Use of a supported catalyst in a friedel-crafts acylation reaction

Abstract

The application provides application of a supported catalyst in a Friedel-Crafts acylation reaction and relates to the technical field of organic synthesis.The method provided by the application uses an aromatic compound as a substrate, uses an anhydride as an acylation reagent, and uses a bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst to catalyze the Friedel-Crafts acylation reaction of the aromatic compound to generate an aromatic ketone.The application of the supported catalyst in the Friedel-Crafts acylation reaction, the alternate distribution state of the two active components and the large specific surface area of the supported catalyst strengthen the acid sites of the catalyst and improve the catalytic activity of the catalyst.The high catalytic activity of the catalyst enables the acylation reagent to use the anhydride with weak activity to replace the acyl chloride with high activity and large pollution.In the reaction process, no waste acid water is generated, the equipment is not corroded, the catalyst can be recycled and reused without high-temperature calcination and regeneration treatment, the catalytic activity and selectivity of the catalyst do not obviously decrease after being reused for 8 times, and the catalyst and the product are easy to separate.

Description

Technical Field

[0001] This application relates to the field of organic synthesis technology, and more specifically, to the application of a supported catalyst in Friedel-Crafts acylation reactions. Background Technology

[0002] Friedel-Crafts acylation is a reaction in which hydrogen atoms on a benzene ring are replaced by acyl groups. It is a very important reaction in organic chemistry, referring to the electrophilic substitution reaction between aromatic compounds and acid-activated acyl chlorides, anhydrides, or other reagents. It is an important method for forming carbon-carbon bonds from carbon-hydrogen bonds in aromatic compounds. Friedel-Crafts acylation generally uses homogeneous Lewis acid or protic acid catalysts. Typical homogeneous catalysts include anhydrous aluminum trichloride, anhydrous ferric chloride, anhydrous zinc chloride, and concentrated sulfuric acid. These catalysts have problems such as environmental pollution and difficulty in separating the catalyst from the reaction solution. For example, when using anhydrous aluminum trichloride as an acylation catalyst, the amount used needs to exceed 3 equivalents. Excess anhydrous aluminum trichloride will rapidly decompose upon contact with water during hydrolysis, releasing a large amount of hydrogen chloride gas with high exothermic activity and forming an acidic solution rich in aluminic acid, which not only corrodes equipment but also seriously pollutes the environment. Another disadvantage of this type of catalyst is its low selectivity, which easily leads to the formation of polyacylation products and isomers. To replace homogeneous catalysts and address the problems of generating difficult-to-treat waste liquid that causes severe environmental pollution, corrodes equipment, and makes it difficult to separate the catalyst from the reaction liquid, heterogeneous catalysts are being researched and developed, which have significant environmental and economic value.

[0003] In the study of heterogeneous catalysts used in Friedel-Crafts acylation reactions, existing technical solutions include:

[0004] (1) Chinese invention patent CN113769780B discloses a magnetic microsphere-supported dual-acidic ionic liquid catalyst and its preparation and application. The method for preparing a magnetic microsphere-supported dual-acidic ionic liquid catalyst for the Friedel-Crafts acylation reaction of anisole and benzoyl chloride is disclosed. The product selectivity is as high as 97%, but after five applications, the selectivity of the raw material anisole gradually decreases. Furthermore, the preparation of this catalyst involves a wide variety of materials and is complex.

[0005] (2) Chinese invention patent with publication number CN108440257B discloses a process for preparing anethole by catalytic dehydration of p-methoxyphenylpropanol. It discloses that anisole and acid anhydride are used as starting materials, and ZSM-5 zeolite molecular sieve is used as catalyst to prepare the acylated product under solvent-free conditions. The reaction formula is as follows:

[0006]

[0007] The catalyst ZSM-5 zeolite molecular sieve used in this synthesis route is severely deactivated after one use and can only be reused after calcination and activation at high temperatures of 500-650℃ in a muffle furnace, making it difficult to achieve large-scale industrial production.

[0008] In summary, existing catalysts for Friedel-Crafts acylation reactions suffer from several problems, including generating difficult-to-treat waste liquids that cause severe environmental pollution, easy hydrolysis and corrosion of equipment, difficulty in separating the catalyst from the reaction liquid, a wide variety of catalyst materials, complex preparation processes, rapid decline in selectivity, and severe deactivation after use. Summary of the Invention

[0009] To address the aforementioned problems, this application employs a supported catalyst in the Friedel-Crafts acylation reaction:

[0010] Using aromatic compounds as substrates and acid anhydrides as acylation reagents, a bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst was used to catalyze the Friedel-Crafts acylation reaction of aromatic compounds to generate aromatic ketones.

[0011] Preferably, the bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst comprises:

[0012] Active component A, active component B, and carrier;

[0013] Active component A is any one of aluminum, copper, zinc, magnesium, and iron;

[0014] Active component B is any one of aluminum, copper, zinc, magnesium, iron, tin, titanium, boron, niobium, and antimony;

[0015] The support is SBA-15 mesoporous molecular sieve;

[0016] Active component A and active component B exist on the surface and in the pores of SBA-15 mesoporous molecular sieve through metal bonding.

[0017] Preferred,

[0018] The mass ratio of SBA-15 mesoporous molecular sieve to the metal source of active component A is 1:0.003-0.28;

[0019] The mass ratio of SBA-15 mesoporous molecular sieve to the metal source of active component B is 1:0.004-0.15.

[0020] Preferably, the preparation method of the bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst includes the following steps:

[0021] S-1: The metal source, support and solvent of mixed active component A are stirred, aged, washed, dried and calcined to obtain the first loaded material A-SBA-15;

[0022] S-2: Mix the first supported material A-SBA-15, the metal source of active component B, and the solvent, and then stir, filter, dry and calcine to obtain a bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst.

[0023] Preferred,

[0024] The metal sources of active component A include nitrates and hydrates of aluminum, copper, zinc, magnesium, and iron;

[0025] The metal source of active component B includes one of the chlorides, bromides, nitrates, sulfates, or hydrates of the chlorides, nitrates, or sulfates of aluminum, copper, zinc, magnesium, iron, tin, titanium, boron, niobium, or antimony.

[0026] Preferably, step S-1 aging is carried out in a hydrothermal synthesis reactor; the aging process temperature is 100-180℃ and the time is 18-26h; the heating rate of the calcination process is 1-8℃ / min, the calcination temperature is 400-800℃, and the calcination time is 3-10h.

[0027] In step S-2, the stirring time is 1-6 hours and the stirring temperature is room temperature; the heating rate during the calcination process is 1-4℃ / min, the calcination temperature is 400-600℃, and the calcination time is 3-12 hours.

[0028] Preferably, the solvent in steps S-1 and S-2 includes deionized water; the calcination in step S-2 is carried out under a protective atmosphere.

[0029] Preferably, the reaction substrate includes any one of the following aromatic compounds: anisole, o-methyl anisole, m-methyl anisole, p-methyl anisole, o-methoxy anisole, m-methoxy anisole, p-methoxy anisole, phenethyl ether, bromobenzene, toluene, m-xylene, mesitylene, furan, thiophene, and β-methoxynaphthalene.

[0030] Preferably, the acylation reagent is any one of acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, benzoic anhydride, succinic anhydride, glutaric anhydride, maleic anhydride, isobutyric anhydride, chloroacetic anhydride, trifluoroacetic anhydride, and phthalic anhydride.

[0031] The molar ratio of aromatic compound to acid anhydride is 1:0.05-5; the mass ratio of acylation reagent to catalyst is 1:0.1wt%-50wt%; the temperature of Friedel-Crafts acylation reaction is 50-180℃, and the time of Friedel-Crafts acylation reaction is 2-18h.

[0032] Preferably, the molar ratio of aromatic compound to acid anhydride is 1:0.1-1.1; the mass ratio of acylation reagent to catalyst is 1:1wt%-10wt%; and the Friedel-Crafts acylation reaction time is 6-12h.

