JP4457761B2 - Catalyst for producing cyclohexylbenzene and method for producing cyclohexylbenzene - Google Patents

Description

  The present invention relates to a catalyst (a catalyst for producing cyclohexylbenzene) used in a method for producing cyclohexylbenzene by bringing benzene into contact with hydrogen. Cyclohexylbenzene is useful as a raw material for the production of cyclohexylbenzene hydroperoxide, and phenol and cyclohexanone, as well as ε-caprolactam.

  Conventionally, as the catalyst for producing cyclohexylbenzene, (a) a catalyst containing a heteropolyacid and a hydrogenation catalyst (Patent Document 1), (b) a catalyst containing aluminum chloride and platinum or palladium (Patent Document 2), ( c) a catalyst in which a Group VIII metal is supported on silica / alumina (Patent Document 3), (d) a catalyst in which an alkali metal is supported on alumina or activated carbon (Patent Document 4), (e) tungsten and a hydrogenated active component ( Nickel, platinum, or palladium) and a catalyst in which a halogen is supported on an acidic carrier (Patent Document 5) are known. However, the catalysts (a) to (c) have a low selectivity for cyclohexylbenzene, the catalyst (d) has a significantly shorter life due to water in benzene, and the catalyst (e) has a complicated system. Each of them had an industrially unsuitable process and could not build a sufficiently satisfactory process.

  Further, (f) a catalyst in which a rare earth element and a hydrogenation active component are supported on zeolite (Patent Document 6), (g) a catalyst comprising a hydrogenation catalyst and a zeolite on which a rare earth element is supported (Patent Document 7), ( h) A hydrogenated active ingredient and a catalyst comprising an alkaline earth metal and zeolite (Patent Document 8) are also known, but none of them has industrially satisfactory activity and selectivity. In particular, the low activity per expensive hydrogenated active ingredient has been a problem.

US Pat. No. 3,153,678 US Pat. No. 3,274,276 US Pat. No. 3,317,611 US Pat. No. 3,347,945 U.S. Pat. No. 3,421,165 JP-A-48-40753 Japanese Patent Laid-Open No. 48-96566 JP 52-62253 A

  The present invention provides a catalyst that provides industrially satisfactory activity and selectivity by solving the above-mentioned problems in a process for producing cyclohexylbenzene by bringing benzene and hydrogen into contact, that is, industrially satisfactory activity and selectivity. It is an object of the present invention to provide a catalyst for producing cyclohexylbenzene.

  As a result of intensive studies to develop a catalyst capable of overcoming the above problems, the present inventors have found that a hydrogenation catalyst using a mesoporous material as a carrier and a solid acid catalyst modified with a Group 2 metal or a Group 3 metal The present invention has been completed by finding that a catalyst comprising a cyclohexylbenzene production catalyst exhibiting industrially satisfactory activity and selectivity. In the present invention, the “group” in the periodic table of each metal follows the IUPAC inorganic chemical nomenclature revised in 1989.

That is, the present invention provides (1) a catalyst for producing cyclohexylbenzene comprising a hydrogenation catalyst using a mesoporous material as a carrier and a solid acid catalyst modified with a Group 2 metal or a Group 3 metal,
(2) The mesoporous material according to (1), wherein a nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 in the nitrogen adsorption isotherm is 20 to 60% of the total adsorption amount. Catalyst for the production of cyclohexylbenzene,
(3) The catalyst for producing cyclohexylbenzene according to the above (1), which uses a hydrogenation catalyst in which at least one metal selected from Group 8 metal, Group 9 metal, and Group 10 metal is supported on a mesoporous material,
(4) The catalyst for cyclohexylbenzene production according to (1), wherein the solid acid is an aluminosilicate,
(5) A method for producing cyclohexylbenzene, comprising bringing benzene and hydrogen into contact in the presence of the catalyst described in (1) above.

