WO2015163221A1 - Hydrogenation catalyst, method for producing same, and method for producing cyclohexanone or derivative thereof using same - Google Patents

Abstract

The present invention provides: a hydrogenation catalyst which enables a hydrogenation reaction to proceed with high conversion rate and high selectivity; and a method for producing cyclohexanone or a derivative thereof from phenol or a derivative thereof with high conversion rate and high selectivity. A hydrogenation catalyst according to the present invention is obtained by having a catalyst precursor, which is obtained by having a carrier contain phosphorus and an alkali metal and/or an alkaline earth metal, support a platinum group metal. The catalyst precursor has a chemisorption amount of ammonia of 100 μmol/g or less at 50°C. A method for producing cyclohexanone or a derivative thereof according to the present invention causes hydrogenation of phenol or a derivative thereof with use of the above-described hydrogenation catalyst.

Description

HYDROGENATION CATALYST, PROCESS FOR PRODUCING THE SAME, AND PROCESS FOR PRODUCING CYCLOHEXANONE OR ITS DERIVATIVE USING THE SAME

The present invention relates to a hydrogenation catalyst and a method for producing the same. More specifically, the present invention relates to a hydrogenation catalyst that suppresses sequential hydrogenation and side reactions and advances the hydrogenation reaction with high selectivity and a method for producing the same. The present invention also relates to a method for producing cyclohexanone or a derivative thereof. More specifically, the present invention relates to a method for producing cyclohexanone or a derivative thereof from phenol or a derivative thereof in one step.

Hydrogenation reaction is widely known as a reduction reaction for synthesizing chemical products. The hydrogenation reaction is a useful reaction with little generation of waste and the like. As a specific example, synthesis of cyclohexanone by hydrogenation of phenol is known. Cyclohexanone is a useful compound as a raw material for caprolactam, which is a raw material for nylon.

As a hydrogenation reaction, a catalyst in which a platinum group metal is supported on silica, alumina, silica alumina, zirconia, or activated carbon is widely used (Non-patent Document 1). However, in the catalyst using a carrier having many acid sites and base sites on the surface such as alumina and silica alumina, the acid sites and base sites promote sequential side reactions other than hydrogenation reaction and hydrogenation reaction, and lower the selectivity. It is the cause. On the other hand, the side reaction is difficult to proceed with a carrier such as silica that does not have a strong acid point or base point on the surface, but the platinum group metal agglomerates during the reaction because the interaction between the platinum group metal and the carrier is small, and the catalyst life is reduced. There is a problem that it is short.

As a method for controlling a side reaction by a catalyst carrier, a method of treating an acid point on the catalyst carrier with an alkali metal or an alkaline earth metal is known. For example, in the hydrogenation reaction of phenol, a method is known in which cyclohexanone is obtained by reacting hydrogen with phenol using a catalyst in which palladium is supported on Al ₂ O ₃ treated with an alkali metal or an alkaline earth metal. (Patent Document 1, Patent Document 2).

International Publication No. 2000/066792 Pamphlet British Patent No. 1332211 International Publication No. 2009/134514 Pamphlet

However, as a result of further testing the methods described in Patent Documents 1 and 2, it was found that the sequential hydrogenation and the suppression of the progress of side reactions were insufficient.

In cyclohexanone production by phenol hydrogenation reaction, cyclohexanol is usually produced by sequential hydrogenation reaction. The by-produced cyclohexanol can be induced to cyclohexanone by a dehydrogenation reaction, but since the reaction is an endothermic reaction, the reaction needs to be performed at a high temperature. From the above, when there are many cyclohexanol by-products, installation cost and energy are required. In addition, 2-cyclohexylcyclohexanone produced by the aldol reaction on the catalyst support is difficult to induce to cyclohexanone, and can only be used as a fuel or the like, reducing the carbon utilization efficiency.

In the hydrogenation reaction, if a hydrogenation catalyst that enables sequential hydrogenation and processes with few side reaction products can be found, equipment costs and energy consumption will be reduced, carbon utilization efficiency will be improved, and productivity will be improved. .

