Process for the production of cyclohexene

Abstract

The present application relates to the production field of organic chemical raw material cyclohexene, and discloses a production method of cyclohexene.The method comprises the following steps: carrying out cracking reaction on cyclohexylbenzene and / or dicyclohexylbenzene raw material and a solid acid catalyst to obtain cyclohexene and benzene; and the solid acid catalyst is selected from at least one of amorphous silicon aluminum, molecular sieve and solid supported inorganic acid.The method has the advantages of high raw material conversion rate, high cyclohexene yield and no by-product cyclohexane, etc.

Description

Technical Field

[0001] This invention relates to the field of production of cyclohexene, an organic chemical raw material, and specifically to a method for producing cyclohexene. Background Technology

[0002] Cyclohexene is an important chemical raw material and intermediate, which can be used to synthesize lysine, cyclohexanol, cyclohexanone, 1,2-cyclohexanediol, adipic acid, cyclohexenone, and cyclohexene oxide, etc., and has a wide range of industrial applications.

[0003] Currently, cyclohexene is produced industrially by partial hydrogenation of benzene. Benzene undergoes selective hydrogenation with hydrogen under the action of a ruthenium-based catalyst to produce a mixture of cyclohexene and cyclohexane, which is then purified by extraction and distillation to obtain cyclohexene. The disadvantages of this method are: (1) The catalyst is a complex aqueous solution system with Ru-Zn as the main catalyst and zinc sulfate and zirconium oxide as auxiliary agents. The catalyst preparation has poor stability, which often brings difficulties to the stable operation of the process, and ruthenium is expensive; (2) The conversion rate and selectivity of the partial hydrogenation of benzene are not high. The ideal result is a benzene conversion rate of 50% and a cyclohexene selectivity of 75%, with a large amount of low-priced cyclohexane as a byproduct; (3) The reaction products are benzene, cyclohexene, and cyclohexane, which have basically the same boiling point. In particular, cyclohexene and cyclohexane are extremely difficult to separate, so the product separation process is complex and energy consumption is very high; (4) The partial hydrogenation reactor for benzene needs to be made of expensive Hastelloy, resulting in high equipment investment. Due to the above factors, the production cost of cyclohexene has remained high for a long time. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems existing in the prior art and provide a method for producing cyclohexene. The method for preparing cyclohexene has advantages such as high raw material conversion rate, high cyclohexene yield, and virtually no byproduct cyclohexane.

[0005] To achieve the above objectives, the present invention provides a method for producing cyclohexene, the method comprising: subjecting cyclohexylbenzene and / or dicyclohexylbenzene raw materials to a cracking reaction with a solid acid catalyst to obtain cyclohexene and benzene;

[0006] The solid acid catalyst is selected from at least one of amorphous silica-alumina, molecular sieves, and immobilized inorganic acids.

[0007] More preferably, the solid acid catalyst is selected from at least one of amorphous silica-alumina, REY molecular sieve and MCM-41 molecular sieve, and is preferably amorphous silica-alumina.

[0008] Preferably, the mass ratio of cyclohexylbenzene to dicyclohexylbenzene is 0-100:100-0, and more preferably 0-45:55-100.

[0009] Preferably, the cyclohexylbenzene and / or dicyclohexylbenzene are prepared by hydrogenation alkylation of benzene with hydrogen, and preferably at least a portion of the benzene is provided by benzene from the products obtained by cracking reaction.

[0010] The beneficial effects of the present invention through the above technical solution include:

[0011] The method described in this invention for preparing cyclohexene has the advantages of high raw material conversion rate, high cyclohexene yield, and virtually no byproduct cyclohexane. Preferably, in the method provided by this invention, cyclohexylbenzene and / or dicyclohexylbenzene raw materials are obtained through a hydrogenation alkylation reaction of benzene and hydrogen, and at least a portion of the benzene is provided by benzene from the products obtained from the cracking reaction, i.e., byproduct recovery and utilization, realizing process recycling, saving costs, reducing energy consumption, and improving economic efficiency.

[0012] The method described in this invention has a simple and easy-to-control reaction process, does not require special materials for production equipment, has low energy consumption, and is environmentally friendly. It can significantly reduce equipment investment, energy consumption, and operating costs, thereby significantly reducing the production cost of cyclohexene. Attached Figure Description

[0013] Figure 1 This is a schematic diagram of the process of the present invention. Detailed Implementation

[0014] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0015] The pressure mentioned in this invention is absolute pressure.

