Solid acid catalysts, their preparation methods and applications

Abstract

This invention discloses a solid acid catalyst, its preparation method, and its application. The solid acid catalyst, based on its weight and by mass fraction, comprises: a) 50%–98% silica support; b) 1%–30% of at least one metal selected from Group IVB and Group IVA, calculated as the corresponding metal oxide; c) 0.01%–10% of at least one metal selected from Group VIB and Group VIII; and d) 0.1%–10% sulfate ions. The ratio of Brønsted acid (B acid) to strong Lewis acid (L acid) in the catalyst is 20:1 to 1:20. This catalyst is used for toluene disproportionation and alkyl transfer reactions, exhibiting characteristics of low reaction temperature, low hydrogen consumption, and high conversion rate.

Description

Technical Field

[0001] This invention belongs to the field of solid catalysts, specifically relating to a solid acid catalyst, its preparation method, and its application. Background Technology

[0002] Xylene is an important basic organic raw material, and the toluene disproportionation and alkyl transfer unit in aromatic hydrocarbon complexes is one of the important industrial pathways for xylene production. With the accompanying energy shortage, achieving energy-saving and high-efficiency xylene production is an urgent issue to be addressed. Improving the catalytic performance of catalysts to reduce energy and material consumption in the disproportionation and alkyl transfer processes is an important way to reduce costs and increase efficiency. Alkyl transfer reactions are acid-catalyzed reactions, and controlling the acid properties of solid acids to match this reaction is a key research focus in catalyst design. Solid acid catalysts are widely used in various industrial production processes. Among them, solid superacids obtained after sulfation are an important type of solid acid. Metal oxides generally achieve a significant increase in acid strength after sulfation. By adding promoters to control the distribution of acid strength, the acid properties of the catalyst can be matched with the reaction.

[0003] CN113492016A discloses a two-component catalyst for toluene disproportionation and alkyl transfer, and its preparation method. The catalyst comprises a modified needle-shaped MOR molecular sieve and a modified nano-ZSM-5 molecular sieve. The modified needle-shaped MOR molecular sieve is prepared by impregnation and modification of needle-shaped hydrogen-form MOR molecular sieves with an aspect ratio of 3–10:1 using inorganic oxides. The modified nano-ZSM-5 molecular sieve is prepared by impregnation and modification of hydrogen-form nano-ZSM-5 molecular sieves with a particle size of 50–300 nm using inorganic oxides. The inorganic oxides are one or more oxides of Co, Mo, Ru, Cu, Be, and W. When using this catalyst, the reaction temperature is required to be 300–500 °C, and the hydrogen-to-hydrogen ratio is required to be 10:1–1:1.

[0004] CN102909066A discloses a toluene disproportionation and alkyl transfer catalyst. This catalyst is composed of a hydrogen-form EU-1 / Beta composite molecular sieve, an inorganic refractory oxide, and a second metal component. CN102909068A discloses a toluene disproportionation and alkyl transfer catalyst. This catalyst is composed of a hydrogen-form EU-1 / ZSM-5 composite molecular sieve, an inorganic refractory oxide, and a second metal component.

[0005] In summary, current research on toluene disproportionation and alkyl transfer catalysts mainly focuses on molecular sieve systems, and the reaction temperatures and hydrogen consumption are generally high. Summary of the Invention

[0006] To address the issues of high reaction temperature and hydrogen consumption in existing alkyl transfer reactions, this invention provides a novel solid acid catalyst, its preparation method, and its application. This catalyst, used in the toluene disproportionation and alkyl transfer reaction, features low reaction temperature, low hydrogen consumption, and high conversion rate.

[0007] The first aspect of this invention provides a solid acid catalyst, which, based on the weight of the catalyst and expressed as a mass fraction, comprises:

[0008] a) 50%–98% silica carrier;

[0009] b) 1% to 30% of at least one metal selected from Group IVB and Group IVA, as the corresponding metal oxide;

[0010] c) 0.01% to 10% of at least one metal selected from Group VIB and Group VIII;

[0011] d) 0.1%–10% sulfate ions;

[0012] The ratio of the amount of Brønsted acid to the amount of strong Lewis acid in the catalyst is 20:1 to 1:20, preferably 10:1 to 1:10, and more preferably 10:1 to 1:5. For example, it is 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:10, etc., and any value within any range formed by any two of these values.

