Catalyst for catalyzing benzene to prepare cyclohexylbenzene as well as preparation method and application of catalyst

Abstract

The invention provides a catalyst for catalyzing benzene to prepare cyclohexylbenzene and a preparation method and application thereof.The catalyst comprises an H-MOR molecular sieve and active metal loaded in the H-MOR molecular sieve, and the active metal comprises a nickel element, a copper element and a zirconium element; the catalyst is prepared from the following components in percentage by mass: 1.6 to 8.3 percent of nickel element, 0.4 to 1.7 percent of copper element, 0.1 to 0.5 percent of zirconium element and the balance of H-MOR molecular sieve. According to the catalyst for catalyzing benzene to prepare cyclohexylbenzene, nickel, copper and zirconium serve as active metal, the H-MOR molecular sieve serves as the carrier, the catalytic activity of the catalyst can be improved through the synergistic effect of the active metal, the copper and the zirconium, and the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved when the catalyst catalyzes benzene to be subjected to a hydroalkylation reaction to generate cyclohexylbenzene.

Description

Technical Field

[0001] The invention belongs to the field of material technology, and in particular relates to a catalyst for preparing cyclohexylbenzene from benzene, and a preparation method and application thereof. Background Art

[0002] Cyclohexylbenzene (CHB), also known as phenylcyclohexane, is composed of a three-dimensional cyclohexyl group and a planar benzene ring, with a boiling point of 239-240°C. Cyclohexylbenzene is widely used in plastics, coatings and other fields. In addition, due to its stable physical and chemical properties and excellent photochemical properties, it is also considered to be one of the ideal materials for display devices. At the same time, cyclohexylbenzene can be used as an additive for lithium-ion battery electrolytes and as a cetane number blending component for diesel. It can produce phenol and cyclohexanone through oxidation reactions. It is a high value-added fine chemical with market potential.

[0003] At present, the main routes for synthesizing cyclohexylbenzene include the alkylation of benzene and cyclohexene, the selective hydrogenation of biphenyl, and the hydroalkylation of benzene. Compared with other routes for producing cyclohexylbenzene, the hydroalkylation of benzene has the advantages of simple reaction route, cheap and easy-to-obtain raw materials, and has broad application prospects. However, the hydroalkylation of benzene still has the problems of low benzene conversion rate and low selectivity of cyclohexylbenzene. Summary of the invention

[0004] The main purpose of the present invention is to provide a catalyst for catalyzing benzene to prepare cyclohexylbenzene. When the catalyst catalyzes the benzene hydrogenation alkylation reaction to prepare cyclohexylbenzene, the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved.

[0005] The present invention also provides a method for preparing a catalyst, which can prepare the above catalyst with simple process and low cost.

[0006] The present invention also provides a method for preparing cyclohexylbenzene, which is obtained by using the above catalyst to catalyze benzene for hydrogenation alkylation reaction, thereby improving the conversion rate of benzene and the selectivity of cyclohexylbenzene.

[0007] In a first aspect, the present invention provides a catalyst for catalyzing benzene to prepare cyclohexylbenzene, comprising an H-MOR molecular sieve and an active metal loaded in the H-MOR molecular sieve, wherein the active metal comprises nickel, copper and zirconium;

[0008] The catalyst comprises, by mass percentage, 1.6-8.3% nickel element, 0.4-1.7% copper element, 0.1-0.5% zirconium element, and the remainder is H-MOR molecular sieve.

[0009] As described above, the SiO 2 and Al2 O 3 The molar ratio is (20-23):1.

[0010] The catalyst as described above comprises, by mass percentage, 5% nickel element, 1% copper element, 0.3% zirconium element, and the remainder is H-MOR molecular sieve.

[0011] The catalyst as described above is prepared by a method comprising the following process:

[0012] The H-MOR molecular sieve is impregnated with a mixed solution including a nickel source, a copper source and a zirconium source in equal volumes, and the obtained impregnation system is subjected to post-treatment including drying and calcination to obtain the catalyst.