  According to the present invention, in the method for producing cyclohexylbenzene by bringing benzene and hydrogen into contact with each other, a catalyst which solves the above problems and gives industrially satisfactory activity and selectivity, that is, industrially satisfactory activity and selectivity. It is possible to provide a catalyst for producing cyclohexylbenzene having:

Hereinafter, the present invention will be described in detail.
The hydrogenation catalyst constituting the catalyst for producing cyclohexylbenzene of the present invention is characterized by using a mesoporous material as a carrier. As this mesoporous material, the pore diameter is 2 nm or more even after firing in a nitrogen or air atmosphere mainly composed of silicon and aluminum, and the X-ray diffraction pattern (Cu-Kα ray) has a low angle region. It has a peak attributed to hexagonal d ₁₀₀ in the range of 2θ = 2.0 to 2.5 °, and abruptly when P / P ₀ is 0.2 to 0.6 in the nitrogen adsorption isotherm. Those exhibiting a gradient adsorption (in particular, the nitrogen adsorption amount in this range is 20 to 60% of the total adsorption amount) are preferred. The Si / Al (atomic ratio) of the mesoporous material is preferably 5 or more, more preferably 50 or more, and is preferably 1000 or less, more preferably 500 or less. The specific surface area of 700 meters ² / g or more, particularly preferably 700~1200m ² / g.

  In addition, the said baking is equivalent to the detemplater process in preparation of a normal mesoporous body, for example, is performed by selecting conditions in the range of 400-900 degreeC and 30 minutes-4 hours. X-ray diffraction pattern (Cu-Kα ray) is measured by powder X-ray diffraction measurement, nitrogen adsorption isotherm and specific surface area are measured by BET specific surface area measurement by nitrogen adsorption, and Si / Al (atomic ratio) is measured by ICP analysis. The

  As the mesoporous material, for example, a mesoporous material having the above-mentioned physical properties made of silicon and aluminum can be mentioned, and specifically, MCM41 (Japanese Patent Publication No. 5-503499), FSM16 (Japanese Patent Laid-Open No. Hei 4-238810). ), HMS (Nature, 368 (1994), 321). In addition, the mesoporous material can be prepared by a known method using a silicon source, an aluminum source, an organic solvent, water, and a template as raw materials, and can also be synthesized by a hydrothermal synthesis method. The method is not particularly limited as long as the method having the physical properties is obtained. One preparation example of the mesoporous material is shown below.

(1) Preparation of liquid mixture 1: 1 mol of a silicon source and 1 to 20 mol of an organic solvent are mixed, and an aluminum source is added thereto so as to have a predetermined Si / Al (atomic ratio), and at 50 to 100 ° C. Stir for 10 minutes to 5 hours. The resulting solution is referred to as “mixed solution 1”.
(2) Preparation of liquid mixture 2: 0.1 to 10 times mol of the template agent and 10 to 50 times mol of water are mixed with respect to the silicon source. The resulting solution is referred to as “mixed solution 2”.

(3) Gel formation and aging: Mixture 1 is added to Mixture 2 and vigorously stirred at 0-50 ° C. (0 to 150 ° C. in the case of hydrothermal synthesis) for 10 minutes to 5 hours to form a gel. Thereafter, aging is carried out in the same temperature range for 12 to 400 hours. The white solid obtained by filtration is then washed with water and ethanol and dried at 80-120 ° C.
(4) Detemplaterization treatment (firing): The solid after drying is 0.1 to 20 ° C./min (preferably 0) in the air or in an inert gas atmosphere (preferably while circulating air or an inert gas). The temperature is raised to a predetermined temperature at 5 to 5 ° C./minute), and the temperature and the time are selected in the range of 400 to 900 ° C. and 10 minutes to 4 hours, and firing is performed until the template agent is removed. The removal of the template agent from the solid is confirmed by infrared absorption spectrum analysis or thermogravimetric analysis.

  The hydrogenation catalyst is preferably one in which at least one metal selected from Group 8 metals, Group 9 metals, and Group 10 metals is supported on the mesoporous material as a hydrogenation active component, and among them, selected from platinum group metals. It is more preferable that at least one kind of metal (particularly palladium and / or rhodium) supported on the mesoporous material. The supported amount of the metal as the hydrogenated active component is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the mesoporous material.

