Process for the preparation of o-sec-butyloxytoluene

Abstract

The application provides a preparation method of o-sec-butyloxytoluene, comprising the following steps: performing catalytic reaction on o-cresol and sec-butanol under the action of a catalyst to obtain o-sec-butyloxytoluene; the catalyst comprises a carrier and at least two metal elements loaded on the carrier; the carrier comprises microporous molecular sieve and mesoporous molecular sieve. The o-sec-butyloxytoluene can be effectively prepared by using the preparation method, and the environment is friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemistry, and particularly relates to a preparation method of o-sec-butyloxyl toluene. BACKGROUND

[0002] O-cresol is an organic compound extracted from coal tar, chemical synthesis and petroleum products. At present, o-cresol is mainly used as a raw material for synthetic resins, but due to the relatively low demand of the downstream market, the production of o-cresol is in a state of oversupply, resulting in the problem of excess capacity, and the industrial economy is poor.

[0003] O-sec-butyloxyl toluene is an important organic compound, which contains a methoxy group and a sec-butyl group substituted benzene ring in its structure. This compound has multiple uses in the chemical industry, mainly as a solvent, intermediate and additive. It acts as a reaction medium or solvent in organic synthesis, promoting the progress of certain chemical reactions; in addition, it is also used as an intermediate for perfumes and dyes, and an additive in certain special chemicals to improve product performance. Due to its unique chemical properties and solubility, o-sec-butyloxyl toluene plays an important role in fine chemicals and special chemicals manufacturing. In the process of converting o-cresol to o-sec-butyloxyl toluene, an acidic catalyst is often used for catalytic reaction, but the catalytic effect of the acidic catalyst is limited and it will pollute the environment.

[0004] Therefore, there is an urgent need for an o-sec-butyloxyl toluene catalyst that can effectively catalyze the synthesis of o-cresol to o-sec-butyloxyl toluene and is environmentally friendly. SUMMARY

[0005] The present application provides a preparation method of o-sec-butyloxyl toluene, which can effectively convert o-cresol to o-sec-butyloxyl toluene by using the above preparation method, and the preparation method is environmentally friendly.

[0006] The present application provides a preparation method of o-sec-butyloxyl toluene, which comprises: catalyzing o-cresol and sec-butyl alcohol under the action of a catalyst to obtain o-sec-butyloxyl toluene.

[0007] The catalyst comprises a carrier and at least two metal elements loaded on the carrier.

[0008] The carrier comprises microporous molecular sieve and mesoporous molecular sieve.

[0009] The preparation method of o-sec-butyloxyl toluene as described above, wherein,

[0010] The catalyst comprises a first catalyst and a second catalyst.

[0011] The at least two metal elements comprise a first metal element and a second metal element.

[0012] the first catalyst comprises a microporous molecular sieve and a first metal element;

[0013] the second catalyst comprises a mesoporous molecular sieve and a second metal element.

[0014] The method for preparing o-sec-butyloxytoluene as described above, wherein the microporous molecular sieve comprises a ZSM-12 molecular sieve;

[0015] The mesoporous molecular sieve comprises a MCM-41 molecular sieve.

[0016] The method for preparing o-sec-butyloxytoluene as described above, wherein,

[0017] The first metal element comprises a manganese metal element;

[0018] The second metal element comprises a gallium metal element.

[0019] The method for preparing o-sec-butyloxytoluene as described above, wherein,

[0020] The catalyst is prepared according to a preparation method comprising the following processes:

[0021] 1) mixing a salt solution comprising a first metal element and the microporous molecular sieve to obtain a first mixed solution, adjusting the pH of the first mixed solution to 8.1-9.5 to obtain a first reaction liquid, and sequentially performing a first drying treatment and a first calcination treatment on the first reaction liquid to obtain the first catalyst;

[0022] 2) mixing a salt solution comprising a second metal element and the mesoporous molecular sieve to obtain a second mixed solution, adjusting the pH of the second mixed solution to 8.0-9.0 to obtain a second reaction liquid, and sequentially performing a second drying treatment and a second calcination treatment on the second reaction liquid to obtain the first catalyst;

[0023] 3) mixing the first catalyst and the second catalyst to obtain the catalyst.

[0024] The method for preparing o-sec-butyloxytoluene as described above, wherein the salt solution comprising a first metal element comprises a first metal salt, the first metal salt comprises at least one of manganese acetate dihydrate, manganese acetate tetrahydrate, manganese (II) sulfate monohydrate, or manganese (II) carbonate; and / or,

[0025] The salt solution comprising a second metal element comprises a second metal salt, the second metal salt comprises at least one of gallium (III) acetylacetonate, anhydrous digallium tetrachloride, gallium sulfate hydrate, and gallium (III) nitrate hydrate.

[0026] The method for preparing o-sec-butyloxyltoluene as described above, wherein the mass ratio of the solvent to the first metal element salt in the salt solution comprising the first metal element is (40-55): 1; and / or,

[0027] The mass ratio of the solvent to the second metal salt in the salt solution comprising the second metal element is (21-46): 1.

[0028] The method for preparing o-sec-butyloxyltoluene as described above, wherein,

[0029] The mass ratio of the microporous molecular sieve to the first metal salt in the first mixed solution is (23-55): 1; and / or,

[0030] The mass ratio of the mesoporous molecular sieve to the second metal salt in the second mixed solution is (32-55): 1; and / or,

[0031] The mass ratio of the first catalyst to the second catalyst in the catalyst is (0.7-3.0): 1.