[0013] In a second aspect, the present invention provides a method for preparing the catalyst as described above, comprising the following steps:

[0014] 1) using a mixed solution including a nickel source, a copper source, and a zirconium source to perform an equal volume impregnation treatment on the H-MOR molecular sieve to obtain an impregnation system;

[0015] 2) performing post-treatment including drying and calcining on the impregnation system to obtain the catalyst.

[0016] The method for preparing the catalyst as described above, wherein the drying treatment temperature is 100-120° C. and the time is 6-8 hours;

[0017] And / or, the calcination temperature is 500-550°C and the time is 4-8h;

[0018] And / or, the immersion treatment time is 1-3 hours.

[0019] In the catalyst preparation method as described above, the equal volume impregnation treatment is carried out under ultrasound.

[0020] In a third aspect, the present invention provides a method for preparing cyclohexylbenzene, comprising the following steps: using the catalyst as described above or a catalyst prepared by the method for preparing the catalyst as described above to catalyze a hydroalkylation reaction of benzene to obtain cyclohexylbenzene.

[0021] The preparation method of cyclohexylbenzene as described above comprises the following steps:

[0022] 1) activating the catalyst using hydrogen to obtain an activated catalyst;

[0023] 2) At a temperature of 180-300° C. and a pressure of 1.5-3 MPa, hydrogen and benzene are introduced into a fixed bed containing the activated catalyst for gas-solid contact to carry out the hydroalkylation reaction to obtain the cyclohexylbenzene.

[0024] In the method for preparing cyclohexylbenzene as described above, the molar ratio of hydrogen to benzene is (3-5):1.

[0025] The catalyst for catalyzing benzene to prepare cyclohexylbenzene provided by the present invention uses nickel, copper and zirconium as active metals and H-MOR molecular sieve as a carrier. The synergistic effect of the catalyst can improve the catalytic activity of the catalyst, so that when the catalyst catalyzes the hydrogenation alkylation reaction of benzene to generate cyclohexylbenzene, the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] In a first aspect, the present invention provides a catalyst for catalyzing benzene to prepare cyclohexylbenzene, comprising an H-MOR (hydrogen-type mordenite) molecular sieve and an active metal loaded in the H-MOR molecular sieve, wherein the active metal comprises nickel, copper and zirconium;

[0028] The catalyst comprises, by mass percentage, 1.6-8.3% nickel element, 0.4-1.7% copper element, 0.1-0.5% zirconium element, and the remainder is H-MOR molecular sieve.

[0029] Exemplarily, the mass percentage of the nickel element can be 1.6%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 8.3% or a range consisting of any two thereof; the mass percentage of the copper element can be 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.7% or a range consisting of any two thereof; the mass percentage of the zirconium element can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5% or a range consisting of any two thereof.

[0030] The catalyst provided by the present invention can be used to catalyze benzene to prepare cyclohexylbenzene. The catalyst includes, by mass percentage, 1.6-8.3% nickel element, 0.4-1.7% copper element, 0.1-0.5% zirconium element, and the remainder is H-MOR molecular sieve. In the process of catalyzing benzene hydrogenation alkylation to generate cyclohexylbenzene, the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved. It is speculated that this may be because: H-MOR molecular sieve, as a porous material, has a large specific surface area and a regular pore structure, which provides a good carrier for the dispersion of active metals, and the loading of active metals further enhances the catalytic performance of the catalyst. Among them, the introduction of nickel, copper, and zirconium elements provides more active sites on the catalyst surface, and these active sites can more effectively adsorb benzene molecules and promote the conversion of benzene molecules on the catalyst surface, thereby improving the catalytic efficiency, and can effectively promote the selective hydrogenation of carbon-carbon double bonds in benzene molecules to generate cyclohexene, and cyclohexene and benzene undergo alkylation reaction to generate cyclohexylbenzene. Therefore, when the catalyst includes, by mass percentage, 1.6-8.3% nickel, 0.4-1.7% copper, 0.1-0.5% zirconium, and the remainder is H-MOR molecular sieve, the catalyst has a high catalytic activity, can improve the conversion rate of benzene and the selectivity of cyclohexylbenzene, and is helpful to reduce energy consumption and production costs, and improve economic benefits. When the mass percentage of nickel in the catalyst is not within 1.6-8.3%, and / or the mass percentage of copper is not within 0.4-1.7%, and / or the mass percentage of zirconium is not within 0.1-0.5%, and / or H-MOR molecular sieve is not used as a carrier, the catalyst does not play such a role, and thus cannot catalyze benzene to generate cyclohexylbenzene by hydroalkylation reaction or benzene to generate cyclohexylbenzene by hydroalkylation reaction, the conversion rate of benzene is low, and the selectivity of cyclohexylbenzene is low.

