Preparation method of o-sec-butoxytoluene

Abstract

The invention provides a preparation method of o-sec-butoxytoluene, which comprises the following steps: carrying out catalytic reaction on o-cresol and sec-butyl alcohol under the action of a catalyst to obtain o-sec-butoxytoluene, the catalyst comprises a carrier and at least two metal elements loaded on the carrier, the carrier comprises a microporous molecular sieve and a mesoporous molecular sieve. The o-sec-butoxytoluene can be effectively prepared by using the preparation method, and the preparation method is relatively environment-friendly.

Description

Technical Field

[0001] The invention relates to the field of chemistry, and in particular to a method for preparing o-sec-butoxytoluene. Background Art

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

[0003] o-Sec-Butyloxytoluene is an important organic compound, which contains a methoxy group and a sec-butyl substituted benzene ring in its structure. This compound has a variety of uses in the chemical industry, mainly as a solvent, intermediate and additive. It can promote certain chemical reactions as a reaction medium or solvent in organic synthesis; in addition, it is also used as an intermediate for fragrances and dyes, and as an additive in certain special chemicals to improve the performance of the product. Due to its unique chemical properties and solubility, o-Sec-Butyloxytoluene plays an important role in the manufacture of fine chemicals and specialty chemicals. In the process of converting o-cresol to o-Sec-Butyloxytoluene, acidic catalysts are often used for catalytic reactions, but the catalytic effect of acidic catalysts is limited and will cause environmental pollution.

[0004] Therefore, there is an urgent need for an o-sec-butyloxytoluene catalyst that can effectively catalyze o-cresol to synthesize o-sec-butyloxytoluene and is relatively environmentally friendly. Summary of the invention

[0005] The invention provides a method for preparing o-sec-butoxytoluene. By using the preparation method, o-cresol can be effectively converted into o-sec-butoxytoluene, and the preparation method is relatively friendly to the environment.

[0006] The present invention provides a method for preparing o-sec-butoxytoluene, which comprises: subjecting o-cresol and sec-butanol to a catalytic reaction under the action of a catalyst to obtain o-sec-butoxytoluene;

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

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

[0009] The method for preparing o-sec-butoxytoluene as described above, wherein:

[0010] The catalyst includes a first catalyst and a second catalyst;

[0011] The at least two metal elements include 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 includes a mesoporous molecular sieve and a second metal element.

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

[0015] The mesoporous molecular sieve includes MCM-41 molecular sieve.

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

[0017] The first metal element includes manganese metal element;

[0018] The second metal element includes gallium metal element.

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

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

[0021] 1) mixing a salt solution including 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 solution, and sequentially performing a first drying treatment and a first calcination treatment on the first reaction solution to obtain a first catalyst;

[0022] 2) mixing a salt solution including 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 solution, and sequentially performing a second drying treatment and a second calcination treatment on the second reaction solution to obtain a first catalyst;

[0023] 3) The first catalyst and the second catalyst are mixed to obtain the catalyst.

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

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

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

[0027] In the salt solution including the second metal element, the mass ratio of the solvent mass to the second metal salt is (21-46):1.

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

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

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

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

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

[0033] The treatment temperature of the first drying treatment is 105-135° C., and the treatment time is 7-15 hours; and / or,

[0034] The treatment temperature of the first calcination treatment is 500-750° C., the treatment time is 10-30 hours and / or,

[0035] The treatment temperature of the second drying treatment is 110-130° C., and the treatment time is 8-20 hours; and / or,

[0036] The treatment temperature of the second calcination treatment is 400-680° C. and the treatment time is 11-25 hours; and / or,

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

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

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

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

[0041] The invention provides a method for preparing o-sec-butoxytoluene. The method uses a molecular sieve carrier and at least two metal elements loaded on the molecular sieve carrier as catalysts to catalyze o-cresol and sec-butanol to obtain o-sec-butoxytoluene. The method has high o-sec-butoxytoluene generation efficiency, and the method does not generate waste liquid, so the method is more environmentally friendly. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] In the process of preparing o-sec-butoxytoluene, an acidic liquid catalyst is often used to catalyze o-cresol and sec-butanol. In this process, the hydroxyl group in o-cresol is replaced by the sec-butoxy group to undergo an etherification reaction to form o-sec-butoxytoluene. However, this type of catalyst is easy to lose, and the acidic catalyst will produce 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 achieve the effective production of o-sec-butyloxytoluene without generating waste liquid, which is beneficial to environmental protection.