Therefore, one of the problems to be solved by the present invention is to control the acid sites and base sites to suppress sequential hydrogenation and side reactions and to proceed with a high conversion and high selectivity hydrogenation reaction. It is to provide a hydrogenation catalyst. Another problem to be solved by the present invention is to provide a method for producing cyclohexanone or a derivative thereof from phenol or a derivative thereof with high conversion and high selectivity.

The present invention relates to the following matters.
1. A hydrogenation catalyst in which a platinum group metal is supported on a catalyst precursor containing phosphorus and an alkali metal and / or an alkaline earth metal on a carrier,
A hydrogenation catalyst having an ammonia chemisorption amount of the catalyst precursor at 50 ° C. of 100 μmol / g or less.
2. A method for producing the above hydrogenation catalyst, comprising:
Mixing an alkali metal and / or alkaline earth metal source, water, carrier and phosphorus source;
Calcination after evaporating the water to obtain a catalyst precursor;
And a step of supporting a platinum group metal on the catalyst precursor.
3. A process for producing cyclohexanone or a derivative thereof, wherein phenol or a derivative thereof is hydrogenated using the hydrogenation catalyst.

By using the hydrogenation catalyst of the present invention, sequential hydrogenation and side reactions can be suppressed, and a hydrogenation reaction with a high conversion rate and a high selectivity can be advanced. For example, an industrially suitable phenol hydrogenation method capable of producing cyclohexanone useful as a raw material such as caprolactam with high selectivity can be provided. Further, according to the method for producing cyclohexanone or a derivative thereof of the present invention, cyclohexanone or a derivative thereof is produced from phenol or a derivative thereof with high conversion and high selectivity while suppressing by-products such as 2-cyclohexylcyclohexanone and cyclohexanol. can do.

It is a schematic diagram of a hydrogenation apparatus.

<Hydrogenation catalyst>
The hydrogenation catalyst of the present invention is obtained by supporting a platinum group metal on a catalyst precursor containing phosphorus and an alkali metal and / or an alkaline earth metal in a carrier.

Examples of the alkali metal and alkaline earth metal include lithium, sodium, potassium, cesium, magnesium, calcium, barium and the like, preferably calcium, lithium or magnesium, and more preferably calcium. In addition, an alkali metal and alkaline-earth metal may be used independently and may be used in combination of 2 or more type.

The catalyst precursor is prepared by supporting an alkali metal and / or alkaline earth metal and phosphorus on a carrier. When the alkali metal and / or alkaline earth metal is supported on the carrier, as a source of the alkali metal and / or alkaline earth metal, for example, nitrate, carbonate of alkali metal and / or alkaline earth metal Hydroxides, oxides, chlorides, acetates, oxalates, and the like can be used. When phosphorus is supported on a carrier, for example, phosphoric acid (including its aqueous solution) or its alkali metal salt and / or alkaline earth metal salt (including its aqueous solution) is used as the phosphorus supply source. Can do.

Examples of the carrier used in the preparation of the catalyst precursor include at least one selected from the group consisting of silica, alumina, silica alumina, zirconia, zeolite, and activated carbon.

The amount of alkali metal and / or alkaline earth metal supported on the carrier is preferably 0.01 to 2 g, more preferably 0.02 to 0.2 g, relative to 1 g of the carrier. The amount of phosphorus supported on the carrier is preferably 0.001 to 1 g, more preferably 0.005 to 0.1 g, relative to 1 g of the carrier. The molar ratio of the alkali metal and / or alkaline earth metal and phosphorus supported on the carrier can be any ratio, but is preferably 1 to 10, and more preferably 1.4 to 4. Note that phosphorus and an alkali metal and / or an alkaline earth metal may be supported on a carrier in a state where a composite oxide or the like is formed.