[0031] The catalyst for catalyzing benzene to prepare cyclohexylbenzene provided by the present invention uses nickel, copper and zirconium as active metals and H-MOR molecular sieve as a carrier. The synergistic effect of the catalyst can improve the catalytic activity of the catalyst, so that when the catalyst catalyzes the hydrogenation alkylation reaction of benzene to generate cyclohexylbenzene, the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved.

[0032] In some embodiments of the present invention, the SiO 2 and Al 2 O 3 The molar ratio is (20-23):1.

[0033] For example, SiO in H-MOR molecular sieve 2 and Al 2 O 3The molar ratio can be 20:1, 20.5:1, 21:1, 21.5:1, 22:1, 22.5:1, 23:1 or a range consisting of any two thereof.

[0034] The SiO in the H-MOR molecular sieve of the present invention 2 and Al 2 O 3 The molar ratio of is within the above range, which is conducive to adjusting the pore size and shape of the molecular sieve, making it more selective for molecules of specific size and shape, such as cyclohexylbenzene, and can selectively adsorb and catalyze certain specific reactants or products, thereby improving the selectivity and efficiency of the reaction. In addition, a higher silica content helps to enhance the thermal stability and hydrothermal stability of the molecular sieve. Under the conditions of high temperature and water vapor, the structure of the molecular sieve can remain relatively stable, and it is not easy to dealumination or structural collapse, thereby extending its service life and maintaining catalytic activity.

[0035] In some embodiments of the present invention, the catalyst comprises, by mass percentage, 5% nickel, 1% copper, 0.3% zirconium, and the remainder is H-MOR molecular sieve. When catalyzing the hydroalkylation reaction of benzene to produce cyclohexylbenzene, the conversion rate of benzene and the selectivity of cyclohexylbenzene can be further improved.

[0036] In some embodiments of the present invention, the catalyst is prepared by a method comprising the following process:

[0037] The H-MOR molecular sieve is impregnated with a mixed solution including a nickel source, a copper source and a zirconium source in equal volumes, and the obtained impregnation system is subjected to post-treatment including drying and calcination to obtain the catalyst.

[0038] In one embodiment, the nickel source, copper source, and zirconium source can be dissolved in an appropriate amount of water, and completely dissolved under stirring to form a mixed solution, and then an equal volume of H-MOR molecular sieve is added to the mixed solution, and the equal volume impregnation treatment is performed for a certain period of time to make the nickel source, copper source, and zirconium source uniformly dispersed on the H-MOR molecular sieve to obtain an impregnation system. The obtained impregnation system is then dried and calcined to obtain an H-MOR molecular sieve loaded with active components of nickel, copper, and zirconium.

[0039] The catalyst preparation method of the present invention can prepare the above catalyst without using precious metals, has simple process, low cost and good industrial application prospect.

[0040] In a second aspect, the present invention provides a method for preparing the catalyst as described above, comprising the following steps:

[0041] 1) using a mixed solution including a nickel source, a copper source, and a zirconium source to perform an equal volume impregnation treatment on the H-MOR molecular sieve to obtain an impregnation system;

[0042] 2) performing post-treatment including drying and calcining on the impregnation system to obtain the catalyst.

[0043] In step 1) of the present invention, optionally, the nickel source can be a nickel salt, for example, nickel nitrate hexahydrate; the copper source can be a copper salt, for example, copper nitrate trihydrate; and the zirconium source can be a zirconium salt, for example, zirconium chloride. The nickel source, copper source, and zirconium source are dissolved in water and completely dissolved under stirring to form a mixed solution, and then an equal volume of H-MOR molecular sieve is added to the mixed solution, and an equal volume impregnation treatment is performed for a certain period of time to uniformly disperse the metal nickel, copper, and zirconium on the H-MOR molecular sieve to obtain an impregnation system.