[0016] This invention provides a method for producing cyclohexene, the method comprising: subjecting cyclohexylbenzene and / or dicyclohexylbenzene raw materials to a cracking reaction with a solid acid catalyst to obtain cyclohexene and benzene;

[0017] The solid acid catalyst is selected from at least one of amorphous silica-alumina, molecular sieves, and immobilized inorganic acids.

[0018] Currently, cyclohexene is mainly produced industrially via partial hydrogenation of benzene on a ruthenium-based catalyst. This method suffers from drawbacks such as poor catalyst reproducibility, large quantities of low-value cyclohexane as a byproduct, and extremely stringent requirements on raw materials and reaction equipment, resulting in high production costs. The method provided by this invention effectively overcomes these shortcomings, offering advantages such as high raw material conversion rate, high cyclohexene yield, and virtually no cyclohexane byproduct, thus potentially significantly reducing the production cost of cyclohexene.

[0019] During the research process, the inventors discovered that the use of a specific type of solid acid catalyst in the method of the present invention is beneficial to improving the cracking performance of cyclohexylbenzene and / or dicyclohexylbenzene raw materials, which can almost quantitatively crack cyclohexylbenzene and dicyclohexylbenzene into cyclohexene and benzene.

[0020] In this invention, the ratio of raw materials cyclohexylbenzene and dicyclohexylbenzene can be arbitrarily adjusted; that is, cyclohexylbenzene can be used alone, dicyclohexylbenzene can be used alone, or a mixture of the two raw materials in any proportion. Preferably, the mass ratio of cyclohexylbenzene to dicyclohexylbenzene is 0-100:100-0, more preferably 0-45:55-100. Using this preferred embodiment can improve the efficiency of cyclohexene production.

[0021] According to the present invention, preferably, the molecular sieve is selected from at least one of Y-type molecular sieve, Beta-type molecular sieve, and MCM-type molecular sieve, more preferably REY molecular sieve and / or MCM-41 molecular sieve. This preferred embodiment is beneficial for improving the pyrolysis performance of the raw material.

[0022] In this invention, immobilized inorganic acid refers to a catalyst obtained by loading an inorganic acid onto a solid support.

[0023] The present invention allows for a wide range of choices regarding the types of supported inorganic acids. Preferably, the supported inorganic acid is H3PW. 12 O 40 / SiO2 and / or H3PO4 / diatomaceous earth.

[0024] More preferably, the solid acid catalyst is selected from at least one of amorphous silica-alumina, REY molecular sieve and MCM-41 molecular sieve, and is particularly preferred to be amorphous silica-alumina.

[0025] The inventors have discovered that using an amorphous silica-alumina catalyst results in significantly higher feedstock cracking performance, enabling more complete cracking of cyclohexylbenzene and dicyclohexylbenzene into cyclohexene and benzene. Furthermore, this catalyst maintains high activity and stability at high temperatures, and its activity can be easily restored through high-temperature calcination after deactivation, making the regeneration method simple.

[0026] According to the present invention, preferably, the amorphous silicon-aluminum contains 10-40% alumina by mass, more preferably 15-30%. Amorphous silicon-aluminum with the above characteristics exhibits stronger acidity, thereby possessing higher pyrolysis activity.

[0027] According to the present invention, preferably, the pore volume of the amorphous silicon aluminum is 0.3-1 mL / g, more preferably 0.5-1 mL / g.

[0028] According to the present invention, preferably, the specific surface area of ​​the amorphous silicon-aluminum is 50-1000 m². 2 / g, preferably 100-400m 2 / g.

[0029] Amorphous silicon-aluminum with the above-mentioned specific surface area and pore volume characteristics exhibits higher pyrolysis activity and stability.

[0030] The present invention does not have any particular limitation on the source of the solid acid catalyst, which can be obtained commercially or prepared by conventional methods.

[0031] According to the present invention, preferably, the conditions for the pyrolysis reaction include: a temperature of 300-500℃, more preferably 350-450℃; a pressure of 0.1-0.5MPa, more preferably 0.1-0.3MPa; and a mass hourly space velocity of 0.1-5h⁻¹. -1 Preferably 0.5-2h -1 This preferred embodiment is beneficial for improving the yield of cyclohexene.