  The hydrogenation catalyst is prepared by supporting the metal compound and reducing the compound to the metal. At this time, the supporting method is not particularly limited, and a commonly performed method such as an evaporation to dryness method, a pore filling method, an ion exchange method or the like can be used. However, considering the improvement of metal dispersibility, the pore filling method and the ion exchange method are preferable. The reduction from the metal compound to the metal may be performed in advance with a reducing agent such as hydrogen before the reaction for producing cyclohexylbenzene, or may be performed by reducing with hydrogen as a reaction raw material at the start of the reaction. .

  The group 8 metal includes iron, ruthenium, the group 9 metal includes cobalt, rhodium, iridium, and the group 10 metal includes nickel, palladium, and platinum. Among these metals, ruthenium, rhodium, iridium, palladium, and platinum (platinum group metal) are preferable, and palladium and rhodium are particularly preferable. In preparing the catalyst, inorganic salts, organic acid salts, complex compounds, and the like of these metals are used as the compounds of these metals.

Specifically, for example, palladium compounds such as palladium chloride, palladium bromide, palladium iodide, palladium sulfate, palladium nitrate and other inorganic acid salts of palladium, palladium acetate, palladium oxalate and other organic acid salts of palladium, And palladium complex compounds such as acetylacetonato palladium. Complex compounds further include those in which palladium is coordinated with other ligands (carbon monoxide, nitrile, amine, phosphine, etc.). For example, Pd (NH ₃ ) ₄ Cl ₂ , PdCl ₂ (CH ₃ CN) ₂ , PdCl ₂ (PPh ₃ ) ₂ and the like. Among the palladium compounds, palladium chloride, palladium acetate, and Pd (NH ₃ ) ₄ Cl ₂ are preferable.

In addition, rhodium compounds include rhodium chloride, rhodium bromide, rhodium iodide, rhodium nitrate and other inorganic rhodium acid salts, rhodium organic acid salts such as rhodium acetate, and rhodium complex compounds such as acetylacetonatodium. Etc. Complex compounds further include those in which other ligands (carbon monoxide, nitrile, amine, phosphine, etc.) are coordinated to rhodium, for example, Rh (NH ₃ ) ₆ Cl ₃ , Rh [(NH _3), and the like _{5 Cl] Cl 2, Rh 6} (CO) 16. Among the rhodium compounds, rhodium chloride, rhodium acetate, and Rh (NH ₃ ) ₆ Cl ₃ are preferable.

  The catalyst for producing cyclohexylbenzene of the present invention comprises a solid acid catalyst modified with a Group 2 metal or a Group 3 metal in addition to the hydrogenation catalyst. Among them, those in which the solid acid is an aluminosilicate (that is, an aluminosilicate modified with a Group 2 metal or a Group 3 metal) are particularly preferable. Specifically, A-type zeolite, X-type zeolite, Y-type zeolite, β-type zeolite, mordenite and the like can be used as the aluminosilicate, and among these, Y-type zeolite and β-type zeolite are preferable.

  Preferred examples of the Group 2 metal used for the modification of the aluminosilicate include magnesium, calcium, and strontium. Specifically, nitrates, sulfates, carbonates, and the like of these metals are used. Of the Group 2 metals, strontium is preferred. Examples of the Group 3 metal used for the modification of the aluminosilicate include scandium, yttrium, lanthanoid, and actinoid. Specifically, nitrates, sulfates, carbonates, and the like of these metals are used. Among group 3 metals, yttrium and lanthanum are preferable.

  The modification of the solid acid catalyst can be performed, for example, by supporting the metal compound on an aluminosilicate. As the supporting method, the metal compound may be simply supported by an evaporation to dryness method or a pore filling method, but it is more preferable to support the metal compound by an ion exchange method. In the former case, firing is preferably performed after supporting, and firing is preferably performed at 400 to 600 ° C. for several hours in an air atmosphere with the decomposition temperature of the metal compound as a guide. The amount of the Group 2 metal or Group 3 metal supported is preferably 1 to 30% by weight, particularly 3 to 20% by weight, based on the aluminosilicate.