[0013] According to the present invention, preferably, the catalyst comprises:

[0014] a) 65%–88% silica carrier;

[0015] b) 10% to 25% selected from at least one metal from Group IVB and Group IVA, calculated as the corresponding metal oxide;

[0016] c) 1% to 5% of at least one metal selected from Group VIB and Group VIII;

[0017] d) 1% to 5% sulfate ions.

[0018] According to the present invention, the silicon oxide in component a) is mesoporous silicon oxide.

[0019] According to the present invention, component b) is at least one selected from Zr, Ti, and Sn, preferably Sn.

[0020] According to the present invention, component c) is at least one selected from Cr, Mo, W, Co, Ni, and Ru, and more preferably at least one selected from W and Ni.

[0021] A second aspect of the present invention provides a method for preparing the above-mentioned solid acid catalyst, comprising:

[0022] (1) Mix the template agent, silicon source, component c) source and solvent, and then add ammonia water dropwise to obtain a mixture;

[0023] (2) The mixture obtained in step (1) is aged to obtain a gel, and then calcined to obtain a solid.

[0024] (3) After mixing the solid obtained in step (2), component b) source and precipitant, carry out the first hydrothermal reaction, the second hydrothermal reaction, and the third hydrothermal reaction, and then separate to obtain the solid;

[0025] (4) The solid obtained in step (3) is treated with a sulfation reagent and then subjected to a second calcination to obtain the catalyst.

[0026] In step (3), the reaction temperature of the second hydrothermal reaction is higher than that of the first hydrothermal reaction; the temperature of the third hydrothermal reaction is higher than that of the second hydrothermal reaction. Preferably, the reaction temperature of the second hydrothermal reaction is 10–50°C higher than that of the first hydrothermal reaction. The reaction temperature of the third hydrothermal reaction is 10–50°C higher than that of the second hydrothermal reaction.

[0027] According to the present invention, in step (1), the template agent is at least one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), hexadecyltrimethylammonium bromide, or hexadecyltrimethylammonium chloride, preferably P123. The silicon source is tetraethyl orthosilicate. The solvent is ethanol. The source of component c) is a metal salt containing component c), preferably a soluble metal salt. Further, the source of component c) is at least one of a nitrate, acetate, or chloride containing the metal of component c). The mass concentration of the ammonia water is 25% to 28%.

[0028] According to the present invention, in step (1), the molar ratio of the feed materials is as follows: silicon source (SiO2): template agent: solvent: NH3: H2O = 1: 0.001~1: 20~200: 0.001~1: 1~50, preferably as follows: silicon source (SiO2): template agent: solvent: NH3: H2O = 1: 0.01~0.1: 50~150: 0.01~0.5: 10~30.

[0029] According to the present invention, in step (1), the mixture is stirred thoroughly until completely dissolved. The stirring temperature is 20–60°C, preferably 30–40°C.

[0030] According to the present invention, in step (1), the ammonia water is added over a period of 0.1 to 0.5 hours. After the ammonia water is added, the mixture is stirred thoroughly. The stirring temperature is 20 to 60°C, preferably 30 to 40°C, and the stirring time is 10 to 50 hours, preferably 15 to 25 hours.

[0031] According to the present invention, in step (2), the aging temperature is 30–60°C, and the aging time is 10–60 h, preferably 20–50 h. The relative humidity during aging is 30%–60%. Relative humidity is defined as the percentage of water vapor pressure in the air to the saturated water vapor pressure at the same temperature.

[0032] According to the present invention, in step (2), the conditions for the first calcination are: calcination temperature of 200-700°C, preferably 300-500°C, and calcination time of 1-10h, preferably 2-5h.

[0033] According to the present invention, the source of component b) in step (3) is a metal salt containing component b), preferably a soluble metal salt. Further, the source of component b) is at least one of a nitrate, acetate, or chloride containing the metal of component b).

[0034] According to the present invention, the precipitant in step (3) is at least one of urea, KOH, and NaOH. The molar ratio of component b) metal to precipitant is 1:1 to 1:30, preferably 1:5 to 15.

