Composite catalyst and preparation method of hydroxyphenetole

Abstract

The invention discloses a preparation method of hydroxyphenetole, p-hydroxyphenetole and o-hydroxyphenetole are obtained through high-selectivity co-production of phenetole and hydrogen peroxide under the action of a catalyst, and the catalyst is a composite catalyst composed of a TS-1 type titanium silicalite molecular sieve / NiHo-A type molecular sieve. The process is green and environment-friendly, few in three wastes, high in catalyst activity and high in product selectivity, and the obtained two products are high-added-value products and have a good industrial application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of chemical synthesis, and particularly relates to a preparation method of hydroxyphenyl ether. BACKGROUND

[0002] p-Hydroxyphenyl ether, also known as 4-ethoxyphenol, p-ethoxyphenol, p-dihydroxybenzene monoethyl ether, hydroquinone monoethyl ether, has a melting point of 64-67 DEG C, is a crystalline powder or block solid, can be used as an important liquid crystal intermediate and organic chemical raw material, and has a wide application in the fields of pesticides, medicines, materials and the like. o-Hydroxyphenyl ether, also known as 2-ethoxyphenol, o-ethoxyphenol, o-dihydroxybenzene monoethyl ether, 2-hydroxyphenyl ether, has a melting point of 20-25 DEG C, is a colorless to light yellow liquid, and has an aroma; is an important fine chemical product, can be used to synthesize valuable spices ethyl vanillin, sandalwood 803 and the like, and can be used to synthesize various downstream chemical products such as medicines, pesticides, dyes and the like.

[0003] At present, the methods for synthesizing p-hydroxyphenyl ether / o-hydroxyphenyl ether are similar, mainly through ethylation substitution reaction of p-dihydroxybenzene / o-dihydroxybenzene and ethylating reagent, wherein the ethylating reagent includes bromoethane, diethyl sulfate, diethyl carbonate and the like. Both bromoethane and diethyl sulfate are highly toxic chemicals, have high requirements for transportation and storage, are highly dangerous, have the defects of serious halogen corrosion to equipment, difficult treatment of three wastes and the like, and have a large difficulty in industrial production; the diethyl carbonate method has the defect of low atomic utilization rate.

[0004] Therefore, it is of great significance to develop a new process which is green, environmentally friendly, has high product selectivity and good catalyst stability for the preparation of p-hydroxyphenyl ether / o-hydroxyphenyl ether. SUMMARY

[0005] The application aims to provide a preparation method of hydroxyphenyl ether, which adopts phenetole and hydrogen peroxide to produce p-hydroxyphenyl ether and o-hydroxyphenyl ether under the action of a catalyst. The process is green and environmentally friendly, has less three wastes, high catalyst activity and high product selectivity, the two products obtained are high value-added products, and has a good industrial application prospect.

[0006] In order to achieve the above application purposes, the technical solutions adopted by the application are as follows:

[0007] In one aspect, the application provides a composite catalyst composed of TS-1 type titanium silicalite and NiHo-A type molecular sieve, and a preparation method of the composite catalyst composed of TS-1 type titanium silicalite and NiHo-A type molecular sieve, which comprises the following steps:

[0008] (1) dissolving a nickel source and a holmium source in pure water, stirring and dissolving to uniformly mix to obtain an aqueous solution;

[0009] (2) impregnating the A-type molecular sieve in the aqueous solution of step (1) and adjusting the pH to alkaline with ammonia water and stirring;

[0010] (3) freeze-drying the solution obtained in step (2) to obtain a molecular sieve;

[0011] (4) calcining the dried molecular sieve under an air atmosphere to obtain a modified NiHo-A-type molecular sieve;

[0012] (5) mixing the TS-1-type titanium-silicon molecular sieve and the NiHo-A-type molecular sieve obtained in step (4) in a proportion to obtain a composite catalyst composed of TS-1-type titanium-silicon molecular sieve / NiHo-A-type molecular sieve.