The catalyst for producing cyclohexylbenzene of the present invention comprises the hydrogenation catalyst and the solid acid catalyst, and in the present invention, by contacting benzene and hydrogen in the presence of such a catalyst for producing cyclohexylbenzene, It is possible to produce cyclohexylbenzene with a satisfactory activity and selectivity. At this time, the catalyst for producing cyclohexylbenzene is preferably used so that the hydrogenated active component is in the range of 10 ⁻⁸ to 10 ⁻² in terms of molar ratio to benzene. When the hydrogenated active component is less than 10 ⁻⁸ , the reaction proceeds, but the reaction time is long, and when it exceeds 10 ⁻² , there is no problem on the reaction surface, but it is economically disadvantageous from the viewpoint of catalyst cost. In addition, if the hydrogenated active ingredient is particularly palladium, the amount of rhodium is determined if the hydrogenated active ingredient is particularly rhodium so that the amount of palladium is in the range of 10 ⁻⁷ to 10 ^{−2 in} molar ratio to benzene. Is preferably in a range of 10 ⁻⁷ to 10 ^{−3 in} molar ratio to benzene. In the catalyst for producing cyclohexylbenzene, the ratio of the hydrogenation catalyst to the solid acid catalyst is 0.1 to 1000 parts by weight, more preferably 1 to 500 parts by weight with respect to 1 part by weight of the hydrogenation catalyst. Preferably there is.

  In the production of cyclohexylbenzene, the reaction temperature is in the range of 20 to 300 ° C., more preferably in the range of 80 to 250 ° C., the reaction pressure is in the range of 1 to 300 atm, further in the range of 1 to 150 atm, and the hydrogen partial pressure is in the range of 1 to 50. Each is preferably in the range of atmospheric pressure. The reaction time varies depending on the reaction conditions, but is usually from several minutes to several hours. In addition, hydrogen may be diluted with other gases that do not affect the reaction, such as argon and carbon dioxide, as well as high purity. The reaction method may be either a batch method or a continuous method, and any reaction method such as a fixed bed, a suspension bed, a fluidized bed, and a moving bed can be employed. The product can be separated after the reaction, such as by distillation.

  In the reaction, a solvent can be used as necessary. For example, an inert solvent such as hexane, heptane, cyclohexane, methylene chloride, chloroform, diethyl ether, diphenyl ether, tetrahydrofuran, dioxane, acetonitrile can be used. . The amount of the solvent used may be in the range of 10,000 equivalents or less, more preferably 1000 equivalents or less based on benzene.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The selectivity (%) of cyclohexylbenzene was determined on a molar basis by a calculation formula of “selectivity (%) = (2 × cyclohexylbenzene production / benzene consumption) × 100”.

[Example 1]
"Preparation of hydrogenation catalyst"
1.7 mmol of aluminum isopropoxide is added to a mixture of 200 mmol of tetraethylorthosilicate, 1.3 mol of ethanol and 200 mmol of isopropanol and stirred at 70 ° C. for 20 minutes. The resulting solution is a mixture of 60 mmol of dodecylamine and 7.2 mol of water. In addition to the liquid, it was stirred vigorously at room temperature for 1 hour. The produced white sol was aged at room temperature for 48 hours, filtered, washed with water and ethanol, dried at 105 ° C. for 24 hours, and calcined at 400 ° C. for 2 hours. The obtained white powder was a mesoporous material with Si / Al (atomic ratio) = 111. Note that Si / Al (atomic ratio) is mesoporous by ICP analysis, and nitrogen in the nitrogen adsorption isotherm (by BET specific surface area measurement) is nitrogen in the range of P / P ₀ = 0.2 to 0.6. It was confirmed from the X-ray diffraction pattern (Cu-Kα ray) that the adsorption amount was 28% of the total adsorption amount. The specific surface area (SSA) was 920 m ² / g.