[0033] The beneficial effects of this invention are:

[0034] 1. This invention fully utilizes the advantages of SBA-15 mesoporous molecular sieves, such as large pore size and specific surface area. The alternating distribution of the two active components and the large specific surface area enhance the acidic sites of the catalyst, thereby improving its catalytic activity. The high catalytic activity of the catalyst allows for the use of less reactive acid anhydrides as acylation reagents, replacing the more reactive and polluting acyl chlorides. No waste acid water is generated during the reaction, and it does not corrode equipment, making the process safer and more environmentally friendly.

[0035] 2. The bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst used in this invention has a stable structure and good thermal stability during use. It does not experience molecular sieve framework collapse, and the pores are not prone to carbon buildup. It can be repeatedly recycled and reused without high-temperature calcination regeneration. After eight reuses, the catalytic activity and selectivity do not significantly decrease. This greatly reduces the cost of the catalyst and enhances its technological competitiveness.

[0036] 3. The heterogeneous solid catalyst used in this invention can replace the traditional Lewis acid catalyst aluminum trichloride in acylation reactions. It has high catalytic activity in the preparation of various aryl ketones by acylation reactions of aromatic compounds and acid anhydrides, and has a wide range of applicable substrates. Moreover, since the catalyst and product are easy to separate, the process is simple, efficient, green and environmentally friendly, and the product yield is high, making it easier to realize large-scale industrial production.

[0037] 4. The catalyst provided by this invention is prepared using only SBA-15 mesoporous molecular sieve, the metal salt corresponding to the active component, and deionized water. It involves fewer material types and is easy to prepare and separate. Furthermore, as a heterogeneous catalyst, the bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst is easily separated from the product after catalysis. Attached Figure Description

[0038] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0039] Figure 1 The gas chromatogram (before purification) of the reaction solution for preparing p-methoxyphenylacetone using a Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst in Example 27 is shown in Example 27.

[0040] Figure 2 The liquid chromatogram (before purification) of the reaction solution for preparing p-toluamide acrylic acid using Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst in Example 55. Detailed Implementation

[0041] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and are not intended to limit the scope of this application.

[0042] Catalyst Preparation Example 1: Preparation of Al / Cu-SBA-15 mesoporous molecular sieve solid catalyst.

[0043] Step S1: Load active component A onto SBA-15.

[0044] S1-1: Accurately weigh 0.20g of active component A aluminum nitrate nonahydrate (Al(NO3)3·9H2O) on an analytical balance and add it to deionized water. Stir at room temperature until completely dissolved.

[0045] S1-2: Weigh 2.0g of the prepared SBA-15 mesoporous molecular sieve, slowly add it to the solution in step S1-1 with stirring, and stir continuously at room temperature for 4 hours.

[0046] S1-3: The resulting mixed solution was transferred into a hydrothermal synthesis reactor lined with polytetrafluoroethylene and crystallized for 22 hours at a crystallization temperature of 120°C.

[0047] S1-4: The crystallized mixture is washed with deionized water, dried, and then calcined at high temperature. During the high-temperature calcination process, the temperature is increased to 500℃ at a rate of 3℃ / min and calcined for 6 hours to obtain the first impregnation product Al-SBA-15.

[0048] Step S2: A-SBA-15 loads active component B.

[0049] S2-1: Weigh 0.10g of active component B, copper chloride, on an analytical balance and dissolve it completely in deionized water. Add the first impregnation product Al-SBA-15 to the solution and stir continuously for 3 hours.

[0050] S2-2: Filter the obtained mixture, place the filter cake in a forced-air drying oven and dry it at 100℃ for 6 hours; after drying, under nitrogen atmosphere protection, heat it to 500℃ at a heating rate of 3℃ / min and calcine it for 9 hours to obtain the secondary impregnation product Cu / Al-SBA-15 bimetallic supported mesoporous molecular sieve solid catalyst.

[0051] When loading active component A onto SBA-15 (step S1), calcination in air promotes oxidation on the catalyst particle surface, forming a dense oxide layer. This helps reduce the shedding of active component A during the second impregnation loading process of the A-SBA-15, which has already undergone the first loading. When only one active component is loaded, the ions of active component A have high freedom of movement within the pores, making them prone to aggregation and affecting the uniformity of active component A loading. Performing a crystallization process during the loading of active component A in step S1 allows active component A to adhere more uniformly to the surface of the support pores.

[0052] When loading active component B onto A-SBA-15 (step S2), to prevent further oxidation of the catalyst and reduction in catalytic activity, nitrogen is used as a protective gas. After impregnation, A-SBA-15 is calcined under a nitrogen atmosphere. A crystallization process is omitted in step S2 because the already loaded active component A hinders the free movement of active component B. Therefore, to avoid damage to the already loaded active component A during the crystallization growth process of active component B and to reduce the loss of the already loaded active component A, a crystallization process is not included in step S2 during the loading of active component B.

[0053] Catalyst Preparation Example 2: Preparation of Al / Zn-SBA-15 mesoporous molecular sieve solid catalyst.

[0054] In Example 1, replace the amount of "active component A, aluminum nitrate nonahydrate" in step S1-1 with 0.006 g; replace the "mixing and stirring" time in step S1-2 with 9 h; replace the "crystallization temperature" in step S1-3 with 180 °C and the "crystallization time" with 18 h. In step S1-4, replace the "heating rate" with 1 °C / min, the "calcination temperature" with 400 °C, and the "calcination time" with 10 h; replace the material and amount of "active component B" in step S2-1 with 0.3 g of zinc chloride, and replace the "mixing and stirring time" with 1 h. In step S2-2, replace the "drying temperature" with 60 °C, the "drying time" with 12 h, the "heating rate" with 4 °C / min, the "calcination temperature" with 400 °C, and the "calcination time" with 12 h. All other steps are the same as in Example 1.

[0055] Catalyst Preparation Example 3: Preparation of Al / Mg-SBA-15 mesoporous molecular sieve solid catalyst.

[0056] In Example 1, replace the amount of "active component A, aluminum nitrate nonahydrate" in step S1-1 with 0.56g; replace the "mixing and stirring" time in step S1-2 with 8h; replace the "crystallization temperature" in step S1-3 with 170℃ and the "crystallization time" with 19h. In step S1-4, replace the "heating rate" with 2℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 9h; replace the material and amount of "active component B" in step S2-1 with 0.008g of magnesium chloride, and replace the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 70℃, the "drying time" with 11h, the "heating rate" with 3℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 11h. All other steps are the same as in Example 1.

[0057] Catalyst Preparation Example 4: Preparation of Al / Fe-SBA-15 mesoporous molecular sieve solid catalyst.

[0058] In Example 1, replace the amount of "active component A, aluminum nitrate nonahydrate" in step S1-1 with 0.52g; replace the "mixing and stirring" time in step S1-2 with 7h; replace the "crystallization temperature" in step S1-3 with 160℃ and the "crystallization time" with 20h. In step S1-4, replace the "heating rate" with 3℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 8h; replace the material and amount of "active component B" in step S2-1 with 0.02g of ferric chloride, and replace the "mixing and stirring time" with 3h. In step S2-2, replace the "drying temperature" with 80℃, the "drying time" with 10h, the "heating rate" with 2℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 10h. All other steps are the same as in Example 1.

[0059] Catalyst Preparation Example 5: Preparation of Al / Sn-SBA-15 mesoporous molecular sieve solid catalyst.

[0060] In Example 1, replace the amount of "active component A, aluminum nitrate nonhydrate" in step S1-1 with 0.48g; replace the "mixing and stirring" time in step S1-2 with 6h; replace the "crystallization temperature" in step S1-3 with 150℃ and the "crystallization time" with 21h. In step S1-4, replace the "heating rate" with 4℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 7h; replace the material and amount of "active component B" in step S2-1 with 0.04g of stannous chloride dihydrate, and replace the "mixing and stirring time" with 4h. In step S2-2, replace the "drying temperature" with 90℃, the "drying time" with 9h, the "heating rate" with 1℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 9h. All other steps are the same as in Example 1.

