, the reaction condition in S2 is anhydrous and anaerobic condition.

[0021] In an embodiment of the present application, water is added in S3 to quench the reaction.

[0022] In an embodiment of the present application, the extraction solvent in S3 is a water-insoluble organic solvent, preferably one or more of dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, butyl acetate, petroleum ether, n-hexane, more preferably dichloromethane and / or ethyl acetate. The solvent in this step of the present application is a commonly used solvent for this kind of step.

[0023] In an embodiment of the present application, the recrystallization solvent in S4 is a water-insoluble organic solvent, preferably one or more of dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, butyl acetate, petroleum ether, n-hexane, more preferably ethyl acetate and / or petroleum ether. The solvent in this step of the present application is a commonly used solvent for this kind of step.

[0024] Another object of the present application is to provide a modified TS-1 powder catalyst.

[0025] A modified TS-1 powder catalyst, which uses the naphthylamine-based phosphine ligand compound described above as a ligand, or uses the naphthylamine-based phosphine ligand compound prepared by the preparation method described above as a ligand, and the raw material of the catalyst comprises a TS-1 powder catalyst and a naphthylamine-based phosphine ligand compound.

[0026] In the present application, the TS-1 powder catalyst is a commercially available TS-1 catalyst, which can be obtained by a conventional synthesis method, i.e. using tetraethyl silicate as a silicon source, tetrabutyl titanate as a titanium source, and tetrapropyl ammonium hydroxide (TPAOH) as a template agent, and hydrothermally crystallizing a reaction mixture in an autoclave, wherein the molar composition of the reaction mixture is SiO2:(0.01-0.10)TiO2:0.36TPAOH:35H2O. In the modified TS-1 powder catalyst, the polar group -NH2 in the naphthylamine-based phosphine ligand compound can form a hydrogen bond with the Si-O and Ti-O bonds in the TS-1 powder for regulating the acid-base sites, and in addition, the P element in the naphthylamine-based phosphine ligand compound can also participate in the coordination effect of Ti or Si atoms, and the synergistic effect of the two can improve the selectivity of the product.

[0027] Another object of the present application is to provide a method for preparing a modified TS-1 powder catalyst.

[0028] A method for preparing a modified TS-1 powder catalyst, wherein the catalyst is the modified TS-1 powder catalyst as described above, or the modified TS-1 powder catalyst prepared by the method as described above, the method comprises the following steps: dissolving a naphthylamine phosphine ligand compound into a solvent N to prepare a solution, adding TS-1 powder catalyst into the solution, heating, stirring, crystallization in a crystallization kettle, washing, drying, and calcining to obtain the modified TS-1 powder catalyst.

[0029] In an embodiment of the present application, when the modified TS-1 powder catalyst is prepared, the solvent N is a polar solvent, preferably one or more of acetone, water, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide, and more preferably acetone or N,N-dimethylformamide; preferably, the mass concentration of the solution is 3%-10%. The solvent in this step is a commonly used solvent in this step.

[0030] In an embodiment of the present application, when the modified TS-1 powder catalyst is prepared, the mass ratio of the naphthylamine phosphine ligand compound solution to the TS-1 powder catalyst is 1:(0.05-0.1).

[0031] In an embodiment of the present application, when the modified TS-1 powder catalyst is prepared, the heating temperature is 50-80℃, and the stirring time is 3-5h.

[0032] In an embodiment of the present application, when the modified TS-1 powder catalyst is prepared, the crystallization temperature is 180-220℃, and the crystallization time is 15-25h.

[0033] In an embodiment of the present application, when the modified TS-1 powder catalyst is prepared, the calcination temperature is 350-550℃, and the calcination time is 8-24h.

[0034] A further object of the present application is to provide a use of the modified TS-1 powder catalyst.

[0035] A use of the modified TS-1 powder catalyst, wherein the catalyst is the modified TS-1 powder catalyst as described above, or the modified TS-1 powder catalyst prepared by the method as described above, the catalyst is used for catalyzing a hydroxylation reaction of anisole.

[0036] A final object of the present application is to provide a synthesis method for catalyzing a hydroxylation reaction of anisole.