100 ml of ion-exchanged water was added to 2 g of the mesoporous material thus obtained, and a solution in which 1 g of sodium nitrate was dissolved in 50 ml of ion-exchanged water was added dropwise thereto, and the mesoporous material was treated overnight at room temperature. . Thereafter, the solid content was centrifuged, washed with ion exchange water (30 ml × 5 times) and dried (105 ° C., 5 hours). The obtained mesoporous material (Na ion exchanger) was suspended in 50 ml of ion exchange water, and a solution obtained by dissolving 0.05 g of Pd (NH ₃ ) ₄ Cl _{2 in} 30 ml of ion exchange water was added to this suspension. The solution was added dropwise over 30 minutes and stirred overnight at room temperature. Thereafter, the solid content was centrifuged, washed with ion-exchanged water until Cl ions were not detected, and dried at 105 ° C. The amount of Pd supported by this catalyst was 1.0% by weight by ICP analysis. Hereinafter, this catalyst is abbreviated as 1% Pd / Al-MS-1.

"Preparation of solid acid catalyst"
A solution obtained by adding 200 ml of ion exchange water to 5 g of Tosoh H-type Y zeolite (HSZ-320HOA; hereinafter abbreviated as HY) and dissolving 2 g of lanthanum nitrate hexahydrate in 100 ml of ion exchange water. Was added dropwise at room temperature and treated at 90 ° C. for 3 hours. The solid content was centrifuged, washed 5 times with 45 ml of ion exchange water, dried at 85 ° C. overnight, and calcined at 500 ° C. for 2 hours in an air atmosphere. The amount of La supported on this catalyst was 5.6% by weight by ICP analysis. Hereinafter, this catalyst is abbreviated as La / HY.

"Manufacture of cyclohexylbenzene"
A glass intubation tube was placed in a 50 ml SUS autoclave, and 1% Pd / Al-MS-1 equivalent to 0.2 μmol of Pd (about 0.002 g) was weighed as a hydrogenation catalyst into this intubation tube as an acid catalyst. 0.03 g of La / HY was added, and 5 ml of benzene and 0.03 g of tridecane (internal standard) were added. Next, after the system was replaced with hydrogen gas three times, hydrogen gas 5 MPa-G was injected, and the reaction was started in an oil bath set at 150 ° C. in advance. After 2.5 hours, the reactor was cooled with water, unreacted hydrogen gas was released, and the solution portion was analyzed by gas chromatography. As a result, 3.18 mmol of cyclohexylbenzene (hereinafter abbreviated as CHB) was produced. The selectivity was 75.7%.

[Comparative Example 1]
In Example 1, CHB was produced in the same manner as in Example 1 except that La / HY, which is a solid acid catalyst, was not added. As a result, only 0.01 mmol of CHB was produced, and the selectivity was less than 0.1%. The main product was 6.32 mmol of cyclohexane (hereinafter abbreviated as CHX).

[Comparative Example 2]
In Example 1, CHB was produced in the same manner as in Example 1 except that the solid acid catalyst was replaced with 0.03 g of HY. As a result, only 0.21 mmol of CHB was produced, and the selectivity was 13.2%. The main product was 2.77 mmol CHX.

[Example 2]
A solid acid catalyst was prepared in the same manner as in Example 1 except that lanthanum nitrate hexahydrate was replaced with yttrium nitrate hexahydrate g in Example 1, and CHB was produced. As a result, 1.69 mmol of CHB was produced, and the selectivity was 68.4%. The amount of supported Y of this solid acid catalyst (abbreviated as Y / HY) was 4.6% by weight by ICP analysis.

Example 3
In Example 1, a solid acid catalyst was prepared and CHB was prepared in the same manner as in Example 1 except that 5 g of HY was replaced with 5 g of Tosoh Na-type Y zeolite (HSZ-320NAA; hereinafter abbreviated as NaY). It was. As a result, 1.83 mmol of CHB was produced, and the selectivity was 72.9%. The amount of La supported on the solid acid catalyst (abbreviated as La / NaY) was 5.2% by weight by ICP analysis.