[0032] The method for preparing o-sec-butyloxyltoluene as described above, wherein,

[0033] The treatment temperature of the first drying treatment is 105-135℃, and the treatment time is 7-15h; and / or,

[0034] The treatment temperature of the first calcination treatment is 500-750℃, and the treatment time is 10-30h; and / or,

[0035] The treatment temperature of the second drying treatment is 110-130℃, and the treatment time is 8-20h; and / or,

[0036] The treatment temperature of the second calcination treatment is 400-680℃, and the treatment time is 11-25h; and / or,

[0037] The reaction temperature of the catalytic reaction is 280-360℃, and the reaction pressure is 0.5-1.5bar; and / or,

[0038] The mass of the o-cresol is 5-30% of the total mass of the o-cresol and sec-butanol; and / or,

[0039] The liquid hourly space velocity of the o-cresol is 0.3-0.8h -1 .

[0040] The method for preparing o-sec-butyloxyltoluene as described above, wherein, in the method for preparing o-sec-butyloxyltoluene, the catalytic reaction is carried out in a fixed bed loaded with the catalyst.

[0041] This invention provides a method for preparing o-sec-butoxytoluene. The method uses a molecular sieve support and at least two metal elements supported on the molecular sieve support as catalysts to catalyze o-cresol and sec-butanol to obtain o-sec-butoxytoluene. This method has a high o-sec-butoxytoluene production efficiency, and the above-mentioned o-sec-butoxytoluene preparation method does not generate waste liquid, making it environmentally friendly. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0043] In the preparation of o-sec-butoxytoluene, acidic liquid catalysts are often used to catalyze o-cresol and sec-butanol. In this process, the hydroxyl group in o-cresol is replaced by sec-butoxy group to undergo etherification reaction to generate o-sec-butoxytoluene. However, this type of catalyst is prone to loss, and acidic catalysts will generate a large amount of acidic waste liquid, which is not conducive to environmental protection.

[0044] Therefore, there is an urgent need for a preparation method that can effectively generate o-sec-butoxytoluene without producing waste liquid, which is beneficial to environmental protection.

[0045] Based on this, the present invention provides a method for preparing o-sec-butoxytoluene, comprising: catalytically reacting o-cresol and sec-butanol under the action of a catalyst to obtain o-sec-butoxytoluene;

[0046] The catalyst includes a support and at least two metal elements supported on the support;

[0047] The carriers include microporous molecular sieves and mesoporous molecular sieves.

[0048] Specifically, in the catalyst, metal elements are supported on the surface and interior of the support. These metal elements can effectively catalyze the reaction of o-cresol and sec-butanol to yield o-sec-butoxytoluene. It should be noted that the metal elements exist on the support in the form of metal oxides. The unsaturated coordinating atoms, oxygen vacancies, or defect sites on the surface of the metal oxides can serve as active centers, effectively adsorbing reactant molecules and lowering the activation energy of the reaction, thereby improving the formation efficiency of o-sec-butoxytoluene.

[0049] In order to improve the loading efficiency of metal elements, the carrier includes a microporous molecular sieve and a mesoporous molecular sieve. The microporous molecular sieve has a uniform and narrow pore size distribution, can realize high dispersion and confinement effect of metal elements, effectively prevent metal aggregation, and provide abundant internal surface for metal element deposition. In the mesoporous molecular sieve, the larger pore size and adjustable pore wall thickness not only facilitate the rapid diffusion of reactants and products, but also can accommodate larger organic molecules or complex reaction systems, which is beneficial to the effective generation of o-sec-butoxytoluene. In addition, the framework structure of the above two molecular sieves can provide additional acid sites or basic sites, which synergistically act with the metal active center to further optimize the catalytic performance of the catalyst.

[0050] The present application uses a carrier including a microporous molecular sieve and a mesoporous molecular sieve, which is beneficial to improve the loading amount of the above-mentioned at least two metal elements, thereby facilitating the effective catalytic reaction of o-cresol and sec-butanol under the action of the catalyst and improving the selectivity of o-sec-butoxytoluene.

[0051] In detail, the above-mentioned catalyst includes a first catalyst and a second catalyst;

[0052] The above-mentioned at least two metal elements include a first metal element and a second metal element;

[0053] The first catalyst includes a microporous molecular sieve and a first metal element;

[0054] The second catalyst includes a mesoporous molecular sieve and a second metal element.

[0055] The present application uses a microporous molecular sieve to load a first metal element to form a first catalyst, and uses a mesoporous molecular sieve to load a second metal element to form a second catalyst, which can avoid mutual interference between metals compared to mixing and loading the first metal element and the second metal element in the above-mentioned molecular sieve, and is beneficial to improve the generation efficiency of o-sec-butoxytoluene.

[0056] In the above-mentioned first catalyst, the microporous molecular sieve includes a ZSM-12 molecular sieve, which includes a large number of acid sites, which is beneficial to promote proton transfer in the process of catalyzing o-cresol and sec-butanol to generate o-sec-butoxytoluene, thereby improving the generation efficiency of o-sec-butoxytoluene.

[0057] In another specific embodiment, the mesoporous molecular sieve in the second catalyst includes a MCM-41 molecular sieve, which has a larger pore size, is beneficial to load more second metal elements and provide a larger specific surface area, is beneficial to increase the contact area of raw materials o-cresol and sec-butanol with the catalyst, and further improve the selectivity of o-sec-butoxytoluene.

[0058] Further, the first metal element in the first catalyst of the present application includes a manganese metal element, which has a relatively variable oxidation state, can provide an acidic site for etherification reaction, accelerate proton transfer, and improve the efficiency of etherification reaction.