[0061] Catalyst Preparation Example 6: Preparation of Al / Ti-SBA-15 mesoporous molecular sieve solid catalyst.

[0062] In Example 1, replace the amount of "active component A, aluminum nitrate nonahydrate" in step S1-1 with 0.44 g; replace the "mixing and stirring" time in step S1-2 with 5 h; replace the "crystallization temperature" in step S1-3 with 140 °C and the "crystallization time" with 22 h. In step S1-4, replace the "heating rate" with 5 °C / min, the "calcination temperature" with 600 °C, and the "calcination time" with 6 h; replace the material and amount of "active component B" in step S2-1 with 0.06 g of titanium sulfate, and replace the "mixing and stirring time" with 5 h. In step S2-2, replace the "drying temperature" with 100 °C, the "drying time" with 8 h, the "heating rate" with 2 °C / min, the "calcination temperature" with 600 °C, and the "calcination time" with 8 h. All other steps are the same as in Example 1.

[0063] Catalyst Preparation Example 7: Preparation of Al / B-SBA-15 mesoporous molecular sieve solid catalyst.

[0064] In Example 1, replace the amount of "active component A, aluminum nitrate nonahydrate" in step S1-1 with 0.4g; replace the "mixing and stirring" time in step S1-2 with 4h; replace the "crystallization temperature" in step S1-3 with 130℃ and the "crystallization time" with 23h. In step S1-4, replace the "heating rate" with 6℃ / min, the "calcination temperature" with 650℃, and the "calcination time" with 5h; replace the material and amount of "active component B" in step S2-1 with 0.08g boric acid, and replace the "mixing and stirring time" with 6h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 7h, the "heating rate" with 3℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 7h. All other steps are the same as in Example 1.

[0065] Catalyst Preparation Example 8: Preparation of Al / Nb-SBA-15 mesoporous molecular sieve solid catalyst.

[0066] In Example 1, replace the amount of "active component A, aluminum nitrate nonahydrate" in step S1-1 with 0.36g; replace the "mixing and stirring" time in step S1-2 with 3h; replace the "crystallization temperature" in step S1-3 with 120℃ and the "crystallization time" with 24h. In step S1-4, replace the "heating rate" with 7℃ / min, the "calcination temperature" with 700℃, and the "calcination time" with 4h; replace the material and amount of "active component B" in step S2-1 with 0.1g of niobium oxalate, and replace the "mixing and stirring time" with 5h. In step S2-2, replace the "drying temperature" with 120℃, the "drying time" with 6h, the "heating rate" with 4℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 6h. All other steps are the same as in Example 1.

[0067] Catalyst Preparation Example 9: Preparation of Al / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0068] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with aluminum nitrate, and replace the amount with 0.32g; replace the "mixing and stirring" time in step S1-2 with 2h; replace the "crystallization temperature" in step S1-3 with 110℃ and the "crystallization time" with 25h. In step S1-4, replace the "heating rate" with 6℃ / min, the "calcination temperature" with 750℃, and the "calcination time" with 3h; replace the material and amount of "Active Component B" in step S2-1 with 0.12g antimony chloride, and replace the "mixing and stirring time" with 4h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 5h, the "heating rate" with 3℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 5h. All other steps are the same as in Example 1.

[0069] Catalyst Preparation Example 10: Preparation of Cu / Al-SBA-15 mesoporous molecular sieve solid catalyst.

[0070] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Copper Nitrate Trihydrate, and replace the dosage with 0.28g; replace the "mixing and stirring" time in step S1-2 with 1h; replace "crystallization temperature" in step S1-3 with 100℃ and "crystallization time" with 26h. In step S1-4, replace "heating rate" with 7℃ / min, "calcination temperature" with 800℃, and "calcination time" with 3h; replace the material and dosage of "Active Component B" in step S2-1 with 0.14g of aluminum sulfate, and replace "mixing and stirring time" with 3h. In step S2-2, replace "drying temperature" with 100℃, "drying time" with 4h, "heating rate" with 2℃ / min, "calcination temperature" with 400℃, and "calcination time" with 4h. All other steps are the same as in Example 1.

[0071] Catalyst Preparation Example 11: Preparation of Cu / Zn-SBA-15 mesoporous molecular sieve solid catalyst.

[0072] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Copper Nitrate Trihydrate, and replace the dosage with 0.24g; replace the "mixing and stirring" time in step S1-2 with 2h; replace the "crystallization temperature" in step S1-3 with 110℃ and the "crystallization time" with 25h. In step S1-4, replace the "heating rate" with 6℃ / min, the "calcination temperature" with 750℃, and the "calcination time" with 3h; replace the material and dosage of "Active Component B" in step S2-1 with 0.16g of Zinc Bromide, and replace the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 90℃, the "drying time" with 5h, the "heating rate" with 1℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0073] Catalyst Preparation Example 12: Preparation of Cu / Mg-SBA-15 mesoporous molecular sieve solid catalyst.

[0074] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Copper Nitrate Trihydrate, and replace the dosage with 0.2g; replace the "mixing and stirring" time in step S1-2 with 3h; replace the "crystallization temperature" in step S1-3 with 120℃ and the "crystallization time" with 24h. In step S1-4, replace the "heating rate" with 5℃ / min, the "calcination temperature" with 700℃, and the "calcination time" with 3h; replace the material and dosage of "Active Component B" in step S2-1 with 0.18g of Magnesium Sulfate, and replace the "mixing and stirring time" with 1h. In step S2-2, replace the "drying temperature" with 80℃, the "drying time" with 6h, the "heating rate" with 2℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0075] Catalyst Preparation Example 13: Preparation of Cu / Fe-SBA-15 mesoporous molecular sieve solid catalyst.

[0076] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Copper Nitrate Trihydrate, and replace the dosage with 0.16g; replace the "mixing and stirring" time in step S1-2 with 4h; replace the "crystallization temperature" in step S1-3 with 130℃ and the "crystallization time" with 23h. In step S1-4, replace the "heating rate" with 4℃ / min, the "calcination temperature" with 650℃, and the "calcination time" with 3h; replace the material and dosage of "Active Component B" in step S2-1 with 0.2g of Ferric Sulfate, and replace the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 70℃, the "drying time" with 7h, the "heating rate" with 3℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0077] Catalyst Preparation Example 14: Preparation of Cu / Sn-SBA-15 mesoporous molecular sieve solid catalyst.

[0078] In Example 1, replace "active component A, aluminum nitrate nonahydrate" in step S1-1 with copper nitrate trihydrate, and replace the dosage with 0.12g; replace the "mixing and stirring" time in step S1-2 with 5h; replace the "crystallization temperature" in step S1-3 with 140℃ and the "crystallization time" with 22h. In step S1-4, replace the "heating rate" with 3℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 4h; replace the material and dosage of "active component B" in step S2-1 with 0.22g tin chloride, and replace the "mixing and stirring time" with 3h. In step S2-2, replace the "drying temperature" with 60℃, the "drying time" with 8h, the "heating rate" with 4℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0079] Catalyst Preparation Example 15: Preparation of Cu / Ti-SBA-15 mesoporous molecular sieve solid catalyst.

[0080] In Example 1, replace "active component A, aluminum nitrate nonahydrate" in step S1-1 with copper nitrate trihydrate, and replace the dosage with 0.08 g; replace the "mixing and stirring" time in step S1-2 with 6 h; replace the "crystallization temperature" in step S1-3 with 150 °C and the "crystallization time" with 21 h. In step S1-4, replace the "heating rate" with 2 °C / min, the "calcination temperature" with 550 °C, and the "calcination time" with 5 h; replace the material and dosage of "active component B" in step S2-1 with 0.24 g titanium chloride, and replace the "mixing and stirring time" with 4 h. In step S2-2, replace the "drying temperature" with 70 °C, the "drying time" with 9 h, the "heating rate" with 3 °C / min, the "calcination temperature" with 550 °C, and the "calcination time" with 3 h. All other steps are the same as in Example 1.