[0035] According to the present invention, in step (3), the mixture is thoroughly stirred after mixing. The stirring temperature is 15-40°C, and the stirring time is 3-12 hours.

[0036] According to the present invention, in step (3), the apparatus for the hydrothermal reaction is a hydrothermal reactor. The temperature of the first hydrothermal reaction is 120-150°C, and the time is 2-20 hours; the temperature of the second hydrothermal reaction is 150-170°C, and the time is 2-20 hours; the temperature of the third hydrothermal reaction is 170-200°C, and the time is 2-20 hours. The reaction times of the first, second, and third hydrothermal reactions can be the same or different.

[0037] According to the present invention, in step (3), the solid obtained after separation can be washed and / or dried. Washing can be performed using at least one of ethanol and deionized water. The drying temperature is 60–120°C, and the time is 2–20 h.

[0038] According to the present invention, in step (4), the sulfation reagent is at least one selected from sulfuric acid, ammonium sulfate, and ammonium bisulfate. The sulfation reagent exists in solution form. The concentration of the sulfation reagent solution is 0.1–3 mol / L, preferably 0.5–1.5 mol / L. The mass of the solid powder and the volume of the sulfation reagent satisfy the following relationship: 1 g / 10 mL to 1 g / 200 mL. The sulfation reagent treatment is performed by immersion, preferably with stirring. The sulfation treatment temperature is 15–40°C, and the time is 2–20 h. After sulfation treatment, drying can be performed. The drying temperature is 60–120°C, and the drying time is 2–20 h.

[0039] According to the present invention, in step (4), the atmosphere for the second roasting is an oxygen-containing atmosphere, preferably air. The temperature for the second roasting is 300–650°C, and the time is 2–20 h.

[0040] The third aspect of the present invention provides the application of the above-described solid acid catalyst or the solid acid catalyst prepared by the above method in the toluene disproportionation and alkyl transfer reaction.

[0041] According to the present invention, the reaction conditions for the application are as follows: reaction temperature of 100–500°C, preferably 100–300°C, more preferably below 300°C; reaction pressure of 1.0–8.0 MPa; hydrogen-to-hydrocarbon molar ratio of 0.1–10, preferably 0.1–5; and liquid feedstock weight hourly space velocity of 0.5–10 h⁻¹. -1 .

[0042] Compared with the prior art, the present invention has the following advantages:

[0043] 1. The catalyst of this invention comprises: a) 50%–98% silica support; b) 1%–30% of at least one metal selected from Group IVB and Group IVA, calculated as the corresponding metal oxide; c) 0.01%–10% of at least one metal selected from Group VIB and Group VIII; d) 0.1%–10% sulfate ions; the ratio of Brønsted acid (B acid) to strong Lewis acid (L acid) in the catalyst is 20:1 to 1:20. The inventors of this invention have discovered that in disproportionation and alkyl transfer reactions, the ratio of strong Lewis acid to Brønsted acid in the catalytic material is related to the transfer process of active protons on the catalyst surface during the reaction. The addition of the bimetallic component can regulate this ratio to obtain superior catalytic performance. Sulfate ions and metal oxides synthesized in situ dispersed in the pore structure of mesoporous silica material have high acid strength and acid density, enabling alkyl transfer reactions at lower temperatures. Introducing metal oxides in situ during the synthesis of mesoporous materials can further enhance their reactivity.

[0044] 2. In the preparation method provided by this invention, the template agent, silicon source, component c) source, and solvent are first mixed, and then ammonia water is added dropwise. After aging and calcination, the resulting solid is mixed with component b) source and precipitant, and then subjected to three hydrothermal reactions. Finally, it is treated with a sulfation reagent and calcined to obtain the catalyst. This method is simple to operate, economical, feasible, and easy to industrialize. The catalyst prepared by this method has a suitable distribution of Brønsted acid and strong Lewis acid, is suitable for toluene disproportionation and alkyl transfer reactions, and features low reaction temperature, low hydrogen consumption, and high conversion rate.

[0045] 3. In existing technologies, the reaction temperature for toluene disproportionation and alkyl transfer reactions is generally required to be relatively high, typically between 300 and 500°C. The solid acid catalyst provided by this invention, used for toluene disproportionation and alkyl transfer reactions, features low reaction temperature, low hydrogen consumption, and high conversion rate. More preferably, the solid acid catalyst provided by this invention is suitable for toluene disproportionation and alkyl transfer reactions at temperatures below 300°C. Detailed Implementation

[0046] The technical solution of the present invention will be further illustrated below with reference to the embodiments, but it is not limited to the following embodiments.