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

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

[0047] The carrier includes microporous molecular sieve and mesoporous molecular sieve.

[0048] Specifically, in the catalyst, the metal element is loaded on the surface and inside of the carrier, and the metal element can effectively catalyze the catalytic reaction of o-cresol and sec-butyl alcohol to obtain o-sec-butyloxytoluene. It should be clear that the metal element exists on the carrier in the form of metal oxide, and the unsaturated coordinated atoms, oxygen vacancies or defect sites on the surface of the metal oxide can serve as active centers, effectively adsorb reactant molecules and reduce the reaction activation energy, thereby improving the production efficiency of o-sec-butyloxytoluene.

[0049] In order to improve the loading efficiency of metal elements, the above-mentioned carrier includes microporous molecular sieves and mesoporous molecular sieves. Among them, the microporous molecular sieve has a uniform and narrow pore size distribution, which can achieve a high degree of dispersion and confinement effect of metal elements, effectively prevent metal agglomeration, and provide abundant internal surfaces for metal element deposition. In mesoporous molecular sieves, the larger pore size and adjustable pore wall thickness are not only conducive to the rapid diffusion of reactants and products, but also can accommodate larger organic molecules or complex reaction systems, which is conducive to the effective generation of o-sec-butyloxytoluene. In addition, the skeleton structure of the above two molecular sieves can provide additional acidic sites or basic sites, which work synergistically with the metal active center to further optimize the catalytic performance of the catalyst.

[0050] The present invention uses a carrier including a microporous molecular sieve and a mesoporous molecular sieve, which is beneficial to increasing the loading amount of the at least two metal elements, thereby facilitating an effective catalytic reaction of o-cresol and sec-butyl alcohol under the action of a catalyst and improving the selectivity of o-sec-butyloxytoluene.

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

[0052] The 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 invention 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. Compared with mixing the first metal element and the second metal element and loading them in the above-mentioned molecular sieve, mutual interference between metals can be avoided, which is beneficial to improving the production efficiency of o-sec-butyloxytoluene.

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

[0057] In another specific embodiment, the mesoporous molecular sieve in the second catalyst includes MCM-41 molecular sieve. The MCM-41 molecular sieve has a larger pore size, which is conducive to loading more second metal elements and providing a larger specific surface area, which is conducive to increasing the contact area between the raw materials o-cresol and 2-butanol and the catalyst, thereby improving the selectivity of o-2-butoxytoluene.

[0058] In addition, the first metal element in the first catalyst of the present invention includes manganese metal element. Manganese metal element has a relatively variable oxidation state, which can provide acidic sites for the etherification reaction, accelerate proton transfer, and improve the efficiency of the etherification reaction.

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

[0060] In order to prepare o-sec-butoxytoluene, the present invention adopts a preparation method comprising the following process to prepare the above-mentioned catalyst for catalytic synthesis of o-sec-butoxytoluene:

[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 solution, and sequentially performing a first drying treatment and a first calcination treatment on the first reaction solution 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 solution, and sequentially performing a second drying treatment and a second calcination treatment on the second reaction solution to obtain a first catalyst;

[0063] 3) The first catalyst and the second catalyst are mixed to obtain a catalyst.

[0064] Specifically, in step 1), in the salt solution including the first metal element, the salt of the first metal element is the metal source of the first metal element, providing 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 invention does not specifically limit 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 and evenly mix, stirring, ultrasound 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 enable the first metal element in the salt solution including the first metal element to be loaded in large quantities on the surface and inside of the first molecular sieve, the present invention uses a precipitant to adjust the pH of the above-mentioned first mixed solution to 8.1-9.5 to obtain a first reaction solution. 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 liquid. In the first drying treatment, a large amount of solvent in the first reaction liquid is removed, leaving a component mainly composed of a first metal hydroxide supported by a microporous molecular sieve, and the above-mentioned component is treated by a first calcination treatment to convert the first hydroxide supported on the surface and inside of the microporous molecular sieve into a first metal oxide, and the obtained catalyst includes a microporous molecular sieve and a first metal oxide (i.e., a first metal element) supported on the surface and inside of the microporous molecular sieve.