[0059] In another specific embodiment, the second metal element in the second catalyst includes a gallium metal element, and the use of the gallium metal element as the second metal element can effectively activate the oxygen atom of sec-butanol during the catalytic reaction of o-cresol and sec-butanol to o-sec-butyloxytoluene, promote its nucleophilic attack, and improve the yield of o-sec-butyloxytoluene.

[0060] In order to prepare o-sec-butyloxytoluene, the above-mentioned catalyst is prepared by a preparation method including the following steps for catalytic synthesis of o-sec-butyloxytoluene:

[0061] 1) mixing a salt solution including a first metal element and a microporous molecular sieve to obtain a first mixed solution, adjusting the pH of the first mixed solution to 8.1-9.5 to obtain a first reaction liquid, and sequentially performing a first drying treatment and a first calcination treatment on the first reaction liquid to obtain a first catalyst;

[0062] 2) mixing a salt solution including a second metal element and a mesoporous molecular sieve to obtain a second mixed solution, adjusting the pH of the second mixed solution to 8.0-9.0 to obtain a second reaction liquid, and sequentially performing a second drying treatment and a second calcination treatment on the second reaction liquid to obtain a first catalyst;

[0063] 3) mixing the first catalyst and the second catalyst to obtain a catalyst.

[0064] Specifically, in step 1), the salt solution including the first metal element is a metal source of the first metal element, which provides the first metal element for the catalyst. In the above-mentioned salt solution including the first metal element, the solute includes the salt of the first metal, and the solution includes pure water. The present application does not make special limitations on the mixing method of the salt solution including the first metal element and the microporous molecular sieve, and the salt solution including the first metal element can be added to the microporous molecular sieve, or the microporous molecular sieve can be added to the salt solution including the first metal element. It can be understood that in order to mix well, stirring, ultrasonic mixing and other mixing methods can be used to make the microporous molecular sieve fully dispersed in the above-mentioned salt solution including the first metal element to obtain a first mixed solution.

[0065] In order to make the first metal element in the salt solution including the first metal element be loaded on the surface and inside of the first molecular sieve in a large amount, the present application adjusts the pH of the above-mentioned first mixed solution to 8.1-9.5 by using a precipitator to obtain a first reaction liquid, at this time, the first metal element exists in the microporous molecular sieve in the form of metal hydroxide.

[0066] The first catalyst is obtained by sequentially performing a first drying treatment and a first calcination treatment on the first reaction solution. In the first drying treatment, a large amount of solvent in the first reaction solution is removed, leaving components mainly including the microporous molecular sieve loaded with the first metal hydroxide. The first calcination treatment is performed on the components to convert the first metal hydroxide loaded on the surface and inside of the microporous molecular sieve into a first metal oxide, so that the obtained catalyst includes the microporous molecular sieve and the first metal oxide (i.e., the first metal element) loaded on the surface and inside of the microporous molecular sieve.

[0067] Similarly, in step 2), the salt of the second metal element is a metal source of the second metal element, and provides the catalyst with the second metal element. In the above solution including the salt of the second metal element, the solute includes the salt of the second metal element, and the solution includes pure water. The present application does not make special limitations on the mixing method of the solution including the salt of the second metal element and the microporous molecular sieve. The solution including the salt of the second metal element can be added to the microporous molecular sieve, or the microporous molecular sieve can be added to the solution including the salt of the second metal element. It can be understood that, in order to mix well, the microporous molecular sieve can be fully dispersed in the above solution including the salt of the second metal element by using a mixing method such as stirring or ultrasonic mixing, so as to obtain a second mixed solution.

[0068] In order to enable the second metal element to be loaded in a large amount on the surface and inside of the second molecular sieve, the present application adjusts the pH of the above second mixed solution to 8.0-9.0 by using a precipitant to obtain a second reaction solution, so that the second metal element exists in the microporous molecular sieve in the form of a metal hydroxide.

[0069] The second catalyst is obtained by sequentially performing a second drying treatment and a second calcination treatment on the second reaction solution. In the second drying treatment, a large amount of solvent in the second reaction solution is removed, leaving components mainly including the microporous molecular sieve loaded with the second metal hydroxide. The second calcination treatment is performed on the components to convert the second metal hydroxide loaded on the surface and inside of the microporous molecular sieve into a second metal oxide, so that the obtained catalyst includes the microporous molecular sieve and the second metal oxide (i.e., the second metal element) loaded on the surface and inside of the microporous molecular sieve.

[0070] The present application does not make special limitation to the kind of the precipitator used in step 1) and step 2), as long as the pH of the solution can be adjusted so that the first metal element in the salt solution including the first metal element is converted into the first metal hydroxide, and the second metal element in the salt solution including the second metal element is converted into the second metal hydroxide, for example, the precipitator includes at least one of ammonia, sodium hydroxide, potassium hydroxide. The present application does not make special limitation to the mass percentage of the precipitator, as long as the above-mentioned precipitated metal element can be realized. Preferably, the present application uses 25-35wt% ammonia as the precipitator.

[0071] Next, the present application mixes the above-mentioned first catalyst and the above-mentioned second catalyst to obtain a catalyst.

[0072] As mentioned above, the first catalyst can effectively provide acidic sites to promote the occurrence of proton transfer, and the second catalyst can provide a higher specific surface area for etherification reaction to promote the occurrence of catalytic reaction, and the present application can make the catalyst have the advantages of the first catalyst and the second catalyst by mixing the first catalyst and the second catalyst, effectively catalyzing the synthesis of o-sec-butoxytoluene.

[0073] In the preparation method of the above-mentioned catalyst, the salt solution including the first metal element includes a first metal salt, and the present application limits the first metal element salt to include at least one of manganese acetate dihydrate, manganese acetate tetrahydrate, manganese (II) sulfate monohydrate or manganese (II) carbonate. The present application further limits the kind of the first metal salt to improve the catalytic performance of the catalyst.