[0047] In this invention, the solid-state nuclear magnetic resonance spectrum using trimethylphosphine as a probe molecule ( 31 The test method for PMAS NMR is as follows: After activating the sample under vacuum, a certain amount of trimethylphosphine molecules are adsorbed onto the sample in situ. The sample is loaded into a glove box protected by N2 and tested using a Bruker AVANCEⅢ 400WB solid-state NMR spectrometer with a rotor diameter of 4 mm and a sample rotation speed of 12 kHz. High-power proton decoupling test 31 The PMAS NMR spectrum was analyzed and calibrated using NH4H2PO4 as a standard reference. The Brønsted acid concentration ranged from 0 to -5 ppm for the sample. 31 The acidity of strong L-acids was calculated from the peak area of ​​the ppm MAS NMR sample, and the acidity was determined by the sample concentration between -5 and -35 ppm. 31 The peak area was calculated using PMAS NMR.

[0048] In this invention, unless otherwise specified, % refers to mass percentage.

[0049]

Example 1

[0050] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 71.5% of the total catalyst weight, and Ni accounted for 4% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0051] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 145, 165, and 185℃ for 10 hours each. After washing with deionized water, it was dried at 90℃ for 12 hours to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, it was stirred together with solid powder A3 at 30℃ for 10 hours, dried at 90℃ for 10 hours, and then calcined at 600℃ for 5 hours to obtain catalyst C1.

[0052] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0053]

Example 2

[0054] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 74.5% of the total catalyst weight, and Ni accounted for 1% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0055] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 145, 165, and 185℃ for 10 hours each. After washing with deionized water, it was dried at 90℃ for 12 hours to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, it was stirred together with solid powder A3 at 30℃ for 10 hours, dried at 90℃ for 10 hours, and then calcined at 600℃ for 5 hours to obtain catalyst C1.

[0056] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0057]

Example 3

[0058] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 71.5% of the total catalyst weight, and Ni accounted for 4% of the total catalyst weight. Mixture A1 was aged at 30°C and 30% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0059] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 145, 165, and 185℃ for 10 hours each. After washing with deionized water, it was dried at 90℃ for 12 hours to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, it was stirred together with solid powder A3 at 30℃ for 10 hours, dried at 90℃ for 10 hours, and then calcined at 600℃ for 5 hours to obtain catalyst C1.

[0060] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0061]

Example 4

[0062] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 83.5% of the total catalyst weight, and Ni accounted for 4% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0063] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 11% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 145, 165, and 185℃ for 10h each. After washing with deionized water, it was dried at 90℃ for 12h to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, it was stirred together with solid powder A3 at 30℃ for 10h, dried at 90℃ for 10h, and then calcined at 600℃ for 5h to obtain catalyst C1.

[0064] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0065]

Example 5

[0066] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 71.5% of the total catalyst weight, and Ni accounted for 4% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0067] 10g of A2 was weighed and mixed with tetrabutyl titanate and urea in deionized water, then stirred thoroughly. The weight percentage of Ti (calculated as TiO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 145, 165, and 185℃ for 10h each. After washing with deionized water, it was dried at 90℃ for 12h to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, it was stirred together with solid powder A3 at 30℃ for 10h, dried at 90℃ for 10h, and then calcined at 600℃ for 5h to obtain catalyst C1.

[0068] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0069]

Example 6

[0070] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 71.5% of the total catalyst weight, and Ni accounted for 4% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0071] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 135, 155, and 175℃ for 10 hours each. After washing with deionized water, the mixture was dried at 90℃ for 12 hours to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, the mixture was stirred together with solid powder A3 at 30℃ for 10 hours, dried at 90℃ for 10 hours, and then calcined at 600℃ for 5 hours to obtain catalyst C1.