In the present invention, the chemical adsorption amount of ammonia at 50 ° C. of the catalyst precursor is 100 μmol / g or less. By reducing the amount of ammonia chemisorbed on the catalyst precursor, a hydrogenation catalyst that promotes a high conversion and high selectivity hydrogenation reaction is obtained. The amount of chemisorption of ammonia at 50 ° C. by the catalyst precursor is preferably 80 μmol / g or less, and more preferably 50 μmol / g or less. The ammonia chemisorption amount of the catalyst precursor at 50 ° C. is preferably as low as possible in terms of conversion and selectivity, but can be set to 9 μmol / g or more, for example, from the viewpoint of interaction with the platinum group metal. The ammonia chemisorption amount of the catalyst precursor at 50 ° C. can be adjusted by the type of alkali metal or alkaline earth metal used and / or the molar ratio of alkali metal or alkaline earth metal to phosphorus.

The reason why the hydrogenation reaction with high conversion and high selectivity can be advanced by controlling the amount of ammonia chemisorption at 50 ° C. of the catalyst precursor is considered as follows. In other words, the base point generated by supporting the alkali metal and / or alkaline earth metal on the carrier is better than the conventional carrier by neutralizing it by controlling the amount of acid sites by carrying phosphorus. Thus, a catalyst precursor having a desired acid point and base point is obtained. As a result, side reactions other than hydrogenation of cyclohexanone or a derivative thereof are suppressed, and a hydrogenation reaction with high selectivity becomes possible. In addition, the product by the side reaction poisons the active sites and causes the conversion rate to decrease, but as a result of the reduction of the product by the side reaction, the hydrogenation reaction at a high conversion rate becomes possible.

In the present invention, the chemical adsorption amount of carbon dioxide at 50 ° C. of the catalyst precursor is preferably 15 μmol / g or less. By reducing the amount of carbon dioxide chemisorption of the catalyst precursor, it becomes a hydrogenation catalyst that promotes a hydrogenation reaction with a higher conversion rate and a higher selectivity. The chemical adsorption amount of carbon dioxide at 50 ° C. of the catalyst precursor is more preferably 10 μmol / g or less, and further preferably 7 μmol / g or less. The chemical adsorption amount of carbon dioxide at 50 ° C. of the catalyst precursor is preferably as low as possible in terms of conversion rate and selectivity. However, from the viewpoint of promoting the reaction by adsorption of phenol or a derivative thereof to the support, for example, 0.4 μmol / g. This can be done. The amount of carbon dioxide adsorbed at 50 ° C. by the catalyst precursor can be adjusted by the type of alkali metal or alkaline earth metal used and / or the molar ratio of alkali metal or alkaline earth metal to phosphorus.

The reason why the hydrogenation reaction with a higher conversion rate and a higher selectivity can be advanced by controlling the amount of carbon dioxide chemisorption at 50 ° C. of the catalyst precursor is considered as follows. That is, the introduction of the base point enhances the interaction between the platinum group metal and the support, suppresses the aggregation of the platinum group metal, and maintains the high activity of the catalyst. Furthermore, the introduction of the base point promotes the adsorption of phenol or its derivative with high acidity to the catalyst, so that the adsorption of cyclohexanone and its derivative with lower acidity to the catalyst is suppressed. As a result, the conversion rate can be improved and the sequential hydrogenation can be suppressed, and the hydrogenation reaction with a high conversion rate and a high selectivity can be advanced.

Measurement of the chemisorption amount of ammonia and the chemisorption amount of carbon dioxide can be performed, for example, by the following procedure.
(1) Keeping the catalyst precursor at 50 ° C. with a heater, etc., gradually exposing it to ammonia or carbon dioxide from a high vacuum state, and measuring the amount of adsorption thereof, the total adsorption isotherm (chemical adsorption and physical Including both adsorption).
(2) Next, the catalyst precursor is placed in a high vacuum, and after only the physically adsorbed ammonia or carbon dioxide is completely removed, it is exposed again to ammonia or carbon dioxide as it is. Corresponding to the physical adsorption isotherm).
(3) A chemical adsorption isotherm is obtained by the difference between the total adsorption isotherm (first adsorption isotherm; including both chemical adsorption and physical adsorption) and physical adsorption isotherm (second adsorption isotherm).
(4) Since the chemisorption isotherm is almost a straight line, by extrapolating this to P (absolute pressure) = 0 of the chemisorption isotherm, the amount of ammonia or CO2 chemisorbed on the catalyst precursor by a monolayer The amount of carbon (amount of chemisorption of ammonia or carbon dioxide) is quantified.