[0074] In another specific embodiment, the salt solution including the second metal element includes a second metal salt, and the second metal element salt includes at least one of gallium (III) acetylacetone, anhydrous digallium chloride, gallium sulfate hydrate and gallium (III) nitrate hydrate. The present application further limits the kind of the second metal salt to improve the catalytic effect of the catalyst.

[0075] Based on the consideration of the catalytic performance of the catalyst, the present application controls the mass ratio of the solvent to the first metal salt in the salt solution including the first metal element to be (40-55):1 in the preparation process of the above-mentioned catalyst, for example, the mass ratio of the solvent to the first metal salt in the salt solution including the first metal element includes but is not limited to 40:1, 45:1, 50:1, 55:1 or a range formed by any two of them.

[0076] In another embodiment, the mass ratio of the solvent to the second metal salt in the second metal element-containing salt solution is (21-46): 1, for example, the mass ratio of the solvent to the second metal salt includes but is not limited to 21:1, 30:1, 39:1, 46:1, or a range formed by any two of them. The present application is beneficial to improving the catalytic effect of the catalyst by controlling the mass ratio of the solvent to the second metal salt in the second metal element-containing salt solution in the above range, thereby improving the selectivity of o-sec-butoxytoluene.

[0077] In addition, in the first mixed solution, the present application further limits the mass ratio of the microporous molecular sieve to the first metal salt to (23-55): 1, for example, the mass ratio of the microporous molecular sieve to the first metal salt in the first mixed solution includes but is not limited to 23:1, 39:1, 55:1, or a range formed by any two of them. The mass ratio of the microporous molecular sieve to the first metal salt in the above range is beneficial to improving the catalytic performance of the catalyst.

[0078] In another embodiment, the mass ratio of the mesoporous molecular sieve to the second metal salt in the second mixed solution is (32-55): 1, for example, the mass ratio of the mesoporous molecular sieve to the second metal salt in the second mixed solution includes but is not limited to 32:1, 37:1, 42:1, 47:1, 55:1, or a range formed by any two of them. The mass ratio of the mesoporous molecular sieve to the second metal salt in the second mixed solution in the above range is beneficial to preparing a catalyst with higher catalytic activity, promoting the generation of o-sec-butoxytoluene.

[0079] In order to balance the proton transfer ability of the catalyst and the specific surface area of the catalyst, the present application further limits the mass ratio of the first catalyst to the second catalyst in the catalyst to (0.7-3.0): 1, for example, the mass ratio of the first catalyst to the second catalyst includes but is not limited to 0.7:1, 1.5:1, 2.2:1, 3.0:1, or a range formed by any two of them. The catalyst with the above-mentioned ratio of the first catalyst and the second catalyst has good proton transfer ability and large specific surface area, so that the etherification reaction effectively occurs, which is beneficial to improving the yield of o-sec-butoxytoluene.

[0080] In one embodiment, in order to remove most of the solvent in the first reaction liquid, the present application further limits the treatment temperature of the first drying treatment to 105-135°C, and the treatment time to 7-15h, for example, the treatment temperature of the first drying treatment includes but is not limited to 105°C, 115°C, 125°C, 135°C, or a range formed by any two of them, and the treatment time of the first drying treatment includes but is not limited to 7h, 10h, 13h, 15h, or a range formed by any two of them.

[0081] In another embodiment, the first calcination treatment has a treatment temperature of 500-750°C and a treatment time of 10-30h, for example, the treatment temperature of the first drying treatment includes but is not limited to 500°C, 550°C, 600°C, 650°C, 650°C, 700°C, 750°C, or a range defined by any two of them, and the treatment time of the first drying treatment includes but is not limited to 10h, 15h, 20h, 25h, 30h, or a range defined by any two of them. By further limiting the treatment temperature and treatment time of the first calcination treatment, the present application is advantageous to oxidize the first metal hydroxide oxide in the first reaction solution to the first metal oxide.

[0082] In another embodiment, the second drying treatment has a treatment temperature of 110-130°C and a treatment time of 8-20h, for example, the treatment temperature of the second drying treatment includes but is not limited to 110°C, 120°C, 130°C, or a range defined by any two of them, and the treatment time of the second drying treatment includes but is not limited to 8h, 12h, 16h, 20h, or a range defined by any two of them. When the treatment temperature and treatment time of the second drying treatment are in the above range, it is advantageous to quickly remove a large amount of solvent in the second reaction solution without destroying the structure of the solute.

[0083] In another embodiment, the second calcination treatment has a treatment temperature of 400-680°C and a treatment time of 11-25h, for example, the treatment temperature of the second drying treatment includes but is not limited to 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 680°C, or a range defined by any two of them, and the treatment time of the second drying treatment includes but is not limited to 11h, 15h, 19h, 25h, or a range defined by any two of them. By further limiting the treatment temperature and treatment time of the second calcination treatment, the present application is advantageous to oxidize the second metal hydroxide oxide in the second reaction solution to the second metal oxide. It can be understood that in order to dehydrate the above-mentioned metal hydroxide to the first metal oxide, air needs to be introduced during the calcination process.

[0084] In the above method for preparing o-sec-butoxytoluene, in order to further improve the yield of o-sec-butoxytoluene, when catalyzing o-cresol and sec-butanol to generate o-sec-butoxytoluene, the present application controls the reaction temperature of the catalytic reaction to be 280-360°C, and the reaction pressure to be 0.5-1.5bar, for example, the reaction temperature of the catalytic reaction includes but is not limited to 280°C, 300°C, 320°C, 340°C, 360°C, or a range defined by any two of them, and the reaction pressure of the catalytic reaction includes but is not limited to 0.5bar, 1.0bar, 1.5bar, or a range defined by any two of them.