[0072] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0073]

Example 7

[0074] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 74.5% of the total catalyst weight, and Ni accounted for 1% of the total catalyst weight. Mixture A1 was aged at 30°C and 30% relative humidity for 20 hours, and then calcined at 350°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0075] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 145, 165, and 185℃ for 10 hours each. After washing with deionized water, it was dried at 90℃ for 12 hours to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, it was stirred together with solid powder A3 at 30℃ for 10 hours, dried at 90℃ for 10 hours, and then calcined at 600℃ for 5 hours to obtain catalyst C1.

[0076] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0077]

Example 8

[0078] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.02:70:0.1:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 83.5% of the total catalyst weight, and Ni accounted for 5% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0079] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 10% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted sequentially at 125, 155, and 175℃ for 10 hours each. After washing with deionized water, the mixture was dried at 90℃ for 12 hours to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, the mixture was stirred with solid powder A3 at 30℃ for 10 hours, dried at 90℃ for 10 hours, and then calcined at 600℃ for 5 hours to obtain catalyst C1.

[0080] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0081] Comparative Example 1

[0082] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 71.5% of the total catalyst weight, and Ni accounted for 4% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0083] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and reacted hydrothermally at 170℃ for 48h. After washing with deionized water, it was dried at 90℃ for 12h to obtain solid powder A3. Using 1mol / L dilute sulfuric acid as the sulfation reagent, it was stirred together with solid powder A3 at 30℃ for 10h, dried at 90℃ for 10h, and then calcined at 600℃ for 5h to obtain catalyst C1.

[0084] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0085] Comparative Example 2

[0086] P123, tetraethyl orthosilicate, ethanol, and nickel nitrate were stirred at 35°C until fully dissolved. Diluted ammonia was then added dropwise over 0.2 hours, and the mixture was stirred at 35°C for 20 hours to obtain mixture A1. The molar ratio of the raw materials was tetraethyl orthosilicate: P123: ethanol: NH3: H2O = 1:0.05:100:0.5:20. Tetraethyl orthosilicate, calculated as SiO2, accounted for 73% of the total catalyst weight, and Ni accounted for 4% of the total catalyst weight. Mixture A1 was aged at 50°C and 50% relative humidity for 48 hours, and then calcined at 400°C for 4 hours to obtain Ni-loaded mesoporous silica material A2.

[0087] 10g of A2 was weighed and mixed with tin chloride and urea in deionized water, then stirred thoroughly. The weight percentage of Sn (calculated as SnO2) was 23% of the total catalyst, and the molar ratio of Sn to urea was 1:10, resulting in mixture A2. Mixture A2 was transferred to a hydrothermal reactor and subjected to hydrothermal reactions at 145, 165, and 185℃ for 10 hours, respectively. After washing with deionized water, the mixture was dried at 90℃ for 12 hours to obtain solid powder A3. This powder was then calcined at 600℃ for 5 hours to obtain catalyst C1.

[0088] The catalyst evaluation conditions were as follows: 5g of catalyst C1 was weighed and loaded into a fixed-bed reactor, hydrogen gas was introduced at a rate of 80mL / min, and the reactor was kept at 460℃ for 2 hours under a pressure of 4Ma. The temperature was then lowered to 285℃, and the hydrogen-hydrogen molar ratio was adjusted to 0.6. After the temperature stabilized, toluene and 1,2,4-trimethylbenzene (mass ratio of 1:1) were introduced and reacted for 18 hours. The reaction results are shown in Table 1.

[0089] Table 1 Catalyst Evaluation Effect

[0090]

[0091]

[0092] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A solid acid catalyst, characterized in that, Based on the weight of the catalyst, and expressed as a mass fraction, the solid acid catalyst comprises: a) 50%~98% silica carrier; b) 1% to 30% is selected from at least one of Ti and Sn, based on the corresponding metal oxide; c) 0.01%~10% Ni; d) 0.1%~10% sulfate ions; The ratio of the amount of Brønsted acid to the amount of strong Lewis acid in the catalyst is 10:1 to 1:

5. use 31 P MAS NMR test for acidity; 31 In the PMAS NMR spectrum, the amount of Brønsted acid is calculated from the peak area of ​​the sample between 0 and -5 ppm, and the amount of strong L acid is calculated from the peak area of ​​the sample between -5 and -35 ppm.

2. The catalyst according to claim 1, characterized in that, The silicon oxide in component a) is mesoporous silicon oxide.