[0032] The pyrolysis reaction described in this invention can be carried out in the presence of a carrier gas or not. Preferably, the pyrolysis reaction is carried out under the condition of a carrier gas, wherein the carrier gas is selected from at least one of nitrogen, argon, neon, helium, and water vapor. This preferred embodiment can improve the reaction conversion rate and reduce the catalyst deactivation rate.

[0033] According to the present invention, preferably, the volume of the carrier gas is 1-20 times the total volume of the raw materials, and more preferably 1-5 times.

[0034] According to the present invention, preferably, the pyrolysis reaction is carried out in a pyrolysis reactor. The present invention does not have any particular limitation on the type of pyrolysis reactor, and various reactor types conventionally used in the art, such as fixed-bed reactors, fluidized-bed reactors, and suspended-bed reactors, can be used. The present invention preferably uses a fixed-bed reactor. Using this preferred embodiment, the reactor manufacturing cost is low and the reaction process is easier to operate.

[0035] In this invention, the pyrolysis reaction may also contain small amounts of heavy components such as polycyclohexylbenzene and cyclohexene polymers.

[0036] Preferably, the method further includes separating the pyrolysis products to obtain cyclohexene and benzene.

[0037] The present invention does not particularly limit the separation method, and various conventional separation methods can be used. Preferably, the separation is carried out by distillation.

[0038] The present invention does not particularly limit the distillation method, and can refer to conventional methods in the art.

[0039] According to the present invention, preferably, the cyclohexylbenzene and / or dicyclohexylbenzene are obtained by a hydrogenation alkylation reaction of benzene and hydrogen, and more preferably, at least a portion of the benzene is provided by benzene from the products obtained from a cracking reaction. Using the above preferred embodiments, cyclohexylbenzene and / or dicyclohexylbenzene can be obtained in a one-step reaction, with simple and readily available raw materials. Furthermore, at least a portion of the benzene is provided by benzene from the products obtained from the cracking reaction, allowing for byproduct recovery and recycling, achieving process recycling, saving costs, reducing energy consumption, and improving economic efficiency.

[0040] According to the present invention, preferably, the hydrogenation alkylation reaction process includes: benzene reacting with hydrogen in the presence of a metal / solid acid catalyst.

[0041] The present invention provides a wide range of conditions for the hydrogenation alkylation reaction. To improve the single-pass conversion of benzene and the selectivity of cyclohexylbenzene and dicyclohexylbenzene feedstocks, the preferred conditions for the hydrogenation alkylation reaction include: a temperature of 100-200℃, preferably 110-160℃; a pressure of 1-5 MPa, preferably 1-4 MPa; and a mass hourly space velocity of 0.1-5 h⁻¹. -1 Preferably 0.2-2h -1 The molar ratio of hydrogen to benzene is 1-10:1, preferably 3-6:1.

[0042] The present invention does not impose any particular limitation on the type of metal / solid acid catalyst, and can use various metal / solid acid catalysts conventionally used in the art. Preferably, the metal / solid acid catalyst includes a solid acid component and a metal hydrogenation component.

[0043] In this invention, the selection range of the solid acid component is relatively wide, and it can be various molecular sieves conventionally used in the art. Preferably, the solid acid component is a molecular sieve, preferably selected from at least one of MCM-type molecular sieves, Y-type molecular sieves, and β-type molecular sieves, and more preferably selected from at least one of MCM-49 molecular sieves, Y-type molecular sieves, and β-type molecular sieves.

[0044] According to the present invention, preferably, the silicon-aluminum molar ratio of the solid acid component is 3-100:1.

[0045] The present invention has a wide range of choices for the types of metal hydrogenation components, which can be noble metals, such as palladium and ruthenium; or non-noble metals, such as nickel.

[0046] When the metal hydrogenation component is a non-precious metal, preferably, based on a metal / solid acid catalyst, the content of the metal hydrogenation component in the metal / solid acid catalyst is 1-5 wt%.

[0047] When the metal hydrogenation component is a noble metal, preferably, based on a metal / solid acid catalyst, the content of the metal hydrogenation component in the metal / solid acid catalyst is 0.1-1 wt%.