[0067] Similarly, in step 2), the salt of the second metal element is the metal source of the second metal element, providing the second metal element for the catalyst. In the above-mentioned salt solution including the second metal element, the solute includes the salt of the second metal element, and the solution includes pure water. The present invention does not specifically limit the mixing method of the salt solution including the second metal element and the microporous molecular sieve. The salt solution including the second metal element can be added to the microporous molecular sieve, or the microporous molecular sieve can be added to the salt solution including the second metal element. It can be understood that in order to mix and evenly mix, stirring, ultrasound and other mixing methods can be used to make the microporous molecular sieve fully dispersed in the above-mentioned salt solution including the second metal element to obtain a second mixed solution.

[0068] In order to load a large amount of the second metal element on the surface and inside of the second molecular sieve, the present invention uses a precipitant to adjust the pH of the second mixed solution to 8.0-9.0 to obtain a second reaction solution. At this time, the second metal element exists in the microporous molecular sieve in the form of metal hydroxide.

[0069] The second catalyst is obtained by sequentially performing a second drying treatment and a second calcination treatment on the second reaction liquid. In the second drying treatment, a large amount of solvent in the second reaction liquid is removed, leaving a component mainly composed of a second metal hydroxide supported by a microporous molecular sieve, and the above-mentioned component is treated by a second calcination treatment to convert the second hydroxide supported on the surface and inside of the microporous molecular sieve into a second metal oxide, and the obtained catalyst includes a microporous molecular sieve and a second metal oxide (i.e., a second metal element) supported on the surface and inside of the microporous molecular sieve.

[0070] The present invention does not specifically limit the type of precipitant 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 precipitant includes at least one of ammonia water, sodium hydroxide, and potassium hydroxide. The present invention does not specifically limit the mass percentage of the precipitant, as long as the above-mentioned effect of precipitating the metal elements can be achieved. Preferably, the present invention uses ammonia water with a mass percentage of 25 to 35wt% as the precipitant.

[0071] Next, in the present invention, the first catalyst and the second catalyst are mixed to obtain a catalyst.

[0072] As mentioned above, the first catalyst can effectively provide acidic sites and promote the occurrence of proton transfer, and the second catalyst can provide a higher specific surface area for the etherification reaction and promote the occurrence of the catalytic reaction. The present invention can make the catalyst have the advantages of the first catalyst and the second catalyst at the same time by mixing the first catalyst with the second catalyst, and effectively catalyze the synthesis of o-sec-butyloxytoluene.

[0073] In the preparation method of the above catalyst, the salt solution including the first metal element includes the first metal salt, and the present invention limits the first metal element salt to include at least one of manganese acetate dihydrate, manganese acetate tetrahydrate, manganese sulfate (II) monohydrate or manganese carbonate (II). The present invention further limits the type of the first metal salt, which is conducive to improving 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) acetylacetonate, anhydrous digallium tetrachloride, gallium sulfate hydrate and gallium (III) nitrate hydrate. The present invention is beneficial to improving the catalytic effect of the catalyst by further limiting the type of the second metal salt.

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

[0076] In another specific embodiment, in the salt solution including the second metal element, the mass ratio of the solvent mass to the second metal salt is (21-46):1. For example, the mass ratio of the solvent mass to the second metal salt includes but is not limited to 21:1, 30:1, 39:1, 46:1 or a range consisting of any two thereof. The present invention is beneficial to improving the catalytic effect of the catalyst by controlling the mass ratio of the solvent mass to the second metal salt in the salt solution including the second metal element within the above range, thereby improving the selectivity of o-sec-butyloxytoluene.

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

[0078] In another specific embodiment, the mass ratio of the mesoporous molecular sieve in the second mixed solution to the mass ratio of the second metal salt is (32-55):1. For example, the mass ratio of the mesoporous molecular sieve in the second mixed solution to the mass ratio of the second metal salt includes but is not limited to 32:1, 37:1:, 42:1, 47:1, 55:1 or a range consisting of any two of them. When the mass ratio of the mesoporous molecular sieve in the second mixed solution to the second metal salt is within the above range, it is beneficial to prepare a catalyst with higher catalytic activity and promote the formation of o-sec-butyloxytoluene.

[0079] In order to balance the proton transfer ability and specific surface area of ​​the catalyst, the present invention 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 any two thereof. The catalyst having the above-mentioned first catalyst and second catalyst ratio has both good proton transfer ability and a large specific surface area to enable the etherification reaction to occur effectively, which is beneficial to improve the yield of o-sec-butyloxytoluene.