3. A method for preparing a catalyst according to any one of claims 1 to 2, comprising: (1) Mix the template agent, silicon source, component c) source and solvent, and then add ammonia water dropwise to obtain a mixture; (2) The mixture obtained in step (1) is aged to obtain a gel, and then calcined to obtain a solid; (3) After mixing the solid obtained in step (2), component b) source and precipitant, carry out the first hydrothermal reaction, the second hydrothermal reaction, and the third hydrothermal reaction, and then separate to obtain the solid; (4) The solid obtained in step (3) is treated with a sulfation reagent and then subjected to a second calcination to obtain the catalyst; In step (3), the reaction temperature of the second hydrothermal reaction is higher than that of the first hydrothermal reaction; the temperature of the third hydrothermal reaction is higher than that of the second hydrothermal reaction.

4. The preparation method according to claim 3, characterized in that, In step (3), the reaction temperature of the second hydrothermal reaction is 10~50℃ higher than that of the first hydrothermal reaction; the reaction temperature of the third hydrothermal reaction is 10~50℃ higher than that of the second hydrothermal reaction.

5. The preparation method according to claim 3, characterized in that, In step (3), the temperature of the first hydrothermal reaction is 120~150℃ and the time is 2~20h; and / or, the temperature of the second hydrothermal reaction is 150~170℃ and the time is 2~20h; and / or, the temperature of the third hydrothermal reaction is 170~200℃ and the time is 2~20h.

6. The preparation method according to claim 3, characterized in that, In step (1), the template agent is at least one of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123, hexadecyltrimethylammonium bromide, or hexadecyltrimethylammonium chloride; And / or, the silicon source is tetraethyl orthosilicate; And / or, the solvent is ethanol; And / or, component c) is a metal salt containing component c).

7. The preparation method according to claim 6, characterized in that, In step (1), the template agent is P123; and / or, the source of component c) is a soluble metal salt.

8. The preparation method according to claim 7, characterized in that, In step (1), the source of component c) is at least one of nitrate, acetate, and chloride containing the metal of component c).

9. The preparation method according to claim 3, characterized in that, In step (1), the molar ratio of the feed materials is as follows: silicon source (SiO2): template agent: solvent: NH3: H2O = 1:0.001~1:20~200:0.001~1:1~50.

10. The preparation method according to claim 9, characterized in that, In step (1), the molar ratio of the feed is as follows: silicon source (SiO2): template agent: solvent: NH3: H2O = 1: 0.01~0.1: 50~150: 0.01~0.5: 10~30.

11. The preparation method according to claim 3, characterized in that, In step (2), the conditions for the first roasting are: roasting temperature of 200~700℃ and roasting time of 1~10h.

12. The preparation method according to claim 11, characterized in that, In step (2), the conditions for the first roasting are: roasting temperature of 300~500℃ and roasting time of 2~5h.

13. The preparation method according to claim 3, characterized in that, In step (4), the sulfation reagent is at least one of sulfuric acid, ammonium sulfate, and ammonium bisulfate; And / or, the sulfation treatment is carried out at a temperature of 15~40℃ for 2~20h.

14. The preparation method according to claim 3, characterized in that, In step (4), the atmosphere of the second roasting is an oxygen atmosphere; the temperature of the second roasting is 300~650℃ and the time is 2~20h.

15. The preparation method according to claim 14, characterized in that, In step (4), the atmosphere for the second roasting is air.

16. The use of a catalyst according to any one of claims 1 to 2 or a solid acid catalyst prepared by any one of claims 3 to 15 in the toluene disproportionation and alkyl transfer reaction.

17. The application according to claim 16, characterized in that, The reaction conditions for this application are: a reaction temperature of 100–500 °C; and / or a reaction pressure of 1.0–8.0 MPa; and / or a hydrogen-to-hydrocarbon molar ratio of 0.1–10; and / or a liquid feedstock weight hourly space velocity of 0.5–10 h⁻¹. -1 .

18. The application according to claim 17, characterized in that, The reaction conditions for the application are: a reaction temperature of 100~300℃; and / or a hydrogen-to-hydrogen molar ratio of 0.1~5.

19. The application according to claim 17, characterized in that, In this application, the reaction temperature is below 300°C.

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