[0048] In this invention, in order to improve the reactivity, the metal hydrogenation component is preferably a noble metal, preferably palladium and / or ruthenium.

[0049] According to a preferred embodiment of the present invention, the metal / solid acid catalyst comprises a solid acid component and a metal hydrogenation component, wherein the metal hydrogenation component is palladium and / or ruthenium; the solid acid component is selected from at least one of MCM-49 molecular sieve, Y-type molecular sieve, and β-type molecular sieve, and the silicon-to-aluminum molar ratio of the solid acid component is 3-100:1. This preferred embodiment is beneficial for further improving the single-pass conversion rate of benzene and the selectivity of cyclohexylbenzene and dicyclohexylbenzene feedstocks.

[0050] According to the present invention, the reactor used in the hydrogenation alkylation reaction includes one or more reactors, and the reactor type can be various reactor types such as fixed bed reactor, suspended bed reactor, continuous stirred tank reactor, etc., preferably a fixed bed reactor, more preferably a tubular fixed bed reactor.

[0051] The hydrogenation alkylation product of the present invention includes cyclohexylbenzene, dicyclohexylbenzene, trace amounts of cyclohexane, methylcyclopentylbenzene, and heavy components such as dicyclohexylcyclohexane and tricyclohexylbenzene, as well as unreacted benzene or excess hydrogen.

[0052] The hydrogenated alkylation products described in this invention can be separated using conventional separation methods, and this invention does not impose any limitations on the separation methods.

[0053] Preferably, the cyclohexylbenzene and / or dicyclohexylbenzene in the hydrogenation alkylation product are sent to the cracking reaction for use as feedstock.

[0054] Preferably, the unreacted benzene is returned to the hydrogenation alkylation reaction for use as a feedstock.

[0055] The present invention will be described in detail below through embodiments.

[0056] In the following examples, the yields of the reaction products were analyzed using gas chromatography. The chromatographic conditions were as follows: Chromatograph: Agilent 7890A; Injector temperature: 250°C; Detector: FID, detector temperature: 250°C; Analytical column: HP-PONA column, 50m × 0.25mm × 1μm; Column program: Hold at 40°C for 2 minutes, then increase to 240°C at a rate of 5°C / min and hold for 60 minutes.

[0057] Example 1

[0058] The tubular fixed-bed reactor used consisted of a 20mm inner diameter, 1000mm long stainless steel tube, containing 30g of amorphous silica-alumina catalyst (alumina mass fraction of 22.5%, pore volume of 0.56mL / g, specific surface area of ​​298.5m²). 2 The feedstock (70% by mass of cyclohexylbenzene and 30% by mass of dicyclohexylbenzene) was introduced into the reactor at a rate of 30 g / h, and carrier nitrogen was introduced into the reactor at a rate of 300 mL / min. The reaction temperature was 400 °C, and the pressure was normal. The cracking reaction products were obtained, and cyclohexene and benzene were obtained by distillation. The reaction results are shown in Table 1.

[0059] In the presence of a metal / solid acid catalyst, benzene undergoes a hydrogenation alkylation reaction with hydrogen in a solid bed reactor, wherein at least a portion of the benzene is provided by benzene from the products obtained from a cracking reaction.

[0060] The aforementioned metal / solid acid catalyst comprises a Y-type molecular sieve (silicon-to-aluminum molar ratio of 5.5) and the noble metal Pd; based on the metal / solid acid catalyst, the content of the noble metal in the metal / solid acid catalyst is 0.15 wt%. The conditions for the hydroalkylation reaction include: a temperature of 120 °C; a pressure of 2 MPa; and a space velocity of 1 h⁻¹. -1 A hydrogen-to-benzene molar ratio of 5:1 was used to separate cyclohexylbenzene and dicyclohexylbenzene. The single-pass conversion of benzene was 54.2%, and the overall selectivity for cyclohexylbenzene and dicyclohexylbenzene was 98.5%.