[0081] Catalyst Preparation Example 16: Preparation of Cu / B-SBA-15 mesoporous molecular sieve solid catalyst.

[0082] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Copper Nitrate Trihydrate, and replace the dosage with 0.12g; replace the "mixing and stirring" time in step S1-2 with 7h; replace the "crystallization temperature" in step S1-3 with 160℃ and the "crystallization time" with 20h. In step S1-4, replace the "heating rate" with 1℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 6h; replace the material and dosage of "Active Component B" in step S2-1 with 0.26g of Boron Chloride, and replace the "mixing and stirring time" with 5h. In step S2-2, replace the "drying temperature" with 80℃, the "drying time" with 10h, the "heating rate" with 2℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 4h. All other steps are the same as in Example 1.

[0083] Catalyst Preparation Example 17: Preparation of Cu / Nb-SBA-15 mesoporous molecular sieve solid catalyst.

[0084] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Copper Nitrate Trihydrate, and replace the dosage with 0.16g; replace the "mixing and stirring" time in step S1-2 with 8h; replace the "crystallization temperature" in step S1-3 with 170℃ and the "crystallization time" with 19h. In step S1-4, replace the "heating rate" with 2℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 7h; replace the material and dosage of "Active Component B" in step S2-1 with 0.28g of niobium chloride, and replace the "mixing and stirring time" with 6h. In step S2-2, replace the "drying temperature" with 90℃, the "drying time" with 11h, the "heating rate" with 1℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 5h. All other steps are the same as in Example 1.

[0085] Catalyst Preparation Example 18: Preparation of Cu / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0086] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with copper nitrate, and replace the amount with 0.2g; replace the "mixing and stirring" time in step S1-2 with 9h; replace the "crystallization temperature" in step S1-3 with 180℃ and the "crystallization time" with 18h. In step S1-4, replace the "heating rate" with 3℃ / min, the "calcination temperature" with 400℃, and the "calcination time" with 8h; replace the material and amount of "Active Component B" in step S2-1 with 0.3g antimony chloride, and replace the "mixing and stirring time" with 5h. In step S2-2, replace the "drying temperature" with 100℃, the "drying time" with 12h, the "heating rate" with 2℃ / min, the "calcination temperature" with 400℃, and the "calcination time" with 6h. All other steps are the same as in Example 1.

[0087] Catalyst Preparation Example 19: Preparation of Zn / Al-SBA-15 mesoporous molecular sieve solid catalyst.

[0088] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and replace the dosage with 0.24g; replace the "mixing and stirring" time in step S1-2 with 8h; replace the "crystallization temperature" in step S1-3 with 170℃ and the "crystallization time" with 19h. In step S1-4, replace the "heating rate" with 4℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 9h; replace the material and dosage of "Active Component B" in step S2-1 with 0.28g of aluminum chloride, and replace the "mixing and stirring time" with 4h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 11h, the "heating rate" with 3℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 7h. All other steps are the same as in Example 1.

[0089] Catalyst Preparation Example 20: Preparation of Zn / Cu-SBA-15 mesoporous molecular sieve solid catalyst.

[0090] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and replace the dosage with 0.28g; replace the "mixing and stirring" time in step S1-2 with 7h; replace the "crystallization temperature" in step S1-3 with 160℃ and the "crystallization time" with 20h. In step S1-4, replace the "heating rate" with 5℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 10h; replace the material and dosage of "Active Component B" in step S2-1 with 0.26g of copper bromide, and replace the "mixing and stirring time" with 3h. In step S2-2, replace the "drying temperature" with 120℃, the "drying time" with 10h, the "heating rate" with 4℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 8h. All other steps are the same as in Example 1.

[0091] Catalyst Preparation Example 21: Preparation of Zn / Mg-SBA-15 mesoporous molecular sieve solid catalyst.

[0092] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and replace the dosage with 0.32g; replace the "mixing and stirring" time in step S1-2 with 6h; replace the "crystallization temperature" in step S1-3 with 150℃ and the "crystallization time" with 21h. In step S1-4, replace the "heating rate" with 6℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 9h; replace the material and dosage of "Active Component B" in step S2-1 with 0.24g Magnesium Sulfate Pentahydrate, and replace the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 9h, the "heating rate" with 3℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 9h. All other steps are the same as in Example 1.

[0093] Catalyst Preparation Example 22: Preparation of Zn / Fe-SBA-15 mesoporous molecular sieve solid catalyst.

[0094] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and change the dosage to 0.36g; replace the "mixing and stirring" time in step S1-2 with 5h; replace the "crystallization temperature" in step S1-3 with 140℃ and the "crystallization time" with 22h. In step S1-4, replace the "heating rate" with 7℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 8h; replace the material and dosage of "Active Component B" in step S2-1 with 0.22g of Ferric Sulfate Monohydrate, and change the "mixing and stirring time" with 1h. In step S2-2, replace the "drying temperature" with 100℃, the "drying time" with 8h, the "heating rate" with 2℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 10h. All other steps are the same as in Example 1.

[0095] Catalyst Preparation Example 23: Preparation of Zn / Sn-SBA-15 mesoporous molecular sieve solid catalyst.

[0096] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and change the dosage to 0.4g; replace the "mixing and stirring" time in step S1-2 with 4h; replace the "crystallization temperature" in step S1-3 with 130℃ and the "crystallization time" with 23h. In step S1-4, replace the "heating rate" with 8℃ / min, the "calcination temperature" with 650℃, and the "calcination time" with 7h; replace the material and dosage of "Active Component B" in step S2-1 with 0.2g of tin chloride, and change the "mixing and stirring time" to 2h. In step S2-2, replace the "drying temperature" with 90℃, the "drying time" with 7h, the "heating rate" with 1℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 11h. All other steps are the same as in Example 1.

[0097] Catalyst Preparation Example 24: Preparation of Zn / Ti-SBA-15 mesoporous molecular sieve solid catalyst.

[0098] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and replace the dosage with 0.44g; replace the "mixing and stirring" time in step S1-2 with 3h; replace the "crystallization temperature" in step S1-3 with 120℃ and the "crystallization time" with 24h. In step S1-4, replace the "heating rate" with 7℃ / min, the "calcination temperature" with 700℃, and the "calcination time" with 6h; replace the material and dosage of "Active Component B" in step S2-1 with 0.18g of Titanium Chloride, and replace the "mixing and stirring time" with 3h. In step S2-2, replace the "drying temperature" with 80℃, the "drying time" with 6h, the "heating rate" with 2℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 12h. All other steps are the same as in Example 1.

[0099] Catalyst Preparation Example 25: Preparation of Zn / B-SBA-15 mesoporous molecular sieve solid catalyst.

[0100] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and replace the dosage with 0.48g; replace the "mixing and stirring" time in step S1-2 with 2h; replace the "crystallization temperature" in step S1-3 with 110℃ and the "crystallization time" with 25h. In step S1-4, replace the "heating rate" with 6℃ / min, the "calcination temperature" with 750℃, and the "calcination time" with 5h; replace the material and dosage of "Active Component B" in step S2-1 with 0.16g of boron chloride, and replace the "mixing and stirring time" with 4h. In step S2-2, replace the "drying temperature" with 70℃, the "drying time" with 5h, the "heating rate" with 3℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 11h. All other steps are the same as in Example 1.

[0101] Catalyst Preparation Example 26: Preparation of Zn / Nb-SBA-15 mesoporous molecular sieve solid catalyst.