[0013] In an embodiment of the present application, the nickel source in step (1) is one or more of nickel nitrate, nickel nitrate hexahydrate, nickel sulfate, nickel chloride, and nickel acetate; and the holmium source is one or more of holmium nitrate pentahydrate, holmium sulfate hydrate, holmium chloride, holmium bromide, holmium iodide, holmium acetate, holmium nitrate, and holmium sulfate octahydrate. Preferably, the total mass of the nickel source and the holmium source is 0.05-0.2 times the mass of the A-type molecular sieve, such as 0.07, 0.1, 0.12, 0.14, 0.16, 0.18, and the molar ratio of Ni element to Ho element is Ni:Ho=1:(0.2-1), such as 1:0.3, 1:0.5, 1:0.7, and 1:0.9.

[0014] In an embodiment of the present application, the A-type molecular sieve in step (2) is selected from one or more of 3A molecular sieve, 4A molecular sieve, and 5A molecular sieve.

[0015] In an embodiment of the present application, the pH value adjusted in step (2) is 8-10, and the stirring is performed at room temperature for 6-10 hours.

[0016] In an embodiment of the present application, the freeze-drying pressure in step (3) is 100-500 PaA, the temperature is -30℃ to -10℃, and the time is 10-30 hours.

[0017] In an embodiment of the present application, the calcination temperature in step (4) is 400-600℃, and the calcination time is 12-24 hours.

[0018] In an embodiment of the present application, the mass ratio of the TS-1-type titanium-silicon molecular sieve to the NiHo-A-type molecular sieve mixed in step (5) is 1:(0.4-1), such as 1:0.5, 1:0.6, 1:0.7, 1:0.8, and 1:0.9.

[0019] Finally, the application provides a preparation method of hydroxyphenetole, comprising the following steps: under the action of a catalyst, phenetole and hydrogen peroxide are high-selectively coproduced to obtain p-hydroxyphenetole and o-hydroxyphenetole; wherein the catalyst is a composite catalyst composed of TS-1 type titanium silicalite and NiHo-A type molecular sieve.

[0020] In the embodiment of the application, in the process of coproduction of p-hydroxyphenetole and o-hydroxyphenetole from phenetole and hydrogen peroxide under the action of a catalyst, the reaction solvent is one or more of water, methanol, ethanol, isopropanol, acetonitrile, acetone, methyl ethyl ketone and methyl isobutyl ketone, and the reaction kettle is operated intermittently.

[0021] In the embodiment of the application, the molar ratio of phenetole to hydrogen peroxide is (1-10):1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, the mass ratio of the reaction solvent to phenetole is (0.5-3):1, and the mass ratio of the catalyst to phenetole is 0.5%-10%. In the embodiment, the mass concentration of hydrogen peroxide is 25%-60%, the reaction temperature is 25-80℃, the stirring speed is 200-1000r / min, the hydrogen peroxide addition time is 0.5-1h, the reaction time is 6-24h, and the reaction pressure is 0.1-2MPaG.

[0022] Compared with the prior art, the application has the following advantages:

[0023] (1) The composite catalyst composed of TS-1 titanium silicalite and NiHo-A type molecular sieve provided by the application firstly modifies the A type molecular sieve by using Ni and Ho elements, which can adjust the distribution of acidic and basic sites on the molecular sieve, reasonably control the adsorption rate, and serve as an active center for specific activation of the raw material phenetole to improve the product selectivity; then the activated phenetole and H2O2 undergo a hydroxylation reaction under the action of TS-1 titanium silicalite to generate o-hydroxyphenetole or p-hydroxyphenetole by substituting a hydroxyl group at the ortho position or para position of phenetole. The synergistic effect of NiHo-A type molecular sieve and TS-1 titanium silicalite makes the composite catalyst composed of TS-1 titanium silicalite and NiHo-A type molecular sieve have a good catalytic effect in the phenetole hydroxylation reaction and a high product selectivity.

[0024] (2) The application provides a preparation method of hydroxyphenetole, which high-selectively coproduces p-hydroxyphenetole and o-hydroxyphenetole from phenetole and hydrogen peroxide under the action of a catalyst. The composite catalyst composed of TS-1 titanium silicalite and NiHo-A type molecular sieve has high activity and high product selectivity, wherein the hydrogen peroxide conversion rate is greater than 99% and the total selectivity of the two products is up to 94.6%.