[0061] Example 2

[0062] The tubular fixed-bed reactor used consists of a 20mm inner diameter, 1000mm long stainless steel tube, containing 30g of amorphous silica-alumina catalyst (alumina mass fraction of 25%, pore volume of 0.6mL / g, specific surface area of ​​275m²). 2 The feedstock (70% by mass of cyclohexylbenzene and 30% by mass of dicyclohexylbenzene) was introduced into the reactor at a rate of 30 g / h, and carrier nitrogen was introduced into the reactor at a rate of 300 mL / min. The reaction temperature was 425 °C, and the pressure was normal. The cracking reaction products were obtained, and cyclohexene and benzene were obtained by distillation. The reaction results are shown in Table 1.

[0063] In the presence of a metal / solid acid catalyst, benzene undergoes a hydrogenation-alkylation reaction with hydrogen in a solid bed reactor, wherein at least a portion of the benzene is provided by benzene from the products obtained from a cracking reaction.

[0064] The aforementioned metal / solid acid catalyst comprises a Y-type molecular sieve (silicon-to-aluminum molar ratio of 5.5) and the noble metal Pd; based on the metal / solid acid catalyst, the content of the noble metal in the metal / solid acid catalyst is 0.2 wt%. The conditions for the hydrogenation alkylation reaction include: a temperature of 115 °C; a pressure of 2 MPa; and a space velocity of 1.2 h⁻¹. -1With a hydrogen-to-benzene molar ratio of 5.5:1, cyclohexylbenzene and dicyclohexylbenzene were separated. The single-pass conversion of benzene was 50.6%, and the overall selectivity for cyclohexylbenzene and dicyclohexylbenzene was 98.2%.

[0065] Example 3

[0066] The tubular fixed-bed reactor used consisted of a 20mm inner diameter, 1000mm long stainless steel tube, containing 30g of amorphous silica-alumina catalyst (alumina mass fraction of 17.9%, pore volume of 0.55mL / g, specific surface area of ​​300.2m²). 2 The raw materials (70% by mass of cyclohexylbenzene and 30% by mass of dicyclohexylbenzene) prepared according to the method described in Example 1 were introduced into the reactor at a rate of 30 g / h, and carrier nitrogen was introduced into the reactor at a rate of 300 mL / min. The reaction temperature was 450 °C, and the pressure was normal. The cracking reaction products were obtained, and cyclohexene and benzene were obtained by distillation. The reaction results are shown in Table 1.

[0067] In the presence of a metal / solid acid catalyst, benzene undergoes a hydroalkylation reaction with hydrogen in a solid bed reactor, wherein at least a portion of the benzene is provided by benzene recovered from the cracking reaction products. The specific method is described in Example 1.

[0068] Example 4

[0069] The reaction was carried out according to the method of Example 2, except that the reaction temperature was changed to 375°C. The reaction results are shown in Table 1.

[0070] Example 5

[0071] The reaction was carried out according to the method of Example 2, except that the carrier gas was changed to water vapor and introduced into the reactor at a rate of 30 g / h. The reaction results are shown in Table 1.

[0072] Example 6

[0073] The reaction was carried out according to the method of Example 2, except that no carrier gas was introduced. The reaction results are shown in Table 1.

[0074] Example 7

[0075] The reaction was carried out according to the method of Example 2, except that 30g of REY type molecular sieve catalyst (silicon-to-aluminum ratio of 5, lanthanum oxide mass fraction of 2.5%) was used instead. The reaction results are shown in Table 1.

[0076] It should be noted that, compared with the catalyst in Example 2, this molecular sieve is prone to carbon buildup and blockage, resulting in easy deactivation and poor stability.

[0077] Example 8

[0078] The procedure was carried out according to Example 2, except that cyclohexylbenzene was used as the feedstock and fed into the reactor at a rate of 30 g / h. The results are shown in Table 1.

[0079] Example 9

[0080] The reaction was carried out according to the method of Example 2, except that dicyclohexylbenzene was used as the raw material and fed into the reactor at a rate of 30 g / h. The reaction results are shown in Table 1.

[0081] Example 10

[0082] The procedure was carried out according to Example 2, except that the amorphous silica-alumina catalyst contained 8% alumina by mass, had a pore volume of 0.45 mL / g, and a specific surface area of ​​420.6 m². 2 / g. The reaction results are shown in Table 1.

[0083] Comparative Example 1

[0084] The reaction was carried out according to the method of Example 2, except that the catalyst was changed to γ-alumina. The reaction results are shown in Table 1.