[0044] In step 2), the obtained impregnation system is post-treated to obtain an H-MOR molecular sieve catalyst loaded with active metals nickel, copper and zirconium. Post-treatment includes drying and calcining. Drying is used to remove moisture from the catalyst surface. The calcining can be carried out in a muffle furnace to remove volatile components in the H-MOR molecular sieve carrier, form a stable structure, and allow the molecular sieve carrier to obtain a certain crystal form, grain size, pore structure and specific surface area, and obtain an H-MOR molecular sieve catalyst loaded with active metals nickel, copper and zirconium, wherein the mass percentage of nickel element is 1.6-8.3%, the mass percentage of copper element is 0.4-1.7%, the mass percentage of zirconium element is 0.1-0.5%, and the remainder is H-MOR molecular sieve.

[0045] The preparation method of the catalyst of the present invention can prepare the catalyst for catalyzing benzene to prepare cyclohexylbenzene provided in the first aspect of the present invention. When the catalyst catalyzes benzene to undergo hydrogenation alkylation to produce cyclohexylbenzene, the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved. The preparation method is simple and easy to implement, and is convenient for industrial scale-up production.

[0046] In some embodiments of the present invention, the drying process is carried out at a temperature of 100-120° C. for 6-8 h;

[0047] In some embodiments, the calcination temperature is 500-550°C and the time is 4-8h;

[0048] In some embodiments, the immersion treatment time is 1-3 hours.

[0049] Exemplarily, the temperature of the drying treatment may be 100°C, 105°C, 110°C, 115°C, 120°C, or a range consisting of any two thereof. The time of the drying treatment may be 6h, 6.5h, 7h, 7.5h, 8h, or a range consisting of any two thereof. The temperature of the calcining treatment may be 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, or a range consisting of any two thereof. The time of the calcining treatment may be 4h, 5h, 6h, 7h, 8h, or a range consisting of any two thereof. The time k of the impregnation treatment may be 1h, 1.5h, 2h, 2.5h, 3h, or a range consisting of any two thereof.

[0050] The temperature and time of the drying treatment in the present invention are within the above ranges, and the moisture on the catalyst surface can be fully removed. The temperature and time of the roasting treatment are within the above ranges, and the volatile components such as organic matter in the catalyst can be ensured to be completely removed, so that the crystal structure of the catalyst is stabilized, and the thermal stability and catalytic activity of the catalyst are improved. The time of the impregnation treatment is within the above range, and the active metal can be uniformly loaded on the catalyst carrier to form an effective catalytic active site. By controlling the impregnation time, the loading amount of the active metal can be adjusted within a suitable range, and the catalytic performance of the catalyst can be improved. In addition, the appropriate impregnation treatment time can also promote the interaction between the active metal and the carrier, and improve the stability and service life of the catalyst.

[0051] In some embodiments of the present invention, the equal volume immersion treatment is performed under ultrasound, that is, ultrasonic immersion is performed.

[0052] Optionally, the equal volume impregnation treatment can be carried out under ultrasound, and the high frequency vibration of ultrasound can be used to evenly disperse and load the active components, namely metal nickel, copper and zirconium, onto the H-MOR molecular sieve, while overcoming the capillary resistance and entering the pores of the H-MOR molecular sieve carrier, thereby improving the catalytic activity of the catalyst, and further improving the conversion rate of benzene and the selectivity of cyclohexylbenzene when benzene is subjected to the hydroalkylation reaction to prepare cyclohexylbenzene.

[0053] In a third aspect, the present invention provides a method for preparing cyclohexylbenzene, comprising the following steps: using the catalyst as described above or a catalyst prepared by the method for preparing the catalyst as described above to catalyze a hydroalkylation reaction of benzene to obtain cyclohexylbenzene.