[0025] (3) The composite catalyst composed of TS-1 titanium silicalite molecular sieve / NiHo-A type molecular sieve has simple separation, good stability, many times of repeated use, and the catalyst can be regenerated by calcination, and has good industrial application prospect. DETAILED DESCRIPTION

[0026] In order to better understand the present application, the content of the present application is further described below in combination with examples, but the content of the present application is not limited to the following examples only.

[0027] In the following examples, the conversion rate of hydrogen peroxide and the selectivity of p-hydroxyphenyl ether and o-hydroxyphenyl ether can be calculated according to the composition of the reaction solution, and the analysis method adopts liquid chromatography and potentiometric titration, and the instruments are Agilent liquid chromatograph and metrohm automatic potentiometric titrator respectively.

[0028] The sources of the used part of raw materials are as follows:

[0029] Phenyl ether, nickel nitrate, nickel sulfate, nickel chloride, holmium nitrate pentahydrate, holmium sulfate hydrate, holmium chloride: Shanghai Maikelin Biochemical Technology Co., Ltd.;

[0030] 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, TS-1 type titanium silicalite molecular sieve: Tianjin Nanhua Catalyst Co., Ltd.;

[0031] Methanol, acetone, acetonitrile, hydrogen peroxide: Beijing Inokai Technology Co., Ltd.

[0032] Example 1

[0033] Preparation of the composite catalyst composed of TS-1 type titanium silicalite molecular sieve / NiHo-A type molecular sieve:

[0034] (1) 1.83g of nickel nitrate and 1.32g of holmium nitrate pentahydrate were dissolved in 300g of pure water, and the mixture was stirred and dissolved uniformly;

[0035] (2) 31.5g of 3A molecular sieve was immersed in the aqueous solution of step (1), and the pH was adjusted to 8 with ammonia water, and stirred at room temperature for 6h;

[0036] (3) The sample obtained in step (2) was freeze-dried at a pressure of 100PaA and a temperature of-30℃ for 10h;

[0037] (4) The dried molecular sieve was calcined in an air atmosphere to obtain modified NiHo-3A type molecular sieve, wherein the calcination temperature was 400℃, and the calcination time was 12h.

[0038] (5) TS-1 type titanium silicalite and NiHo-3A type molecular sieve obtained in step (4) are mixed in a mass ratio of 1:0.4 to obtain a composite catalyst composed of TS-1 type titanium silicalite / NiHo-3A type molecular sieve.

[0039] Reaction kettle batch operation conditions of phenetole and hydrogen peroxide:

[0040] First, 366 g of phenetole, 366 g of methanol, and 21.96 g of a composite catalyst composed of TS-1 type titanium silicalite / NiHo-3A type molecular sieve are added to the reaction kettle, and stirring and temperature rising are performed. When the system reaches the set reaction temperature and reaction pressure, timing is started, and 136 g of hydrogen peroxide (25% concentration) is slowly added by means of a laminar flow pump. The reaction temperature is 50°C, the stirring speed is 500 r / min, the hydrogen peroxide addition time is 0.5 h, the total reaction time is 10 h, and the reaction pressure is 0.2 MPaG.

[0041] Under the above conditions, sampling analysis shows that the hydrogen peroxide conversion rate is 99.3%, and the total selectivity of the two products is 89.5%.

[0042] Example 2

[0043] Preparation of a composite catalyst composed of TS-1 type titanium silicalite / NiHo-A type molecular sieve:

[0044] (1) 1.55 g of nickel sulfate and 3.82 g of holmium sulfate hydrate are dissolved in 300 g of pure water, and stirring and dissolution are performed to mix uniformly;

[0045] (2) 35.8 g of 4A molecular sieve is immersed in the aqueous solution obtained in step (1), ammonia water is used to adjust the pH to 9, and stirring is performed at room temperature for 8 h;

[0046] (3) The sample obtained in step (2) is freeze-dried at a pressure of 200 PaA and a temperature of -20°C for 20 h;

[0047] (4) The dried molecular sieve is calcined in an air atmosphere to obtain modified NiHo-4A type molecular sieve, wherein the calcination temperature is 500°C, and the calcination time is 18 h.