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

[0081] In another specific embodiment, the treatment temperature of the first calcination treatment is 500-750°C, and the treatment time is 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, and the treatment time of the first drying treatment includes but is not limited to 10h, 15h, 20h, 25h, 30h, or the range of any two thereof. The present invention is beneficial to oxidizing the first metal hydroxide in the first reaction solution to the first metal oxide by further limiting the treatment temperature and treatment time of the first calcination treatment.

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

[0083] In another specific embodiment, the treatment temperature of the second calcination treatment is 400-680°C, and the treatment time is 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 any two thereof, and the treatment time of the second drying treatment includes but is not limited to 11h, 15h, 19h, 25h or any two thereof. The present invention further limits the treatment temperature and treatment time of the second calcination treatment, which is conducive to oxidizing the second metal hydroxide 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-mentioned preparation method of 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 invention controls the reaction temperature of the catalytic reaction to be 280-360° C. and the reaction pressure to be 0.5-1.5 bar. 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 consisting of any two thereof, and the reaction pressure of the catalytic reaction includes but is not limited to 0.5 bar, 1.0 bar, 1.5 bar or a range consisting of any two thereof.

[0085] In another specific embodiment, the mass of o-cresol is 5-30% of the total mass of o-cresol and sec-butanol. The present invention controls the mass ratio of the raw materials o-cresol and sec-butanol, which is beneficial to making the etherification reaction more complete and reducing the generation of by-products, thereby improving the output rate and purity of o-sec-butoxytoluene.

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

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

[0088] The technical solution of the present invention is further described below in conjunction with specific embodiments.

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

[0090] Table 1

[0091]

[0092] Example 1

[0093] The preparation method of the present embodiment o-sec-butoxytoluene is as follows:

[0094] (1) dissolving 10 g of manganese (II) sulfate monohydrate in pure water, wherein the mass of the pure water is 45 times the mass of the manganese (II) sulfate monohydrate, and stirring to obtain a salt solution including the first metal element;

[0095] (2) adding ZSM-12 molecular sieve to the salt solution including the first metal element, wherein the amount of ZSM-12 molecular sieve added is 24 times the mass of manganese (II) sulfate monohydrate, and stirring to obtain a first mixed solution;

[0096] (3) adding 28% by weight ammonia water to the first mixed solution and adjusting the pH to 8.5 to obtain a first reaction solution;

[0097] (4) subjecting the first reaction liquid to a first drying treatment at 105° C. for 15 h to obtain a first catalyst precursor;

[0098] (5) subjecting the first catalyst precursor to a first calcination treatment at 590° C. for 15 h in an air atmosphere to obtain a ZSM-12 molecular sieve-supported manganese-based catalyst (i.e., the first catalyst);

[0099] (6) dissolving 10 g of gallium acetylacetonate in pure water, the mass of which is 31 times that of gallium acetylacetonate, and stirring the mixture to obtain a salt solution including the second metal element;

[0100] (7) adding MCM-41 molecular sieve to the salt solution including the second metal element, wherein the amount of MCM-41 molecular sieve added is 52 times the mass of gallium acetylacetonate, and stirring to obtain a second mixed solution;

[0101] (8) adding 28% by mass of aqueous ammonia to the second mixed solution and adjusting the pH to 8.9 to obtain a second reaction solution;

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

[0103] (10) subjecting the second catalyst precursor to a second calcination treatment at 490° C. for 13 h in an air atmosphere to obtain a gallium-based catalyst supported on an MCM-41 molecular sieve (i.e., a second catalyst);

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

[0105] (12) allowing o-cresol and sec-butyl alcohol to undergo a catalytic reaction under the action of the above catalyst to obtain a reaction solution comprising o-sec-butyloxytoluene, wherein 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 19 mm, and 3 mm θ rings are loaded at both ends of the above catalyst;

[0107] The amount of o-cresol added 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 0.7 bar(G);

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

[0110] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0111] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0112] Example 2

[0113] The preparation method of the present embodiment o-sec-butoxytoluene is as follows:

[0114] (1) dissolving 10 g of manganese acetate dihydrate in pure water, wherein the mass of the pure water is 41 times the mass of the manganese acetate dihydrate, and stirring to obtain a salt solution including the first metal element;

[0115] (2) adding ZSM-12 molecular sieve to the salt solution including the first metal element, wherein the amount of ZSM-12 molecular sieve added is 46 times the mass of manganese acetate dihydrate, and stirring to obtain a first mixed solution;