[0037] The synthesis method for catalyzing the hydroxylation reaction of anisole, which uses the modified TS-1 raw powder catalyst or the modified TS-1 raw powder catalyst prepared by the method, catalyzes the hydroxylation reaction of anisole and hydrogen peroxide in a solvent P to obtain a reaction solution containing guaiacol and p-hydroxyanisole.

[0038] In an embodiment of the present application, the mass ratio of anisole, hydrogen peroxide and solvent P in the synthesis method is (2-8) : 1 : (3-10).

[0039] In an embodiment of the present application, the mass concentration of hydrogen peroxide in the synthesis method is 30-60%.

[0040] In an embodiment of the present application, the solvent P in the synthesis method is a polar solvent, preferably one or more of methanol, ethanol, acetone and water. The solvent in this step is a commonly used solvent for this type of step.

[0041] In an embodiment of the present application, the reaction temperature in the synthesis method is 30-75°C, preferably 50-60°C.

[0042] In an embodiment of the present application, the reaction time in the synthesis method is 15-20h.

[0043] Compared with the prior art, the present application has the following beneficial effects:

[0044] (1) The present application provides a naphthylamine phosphine ligand compound modified TS-1 raw powder catalyst, which is applied in the hydroxylation reaction of anisole, significantly improves the activity of the catalyst, and the addition of basic groups makes the distribution of acid sites in the catalyst more uniform, thereby improving the selectivity of the product. Under the preferred reaction conditions, the conversion rate of hydrogen peroxide is as high as 93.5%, and the total selectivity of the two products is 95.4%.

[0045] (2) In the batch process of the reaction kettle, the modified TS-1 raw powder catalyst can be used for a large number of times, and still has strong activity after being used for more than 15 times. The conversion rate of hydrogen peroxide obtained by using the used catalyst is still more than 85%. The catalyst has a long service life and can be calcined and regenerated, and has an industrial application prospect. DETAILED DESCRIPTION

[0046] In order to better understand the present application, the content of the present application will be further described below in conjunction with examples, but the content of the present application is not limited to the following examples.

[0047] The conversion of anisole and the selectivity of phenol and ether in the following examples can be calculated according to the composition of the reaction solution. The analysis method uses liquid chromatography, and the instrument is an Agilent liquid chromatograph. Compound elemental analysis uses an ICP-OES inductively coupled plasma emission spectrometer and an XRF spectrometer, and compound structure uses a 400 MHz nuclear magnetic resonance spectrometer.

[0048] The source of the part of the raw material used:

[0049] TS-1 raw powder catalyst: Dalian Evolution Technology Co., Ltd.

[0050] Anisole, 4-bromo-1-naphthylamine, dichloro(diethylamino)phosphine: Shanghai Maikelin Biochemical Technology Co., Ltd.

[0051] Methanol, ethyl acetate, petroleum ether, N,N-dimethylformamide, acetonitrile: Beijing Inokai Technology Co., Ltd.

[0052] Example 1

[0053] In an anhydrous and anaerobic three-necked flask, 44.4 g of 4-bromo-1-naphthylamine and 222 g of N,N-dimethylformamide were added, and stirring was started under the condition of-60°C. Then 0.16 mol of butyllithium solution (2.2 M) was added dropwise to the system, and after the addition was completed, 17.4 g of dichloro(diethylamino)phosphine was added. After adding, slowly warm up, control the reaction temperature to be 35°C, and the reaction time is 8h. After the reaction is completed, 500 g of water is added to quench the reaction, and then 300 ml of ethyl acetate is added to extract the mixed solution, and the organic phase is obtained by liquid separation. Rotary evaporation is carried out at 50°C and a vacuum degree of 40 kPa to obtain the crude product. Then add a mixture of ethyl acetate: petroleum ether = 2:1 (volume ratio) to the crude product, the amount of which is 1 / 3 of the mass of the crude product, and recrystallize at 0°C to obtain the pure naphthylamine phosphine ligand compound. Elemental analysis is as follows: C 74.42%, H 6.72%, N 10.85%, P 8.01%. The compound nuclear magnetic hydrogen spectrum is as follows:1H NMR (400 MHz, DMSO-d6) δ 8.01-7.94 (m, 2H), 7.86 (dt, J = 7.0, 1.0 Hz, 2H), 7.57-7.44 (m, 4H), 7.25 (d, J = 0.6 Hz, 1H), 7.23 (s, 1H), 7.12-7.05 (m, 2H), 5.63 (d, J = 7.0 Hz, 2H), 5.57 (d, J = 7.0 Hz, 2H), 3.03 (d, J = 8.2 Hz, 3H), 3.00 (s, 1H), 0.92 (t, J = 8.2 Hz, 6H).