[0102] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Zinc Nitrate Hexahydrate, and replace the dosage with 0.52g; replace the "mixing and stirring" time in step S1-2 with 1h; replace "crystallization temperature" in step S1-3 with 100℃ and "crystallization time" with 26h. In step S1-4, replace "heating rate" with 5℃ / min, "calcination temperature" with 800℃, and "calcination time" with 4h; replace the material and dosage of "Active Component B" in step S2-1 with 0.14g of niobium chloride, and replace "mixing and stirring time" with 5h. In step S2-2, replace "drying temperature" with 60℃, "drying time" with 4h, "heating rate" with 4℃ / min, "calcination temperature" with 400℃, and "calcination time" with 10h. All other steps are the same as in Example 1.

[0103] Catalyst Preparation Example 27: Preparation of Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0104] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with zinc nitrate, and replace the amount with 0.56g; replace the "mixing and stirring" time in step S1-2 with 2h; replace the "crystallization temperature" in step S1-3 with 110℃ and the "crystallization time" with 25h. In step S1-4, replace the "heating rate" with 4℃ / min, the "calcination temperature" with 750℃, and the "calcination time" with 3h; replace the material and amount of "Active Component B" in step S2-1 with 0.12g antimony chloride, and replace the "mixing and stirring time" with 6h. In step S2-2, replace the "drying temperature" with 70℃, the "drying time" with 5h, the "heating rate" with 3℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 9h. All other steps are the same as in Example 1.

[0105] Catalyst Preparation Example 28: Preparation of Mg / Al-SBA-15 mesoporous molecular sieve solid catalyst.

[0106] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and replace the amount with 0.52g; replace the "mixing and stirring" time in step S1-2 with 3h; replace the "crystallization temperature" in step S1-3 with 120℃ and the "crystallization time" with 24h. In step S1-4, replace the "heating rate" with 3℃ / min, the "calcination temperature" with 700℃, and the "calcination time" with 3h; replace the material and amount of "Active Component B" in step S2-1 with 0.1g of Aluminum Sulfate Octadecahydrate, and replace the "mixing and stirring time" with 5h. In step S2-2, replace the "drying temperature" with 80℃, the "drying time" with 6h, the "heating rate" with 2℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 8h. All other steps are the same as in Example 1.

[0107] Catalyst Preparation Example 29: Preparation of Mg / Cu-SBA-15 mesoporous molecular sieve solid catalyst.

[0108] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and change the dosage to 0.48g; replace the "mixing and stirring" time in step S1-2 with 4h; replace the "crystallization temperature" in step S1-3 with 130℃ and the "crystallization time" with 23h. In step S1-4, replace the "heating rate" with 2℃ / min, the "calcination temperature" with 650℃, and the "calcination time" with 3h; replace the material and dosage of "Active Component B" in step S2-1 with 0.08g of Copper Sulfate Pentahydrate, and change the "mixing and stirring time" to 4h. In step S2-2, replace the "drying temperature" with 90℃, the "drying time" with 7h, the "heating rate" with 1℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 7h. All other steps are the same as in Example 1.

[0109] Catalyst Preparation Example 30: Preparation of Mg / Zn-SBA-15 mesoporous molecular sieve solid catalyst.

[0110] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and replace the dosage with 0.44g; replace the "mixing and stirring" time in step S1-2 with 5h; replace the "crystallization temperature" in step S1-3 with 140℃ and the "crystallization time" with 22h. In step S1-4, replace the "heating rate" with 1℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 3h; replace the material and dosage of "Active Component B" in step S2-1 with 0.06g of zinc chloride, and replace the "mixing and stirring time" with 3h. In step S2-2, replace the "drying temperature" with 100℃, the "drying time" with 8h, the "heating rate" with 2℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 6h. All other steps are the same as in Example 1.

[0111] Catalyst Preparation Example 31: Preparation of Mg / Fe-SBA-15 mesoporous molecular sieve solid catalyst.

[0112] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and change the dosage to 0.4g; replace the "mixing and stirring" time in step S1-2 with 6h; replace the "crystallization temperature" in step S1-3 with 150℃ and the "crystallization time" with 21h. In step S1-4, replace the "heating rate" with 2℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 3h; replace the material and dosage of "Active Component B" in step S2-1 with 0.04g of Ferric Nitrate Nonhydrate, and change the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 9h, the "heating rate" with 3℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 5h. All other steps are the same as in Example 1.

[0113] Catalyst Preparation Example 32: Preparation of Mg / Sn-SBA-15 mesoporous molecular sieve solid catalyst.

[0114] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and replace the dosage with 0.36g; replace the "mixing and stirring" time in step S1-2 with 7h; replace the "crystallization temperature" in step S1-3 with 160℃ and the "crystallization time" with 20h. In step S1-4, replace the "heating rate" with 3℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 4h; replace the material and dosage of "Active Component B" in step S2-1 with 0.06g of tin chloride, and replace the "mixing and stirring time" with 1h. In step S2-2, replace the "drying temperature" with 120℃, the "drying time" with 10h, the "heating rate" with 4℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 4h. All other steps are the same as in Example 1.

[0115] Catalyst Preparation Example 33: Preparation of Mg / Ti-SBA-15 mesoporous molecular sieve solid catalyst.

[0116] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and replace the dosage with 0.32g; replace the "mixing and stirring" time in step S1-2 with 8h; replace the "crystallization temperature" in step S1-3 with 170℃ and the "crystallization time" with 19h. In step S1-4, replace the "heating rate" with 4℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 5h; replace the material and dosage of "Active Component B" in step S2-1 with 0.08g of titanium chloride, and replace the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 11h, the "heating rate" with 3℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0117] Catalyst Preparation Example 34: Preparation of Mg / B-SBA-15 mesoporous molecular sieve solid catalyst.

[0118] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and replace the dosage with 0.28g; replace the "mixing and stirring" time in step S1-2 with 9h; replace the "crystallization temperature" in step S1-3 with 180℃ and the "crystallization time" with 18h. In step S1-4, replace the "heating rate" with 5℃ / min, the "calcination temperature" with 400℃, and the "calcination time" with 6h; replace the material and dosage of "Active Component B" in step S2-1 with 0.1g of boron chloride, and replace the "mixing and stirring time" with 3h. In step S2-2, replace the "drying temperature" with 100℃, the "drying time" with 12h, the "heating rate" with 2℃ / min, the "calcination temperature" with 400℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0119] Catalyst Preparation Example 35: Preparation of Mg / Nb-SBA-15 mesoporous molecular sieve solid catalyst.

[0120] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Magnesium Nitrate Hexahydrate, and change the dosage to 0.24g; replace the "mixing and stirring" time in step S1-2 with 8h; replace the "crystallization temperature" in step S1-3 with 170℃ and the "crystallization time" with 19h. In step S1-4, replace the "heating rate" with 6℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 7h; replace the material and dosage of "Active Component B" in step S2-1 with 0.12g of niobium bromide, and change the "mixing and stirring time" with 4h. In step S2-2, replace the "drying temperature" with 90℃, the "drying time" with 11h, the "heating rate" with 1℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0121] Catalyst Preparation Example 36: Preparation of Mg / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0122] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with magnesium nitrate, and replace the amount with 0.2g; replace the "mixing and stirring" time in step S1-2 with 7h; replace the "crystallization temperature" in step S1-3 with 160℃ and the "crystallization time" with 20h. In step S1-4, replace the "heating rate" with 7℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 8h; replace the material and amount of "Active Component B" in step S2-1 with 0.14g of antimony bromide, and replace the "mixing and stirring time" with 5h. In step S2-2, replace the "drying temperature" with 80℃, the "drying time" with 10h, the "heating rate" with 2℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0123] Catalyst Preparation Example 37: Preparation of Fe / Al-SBA-15 mesoporous molecular sieve solid catalyst.

[0124] In Example 1, replace "active component A, aluminum nitrate nonahydrate" in step S1-1 with ferric nitrate nonahydrate, and replace the dosage with 0.16g; replace the "mixing and stirring" time in step S1-2 with 6h; replace the "crystallization temperature" in step S1-3 with 150℃ and the "crystallization time" with 21h. In step S1-4, replace the "heating rate" with 8℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 9h; replace the material and dosage of "active component B" in step S2-1 with 0.16g aluminum nitrate, and replace the "mixing and stirring time" with 6h. In step S2-2, replace the "drying temperature" with 70℃, the "drying time" with 9h, the "heating rate" with 3℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 3h. All other steps are the same as in Example 1.