[0116] (3) adding 28% ammonia water to the first mixed solution and adjusting the pH to 8.8 to obtain a first reaction solution;

[0117] (4) subjecting the first reaction liquid to a first drying treatment at 110° C. for 12 h to obtain a first catalyst precursor;

[0118] (5) subjecting the first catalyst precursor to a first calcination treatment at 620° C. for 26 h in an air atmosphere to obtain a ZSM-12 molecular sieve-supported manganese-based catalyst (i.e., the first catalyst);

[0119] (6) dissolving 10 g of anhydrous gallium tetrachloride in pure water, wherein the mass of the pure water is 43 times that of the anhydrous gallium tetrachloride, and stirring the water to obtain a salt solution including the second metal element;

[0120] (7) adding MCM-41 molecular sieve to the salt solution including the second metal element, wherein the amount of MCM-41 molecular sieve added is 47 times the mass of anhydrous gallium tetrachloride, and stirring to obtain a second mixed solution;

[0121] (8) adding 28% by mass of ammonia water to the second reaction solution and adjusting the pH to 8.5 to obtain a second reaction solution;

[0122] (9) subjecting the second mixed solution to a second drying treatment at 130° C. for 15 h to obtain a second catalyst precursor;

[0123] (10) subjecting the second catalyst precursor to a second calcination treatment at 580° C. for 22 h in an air atmosphere to obtain a gallium-based catalyst supported on an 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) allowing o-cresol and sec-butyl alcohol to undergo a catalytic reaction under the action of the above catalyst to obtain a reaction solution comprising o-sec-butyloxytoluene, wherein the catalytic reaction conditions are as follows:

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

[0127] The amount of o-cresol added 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°C and the reaction pressure is 0.5 bar(G);

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

[0130] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0131] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0132] Example 3

[0133] The preparation method of the present embodiment o-sec-butoxytoluene is as follows:

[0134] (1) dissolving 10 g of manganese (II) carbonate in pure water, wherein the mass of the pure water is 49 times the mass of the manganese (II) carbonate, and stirring to obtain a salt solution including a first metal element;

[0135] (2) adding ZSM-12 molecular sieve to the salt solution including the first metal element, wherein the amount of ZSM-12 molecular sieve added is 52 times the mass of manganese (II) carbonate, and stirring to obtain a first mixed solution;

[0136] (3) adding 28% ammonia water to the first mixed solution and adjusting the pH to 8.2 to obtain a first reaction solution;

[0137] (4) subjecting the first reaction liquid to a first drying treatment at 125° C. for 10 h to obtain a first catalyst precursor;

[0138] (5) subjecting the first catalyst precursor to a first calcination treatment at 670° C. for 19 h in an air atmosphere to obtain a ZSM-12 molecular sieve-supported manganese-based catalyst (i.e., the first catalyst);

[0139] (6) dissolving 10 g of gallium sulfate hydrate in pure water, wherein the mass of the pure water is 25 times that of the gallium sulfate hydrate, and stirring evenly to obtain a salt solution including the second metal element;

[0140] (7) adding MCM-41 molecular sieve to the salt solution including the second metal element, wherein the amount of MCM-41 molecular sieve added is 39 times the mass of gallium sulfate hydrate, and stirring to obtain a second mixed solution;

[0141] (8) adding 28% by mass of ammonia water to the second mixed solution and adjusting the pH to 8.7 to obtain a second reaction solution;

[0142] (9) subjecting the second reaction liquid to a second drying treatment at 115° C. for 19 h to obtain a second catalyst precursor;

[0143] (10) subjecting the second catalyst precursor to a second calcination treatment at 650° C. for 18 h in an air atmosphere to obtain a gallium-based catalyst supported on an MCM-41 molecular sieve (i.e., a second catalyst);

[0144] (11) mixing the first catalyst and the second catalyst in a mass ratio of 1.5:1 to obtain a catalyst;

[0145] (12) allowing o-cresol and sec-butyl alcohol to undergo a catalytic reaction under the action of the above catalyst to obtain a reaction solution comprising o-sec-butyloxytoluene, wherein the catalytic reaction conditions are as follows:

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

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

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

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

[0150] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

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

[0152] Example 4

[0153] The preparation method of the present embodiment o-sec-butoxytoluene is as follows:

[0154] (1) dissolving 10 g of manganese acetate tetrahydrate in pure water, wherein the mass of the pure water is 53 times the mass of manganese acetate tetrahydrate, and stirring to obtain a salt solution including the first metal element;

[0155] (2) adding ZSM-12 molecular sieve to the salt solution including the first metal element, wherein the amount of ZSM-12 molecular sieve added is 38 times the mass of manganese acetate tetrahydrate, and stirring to obtain a first mixed solution;

[0156] (3) adding 28% ammonia water to the first mixed solution and adjusting the pH to 9.3 to obtain a first reaction solution;

[0157] (4) subjecting the first reaction liquid to a first drying treatment at 135° C. for 8 h to obtain a first catalyst precursor;

[0158] (5) subjecting the first catalyst precursor to a first calcination treatment at 730° C. for 29 h in an air atmosphere to obtain a ZSM-12 molecular sieve-supported manganese-based catalyst (i.e., the first catalyst);

[0159] (6) dissolving 10 g of gallium (III) nitrate hydrate in pure water, wherein the mass of the pure water is 38 times that of the gallium (III) nitrate hydrate, and stirring to obtain a salt solution including the second metal element;

[0160] (7) adding MCM-41 molecular sieve to the salt solution including the second metal element, wherein the amount of MCM-41 molecular sieve added is 33 times the mass of gallium nitrate (III) hydrate, and stirring to obtain a second mixed solution;

[0161] (8) adding 28% by mass of aqueous ammonia to the second mixed solution and adjusting the pH to 8.2 to obtain a second reaction solution;

[0162] (9) subjecting the second reaction liquid to a second drying treatment at 120° C. for 12 h to obtain a second catalyst precursor;

[0163] (10) subjecting the second catalyst precursor to a second calcination treatment at 430° C. in an air atmosphere for 24 h to obtain a gallium-type catalyst supported on an MCM-41 molecular sieve (i.e., a second catalyst);

[0164] (11) mixing the first catalyst and the second catalyst in a mass ratio of 0.8:1 to obtain a catalyst;

[0165] (12) allowing o-cresol and sec-butyl alcohol to undergo a catalytic reaction under the action of the above catalyst to obtain a reaction solution comprising o-sec-butyloxytoluene, wherein 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 is 17% of the total mass of o-cresol and sec-butyl alcohol;

[0168] The reaction temperature of o-cresol and sec-butyl alcohol is 330°C and the reaction pressure is 0.9 bar(G);

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

[0170] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0171] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0172] Example 5

[0173] This embodiment is substantially the same as embodiment 1, except that in step (2), the amount of ZSM-12 molecular sieve added is 15 times the mass of manganese (II) sulfate monohydrate.

[0174] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0175] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0176] Example 6

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

[0178] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0179] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0180] Example 7

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

[0182] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0183] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0184] Example 8

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

[0186] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0187] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0188] Example 9

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

[0190] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0191] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0192] Example 10

[0193] This embodiment is substantially the same as embodiment 1, except that in step (12), the amount of o-cresol added is 33% of the total mass of o-cresol and sec-butyl alcohol.

[0194] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0195] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0196] Comparative Example 1

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

[0198] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0199] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0200] Comparative Example 2

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

[0202] After the reaction stabilized, samples were taken from the reaction solution including o-sec-butyloxytoluene and analyzed using gas chromatography. The results are shown in Table 2.

[0203] After the above catalytic reaction was carried out for 3000 hours, a sample was taken from the reaction liquid including o-sec-butyloxytoluene obtained by the catalytic reaction at 3000 hours, and the results were analyzed by gas chromatography. The results are shown in Table 2.

[0204] Test example

[0205] Gas chromatography analysis: The reaction liquid including o-sec-butyloxytoluene obtained in the examples and comparative examples was subjected to gas chromatography analysis;

[0206] The operating conditions were as follows: Shimadzu GC-2030 gas chromatograph, DB-5MS UI (20m×0.25mm×0.25μm) chromatographic column, and acetonitrile as diluent;

[0207] Vaporization chamber temperature 300°C, column flow 1.00 mL / min, injection volume 0.2 μL;

[0208] The column was heated by program: first from 40°C to 100°C at a heating rate of 2°C / min, and finally to 300°C at a heating rate of 10°C / min;

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

[0210] Selectivity of o-sec-butyloxytoluene = consumption of o-cresol corresponding to o-sec-butyloxytoluene / conversion amount of o-cresol before and after the reaction.