[0054] The present invention uses the catalyst provided in the first aspect or the catalyst prepared by the preparation method provided in the second aspect to catalyze benzene for a hydroalkylation reaction to obtain cyclohexylbenzene, thereby improving the conversion rate of benzene and the selectivity of cyclohexylbenzene. The reaction that occurs is as follows:

[0055]

[0056] In some embodiments, the temperature of the hydroalkylation reaction can be 180-300°C, and the pressure can be 1.5-3MPa. Exemplarily, the temperature of the hydroalkylation reaction can be 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, or a range consisting of any two thereof. The pressure of the hydroalkylation can be 1.5MPa, 1.7MPa, 2MPa, 2.2MPa, 2.5MPa, 2.7MPa, 3MPa, or a range consisting of any two thereof. The reaction temperature and time can improve the conversion rate of benzene and the selectivity of cyclohexylbenzene when the catalyst catalyzes the hydroalkylation reaction of benzene to obtain cyclohexylbenzene.

[0057] In some embodiments of the present invention, the preparation method comprises the following steps:

[0058] 1) activating the catalyst using hydrogen to obtain an activated catalyst;

[0059] 2) At a temperature of 180-300° C. and a pressure of 1.5-3 MPa, hydrogen and benzene are introduced into a fixed bed containing the activated catalyst for gas-solid contact to carry out the hydroalkylation reaction to obtain the cyclohexylbenzene.

[0060] In the present invention, hydrogen is first used to activate the catalyst to obtain an activated catalyst, and then the activated catalyst is used to carry out a hydrogenation alkylation reaction on benzene to obtain cyclohexylbenzene.

[0061] In some embodiments, the temperature of the activation treatment may be 200-400° C., and the time of the activation treatment may be 1-3 hours. For example, the temperature of the activation treatment may be 200° C., 300° C., 400° C., or a range consisting of any two thereof. The time of the activation treatment may be 1 hour, 2 hours, 3 hours, or a range consisting of any two thereof.

[0062] Specifically, in step 1), the catalyst is activated by hydrogen at 200-400° C. for 1-3 hours under the protection of an inert gas, such as nitrogen, to obtain an activated catalyst. It can be understood that after the catalyst is prepared, it is often necessary to activate it so that the passive catalyst is converted into an activated catalyst. The purpose of activation is to form active sites required for the catalytic reaction on the catalyst, especially on the catalyst surface.

[0063] In step 2), a certain amount of activated catalyst, for example 0.5 g, is loaded into a fixed bed reaction tube, wherein the reaction tube of the fixed bed reaction device has an inner diameter of 10 mm and a length of 40 cm, and then the temperature of the fixed bed is adjusted to a range of 180-300° C., and the reaction raw materials hydrogen and benzene are introduced for gas-solid contact to carry out a hydroalkylation reaction, and the pressure is controlled within a range of 1.5-3 MPa. Under the action of the catalyst, the carbon-carbon double bonds in the benzene molecules are selectively hydrogenated to produce cyclohexene, and the cyclohexene and benzene undergo an alkylation reaction to produce cyclohexylbenzene.

[0064] The present invention uses the H-MOR molecular sieve catalyst loaded with metal nickel, copper and zirconium to catalyze benzene for hydrogenation alkylation reaction to obtain cyclohexylbenzene. The catalyst has high activity, so the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved. After the reaction is completed, the catalyst is easy to separate, has little pollution, and is easy to be applied to industrial production.

[0065] In some embodiments of the present invention, the molar ratio of hydrogen to benzene is (3-5):1, for example, it can be 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or a range consisting of any two of them.

[0066] In the present invention, the volume ratio of hydrogen to benzene is within the above range, so that benzene and hydrogen can fully react to finally generate cyclohexylbenzene, which can further improve the conversion rate of benzene and the selectivity of cyclohexylbenzene.

[0067] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0068] Example 1

[0069] The preparation method of cyclohexylbenzene of the present embodiment comprises the following steps:

[0070] 1) 124g Ni(NO 3 ) 2 6H 2 O, 19g Cu(NO 3 ) 2 ·3H 2 O and 3.83g ZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 5% Ni1% Cu0.3% Zr / H-MOR.