[0085] In another specific embodiment, the mass of o-cresol is 5-30% of the total mass of o-cresol and sec-butanol, and the present application controls the mass ratio of raw materials o-cresol and sec-butanol, which is beneficial to make the etherification reaction more complete, reduce the generation of by-products, and thus improve the yield and purity of o-sec-butoxytoluene.

[0086] In another specific embodiment, the liquid hourly mass space velocity of o-cresol is 0.3-0.8h -1 When the liquid hourly mass space velocity of o-cresol is controlled in the above range, the present application is beneficial to the raw materials to stay in the catalytic reaction for sufficient time to be fully converted.

[0087] It should be clear that the catalyst prepared by the present application can be repeatedly used in the preparation of o-sec-butoxytoluene, and therefore, the above-mentioned method for preparing o-sec-butoxytoluene is carried out in a fixed bed loaded with the above-mentioned catalyst. The inventors have found that the catalytic reaction in the above-mentioned preparation of o-sec-butoxytoluene can be stably operated in the above-mentioned fixed bed loaded with the catalyst for 3000h, which greatly improves the industrial economy, and no excess waste liquid is generated, which is beneficial to environmental protection.

[0088] The technical solutions of the present application will be further described below in combination with specific examples.

[0089] The reagents used in the examples and comparative examples of the present application are shown in Table 1:

[0090] Table 1

[0091]

[0092] Example 1

[0093] The preparation method of o-sec-butoxytoluene in this example is as follows:

[0094] (1) Dissolve 10g of manganese (II) sulfate monohydrate in pure water, the mass of pure water is 45 times the mass of manganese (II) sulfate monohydrate, and after stirring uniformly, a salt solution containing a first metal element is obtained;

[0095] (2) Add ZSM-12 molecular sieve to the above-mentioned salt solution containing the first metal element, the addition amount of ZSM-12 molecular sieve is 24 times the mass of manganese (II) sulfate monohydrate, and after stirring uniformly, a first mixed solution is obtained;

[0096] (3) Add ammonia water with a mass percentage of 28% to the above-mentioned first mixed solution, and adjust the pH to 8.5 to obtain a first reaction liquid;

[0097] (4) Perform first drying treatment on the above-mentioned first reaction liquid at 105℃ for 15h to obtain a first catalyst precursor;

[0098] (5) the first catalyst precursor is subjected to a first calcination treatment at 590°C for 15h under an air atmosphere to obtain a ZSM-12 molecular sieve loaded manganese type catalyst (i.e. the first catalyst);

[0099] (6) 10g of acetylacetone gallium is dissolved in pure water, the mass of the pure water is 31 times that of the acetylacetone gallium, and after stirring uniformly, a salt solution containing the second metal element is obtained;

[0100] (7) MCM-41 molecular sieve is added to the above salt solution containing the second metal element, the addition amount of the MCM-41 molecular sieve is 52 times the mass of the acetylacetone gallium, and after stirring uniformly, a second mixed solution is obtained;

[0101] (8) 28% ammonia water is added to the above second mixed solution, and the pH is adjusted to 8.9 to obtain a second reaction liquid;

[0102] (9) the above second reaction liquid is subjected to a second drying treatment at 125°C for 10h to obtain a second catalyst precursor;

[0103] (10) the above second catalyst precursor is subjected to a second calcination treatment at 490°C for 13h under an air atmosphere to obtain a MCM-41 molecular sieve loaded gallium type catalyst (i.e. the second catalyst);

[0104] (11) the above first catalyst and the second catalyst are mixed in a mass ratio of 2.8:1 to obtain a catalyst;

[0105] (12) o-cresol and sec-butyl alcohol are subjected to a catalytic reaction under the action of the above catalyst to obtain a reaction liquid containing o-sec-butoxytoluene, and the catalytic reaction conditions are as follows:

[0106] The reaction of o-cresol and sec-butyl alcohol adopts a continuous fixed bed process, the inner diameter of the reaction tube is 19mm, and the above catalyst is filled with a Ф3mm θ ring at both ends;

[0107] The addition amount of o-cresol is 26% of the total mass of o-cresol and sec-butyl alcohol;

[0108] The reaction temperature of o-cresol and sec-butyl alcohol is 290°C, and the reaction pressure is 0.7bar(G);

[0109] The liquid hourly space velocity of o-cresol is 0.4h -1 .

[0110] After the reaction is stable, samples are taken from the reaction liquid containing o-sec-butoxytoluene for gas chromatography analysis, and the results are shown in Table 2.

[0111] After the catalytic reaction was carried out for 3000 h, the reaction liquid obtained by the catalytic reaction at 3000 h, which included o-sec-butoxytoluene, was sampled and analyzed by gas chromatography. The results are shown in Table 2.