[0125] Catalyst Preparation Example 38: Preparation of Fe / Cu-SBA-15 mesoporous molecular sieve solid catalyst.

[0126] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Ferric Nitrate Nonhydrate, and replace the dosage with 0.12g; replace the "mixing and stirring" time in step S1-2 with 5h; replace the "crystallization temperature" in step S1-3 with 140℃ and the "crystallization time" with 22h. In step S1-4, replace the "heating rate" with 7℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 10h; replace the material and dosage of "Active Component B" in step S2-1 with 0.18g of Copper Sulfate, and replace the "mixing and stirring time" with 5h. In step S2-2, replace the "drying temperature" with 60℃, the "drying time" with 8h, the "heating rate" with 4℃ / min, the "calcination temperature" with 600℃, and the "calcination time" with 4h. All other steps are the same as in Example 1.

[0127] Catalyst Preparation Example 39: Preparation of Fe / Zn-SBA-15 mesoporous molecular sieve solid catalyst.

[0128] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Ferric Nitrate Nonhydrate, and replace the dosage with 0.08g; replace the "mixing and stirring" time in step S1-2 with 4h; replace the "crystallization temperature" in step S1-3 with 130℃ and the "crystallization time" with 23h. In step S1-4, replace the "heating rate" with 6℃ / min, the "calcination temperature" with 650℃, and the "calcination time" with 9h; replace the material and dosage of "Active Component B" in step S2-1 with 0.2g of Zinc Nitrate, and replace the "mixing and stirring time" with 4h. In step S2-2, replace the "drying temperature" with 70℃, the "drying time" with 7h, the "heating rate" with 3℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 5h. All other steps are the same as in Example 1.

[0129] Catalyst Preparation Example 40: Preparation of Fe / Mg-SBA-15 mesoporous molecular sieve solid catalyst.

[0130] In Example 1, replace "active component A, aluminum nitrate nonhydrate" in step S1-1 with ferric nitrate nonhydrate, and replace the amount with 0.12g; replace the "mixing and stirring" time in step S1-2 with 3h; replace the "crystallization temperature" in step S1-3 with 120℃ and the "crystallization time" with 24h. In step S1-4, replace the "heating rate" with 5℃ / min, the "calcination temperature" with 700℃, and the "calcination time" with 8h; replace the material and amount of "active component B" in step S2-1 with 0.22g magnesium sulfate dihydrate, and replace the "mixing and stirring time" with 3h. In step S2-2, replace the "drying temperature" with 80℃, the "drying time" with 6h, the "heating rate" with 2℃ / min, the "calcination temperature" with 500℃, and the "calcination time" with 6h. All other steps are the same as in Example 1.

[0131] Catalyst Preparation Example 41: Preparation of Fe / Sn-SBA-15 mesoporous molecular sieve solid catalyst.

[0132] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Ferric Nitrate Nonhydrate, and replace the dosage with 0.16g; replace the "mixing and stirring" time in step S1-2 with 2h; replace the "crystallization temperature" in step S1-3 with 110℃ and the "crystallization time" with 25h. In step S1-4, replace the "heating rate" with 4℃ / min, the "calcination temperature" with 750℃, and the "calcination time" with 7h; replace the material and dosage of "Active Component B" in step S2-1 with 0.24g of Tin Bromide, and replace the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 90℃, the "drying time" with 5h, the "heating rate" with 1℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 7h. All other steps are the same as in Example 1.

[0133] Catalyst Preparation Example 42: Preparation of Fe / Ti-SBA-15 mesoporous molecular sieve solid catalyst.

[0134] In Example 1, replace "active component A, aluminum nitrate nonahydrate" in step S1-1 with ferric nitrate nonahydrate, and replace the amount with 0.2g; replace the "mixing and stirring" time in step S1-2 with 1h; replace "crystallization temperature" in step S1-3 with 100℃ and "crystallization time" with 26h. In step S1-4, replace "heating rate" with 3℃ / min, "calcination temperature" with 800℃, and "calcination time" with 6h; replace the material and amount of "active component B" in step S2-1 with 0.26g titanium bromide, and replace "mixing and stirring time" with 1h. In step S2-2, replace "drying temperature" with 100℃, "drying time" with 4h, "heating rate" with 2℃ / min, "calcination temperature" with 400℃, and "calcination time" with 8h. All other steps are the same as in Example 1.

[0135] Catalyst Preparation Example 43: Preparation of Fe / B-SBA-15 mesoporous molecular sieve solid catalyst.

[0136] In Example 1, replace "active component A, aluminum nitrate nonhydrate" in step S1-1 with ferric nitrate nonhydrate, and replace the amount with 0.24g; replace the "mixing and stirring" time in step S1-2 with 2h; replace the "crystallization temperature" in step S1-3 with 110℃ and the "crystallization time" with 25h. In step S1-4, replace the "heating rate" with 2℃ / min, the "calcination temperature" with 750℃, and the "calcination time" with 5h; replace the material and amount of "active component B" in step S2-1 with 0.28g of boron bromide, and replace the "mixing and stirring time" with 2h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 5h, the "heating rate" with 3℃ / min, the "calcination temperature" with 450℃, and the "calcination time" with 9h. All other steps are the same as in Example 1.

[0137] Catalyst Preparation Example 44: Preparation of Fe / Nb-SBA-15 mesoporous molecular sieve solid catalyst.

[0138] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with Ferric Nitrate Nonhydrate, and replace the dosage with 0.28g; replace the "mixing and stirring" time in step S1-2 with 3h; replace "crystallization temperature" in step S1-3 with 120℃ and "crystallization time" with 24h. In step S1-4, replace "heating rate" with 1℃ / min, "calcination temperature" with 700℃, and "calcination time" with 4h; replace the material and dosage of "Active Component B" in step S2-1 with 0.3g Boron Bromide, and replace "mixing and stirring time" with 3h. In step S2-2, replace "drying temperature" with 120℃, "drying time" with 6h, "heating rate" with 4℃ / min, "calcination temperature" with 500℃, and "calcination time" with 10h. All other steps are the same as in Example 1.

[0139] Catalyst Preparation Example 45: Preparation of Fe / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0140] In Example 1, replace "Active Component A, Aluminum Nitrate Nonhydrate" in step S1-1 with ferric nitrate, and replace the amount with 0.32g; replace the "mixing and stirring" time in step S1-2 with 4h; replace the "crystallization temperature" in step S1-3 with 130℃ and the "crystallization time" with 23h. In step S1-4, replace the "heating rate" with 2℃ / min, the "calcination temperature" with 650℃, and the "calcination time" with 3h; replace the material and amount of "Active Component B" in step S2-1 with 0.28g of antimony chloride, and replace the "mixing and stirring time" with 4h. In step S2-2, replace the "drying temperature" with 110℃, the "drying time" with 7h, the "heating rate" with 3℃ / min, the "calcination temperature" with 550℃, and the "calcination time" with 11h. All other steps are the same as in Example 1.

[0141] Table 1 Summary of experimental conditions in Catalyst Preparation Examples 1-45

[0142]

[0143]

[0144]

[0145]

[0146] Table 1 (continued) Summary of experimental conditions in Catalyst Preparation Examples 1-45

[0147]

[0148]

[0149] Catalyst Application Examples: 1-45

[0150] To investigate the catalytic activity of the catalyst prepared in the above examples in the Friedel-Crafts acylation reaction of anisole and propionic anhydride, the following experiment was conducted: the performance of the catalyst was evaluated in a round-bottom flask equipped with a reflux condenser.