[0071] 2) The above catalyst is heated in H 2 The activated catalyst was obtained by activation treatment at 400°C in an atmosphere for 1 hour. The reaction tube of the fixed bed reactor had an inner diameter of 10 mm and a length of 40 cm. 0.5 g of the activated catalyst was loaded into the reaction tube, the temperature was adjusted to 200°C, and the reaction raw materials hydrogen and benzene were introduced for gas-solid contact to carry out a hydroalkylation reaction, wherein the molar ratio of hydrogen to benzene was 5:1, and the reaction pressure was controlled at 2.5 MPa. After the reaction system was stable, the obtained reaction product was cooled and collected and analyzed by a gas chromatograph. The results are shown in Table 1.

[0072] Example 2

[0073] The preparation method of cyclohexylbenzene in Example 2 is basically the same as that in Example 1, except that in step 1), 148.64 g Ni(NO 3 ) 2 6H 2 O, 22.81 g Cu(NO 3 ) 2 ·3H 2 O and 4.6gZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 6% Ni1.2% Cu0.36% Zr / H-MOR.

[0074] Example 3

[0075] The preparation method of cyclohexylbenzene in Example 3 is basically the same as that in Example 1, except that in step 1), 39.64 g Ni(NO 3 ) 2 6H 2 O, 19g Cu(NO 3 ) 2 ·3H 2 O and 3.83g ZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 320) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 1.6% Ni1% Cu0.3% Zr / H-MOR.

[0076] Example 4

[0077] The preparation method of cyclohexylbenzene in Example 4 is basically the same as that in Example 1, except that in step 1), 205.62 g Ni(NO 3 ) 2 6H 2 O, 19g Cu(NO 3 ) 2 ·3H 2 O and 3.83g ZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 8.3% Ni1% Cu0.3% Zr / H-MOR.

[0078] Example 5

[0079] The preparation method of cyclohexylbenzene in Example 5 is basically the same as that in Example 1, except that in step 1), 124 g Ni(NO 3 ) 2 6H 2 O, 7.6 g Cu(NO 3 ) 2 ·3H 2 O and 3.83g ZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 5% Ni0.4% Cu0.3% Zr / H-MOR.

[0080] Example 6

[0081] The preparation method of cyclohexylbenzene in Example 6 is basically the same as that in Example 1, except that in step 1), 124 g Ni(NO 3 ) 2 6H 2 O, 32.31 g Cu(NO 3 ) 2 ·3H 2 O and 3.83g ZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 5% Ni1.7% Cu0.3% Zr / H-MOR.

[0082] Example 7

[0083] The preparation method of cyclohexylbenzene in Example 7 is basically the same as that in Example 1, except that in step 1), 124 g Ni(NO 3 ) 2 6H 2 O, 19g Cu(NO 3 ) 2 ·3H 2 O and 1.28 g ZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 5% Ni1% Cu0.1% Zr / H-MOR.

[0084] Example 8

[0085] The preparation method of cyclohexylbenzene in Example 8 is basically the same as that in Example 1, except that in step 1), 124 g Ni(NO 3 ) 2 6H 2 O, 19g Cu(NO 3 ) 2 ·3H 2O and 6.39 g ZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to equal volume ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni, Cu, and Zr, and the chemical composition of the catalyst was 5% Ni1% Cu0.5% Zr / H-MOR.

[0086] Example 9

[0087] The preparation method of cyclohexylbenzene in Example 9 is basically the same as that in Example 1, except that in step 1), SiO 2 and Al 2 O 3 The molar ratio is 23.

[0088] Example 10

[0089] The preparation method of cyclohexylbenzene in Example 10 is basically the same as that in Example 1, except that in step 1), SiO 2 and Al 2 O 3 The molar ratio is 22.

[0090] Embodiment 11

[0091] The preparation method of cyclohexylbenzene in Example 11 is basically the same as that in Example 1, except that in step 1), the calcination temperature is 550° C. and the time is 4 hours.