[0112] Example 2

[0113] The preparation method of o-sec-butoxytoluene in this example is as follows:

[0114] (1) 10 g of manganese acetate dihydrate was dissolved in pure water, the mass of the pure water was 41 times the mass of the manganese acetate dihydrate, and after stirring uniformly, a salt solution including a first metal element was obtained;

[0115] (2) ZSM-12 molecular sieve was added to the above salt solution including the first metal element, the addition amount of the ZSM-12 molecular sieve was 46 times the mass of the manganese acetate dihydrate, and after stirring uniformly, a first mixed solution was obtained;

[0116] (3) 28% ammonia water was added to the above first mixed solution, and the pH was adjusted to 8.8 to obtain a first reaction liquid;

[0117] (4) The above first reaction liquid was subjected to a first drying treatment at 110°C for 12 h to obtain a first catalyst precursor;

[0118] (5) The above first catalyst precursor was subjected to a first calcination treatment at 620°C under an air atmosphere for 26 h to obtain a manganese type catalyst loaded with ZSM-12 molecular sieve (i.e., a first catalyst);

[0119] (6) 10 g of anhydrous digallium tetrachloride was dissolved in pure water, the mass of the pure water was 43 times the mass of the anhydrous digallium tetrachloride, and after stirring uniformly, a salt solution including a second metal element was obtained;

[0120] (7) MCM-41 molecular sieve was added to the above salt solution including the second metal element, the addition amount of the MCM-41 molecular sieve was 47 times the mass of the anhydrous digallium tetrachloride, and after stirring uniformly, a second mixed solution was obtained;

[0121] (8) 28% ammonia water was added to the above second reaction liquid, and the pH was adjusted to 8.5 to obtain a second reaction liquid;

[0122] (9) The above second mixed solution was subjected to a second drying treatment at 130°C for 15 h to obtain a second catalyst precursor;

[0123] (10) The above second catalyst precursor was subjected to a second calcination treatment at 580°C under an air atmosphere for 22 h to obtain a gallium type catalyst loaded with MCM-41 molecular sieve (i.e., a second catalyst);

[0124] (11) mixing the first catalyst and the second catalyst in a mass ratio of 2.2:1 to obtain a catalyst;

[0125] (12) performing catalytic reaction on o-cresol and sec-butyl alcohol under the action of the catalyst to obtain a reaction liquid comprising o-sec-butyloxymethylbenzene, and the catalytic reaction conditions are as follows:

[0126] The reaction of o-cresol and sec-butyl alcohol adopts the continuous fixed-bed process in the embodiment 1;

[0127] The addition amount of o-cresol is 20% of the total mass of o-cresol and sec-butyl alcohol;

[0128] The reaction temperature of o-cresol and sec-butyl alcohol is 350℃, and the reaction pressure is 0.5 bar (G);

[0129] The liquid hourly space velocity of o-cresol is 0.6 h -1 .

[0130] After the reaction is stable, the reaction liquid comprising o-sec-butyloxymethylbenzene is sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0131] After the catalytic reaction is performed for 3000h, the reaction liquid comprising o-sec-butyloxymethylbenzene obtained by the catalytic reaction at 3000h is sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0132] Embodiment 3

[0133] The preparation method of o-sec-butyloxymethylbenzene in this embodiment is as follows:

[0134] (1) 10g of manganese (II) carbonate is dissolved in pure water, the mass of the pure water is 49 times that of the manganese (II) carbonate, and after stirring uniformly, a salt solution comprising a first metal element is obtained;

[0135] (2) ZSM-12 molecular sieve is added to the above-mentioned salt solution comprising the first metal element, the addition amount of the ZSM-12 molecular sieve is 52 times that of the manganese (II) carbonate, and after stirring uniformly, a first mixed solution is obtained;

[0136] (3) 28% ammonia water is added to the above-mentioned first mixed solution, and the pH is adjusted to 8.2 to obtain a first reaction liquid;

[0137] (4) The above-mentioned first reaction liquid is subjected to a first drying treatment at 125℃ for 10h to obtain a first catalyst precursor;

[0138] (5) The above-mentioned first catalyst precursor is subjected to a first calcination treatment at 670℃ in an air atmosphere for 19h to obtain a manganese type catalyst loaded with ZSM-12 molecular sieve (i.e. a first catalyst);

[0139] (6) 10 g of gallium sulfate hydrate was dissolved in pure water, the mass of the pure water was 25 times of the gallium sulfate hydrate, and a salt solution containing the second metal element was obtained after uniform stirring;

[0140] (7) MCM-41 molecular sieve was added to the above-mentioned salt solution containing the second metal element, the addition amount of the MCM-41 molecular sieve was 39 times of the mass of the gallium sulfate hydrate, and a second mixed solution was obtained after uniform stirring;

[0141] (8) 28% ammonia water was added to the above-mentioned second mixed solution, and the pH was adjusted to 8.7 to obtain a second reaction solution;

[0142] (9) The above-mentioned second reaction solution was subjected to a second drying treatment at 115°C for 19 h to obtain a second catalyst precursor;

[0143] (10) The above-mentioned second catalyst precursor was subjected to a second calcination treatment at 650°C for 18 h under an air atmosphere to obtain a MCM-41 molecular sieve loaded gallium type catalyst (i.e. a second catalyst);

[0144] (11) The above-mentioned first catalyst and second catalyst were mixed in a mass ratio of 1.5:1 to obtain a catalyst;

[0145] (12) O-cresol and sec-butyl alcohol were subjected to a catalytic reaction under the action of the above-mentioned catalyst to obtain a reaction solution containing o-sec-butyloxytoluene, and the catalytic reaction conditions were as follows:

[0146] The reaction of o-cresol and sec-butyl alcohol adopted the continuous fixed bed process in Example 1;

[0147] The addition amount of o-cresol was 13% of the total mass of o-cresol and sec-butyl alcohol;

[0148] The reaction temperature of o-cresol and sec-butyl alcohol was 310°C, and the reaction pressure was 1.4 bar (G);

[0149] The liquid hourly space velocity of o-cresol was 0.7 h -1 .

[0150] After the reaction was stable, a sample was taken from the reaction solution containing o-sec-butyloxytoluene and analyzed by gas chromatography, and the results are shown in Table 2.