[0048] (5) TS-1 type titanium silicalite and NiHo-4A type molecular sieve obtained in step (4) are mixed in a mass ratio of 1:0.8 to obtain a composite catalyst composed of TS-1 type titanium silicalite / NiHo-4A type molecular sieve.

[0049] Reaction kettle batch operation conditions of phenetole and hydrogen peroxide:

[0050] First, 732 g of phenetole, 1464 g of acetone and 29.28 g of a composite catalyst composed of TS-1 titanium silicalite molecular sieve / NiHo-4A molecular sieve were added into a reactor, and stirred and heated. When the system reached the set reaction temperature and reaction pressure, timing was started, and 97 g of hydrogen peroxide (35% concentration) was slowly added by a laminar flow pump. The reaction temperature was 60°C, the stirring speed was 600 r / min, the hydrogen peroxide addition time was 0.8 h, the total reaction time was 12 h, and the reaction pressure was 0.5 MPaG.

[0051] Under the above conditions, sampling analysis showed that the hydrogen peroxide conversion rate was 99.8%, and the total selectivity of the two products was 94.6%.

[0052] Example 3

[0053] Preparation of a composite catalyst composed of TS-1 titanium silicalite molecular sieve / NiHo-4A molecular sieve:

[0054] (1) 1.3 g of nickel chloride and 2.44 g of holmium chloride were dissolved in 300 g of pure water, and stirred and dissolved to mix uniformly;

[0055] (2) 18.7 g of 5A molecular sieve was immersed in the aqueous solution of step (1), and the pH was adjusted to 10 with ammonia water, and stirred at room temperature for 10 h;

[0056] (3) The sample obtained in step (2) was freeze-dried at a pressure of 400 PaA and a temperature of -10°C for 30 h;

[0057] (4) The dried molecular sieve was calcined in an air atmosphere to obtain modified NiHo-5A molecular sieve, wherein the calcination temperature was 600°C, and the calcination time was 24 h.

[0058] (5) TS-1 titanium silicalite molecular sieve and NiHo-5A molecular sieve obtained in step (4) were mixed in a mass ratio of 1:1 to obtain a composite catalyst composed of TS-1 titanium silicalite molecular sieve / NiHo-5A molecular sieve.

[0059] Batch operation conditions of the reaction kettle of phenetole and hydrogen peroxide:

[0060] First, 1098 g of phenetole, 2745 g of acetonitrile and 32.94 g of a composite catalyst composed of TS-1 titanium silicalite molecular sieve / NiHo-5A molecular sieve were added into a reactor, and stirred and heated. When the system reached the set reaction temperature and reaction pressure, timing was started, and 68 g of hydrogen peroxide (50% concentration) was slowly added by a laminar flow pump. The reaction temperature was 70°C, the stirring speed was 800 r / min, the hydrogen peroxide addition time was 1 h, the total reaction time was 16 h, and the reaction pressure was 1 MPaG.

[0061] The reaction was carried out under the above conditions, and sampling analysis showed that the conversion rate of hydrogen peroxide was 99.5%, and the total selectivity of the two products was 91.8%.

[0062] Example 4

[0063] The catalyst was the catalyst obtained after 10 times of reuse under the conditions of Example 2, and the initial catalyst preparation method, reaction conditions and raw material ratio were the same as those of Example 2. The reaction was carried out under the above conditions, and sampling analysis showed that the conversion rate of hydrogen peroxide was 99.1%, and the total selectivity of the two products was 90.3%.

[0064] Comparative Example 1

[0065] The catalyst was prepared in the same way as Example 2, and the main difference was that the catalyst was only TS-1 type titanium silicate molecular sieve, without adding NiHo-4A type molecular sieve, and other preparation conditions, reaction conditions and raw material ratio were the same as those of Example 2. The reaction was carried out under the above conditions, and sampling analysis showed that the conversion rate of hydrogen peroxide was 73.6%, and the total selectivity of the two products was 45.9%.