[0092] Example 12

[0093] The preparation method of cyclohexylbenzene in Example 12 is basically the same as that in Example 1, except that in step 1), the calcination temperature is 500° C. and the time is 8 hours.

[0094] Example 13

[0095] The preparation method of cyclohexylbenzene in Example 13 is basically the same as that in Example 1, except that in step 1), the drying temperature is 100° C. and the time is 8 hours.

[0096] Embodiment 14

[0097] The preparation method of cyclohexylbenzene in Example 14 is basically the same as that in Example 1, except that in step 1), the immersion treatment time is 1 hour.

[0098] Embodiment 15

[0099] The preparation method of cyclohexylbenzene in Example 15 is basically the same as that in Example 1, except that in step 2), the temperature of the hydroalkylation reaction is 300°C.

[0100] Example 16

[0101] The preparation method of cyclohexylbenzene in Example 16 is basically the same as that in Example 1, except that in step 2), the temperature of the hydroalkylation reaction is 180°C.

[0102] Embodiment 17

[0103] The preparation method of cyclohexylbenzene in Example 17 is basically the same as that in Example 1, except that in step 2), the pressure of the hydroalkylation reaction is 1.5 MPa.

[0104] Embodiment 18

[0105] The preparation method of cyclohexylbenzene in Example 18 is basically the same as that in Example 1, except that in step 2), the pressure of the hydroalkylation reaction is 3 MPa.

[0106] Embodiment 19

[0107] The preparation method of cyclohexylbenzene in Example 19 is basically the same as that in Example 1, except that in step 2), the molar ratio of hydrogen to benzene is 3:1.

[0108] Comparative Example 1

[0109] The preparation methods of cyclohexylbenzene in Comparative Example 1 and Example 1 are basically the same, except that in step 1), 124 g Ni(NO 3 ) 2 6H 2 O, 19g Cu(NO 3 ) 2 ·3H 2 O was dissolved in 300 g of water and completely dissolved under stirring to obtain a mixed solution. 500 g of H-MOR (SiO 2 :Al 2 O 3 20) was subjected to ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 8 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni and Cu, the chemical composition of the catalyst being 5% Ni1% Cu / H-MOR.

[0110] Comparative Example 2

[0111] The preparation method of cyclohexylbenzene in Comparative Example 2 is basically the same as that in Example 1, except that in step 1), 0.5 g H-MOR (SiO 2 :Al 2 O 3 50) was calcined at 500°C for 5h to obtain catalyst H-MOR.

[0112] Comparative Example 3

[0113] The preparation method of cyclohexylbenzene in Comparative Example 3 is basically the same as that in Example 1, except that in step 1), 124 g Ni(NO 3 ) 2 6H 2 O was dissolved in 300 g of water and completely dissolved under stirring to obtain a mixed solution. 500 g of H-MOR (SiO 2 :Al 2 O 3 20) was subjected to ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active component Ni, the chemical composition of the catalyst being 5% Ni / H-MOR.

[0114] Comparative Example 4

[0115] Comparative Example 4 is basically the same as the preparation method of cyclohexylbenzene in Example 1, except that in step 1), 19 g Cu(NO 3 ) 2 ·3H 2 O was dissolved in 300 g of water and completely dissolved under stirring to obtain a mixed solution. 500 g of H-MOR (SiO 2 :Al 2 O 3 20) was subjected to ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active component Cu, the chemical composition of the catalyst being 1% Cu / H-MOR.

[0116] Comparative Example 5

[0117] The preparation method of cyclohexylbenzene in Comparative Example 5 is basically the same as that in Example 1, except that in step 1), 124 g Ni(NO 3 ) 2 6H 2 O, 3.83gZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al2 O 3 20) was subjected to ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Ni and Zr, the chemical composition of the catalyst being 5% Ni0.3% Zr / H-MOR.