It should be noted that pretreatment for desorbing water, acidic substances, and basic substances adsorbed on the catalyst precursor is preferably performed in advance in measuring the chemical adsorption amounts of ammonia and carbon dioxide. The pretreatment method may be appropriately selected in consideration of the properties of the catalyst precursor, and specific examples thereof include heat treatment, vacuum exhaust treatment, treatment combining these, and the like. Processing conditions such as heating temperature, degree of vacuum and time are not particularly limited as long as the properties of the catalyst precursor are not impaired.

In the present invention, a platinum group metal is further supported on the catalyst precursor containing phosphorus and an alkali metal and / or an alkaline earth metal. Examples of the platinum group metal include ruthenium, rhodium, palladium, osmium, iridium, and platinum, with palladium being preferred. The amount of the platinum group metal supported on the catalyst precursor is preferably 0.001 to 0.05 g, more preferably 0.002 to 0.01 g, with respect to 1 g of the catalyst precursor.

<Method for producing hydrogenation catalyst>
The catalyst precursor is prepared by mixing an alkali metal and / or alkaline earth metal source, water, a support, and a phosphorus source, evaporating the water, and calcining. The firing temperature at that time is preferably 200 to 1000 ° C., more preferably 400 to 800 ° C., and the pressure is not particularly limited. Further, although the firing atmosphere is not particularly limited, the firing is preferably performed in the presence of oxygen (for example, in air). Thereafter, a platinum group metal is supported on the catalyst precursor and dried to obtain a hydrogenation catalyst (solid catalyst).

The support on the carrier and the catalyst precursor is carried out by a conventional method. For example, it is carried out by bringing the carrier or catalyst precursor into contact with an aqueous metal salt solution of the metal to be supported.

The shape of the hydrogenation catalyst (solid catalyst) of the present invention can be selected regardless of the form such as a cylindrical shape, an extrusion shape, a spherical shape, a granular shape, a powder shape, a honeycomb shape, etc. It is preferable that the molded body has a cylindrical shape, an extrusion shape, a spherical shape, a granular shape, a honeycomb shape, or the like.

<Method for producing cyclohexanone or a derivative thereof>
As an example of the hydrogenation reaction using the hydrogenation catalyst of the present invention, a method for producing cyclohexanone or a derivative thereof (cyclohexanone) by a hydrogenation reaction of phenol or a derivative thereof (phenol) is shown.

Phenols that are raw material compounds are represented by the following formula (1).

[In the formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a hydroxy group, a phenol group, a phenyl group, a C1-C10 alkyl group or a C1-C10 An alkoxy group; ]

The C1-C10 alkyl group may be a linear, branched or cyclic alkyl group, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonanyl, decyl, cyclopentyl. , Cyclohexyl, cycloheptyl, cyclooctyl, cyclononanyl, cyclodecyl and isomers thereof.

The C1-C10 alkoxy group may be a linear or branched alkoxy group, and specific examples thereof include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonanyloxy, decyloxy And isomers thereof.

Specific examples of the phenol group include 2-hydroxyphenyl group, 3-hydroxyphenyl group and 4-hydroxyphenyl group.

Specific examples of phenols include phenol, catechol, o-cresol, 2,5-xylenol, 2,6-xylenol, 2,3,6-trimethylphenol, 2-cyclohexylphenol, 2-cyclopentylphenol, 2-phenyl Examples thereof include phenol, 2-isopropylphenol, 2-t-butylphenol, 2-t-butyl-6-methylphenol, 2-sec-butylphenol, 2-isobutylphenol, 2-methoxyphenol and bisphenol.

Cyclohexanones obtained by the hydrogenation reaction of phenols are represented by the following formula (2).