[0211] Table 2

[0212]

[0213]

[0214] As can be seen from the table, compared with Comparative Examples 1-2, Examples 1-10 have higher o-cresol conversion and o-sec-butoxytoluene selectivity. Specifically, the o-cresol conversion in the examples is as high as 54%, the o-sec-butoxytoluene selectivity is more than 97%, and the catalyst prepared in the examples of the present invention has no significant decrease in o-cresol conversion and o-sec-butoxytoluene selectivity after running for 3000h. Therefore, the preparation method of o-sec-butoxytoluene provided by the present invention can efficiently synthesize o-sec-butoxytoluene under the action of a catalyst, and the catalyst has a long service life, which is conducive to improving industrial economy.

[0215] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing o-sec-butoxytoluene, characterized in that: include: The o-cresol and sec-butyl alcohol are subjected to a catalytic reaction under the action of a catalyst to obtain o-sec-butyloxytoluene; The catalyst comprises a carrier and at least two metal elements supported on the carrier; The carrier includes microporous molecular sieve and mesoporous molecular sieve.

2. The method for preparing o-sec-butoxytoluene according to claim 1, characterized in that: The catalyst includes a first catalyst and a second catalyst; The at least two metal elements include a first metal element and a second metal element; The first catalyst comprises a microporous molecular sieve and a first metal element; The second catalyst includes a mesoporous molecular sieve and a second metal element.

3. The method for preparing o-sec-butoxytoluene according to claim 2, characterized in that: The microporous molecular sieve comprises ZSM-12 molecular sieve; The mesoporous molecular sieve includes MCM-41 molecular sieve.

4. The method for preparing o-sec-butoxytoluene according to claim 2 or 3, characterized in that: The first metal element includes manganese metal element; The second metal element includes gallium metal element.

5. The method for preparing o-sec-butoxytoluene according to any one of claims 2 to 4, characterized in that: The catalyst is prepared according to a preparation method comprising the following process: 1) mixing a salt solution including 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 solution, and sequentially performing a first drying treatment and a first calcination treatment on the first reaction solution to obtain a first catalyst; 2) mixing a salt solution including 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 solution, and sequentially performing a second drying treatment and a second calcination treatment on the second reaction solution to obtain a second catalyst; 3) The first catalyst and the second catalyst are mixed to obtain the catalyst.

6. The method for preparing o-sec-butoxytoluene according to claim 5, characterized in that: The salt solution including the first metal element includes a first metal salt, wherein the first metal salt includes at least one of manganese acetate dihydrate, manganese acetate tetrahydrate, manganese (II) sulfate monohydrate or manganese (II) carbonate; and / or, The salt solution including the second metal element includes a second metal salt including at least one of gallium (III) acetylacetonate, anhydrous gallium chloride, gallium sulfate hydrate, and gallium (III) nitrate hydrate.

7. The method for preparing o-sec-butoxytoluene according to claim 6, characterized in that: In the salt solution comprising the first metal element, the mass ratio of the solvent mass to the first metal salt mass is (40-55):1; and / or, In the salt solution including the second metal element, the mass ratio of the solvent mass to the second metal salt is (21-46):

1.

8. The method for preparing o-sec-butoxytoluene according to claim 6 or 7, 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; and / or, In the catalyst, the mass ratio of the first catalyst to the second catalyst is (0.7-3.0):

1.

9. The method for preparing o-sec-butoxytoluene according to any one of claims 5 to 8, characterized in that: The treatment temperature of the first drying treatment is 105-135° C., and the treatment time is 7-15 hours; and / or, The treatment temperature of the first calcination treatment is 500-750° C. and the treatment time is 10-30 hours; and / or, The treatment temperature of the second drying treatment is 110-130°C and the treatment time is 8-20h; The treatment temperature of the second calcination treatment is 400-680° C. and the treatment time is 11-25 hours; and / or, The reaction temperature of the catalytic reaction is 280-360°C, and the reaction pressure is 0.5-1.5 bar; The mass of the o-cresol is 5 to 30% of the total mass of o-cresol and sec-butyl alcohol; The liquid hourly mass space velocity of o-cresol is 0.3 to 0.8 h -1 .

10. The method for preparing o-sec-butoxytoluene according to any one of claims 1 to 9, characterized in that: In the method for preparing o-sec-butyloxytoluene, the catalytic reaction is carried out in a fixed bed filled with the catalyst.

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