[0151] The specific process of the Friedel-Crafts acylation reaction is as follows: Anisole and propionic anhydride were added to a 250 mL three-necked flask at a molar ratio of 3:1. The amount of anisole added was 32.44 g, and the amount of propionic anhydride added was 13.01 g. Then, 1 g of modified SBA-15 mesoporous molecular sieve solid catalyst was added, and the mixture was stirred at a rate of 400 rpm and heated to 130 °C for 9 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product p-methoxyphenylacetone.

[0152] The solid catalysts mentioned above were successively replaced with the products obtained in Catalyst Preparation Examples 1-45 and the blank test. Gas chromatography was used to analyze the conversion rate of raw materials, the selectivity of products, and the separation yield. The analysis results are shown in Table 2.

[0153] Gas chromatography: Fuli G9790Plus; Column: DB-17 (30m×0.25mm×0.25um), FID detector, column temperature 100℃ held for 5 min, then increased to 200℃ at 40℃ / min and held for 10 min.

[0154] like Figure 1 As shown, the peak elution time of p-methoxyphenylacetone was 12.349 min, and the yield was 98.34%.

[0155] Table 2 Summary of experimental results from catalyst application examples

[0156]

[0157]

[0158] As can be seen from Table 2, the bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst exhibits a selectivity of over 90% and a conversion rate of over 81% in the Friedel-Crafts acylation reaction of anisole and propionic anhydride. Based on the separation yield, the Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst provided in Example 27 demonstrates the best catalytic activity.

[0159] The alternating distribution of the two active components and the large specific surface area of ​​the supported catalyst enhance the acidic sites and improve the catalytic activity. In monometallic support, the active components have a high degree of freedom and are easy to aggregate, while in bimetallic support, the particle growth of active component B is restricted by the supported active component A, which improves the particle stability and uniformity of active component B and enhances the interaction between active component B and the support.

[0160] Example 46: Catalyst Application in Example

[0161] Anisole and propionic anhydride were added to a 250 mL three-necked flask at a molar ratio of 3:1. The amount of anisole added was 32.44 g, and the amount of propionic anhydride added was 13.01 g. Then, 1 g of the Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst provided in Example 27 was added. The mixture was stirred at 400 rpm and heated to 130 °C, and the reaction was maintained at this temperature for 9 h. After the reaction was completed, the mixture was cooled to room temperature. The resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product p-methoxyphenylacetone. The resulting filter cake could be used directly in the next batch of reaction without drying, and the reaction conditions remained unchanged. The catalytic effect of each batch of Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst was statistically analyzed, and the results are shown in Table 3.

[0162] Table 3 Catalyst Application Results

[0163]

[0164]

[0165] As shown in Table 3, the optimal catalyst Zn / Sb-SBA-15 did not show a significant decrease in activity after eight cycles, and its selectivity for acylation products remained above 99%. The experimental results indicate that this catalyst exhibits very stable activity in catalyzing Friedel-Crafts acylation reactions.

[0166] This is because there is a difference in redox potential between the two active components supported by the bimetallic SBA-15. While the protons provided by the active components induce the acylation reagent to generate positive ions that attack the electron-rich benzene ring, and then the positive ions and the benzene ring undergo π-complexation and σ-complexation to finally leave the hydrogen ion, the two active components are also spontaneously undergoing a redox cycle, which not only further improves the reaction efficiency, but also ensures that the catalyst can maintain its activity and be reused.

[0167] To investigate the catalytic activity of Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst in Friedel-Crafts acylation reactions with different substrate aromatic compounds and different acid anhydrides as acylation reagents, Examples 47-60 were conducted as follows. The conversion rate of raw materials and the selectivity of products were analyzed by liquid chromatography. The reaction results are shown in Table 4.

[0168] Example 47: The reaction of o-methyl anisole with acetic anhydride catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0169] 100.0 g of o-methyl anisole, 4.18 g of acetic anhydride, and 2.09 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 400 rpm and heated to 150 °C, and the reaction was maintained at this temperature for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC (High Performance Liquid Chromatography) analysis showed that the starting material conversion rate was 90.58% and the product selectivity was 94.24%.

[0170] Liquid chromatography: Agilent 1260II; Column: Kromasil C18 (250mm×4.6mm×5um), wavelength 260nm, column temperature 35℃, injection volume 10ul, mobile phase methanol-water (85:15), flow rate 0.8ml / min.

[0171] Example 48: The reaction of m-methyl anisole with propionic anhydride was catalyzed by a Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0172] 90.0 g of m-methyl anisole, 9.59 g of propionic anhydride, and 3.84 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 500 rpm and heated to 130 °C, and the reaction was maintained at this temperature for 9 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 95.69% and the product selectivity was 97.89%.

[0173] Example 49: The reaction of p-methyl anisole with butyric anhydride catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0174] 70.0 g of p-methyl anisole, 27.19 g of butyric anhydride, and 8.16 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 600 rpm and heated to 100 °C, and the reaction was maintained at this temperature for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 89.27% ​​and the product selectivity was 90.25%.

[0175] Example 50: The reaction of o-phenylenediamine (o-methoxyanisole) with valeric anhydride was catalyzed by a Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0176] 50.0 g of o-phenylenedimethyl ether, 47.18 g of valeric anhydride, and 9.44 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 400 rpm and heated to 120 °C, and the reaction was maintained at this temperature for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 92.57% and the product selectivity was 85.34%.

[0177] Example 51: The reaction of m-phenylenedimethyl ether (m-methoxyanisole) with hexanoic anhydride was catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0178] 35.0 g of m-phenylenedimethyl ether, 59.72 g of hexanoic anhydride, and 5.97 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 500 rpm and heated to 140 °C, and the reaction was maintained at this temperature for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 98.61% and the product selectivity was 99.26%.

[0179] Example 52: The reaction of p-phenylenedimethyl ether (p-methoxyanisole) with benzoic anhydride was catalyzed by a Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0180] 20.0 g of diphenyl ether, 65.50 g of benzoic anhydride, and 3.27 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 600 rpm and heated to 160 °C, and the reaction was maintained at this temperature for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 82.43% and the product selectivity was 95.62%.

[0181] Example 53: The reaction of phenethyl ether with succinic anhydride (succinic anhydride) catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0182] 30.0 g of phenethyl ether, 73.73 g of succinic anhydride, and 0.74 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 800 rpm and heated to 180 °C, and the reaction was maintained at this temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 99.52% and the product selectivity was 94.92%.

[0183] Example 54: The reaction of bromobenzene with glutaric anhydride catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0184] 25.0 g of bromobenzene, 72.68 g of glutaric anhydride, and 0.36 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 1000 rpm and heated to 150 °C, and the reaction was maintained at this temperature for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 78.16% and the product selectivity was 92.85%.

[0185] Example 55: The reaction of toluene and maleic anhydride catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0186] 15.0 g of toluene, 79.81 g of maleic anhydride, and 0.08 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 800 rpm and heated to 110 °C, and the reaction was maintained at this temperature for 9 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 91.86% and the product selectivity was 64.08%.

[0187] like Figure 2As shown, the elution time of p-toluamide was 5.18 min, and the yield was 58.86%.

[0188] Example 56: The reaction of m-xylene with isobutyric anhydride was catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0189] 660.0 g of m-xylene, 49.17 g of isobutyric anhydride, and 3.13 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 600 rpm and heated to 100 °C, and the reaction was maintained at this temperature for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 91.28% and the product selectivity was 95.91%.

[0190] Example 57: The reaction of mesitylene and chloroacetic anhydride catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0191] 90.0 g of mesitylene, 12.80 g of chloroacetic anhydride, and 1.28 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 400 rpm and heated to 100 °C, and the reaction was maintained at this temperature for 14 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 78.37% and the product selectivity was 97.28%.

[0192] Example 58: The reaction of furan with trifluoroacetic anhydride catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0193] 90.0 g of furan, 20.41 g of trifluoroacetic anhydride, and 1.39 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 200 rpm and heated to 50 °C, and the reaction was maintained at this temperature for 18 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 64.72% and the product selectivity was 90.56%.