[0118] Comparative Example 6

[0119] The preparation method of cyclohexylbenzene in Comparative Example 6 is basically the same as that in Example 1, except that in step 1), 19 g Cu(NO 3 ) 2 ·3H 2 O, 3.83gZrCl 4 Dissolve in 300g water and stir to dissolve completely to obtain a mixed solution. Add 500g H-MOR (SiO 2 :Al 2 O 3 20) was subjected to ultrasonic impregnation treatment for 2 hours to obtain an impregnation system; the impregnation system was dried at 120°C for 6 hours and calcined at 500°C for 5 hours to obtain a catalyst loaded with active components Cu and Zr, the chemical composition of the catalyst being 1% Cu0.3% Zr / H-MOR.

[0120] Table 1

[0121]

[0122]

[0123] As can be seen from Table 1, compared with the comparative example, the catalyst for catalyzing the preparation of cyclohexylbenzene from benzene provided by the present invention has nickel, copper and zirconium as active metals and H-MOR molecular sieve as a carrier, and the synergistic effect thereof can improve the catalytic activity of the catalyst, so that when the catalyst catalyzes the hydroalkylation reaction of benzene to produce cyclohexylbenzene, the conversion rate of benzene and the selectivity of cyclohexylbenzene can be improved.

[0124] From the comparison between Example 1 and Comparative Examples 1-6, it can be seen that the catalyst for catalyzing benzene to prepare cyclohexylbenzene provided by the present invention can improve the conversion rate of benzene and the selectivity of cyclohexylbenzene when catalyzing the hydroalkylation reaction of benzene to produce cyclohexylbenzene.

[0125] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A catalyst for catalyzing benzene to prepare cyclohexylbenzene, characterized in that: It comprises an H-MOR molecular sieve and an active metal loaded in the H-MOR molecular sieve, wherein the active metal comprises nickel, copper and zirconium; The catalyst comprises, by mass percentage, 1.6-8.3% nickel element, 0.4-1.7% copper element, 0.1-0.5% zirconium element, and the remainder is H-MOR molecular sieve.

2. The catalyst according to claim 1, characterized in that The molar ratio of SiO2 to Al2O3 in the H-MOR molecular sieve is (20-23):

1.

3. The catalyst according to claim 1 or 2, characterized in that The catalyst comprises, by mass percentage, 5% nickel element, 1% copper element, 0.3% zirconium element, and the remainder is H-MOR molecular sieve.

4. The catalyst according to any one of claims 1 to 3, characterized in that The catalyst is prepared by a method comprising the following steps: The H-MOR molecular sieve is impregnated with a mixed solution including a nickel source, a copper source and a zirconium source in equal volumes, and the obtained impregnation system is subjected to post-treatment including drying and calcination to obtain the catalyst.

5. A method for preparing the catalyst according to any one of claims 1 to 4, characterized in that: The following steps are involved: 1) using a mixed solution including a nickel source, a copper source, and a zirconium source to perform an equal volume impregnation treatment on the H-MOR molecular sieve to obtain an impregnation system; 2) performing post-treatment including drying and calcining on the impregnation system to obtain the catalyst.

6. The method for preparing the catalyst according to claim 5, characterized in that: The drying process is carried out at a temperature of 100-120°C and a time of 6-8 hours; And / or, the calcination temperature is 500-550°C and the time is 4-8h; And / or, the immersion treatment time is 1-3 hours.

7. The method for preparing the catalyst according to claim 5 or 6, characterized in that: The equal volume immersion treatment is performed under ultrasonication.

8. A method for preparing cyclohexylbenzene, characterized in that: The method comprises the following steps: using the catalyst described in any one of claims 1 to 4 or the catalyst prepared by the preparation method of the catalyst described in any one of claims 5 to 7 to catalyze benzene for hydrogenation alkylation reaction to obtain cyclohexylbenzene.

9. The method for preparing cyclohexylbenzene according to claim 8, characterized in that: The preparation method comprises the following steps: 1) activating the catalyst using hydrogen to obtain an activated catalyst; 2) At a temperature of 180-300° C. and a pressure of 1.5-3 MPa, hydrogen and benzene are introduced into a fixed bed containing the activated catalyst for gas-solid contact to carry out the hydroalkylation reaction to obtain the cyclohexylbenzene.

10. The method for preparing cyclohexylbenzene according to claim 9, characterized in that: The molar ratio of hydrogen to benzene is (3-5):1.

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