[0151] After the above-mentioned catalytic reaction was carried out for 3000 h, a sample was taken from the reaction solution containing o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 h and analyzed by gas chromatography, and the results are shown in Table 2.

[0152] Example 4

[0153] The preparation method of o-sec-butyloxytoluene in this example was as follows:

[0154] (1) 10 g of manganese acetate tetrahydrate is dissolved in pure water, the mass of the pure water is 53 times the mass of the manganese acetate tetrahydrate, and after stirring uniformly, a salt solution containing a first metal element is obtained;

[0155] (2) ZSM-12 molecular sieve is added to the above salt solution containing the first metal element, the addition amount of the ZSM-12 molecular sieve is 38 times the mass of the manganese acetate tetrahydrate, and after stirring uniformly, a first mixed solution is obtained;

[0156] (3) 28% ammonia water is added to the above first mixed solution, and the pH is adjusted to 9.3 to obtain a first reaction liquid;

[0157] (4) The above first reaction liquid is subjected to a first drying treatment at 135°C for 8h to obtain a first catalyst precursor;

[0158] (5) The above first catalyst precursor is subjected to a first calcination treatment at 730°C under an air atmosphere for 29h to obtain a ZSM-12 molecular sieve loaded manganese type catalyst (i.e. a first catalyst);

[0159] (6) 10 g of gallium (III) nitrate hydrate is dissolved in pure water, the mass of the pure water is 38 times the mass of the gallium (III) nitrate hydrate, and after stirring uniformly, a salt solution containing a second metal element is obtained;

[0160] (7) MCM-41 molecular sieve is added to the above salt solution containing the second metal element, the addition amount of the MCM-41 molecular sieve is 33 times the mass of the gallium (III) nitrate hydrate, and after stirring uniformly, a second mixed solution is obtained;

[0161] (8) 28% ammonia water is added to the above second mixed solution, and the pH is adjusted to 8.2 to obtain a second reaction liquid;

[0162] (9) The above second reaction liquid is subjected to a second drying treatment at 120°C for 12h to obtain a second catalyst precursor;

[0163] (10) The above second catalyst precursor is subjected to a second calcination treatment at 430°C under an air atmosphere for 24h to obtain a MCM-41 molecular sieve loaded gallium type catalyst (i.e. a second catalyst);

[0164] (11) The above first catalyst and second catalyst are mixed in a mass ratio of 0.8:1 to obtain a catalyst;

[0165] (12) o-Cresol and sec-butyl alcohol are subjected to a catalytic reaction under the action of the above catalyst to obtain a reaction liquid containing o-sec-butyloxytoluene, and the catalytic reaction conditions are as follows:

[0166] The reaction of o-cresol and sec-butyl alcohol adopts the continuous fixed bed process in Example 1;

[0167] The amount of o-cresol added was 17% of the total mass of o-cresol and sec-butanol;

[0168] The reaction temperature of o-cresol and sec-butanol was 330°C, and the reaction pressure was 0.9 bar (G);

[0169] The liquid hourly space velocity of o-cresol was 0.5 h -1 .

[0170] After the reaction was stabilized, the reaction liquid including o-sec-butyloxytoluene was sampled and analyzed using gas chromatography, and the results are shown in Table 2.

[0171] After the above catalytic reaction was performed for 3000 h, the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 h was sampled and analyzed using gas chromatography, and the results are shown in Table 2.

[0172] Example 5

[0173] This example is basically the same as Example 1, except that in step (2), the amount of ZSM-12 zeolite added was 15 times the mass of manganese (II) sulfate monohydrate.

[0174] After the reaction was stabilized, the reaction liquid including o-sec-butyloxytoluene was sampled and analyzed using gas chromatography, and the results are shown in Table 2.

[0175] After the above catalytic reaction was performed for 3000 h, the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 h was sampled and analyzed using gas chromatography, and the results are shown in Table 2.

[0176] Example 6

[0177] This example is basically the same as Example 1, except that in step (5), the treatment temperature of the first calcination treatment was 400°C.

[0178] After the reaction was stabilized, the reaction liquid including o-sec-butyloxytoluene was sampled and analyzed using gas chromatography, and the results are shown in Table 2.

[0179] After the above catalytic reaction was performed for 3000 h, the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 h was sampled and analyzed using gas chromatography, and the results are shown in Table 2.

[0180] Example 7

[0181] This example is basically the same as Example 1, except that in step (7), the amount of MCM-41 zeolite added was 60 times the mass of gallium (III) acetylacetonate.

[0182] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0183] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0184] Example 8

[0185] This example is basically the same as Example 1, except that in step (10), the treatment temperature of the second calcination treatment is 730°C.

[0186] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0187] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0188] Example 9

[0189] This example is basically the same as Example 1, except that in step (11), the first catalyst and the second catalyst are mixed at a mass ratio of 4:1 to obtain the catalyst.

[0190] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0191] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0192] Example 10

[0193] This example is basically the same as Example 1, except that in step (12), the amount of o-cresol added is 33% of the total mass of o-cresol and sec-butanol.

[0194] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0195] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0196] Comparative Example 1

[0197] This comparative example is basically the same as Example 2, except that the catalyst only includes the first catalyst.

[0198] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0199] After the above catalytic reaction was performed for 3000 h, the reaction liquid including o-sec-butoxytoluene obtained by the catalytic reaction at 3000 h was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0200] Comparative Example 2

[0201] This comparative example is basically the same as Example 2, except that the catalyst includes only the second catalyst.

[0202] After the reaction was stabilized, the reaction liquid including o-sec-butoxytoluene was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0203] After the above catalytic reaction was performed for 3000 h, the reaction liquid including o-sec-butoxytoluene obtained by the catalytic reaction at 3000 h was sampled and analyzed by gas chromatography, and the results are shown in Table 2.