Example 4
In Example 1, CHB was produced in the same manner as in Example 1 except that the hydrogen pressure was changed to 3 MPa-G. As a result, 2.01 mmol of CHB was produced, and the selectivity was 80.2%.

Example 5
A solid acid catalyst was prepared in the same manner as in Example 4 except that lanthanum nitrate hexahydrate was replaced with strontium nitrate hexahydrate g in Example 4, and CHB was produced. As a result, 1.40 mmol of CHB was produced and the selectivity was 70.7%. The amount of Sr supported by this solid acid catalyst (abbreviated as Sr / HY) was 4.6% by weight by ICP analysis.

Example 6
In Example 1, a hydrogenation catalyst was prepared and CHB was produced in the same manner as in Example 1 except that 0.05 g of Rh (NH ₃ ) ₆ Cl ₃ was used instead of Pd (NH ₃ ) ₄ Cl ₂ . . As a result, 3.63 mmol of CHB was produced, and the selectivity was 67.0%. The amount of Rh supported by this hydrogenation catalyst (abbreviated as 1% Rh / Al-MS-1) was 1.0% by weight by ICP analysis. The results of Examples 1 to 6 and Comparative Examples 1 and 2 are collectively shown in Table 1.

Example 7
"Preparation of hydrogenation catalyst"
In a solution prepared by dissolving 5.98 g of cetyltrimethylammonium bromide in 100 ml of ion-exchanged water, 0.6 g of aluminum nitrate hexahydrate and 20 ml of an aqueous sodium silicate solution (27% SiO ₂ ; manufactured by Aldrich) were previously added to 70 ml of ion-exchanged water. The dissolved solution was added and stirred at room temperature for 3 hours, and then adjusted to pH 8.5 with 0.5N hydrochloric acid. The obtained liquid was placed in a SUS autoclave with a Teflon (registered trademark) intubation tube and sealed, and immersed in an oil bath at 110 ° C. for hydrothermal synthesis for one day. After completion of hydrothermal synthesis, water-cool and filter off the white solid from the Teflon (registered trademark) intubation tube, wash with 500 ml of ion-exchanged water, dry overnight at 85 ° C, and calcinate at 600 ° C for 2 hours in an air stream did. The obtained white powder was a mesoporous material with Si / Al (atomic ratio) = 68, and its SSA was 905 m ² / g. This shows an X-ray diffraction pattern (Cu-Kα line) similar to that of the known MCM41, and the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 is 42% of the total adsorption amount. there were.

100 ml of ion-exchanged water was added to 3 g of the mesoporous material thus obtained, and a solution prepared by dissolving 1 g of sodium nitrate in 50 ml of ion-exchanged water was added dropwise thereto, and the mesoporous material was treated overnight at room temperature. . Thereafter, the solid content was centrifuged, washed with ion exchange water (30 ml × 5 times) and dried (105 ° C., 5 hours). The obtained mesoporous material (Na ion exchanger) was suspended in 50 ml of ion exchange water, and a solution obtained by dissolving 0.04 g of Pd (NH ₃ ) ₄ Cl _{2 in} 30 ml of ion exchange water was added to this suspension. The solution was added dropwise over 30 minutes and stirred overnight at room temperature. Thereafter, the solid content was centrifuged, washed with ion-exchanged water until Cl ions were not detected, and dried at 105 ° C. The amount of Pd supported by this catalyst was 0.5% by weight by ICP analysis. Hereinafter, this catalyst is abbreviated as 0.5% Pd / Al-MS-2.