[0066] Comparative Example 2

[0067] The catalyst was prepared in the same way as Example 2, and the main difference was that the catalyst was only NiHo-4A type molecular sieve, without adding TS-1 type titanium silicate molecular sieve, and other preparation conditions, reaction conditions and raw material ratio were the same as those of Example 2. The reaction was carried out under the above conditions, and sampling analysis showed that the conversion rate of hydrogen peroxide was 31.9%, and the total selectivity of the two products was 86.3%.

[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 composite catalyst of TS-1 type titanium silicalite / NiHo-A type molecular sieve, wherein a preparation method of the composite catalyst of TS-1 type titanium silicalite / NiHo-A type molecular sieve comprises the following steps: (1) dissolving a nickel source and a holmium source in pure water, stirring and dissolving to mix uniformly to obtain an aqueous solution; (2) immersing A type molecular sieve in the aqueous solution of step (1), adjusting pH to alkaline with ammonia water, and stirring; (3) freeze-drying the solution obtained in step (2) to obtain the molecular sieve; (4) calcining the dried molecular sieve under an air atmosphere to obtain modified NiHo-A type molecular sieve; (5) mixing TS-1 type titanium silicalite and the NiHo-A type molecular sieve obtained in step (4) in a certain proportion to obtain the composite catalyst of TS-1 type titanium silicalite / NiHo-A type molecular sieve.

2. The composite catalyst according to claim 1, wherein In step (1), the nickel source is one or more of nickel nitrate, nickel nitrate hexahydrate, nickel sulfate, nickel chloride, and nickel acetate; the holmium source is one or more of holmium nitrate pentahydrate, holmium sulfate hydrate, holmium chloride, holmium bromide, holmium iodide, holmium acetate, holmium nitrate, and holmium sulfate octahydrate; preferably, the total mass of the nickel source and the holmium source is 0.05-0.2 times the mass of the A type molecular sieve; and / or, the molar ratio of Ni element to Ho element is Ni:Ho=1:(0.2-1).

3. The composite catalyst according to claim 1 or 2, wherein In step (2), the A type molecular sieve is selected from one or more of 3A molecular sieve, 4A molecular sieve, and 5A molecular sieve; and / or, the adjusted pH value in step (2) is 8-10, and the stirring is performed at room temperature for 6-10 hours.

4. The composite catalyst according to any one of claims 1 to 3, wherein In step (3), the freeze-drying pressure is 100-500 PaA, the temperature is -30℃ to -10℃, and the time is 10-30 hours; in step (4), the calcination temperature is 400-600℃, and the calcination time is 12-24 hours; and / or, in step (5), the mass ratio of TS-1 type titanium silicalite to NiHo-A type molecular sieve is 1:(0.4-1).

5. A method for preparing hydroxyphenyl ether, comprising the following steps: producing p-hydroxyphenyl ether and o-hydroxyphenyl ether by the reaction of phenyl ether and hydrogen peroxide in the presence of a catalyst; wherein, The catalyst is selected from the composite catalyst of TS-1 type titanium silicalite / NiHo-A type molecular sieve according to any one of claims 1-4.

6. The production method according to claim 5, wherein In the process for co-production of p-hydroxyphenetol and o-hydroxyphenetol by benzene ether and hydrogen peroxide under the action of a catalyst, the reaction solvent is one or more of water, methanol, ethanol, isopropyl alcohol, acetonitrile, acetone, methyl ethyl ketone, and methyl isobutyl ketone.

7. The production method according to claim 5 or 6, characterized by, The molar ratio of benzene ether to hydrogen peroxide is (1-10):1; and / or, the mass ratio of the reaction solvent to benzene ether is (0.5-3):1; and / or, the mass ratio of the catalyst to benzene ether is 0.5%-10%.

8. The production method according to any one of claims 5 to 7, wherein The mass concentration of hydrogen peroxide is 25%-60%; The reaction temperature is 25-80℃, the stirring speed is 200-1000 r / min, the hydrogen peroxide addition time is 0.5-1 hour, the reaction time is 6-24 hours, and the reaction pressure is 0.1-2 MPaG.