[0054] The naphthylamine phosphine ligand compound obtained above is dissolved in acetone to form a 3% mass concentration solution, 0.1 times the mass of TS-1 original powder catalyst is added, and the mixture is heated and stirred until uniform, with the heating temperature controlled at 50°C and the stirring time controlled at 3h; then the mixture is transferred into a crystallization kettle, and crystallization is carried out at 180°C for 15h; the crystalline product obtained is washed with acetone, dried at 100°C, and finally calcined at 350°C for 8h to obtain the modified TS-1 original powder catalyst.

[0055] 150g of anisole, 225g of methanol and 3g of the modified TS-1 original powder catalyst are added into a reaction kettle, and the mixture is heated and stirred until the reaction temperature is reached, and then 50g of hydrogen peroxide (30% concentration) is added through a peristaltic pump. The reaction temperature is 45°C, the stirring speed is 300r / min, the hydrogen peroxide addition time is 0.5h, and the reaction time is 15h. Under the above conditions, the hydrogen peroxide conversion rate is 88.3% and the total selectivity of the two products is 90.2% as determined by sampling analysis.

[0056] Example 2

[0057] In an anhydrous and anaerobic three-necked flask, 44.4g of 4-bromo-1-naphthylamine and 355.2g of tetrahydrofuran are added, and stirring is started under the condition of -78°C, and then 0.22mol of butyllithium solution (2.2M) is added dropwise into the system, and after the dropwise addition is completed, 27.8g of dichloro(diethylamino)phosphine is added, and then the reaction temperature is slowly increased, with the control of the reaction temperature at 50°C and the reaction time at 10h. After the reaction is completed, 500g of water is added to quench the reaction, and then 400ml of ethyl acetate is added to extract the mixture, and the organic phase is obtained by liquid separation, and the crude product is obtained by rotary evaporation under the condition of 50°C and a vacuum degree of 40kPa. Then, a mixture of ethyl acetate: petroleum ether = 2:1 (volume ratio) is added to the crude product in an amount of 1 / 3 of the mass of the crude product, and the pure naphthylamine phosphine ligand compound is obtained by recrystallization at 0°C.

[0058] The naphthylamine phosphine ligand compound obtained above is dissolved in N,N-dimethylformamide to form a 5% mass concentration solution, 0.07 times the mass of TS-1 original powder catalyst is added, and the mixture is heated and stirred until uniform, with the heating temperature controlled at 65°C and the stirring time controlled at 4h; then the mixture is transferred into a crystallization kettle, and crystallization is carried out at 200°C for 20h; the crystalline product obtained is washed with N,N-dimethylformamide, dried at 100°C, and finally calcined at 450°C for 12h to obtain the modified TS-1 original powder catalyst.

[0059] Into a reactor, 200 g of anisole, 200 g of acetone and 4 g of the modified TS-1 raw catalyst were added, and the mixture was stirred and heated to the reaction temperature, and then 50 g of hydrogen peroxide (40% concentration) was added by a peristaltic pump. The reaction temperature was 55°C, the stirring speed was 400 r / min, the hydrogen peroxide addition time was 0.75 h, and the reaction time was 18 h. Under the above conditions, the hydrogen peroxide conversion rate was 93.5%, and the total selectivity of the two products was 95.4% (determined by sampling analysis).