[0085] Table 1

[0086]

[0087]

[0088] As can be seen from the results in Table 1, the method of the present invention has a significantly higher raw material conversion rate and a higher cyclohexene yield.

[0089] Moreover, the method described in this invention produces virtually no cyclohexane byproducts, effectively overcoming the drawbacks of complex subsequent product separation processes and reducing energy consumption; the reaction equipment used in the method described in this invention does not require special materials, which can significantly reduce the production cost of cyclohexene.

[0090] In addition, the byproduct benzene obtained by the method of the present invention can be used as a raw material to produce cyclohexylbenzene and / or dicyclohexylbenzene, realizing process recycling, saving costs, reducing energy consumption, and improving economic efficiency.

[0091] The preferred 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 combinations of 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 method for producing cyclohexene, the method comprising: Cyclohexylbenzene and / or dicyclohexylbenzene feedstocks are subjected to a cracking reaction with a solid acid catalyst to obtain cyclohexene and benzene; The solid acid catalyst is amorphous silicon-aluminum; In the amorphous silicon-aluminum, the mass fraction of alumina is 10-40%; The amorphous silicon-aluminum has a pore volume of 0.3-1 mL / g and a specific surface area of ​​50-1000 m². 2 / g.

2. The method according to claim 1, wherein, The raw material is dicyclohexylbenzene.

3. The method according to claim 1, wherein, In the amorphous silicon-aluminum, the mass fraction of alumina is 15-30%.

4. The method according to claim 1, wherein, The amorphous silica-alumina has a pore volume of 0.5-1 mL / g and a specific surface area of ​​100-400 m². 2 / g.

5. The method according to any one of claims 1-4, wherein, The conditions for the pyrolysis reaction include: a temperature of 300-500℃; a pressure of 0.1-0.5 MPa; and a mass hourly space velocity (HHSV) of 0.1-5 h⁻¹. -1 .

6. The method according to claim 5, wherein, The conditions for the pyrolysis reaction include: a temperature of 350-450℃; a pressure of 0.1-0.3 MPa; and a mass hourly space velocity (HHSV) of 0.5-2 h⁻¹. -1 .

7. The method according to any one of claims 1-4, wherein, The pyrolysis reaction is carried out under the condition of a carrier gas, which is selected from at least one of nitrogen, argon, neon, helium and water vapor; The volume of the carrier gas used is 1-20 times the total volume of the raw materials.

8. The method according to claim 7, wherein, The volume of the carrier gas used is 1-5 times the total volume of the raw materials.

9. The method according to any one of claims 1-4, wherein, The pyrolysis reaction is carried out in a pyrolysis reactor, which is selected from at least one of a fluidized bed reactor, a suspended bed reactor, and a fixed bed reactor.

10. The method according to claim 9, wherein, The pyrolysis reactor is a fixed-bed reactor.

11. The method according to claim 1, wherein, The cyclohexylbenzene and / or dicyclohexylbenzene are prepared by hydrogenation alkylation of benzene with hydrogen, and at least a portion of the benzene is provided by benzene from the products obtained by the cracking reaction.

12. The method according to claim 11, wherein, The hydrogenation alkylation reaction process includes: benzene reacting with hydrogen in the presence of a metal / solid acid catalyst; The conditions for the hydrogenation alkylation reaction include: a temperature of 100-200℃; a pressure of 1-5 MPa; and a mass hourly space velocity of 0.1-5 h⁻¹. -1 The molar ratio of hydrogen to benzene is 1-10:

1.

13. The method according to claim 12, wherein, The metal / solid acid catalyst comprises a solid acid component and a metal hydrogenation component, wherein the metal hydrogenation component is a noble metal; the solid acid component is selected from at least one of MCM molecular sieves, Y-type molecular sieves and Beta-type molecular sieves.

14. The method according to claim 13, wherein, The silicon-aluminum molar ratio of the solid acid component is 3-100:1; The solid acid component is selected from at least one of MCM-49 molecular sieve, Y-type molecular sieve and Beta-type molecular sieve; The metal hydrogenation component is palladium and / or ruthenium; Based on a metal / solid acid catalyst, the content of the metal hydrogenation component in the metal / solid acid catalyst is 0.1-1 wt%.

Images