"Manufacture of cyclohexylbenzene"
A 50 ml glass intubation tube was placed in a SUS autoclave, and 0.5% Pd / Al-MS-2 corresponding to 0.15 μmol of Pd was weighed as a hydrogenation catalyst into this intubation tube, and La / HY0. 03 g was added, and 5 ml of benzene and 0.03 g of tridecane (internal standard) were added. Next, after the system was replaced with hydrogen gas three times, hydrogen gas 3 MPa-G was injected, and the reaction was started in an oil bath set at 180 ° C. in advance. After 1 hour, the reactor was cooled with water, unreacted hydrogen gas was released, and the solution portion was analyzed by gas chromatography. As a result, 2.23 mmol of cyclohexylbenzene (hereinafter abbreviated as CHB) was produced, and its selectivity Was 86.6%.

Example 8
"Preparation of hydrogenation catalyst"
Aluminum isopropoxide (0.8 mmol) was added to a mixture of tetraethylorthosilicate (200 mmol), ethanol (1.3 mol) and isopropanol (200 mmol) and stirred at 70 ° C. for 20 minutes. The resulting solution was mixed with dodecylamine (60 mmol) and water (7.2 mol). In addition to the liquid, it was stirred vigorously at room temperature for 1 hour. The produced white sol was aged at room temperature for 48 hours, filtered, washed with water and ethanol, dried at 105 ° C. for 24 hours, and calcined at 400 ° C. for 2 hours. The obtained white powder was a mesoporous material with Si / Al (atomic ratio) = 240, and its SSA was 935 m ² / g.

100 g of ion-exchanged water is added to 1 g of the mesoporous material thus obtained, and a solution in which 0.5 g of sodium nitrate is dissolved in 50 ml of ion-exchanged water is added dropwise to the mesoporous material at room temperature overnight. Processed. Thereafter, the solid content was centrifuged, washed with ion exchange water (30 ml × 5 times) and dried (105 ° C., 5 hours). The obtained mesoporous material (Na ion exchanger) was suspended in 50 ml of ion exchanged water, and a solution obtained by dissolving 0.015 g of Pd (NH ₃ ) ₄ Cl _{2 in} 30 ml of ion exchanged water was added to this suspension. The solution was added dropwise over 30 minutes and stirred overnight at room temperature. Thereafter, the solid content was centrifuged, washed with ion-exchanged water until Cl ions were not detected, and dried at 105 ° C. The amount of Pd supported by this catalyst was 0.5% by weight by ICP analysis. Hereinafter, this catalyst is abbreviated as 0.5% Pd / Al-MS-3.

"Manufacture of cyclohexylbenzene"
In Example 7, CHB was produced in the same manner as in Example 7 except that the hydrogenation catalyst was changed to 0.5% Pd / Al-MS-3. As a result, 2.21 mmol of CHB was produced, and the selectivity was 84.3%.

[Comparative Example 3]
In Example 7, a mesoporous material (Na ion exchanger) was replaced with NaY 5 g to prepare a hydrogenation catalyst (abbreviated as 0.5% Pd / NaY), and the hydrogenation catalyst was replaced with this catalyst. CHB was produced in the same manner as in Example 7. As a result, 1.19 mmol of CHB was produced, and the selectivity was 83.7%.

[Comparative Example 4]
In Example 7, CHB was produced in the same manner as in Example 7 except that the hydrogenation catalyst was changed to 0.5% Pd / SiO ₂ (manufactured by NE Chemcat). As a result, 1.31 mmol of CHB was produced, and the selectivity was 86.5%. Table 2 shows the results of Examples 7 to 8 and Comparative Examples 3 to 4.

  The catalyst for producing cyclohexylbenzene of the present invention is very useful in a method for producing cyclohexylbenzene by bringing benzene into contact with hydrogen, and cyclohexylbenzene can be produced with industrially satisfactory activity and selectivity.

Claims (3)

A catalyst for producing cyclohexylbenzene, comprising a hydrogenation catalyst of Pd or Rh as a catalytic active component having a mesoporous material as a carrier and a zeolite modified with a Group 2 metal or a Group 3 metal. The mesoporous material according to claim 1, wherein the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 in the nitrogen adsorption isotherm is 20 to 60% of the total adsorption amount, is used. catalyst. A method for producing cyclohexylbenzene, comprising contacting benzene and hydrogen in the presence of the catalyst according to claim 1.