[0060] Example 3

[0061] Into a three-necked flask, 44.4 g of 4-bromo-1-naphthylamine and 532.8 g of dichloromethane were added, and stirring was started at -85°C, and then 0.3 mol of butyl lithium solution (2.2 M) was added dropwise, and after the addition was completed, 38.3 g of dichloro(diethylamino)phosphine was added, and the reaction temperature was slowly increased to 65°C, and the reaction time was 12 h. After the reaction was completed, 500 g of water was added to quench the reaction, and then 500 ml of ethyl acetate was added to extract the mixture, and the organic phase was separated, and the crude product was obtained by rotary evaporation at 50°C and a vacuum degree of 40 kPa. Then, a mixture of ethyl acetate and petroleum ether (2:1 by volume) was added to the crude product in an amount of 1 / 3 of the mass of the crude product, and the pure naphthylamine phosphine ligand compound was obtained by recrystallization at 0°C.

[0062] The naphthylamine phosphine ligand compound obtained above was dissolved in N,N-dimethylformamide to prepare a dilute solution with a mass concentration of 6%, and then TS-1 raw catalyst was added in an amount of 0.05 times the mass of the compound solution, and the mixture was heated and stirred uniformly, and the heating temperature was controlled at 75°C, and the stirring time was 5 h; then the mixture was transferred into a crystallization kettle, and crystallization was carried out at 220°C for 25 h; the obtained crystalline product was washed with N,N-dimethylformamide, dried at 100°C, and finally calcined at 550°C for 16 h to obtain the modified TS-1 raw catalyst.

[0063] Into a reactor, 400 g of anisole, 300 g of acetone and 5 g of the modified TS-1 raw catalyst were added, and the mixture was stirred and heated to the reaction temperature, and then 50 g of hydrogen peroxide (50% concentration) was added by a peristaltic pump. The reaction temperature was 65°C, the stirring speed was 500 r / min, the hydrogen peroxide addition time was 1 h, and the reaction time was 20 h. Under the above conditions, the hydrogen peroxide conversion rate was 91.8%, and the total selectivity of the two products was 92.3% (determined by sampling analysis).

[0064] Example 4

[0065] The catalyst is the catalyst obtained after 15 times of reuse under the conditions of Example 2, and the initial catalyst preparation method, reaction conditions and raw material ratio are the same as those of Example 2. The reaction is carried out under the above conditions, and sampling analysis shows that the conversion rate of hydrogen peroxide is 85.7%, and the total selectivity of the two products is 90.5%.

[0066] Comparative Example 1

[0067] The commercially available TS-1 raw catalyst is used without modification, and is directly used as the catalyst. The other reaction conditions and raw material ratio are the same as those of Example 2. The reaction is carried out under the above conditions, and sampling analysis shows that the conversion rate of hydrogen peroxide is 65.3%, and the total selectivity of the two products is 77.2%.

[0068] Although the content of the present application has been described in detail through the above preferred examples, it should be recognized that the above description should not be considered as a limitation of the present application. Those skilled in the art can understand that some modifications or adjustments can be made to the present application under the teaching of the present specification. These modifications or adjustments should also be within the scope defined by the claims of the present application.

Claims

1. A naphthylaminophosphine ligand compound, characterized in that, The structure of the compound is as follows:

2. A method for preparing a naphthylaminophosphine ligand compound, wherein the ligand compound is the naphthylaminophosphine ligand compound of claim 1, characterized in that, The preparation method involves reacting 4-bromo-1-naphthylamine, butyllithium, and dichloro(diethylamino)phosphine, and includes the following steps: S1: 4-Bromo-1-naphthylamine is mixed with solvent M; S2: Add butyllithium solution, then add dichloro(diethylamino)phosphine, and heat to react; S3: Quenching reaction, extraction and separation to obtain crude product; Optionally, S4: recrystallize to obtain the pure product.

3. The preparation method according to claim 2, characterized in that, The solvent M in S1 is a polar solvent, preferably one or more of acetone, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide, more preferably tetrahydrofuran and / or N,N-dimethylformamide; Preferably, the mass ratio of 4-bromo-1-naphthylamine to solvent M is 1:(2-20), more preferably 1:(5-10).