[0194] Example 59: The reaction of thiophene with propionic anhydride was catalyzed by a Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0195] 90.0 g thiophene, 13.92 g propionic anhydride, and 0.70 g catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 100 rpm and heated to 80 °C, and the reaction was maintained at this temperature for 16 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 75.49% and the product selectivity was 90.26%.

[0196] Example 60: The reaction of 2-methoxynaphthalene (β-methoxynaphthalene) with phthalic anhydride was catalyzed by Zn / Sb-SBA-15 mesoporous molecular sieve solid catalyst.

[0197] 70.0 g of 2-methoxynaphthalene, 32.77 g of phthalic anhydride, and 0.98 g of catalyst were added sequentially to a 250 mL three-necked flask equipped with a reflux condenser. The mixture was stirred at 500 rpm and heated to 110 °C, and the reaction was maintained at this temperature for 10 h. After the reaction was completed, the mixture was cooled to room temperature, and the resulting reaction solution was filtered, concentrated, and distilled to obtain the acylated product. HPLC analysis showed that the starting material conversion rate was 98.34% and the product selectivity was 98.92%.

[0198] Table 4 Summary of Experimental Data from Examples 47-60

[0199]

[0200] Table 5. Results of Friedel-Crafts acylation reactions of different substrates with different acid anhydrides.

[0201]

[0202]

[0203] As can be seen from Table 5, the bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst has a good effect on the Friedel-Crafts acylation reaction of aromatic ethers, with a conversion rate of over 82% and a selectivity of over 85%.

[0204] When the substrate has many substituents and generates significant steric hindrance, it hinders the reaction, resulting in a lower conversion rate. For example, the conversion rate decreased to 78.37% when catalyzing mesitylene. When using five-membered heterocyclic substrates, due to their high electron cloud density, they are prone to polymerization and deterioration; the conversion rates for furan and thiophene were 64.72% and 75.49%, respectively.

[0205] The above-described embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application, and should all be included within the protection scope of this application.

Claims

1. The application of a supported catalyst in a Friedel-Crafts acylation reaction, characterized in that: Using aromatic compounds as substrates and acid anhydrides as acylation reagents, a bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst was used to catalyze the Friedel-Crafts acylation reaction of aromatic compounds to generate aromatic ketones. The bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst comprises: Active component A, active component B, and carrier; The preparation method of the bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst includes the following steps: S-1: The metal source, support and solvent of the active component A are mixed, and then stirred, aged, washed, dried and calcined to obtain the first loading material A-SBA-15; S-2: Mix the first supported material A-SBA-15, the active component B, the metal source, and the solvent, and then stir, filter, dry, and calcine to obtain the bimetallic supported SBA-15 mesoporous molecular sieve solid catalyst. The active component A is aluminum, and the active component B is any one of copper, zinc, magnesium, iron, tin, titanium, boron, niobium, and antimony; or, The active component A is copper, and the active component B is any one of aluminum, zinc, magnesium, iron, tin, titanium, boron, niobium, and antimony; or, The active component A is zinc, and the active component B is any one of aluminum, copper, magnesium, iron, tin, titanium, boron, niobium, and antimony; or, The active component A is magnesium, and the active component B is any one of aluminum, copper, zinc, iron, tin, titanium, boron, niobium, and antimony; or, The active component A is iron, and the active component B is any one of aluminum, copper, zinc, magnesium, tin, titanium, boron, niobium, and antimony.

2. The application of the supported catalyst as described in claim 1 in the Friedel-Crafts acylation reaction, characterized in that: The carrier is SBA-15 mesoporous molecular sieve; The active components A and B exist on the surface and in the pores of the SBA-15 mesoporous molecular sieve through metal bonding.

3. The application of the supported catalyst as described in claim 2 in the Friedel-Crafts acylation reaction, characterized in that: The mass ratio of the SBA-15 mesoporous molecular sieve to the metal source of the active component A is 1:0.003-0.28; The mass ratio of the SBA-15 mesoporous molecular sieve to the metal source of the active component B is 1:0.004-0.

15.

4. The application of the supported catalyst as described in claim 2 in the Friedel-Crafts acylation reaction, characterized in that: The metal source of the active component A is aluminum nitrate and its hydrate. The metal source of the active component B is one of the following: chlorides, bromides, nitrates, sulfates, or hydrates of chlorides, nitrates, or sulfates of copper, zinc, magnesium, iron, tin, titanium, boron, niobium, or antimony; or, The metal source of active component A is copper nitrate and its hydrate. The metal source of the active component B is one of the following: chlorides, bromides, nitrates, sulfates, or hydrates of chlorides, nitrates, or sulfates of aluminum, zinc, magnesium, iron, tin, titanium, boron, niobium, or antimony; or, The metal source of active component A is zinc nitrate and its hydrate; The metal source of the active component B is one of the following: chlorides, bromides, nitrates, sulfates, or hydrates of chlorides, nitrates, or sulfates of aluminum, copper, magnesium, iron, tin, titanium, boron, niobium, or antimony; or, The metal source of the active component A is magnesium nitrate and its hydrate. The metal source of the active component B is one of the following: chlorides, bromides, nitrates, sulfates, or hydrates of chlorides, nitrates, or sulfates of aluminum, copper, zinc, iron, tin, titanium, boron, niobium, or antimony; or, The metal source of active component A is iron nitrate and its hydrate. The metal source of the active component B is one of the chlorides, bromides, nitrates, sulfates, or hydrates of the chlorides, nitrates, or sulfates of aluminum, copper, zinc, magnesium, tin, titanium, boron, niobium, or antimony.

5. The application of the supported catalyst as described in claim 1 in the Friedel-Crafts acylation reaction, characterized in that: The aging process described in step S-1 is carried out in a hydrothermal synthesis reactor; the aging process temperature is 100-180℃ and the time is 18-26h; the heating rate of the calcination process is 1-8℃ / min, the calcination temperature is 400-800℃, and the calcination time is 3-10h. The stirring time in step S-2 is 1-6 hours, and the stirring temperature is room temperature; the heating rate in the calcination process is 1-4℃ / min, the calcination temperature is 400-600℃, and the calcination time is 3-12 hours.

6. The application of the supported catalyst as described in claim 1 in the Friedel-Crafts acylation reaction, characterized in that: The solvent used in steps S-1 and S-2 is deionized water; the calcination in step S-2 is carried out under a protective atmosphere.

7. The application of the supported catalyst as described in any one of claims 1-6 in the Friedel-Crafts acylation reaction, characterized in that: The aromatic compound is any one of anisole, o-methyl anisole, m-methyl anisole, p-methyl anisole, o-methoxy anisole, m-methoxy anisole, p-methoxy anisole, phenethyl ether, bromobenzene, toluene, m-xylene, mesitylene, furan, thiophene, and β-methoxynaphthalene.

8. The application of the supported catalyst as described in any one of claims 1-6 in the Friedel-Crafts acylation reaction, characterized in that: The acylation reagent is any one of acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, benzoic anhydride, succinic anhydride, glutaric anhydride, maleic anhydride, isobutyric anhydride, chloroacetic anhydride, trifluoroacetic anhydride, and phthalic anhydride. The molar ratio of the aromatic compound to the acid anhydride is 1:0.05-5; the mass ratio of the acylation reagent to the catalyst is 1:0.1wt%-50wt%; the temperature of the Friedel-Crafts acylation reaction is 50-180℃; and the time of the Friedel-Crafts acylation reaction is 2-18h.

9. The application of the supported catalyst as described in any one of claims 1-6 in the Friedel-Crafts acylation reaction, characterized in that: The molar ratio of the aromatic compound to the acid anhydride is 1:0.1-1.1; the mass ratio of the acylation reagent to the catalyst is 1:1wt%-10wt%; and the Friedel-Crafts acylation reaction time is 6-12h.

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