[0204] Test Example

[0205] Gas chromatography analysis: The reaction liquid including o-sec-butoxytoluene obtained in the examples and comparative examples was analyzed by gas chromatography;

[0206] The operation conditions were as follows: GC-2030 gas chromatograph manufactured by Shimadzu Corporation, DB-5MS UI (20 m x 0.25 mm x 0.25 μm) chromatographic column, acetonitrile as dilution solvent;

[0207] Vaporizing chamber temperature 300°C, column flow rate 1.00 mL / min, sample amount 0.2 μL;

[0208] Chromatographic column temperature program: first, 40°C to 100°C at a temperature increase rate of 2°C / min, and finally, 300°C at a temperature increase rate of 10°C / min;

[0209] o-Cresol conversion rate = (o-cresol content in raw material - o-cresol content in reaction liquid) / o-cresol content in raw material;

[0210] o-sec-Butoxytoluene selectivity = o-cresol consumption amount corresponding to o-sec-butoxytoluene / conversion amount of o-cresol before and after reaction.

[0211] Table 2

[0212]

[0213]

[0214] As shown in the table, compared with Comparative Example 1-2, the Examples 1-10 have higher o-cresol conversion rate and o-sec-butoxytoluene selectivity, specifically, the o-methylphenol conversion rate in the Examples is up to 54%, the selectivity of o-sec-butoxytoluene is up to 97%, and the o-cresol conversion rate and o-sec-butoxytoluene selectivity of the catalyst prepared in the Examples do not decrease significantly after running for 3000h. Therefore, the preparation method of o-sec-butoxytoluene provided by the present application can efficiently synthesize o-sec-butoxytoluene under the action of the catalyst, and the catalyst has a long service life, which is conducive to improving the industrial economy.

[0215] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing o-sec-butoxytoluene, characterized in that, include: o-Cresol and sec-Butanol were reacted under the action of a catalyst to obtain o-sec-butoxytoluene; The catalyst includes a support and at least two metal elements supported on the support; The carrier includes microporous molecular sieves and mesoporous molecular sieves; The catalyst is composed of a first catalyst and a second catalyst; the at least two metal elements include a first metal element and a second metal element; the mass ratio of the first catalyst to the second catalyst is (0.7~3.0):1; The first catalyst is composed of a microporous molecular sieve and a first metal element; the second catalyst is composed of a mesoporous molecular sieve and a second metal element. The microporous molecular sieve is ZSM-12 molecular sieve; the mesoporous molecular sieve is MCM-41 molecular sieve; The first metal element is manganese; the second metal element is gallium.

2. The method for preparing o-sec-butoxytoluene according to claim 1, characterized in that, The catalyst is prepared by a method comprising the following steps: 1) A first mixed solution is obtained by mixing a salt solution containing a first metal element and the microporous molecular sieve. The pH of the first mixed solution is adjusted to 8.1~9.5 to obtain a first reaction solution. The first reaction solution is subjected to a first drying treatment and a first calcination treatment in sequence to obtain a first catalyst. 2) A second mixed solution is obtained by mixing a salt solution containing a second metal element and the mesoporous molecular sieve. The pH of the second mixed solution is adjusted to 8.0~9.0 to obtain a second reaction solution. The second reaction solution is subjected to a second drying treatment and a second calcination treatment in sequence to obtain a second catalyst. 3) The catalyst is obtained by mixing the first catalyst and the second catalyst.

3. The method for preparing o-sec-butoxytoluene according to claim 2, characterized in that, The salt solution comprising a first metal element comprises a first metal salt, wherein the first metal salt comprises at least one selected from manganese acetate dihydrate, manganese acetate tetrahydrate, manganese sulfate monohydrate (II), or manganese carbonate (II); and / or, The salt solution containing the second metal element includes a second metal salt, which includes at least one of gallium acetylacetonate (III), anhydrous gallium chloride, gallium sulfate hydrate, and gallium nitrate (III) hydrate.

4. The method for preparing o-sec-butoxytoluene according to claim 3, characterized in that, In the salt solution containing the first metal element, the mass ratio of the solvent to the first metal salt is (40~55):1; and / or, In the salt solution containing the second metal element, the mass ratio of the solvent to the second metal salt is (21~46):

1.

5. The method for preparing o-sec-butoxytoluene according to claim 3 or 4, characterized in that, In the first mixed solution, the mass ratio of the microporous molecular sieve to the first metal salt is (23~55):1; and / or, In the second mixed solution, the mass ratio of the mesoporous molecular sieve to the second metal salt is (32~55):

1.

6. The method for preparing o-sec-butoxytoluene according to claim 2, characterized in that, The first drying process is carried out at a temperature of 105~135℃ for a duration of 7~15 hours; and / or, The first calcination treatment is carried out at a temperature of 500~750℃ for a time of 10~30h; and / or, The second drying process is carried out at a temperature of 110~130℃ for 8~20 hours. The second calcination treatment is carried out at a temperature of 400~680℃ for a time of 11~25h; and / or, The catalytic reaction is carried out at a temperature of 280~360℃ and a pressure of 0.5~1.5 bar. The mass of o-cresol is 5-30% of the total mass of o-cresol and sec-butanol; The liquid hourly space velocity (LHSV) of the o-cresol is 0.3–0.8 h⁻¹. -1 .

7. The method for preparing o-sec-butoxytoluene according to claim 1, characterized in that, In the method for preparing o-sec-butoxytoluene, the catalytic reaction is carried out in a fixed bed packed with the catalyst.

Images