4. The preparation method according to claim 2, characterized in that, In S2, butyllithium is added dropwise to a 4-bromo-1-naphthylamine solution, with the dropping temperature controlled at -100℃ to -60℃, preferably at -78℃. Preferably, the molar ratio of 4-bromo-1-naphthylamine to butyllithium is 1:(0.6-1.8), more preferably 1:(1-1.2); And / or, the molar ratio of 4-bromo-1-naphthylamine to dichloro(diethylamino)phosphine in S2 is 1:(0.4-1.2), preferably 1:(0.5-1); And / or, the reaction temperature in S2 is 30-90℃, preferably 40-55℃; the reaction time is 5-15h, preferably 8-12h; And / or, the reaction conditions in S2 are anhydrous and oxygen-free conditions.

5. The preparation method according to claim 2, characterized in that, Add water to S3 to quench the reaction; And / or, the extraction solvent in S3 is a water-insoluble organic solvent, preferably one or more of dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, butyl acetate, petroleum ether, and n-hexane, more preferably dichloromethane and / or ethyl acetate.

6. The preparation method according to claim 2, characterized in that, The recrystallization solvent in S4 is a water-insoluble organic solvent, preferably one or more of dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, butyl acetate, petroleum ether, and n-hexane, more preferably ethyl acetate and / or petroleum ether.

7. A modified TS-1 raw material catalyst, wherein the catalyst uses the naphthylaminophosphine ligand compound of claim 1 as a ligand, or uses the naphthylaminophosphine ligand compound prepared by any one of claims 2-6 as a ligand, characterized in that, The catalyst's raw materials include TS-1 raw catalyst powder and naphthylamine phosphine ligand compound.

8. A method for preparing a modified TS-1 raw catalyst, wherein the catalyst uses the naphthylaminophosphine ligand compound of claim 1 as a ligand, or uses the naphthylaminophosphine ligand compound prepared by any one of claims 2-6 as a ligand, or is the modified TS-1 raw catalyst of claim 7, characterized in that, The method involves dissolving a naphthylaminophosphine ligand compound in solvent N to prepare a solution, adding the TS-1 original powder catalyst to the solution, heating, stirring, crystallizing in a crystallization kettle, washing, drying, and calcining to obtain the modified TS-1 original powder catalyst.

9. The method according to claim 8, characterized in that, The solvent N is a polar solvent, preferably one or more of acetone, water, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide, more preferably acetone or N,N-dimethylformamide; Preferably, the solution mass concentration is 3%-10%; And / or, the mass ratio of the naphthylaminophosphine ligand compound solution to the TS-1 original catalyst powder is 1:(0.05-0.1); And / or, the heating temperature is 50-80℃, and the stirring time is 3-5 hours; And / or, the crystallization temperature is 180-220℃, and the crystallization time is 15-25h; And / or, the calcination temperature is 350-550℃, and the calcination time is 8-24h.

10. Use of a modified TS-1 raw material catalyst, wherein the catalyst is the modified TS-1 raw material catalyst according to claim 7, or the modified TS-1 raw material prepared by the method according to claim 8 or 9, characterized in that, The catalyst is used to catalyze the hydroxylation reaction of anisole.

11. A method for synthesizing a catalytic hydroxylation reaction of anisole, wherein the method uses the modified TS-1 raw powder catalyst as described in claim 7, or the modified TS-1 raw powder catalyst prepared by the method described in claim 8 or 9, characterized in that, The synthesis method uses a modified TS-1 raw powder catalyst to catalyze the hydroxylation reaction of anisole and hydrogen peroxide in solvent P, and the reaction yields a reaction solution containing guaiacol and p-hydroxyanisole.

12. The synthesis method according to claim 11, characterized in that, In the synthesis method described above, the mass ratio of anisole, hydrogen peroxide, and solvent P is (2-8):1:(3-10); And / or, the hydrogen peroxide mass concentration in the synthesis method is 30-60%; And / or, in the synthesis method, solvent P is a polar solvent, preferably one or more of methanol, ethanol, acetone, and water; And / or, the reaction temperature in the synthesis method is 30-75℃, preferably 50-60℃; And / or, the reaction time in the synthesis method is 15-20 h.

Images