[In formula (2), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as in formula (1). ]

Specific examples of cyclohexanones include cyclohexanone, 2-hydroxycyclohexanone, 2-methylcyclohexanone, 2,5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,3,6-trimethylcyclohexanone, 2-cyclohexylcyclohexanone, 2- Cyclopentylcyclohexanone, 2-phenylcyclohexanone, 2-isopropylcyclohexanone, 2-t-butylcyclohexanone, 2-t-butyl-6-methylcyclohexanone, 2-sec-butylcyclohexanone, 2-isobutylcyclohexanone, 2-methoxycyclohexanone, 2, Examples include 2-bis (4-oxocyclohexyl) propane.

A process for producing cyclohexanones by a hydrogenation reaction of phenols will be described below by taking a process for producing cyclohexanones by a hydrogenation reaction of phenol, which is a typical phenol, as an example.

As a method for producing cyclohexanone by a hydrogenation reaction of phenol, there are generally a method using cyclohexane or water as a solvent and a method using no solvent other than phenol and main product cyclohexanone.

As a hydrogenation reaction of phenol using a solvent, a catalyst in which palladium is supported on activated carbon and hydrogenated in the presence of aluminum chloride (Non-patent Document 2), or a catalyst in which palladium is supported on carbon nitride is used. A method of hydrogenation using water as a solvent is known (Non-Patent Document 3).

Since the former uses aluminum chloride, there is a problem that a large amount of waste is generated with the treatment, and the latter is not suitable for industrial implementation because the preparation method of the catalyst is complicated. In addition, the use of a solvent causes an increase in the number of reactors and an increase in solvent separation costs, and is not suitable as an industrial production method.

On the other hand, as a hydrogenation reaction of phenol without using a solvent, a catalyst in which palladium is supported on Al ₂ O ₃ treated with an alkali metal or an alkaline earth metal is used, and cyclohexanone is reacted by reacting hydrogen with phenol. Methods of obtaining are known (Patent Document 1, Patent Document 2).

Such a hydrogenation reaction of phenol without using a solvent has a high productivity and is industrially carried out. However, the phenol hydrogenation reaction solution without using a solvent contains cyclohexanone, cyclohexanol, other products, and unreacted phenol. Normally, unreacted phenol is separated and introduced again into the phenol hydrogenation process. However, in order to form an azeotropic composition with cyclohexanone, much equipment cost and energy are required for separation and circulation of phenol. Although it is possible to reduce the phenol content in the reaction solution by increasing the phenol conversion rate, the side reaction of cyclohexanone produced at the same time proceeds and the selectivity decreases. The produced cyclohexanol can be induced to cyclohexanone by a dehydrogenation reaction. However, since this reaction is an endothermic reaction, it is necessary to carry out the reaction at a high temperature, which requires equipment cost and energy. In addition, other by-products include 2-cyclohexylcyclohexanone produced by the aldol reaction on the catalyst support. However, 2-cyclohexylcyclohexanone is difficult to induce to cyclohexanone and is used as a fuel or the like. No other carbon efficiency is reduced.

On the other hand, the method for producing cyclohexanone by the hydrogenation reaction of phenol using the hydrogenation catalyst of the present invention, for example, as in the hydrogenation apparatus shown in FIG. This is carried out by supplying hydrogen 8 and phenol 7 (or a mixture of phenol and cyclohexanone) to the reaction tube 1 having the preheating layer 3 on the side after flowing hydrogen 8 from the preheating layer 3 side and performing pretreatment reduction. . By doing so, cyclohexanone can be obtained with high conversion and high selectivity.

As the reaction tube 1, a straight tube is used. Examples of the material include stainless steel (SUS), glass, quartz, and the like, and stainless steel (SUS) is preferable from the viewpoint of an industrial manufacturing method.

The reaction tube 1 is filled with the hydrogenation catalyst of the present invention. The reaction tube 1 is provided with a bottom plate 5 such as a plate, a net or a punching metal having air permeability to support the hydrogenation catalyst, and quartz wool 4 or the like is placed on this plate. Next, the catalyst layer 2 filled with the hydrogenation catalyst is formed. This prevents the hydrogenation catalyst from coming off.

On the phenol introduction side of the catalyst layer 2, a preheat layer 3 is provided after spreading quartz wool 4 as necessary. The preheating layer 3 is formed, for example, on the introduction side of phenol of the hydrogenation catalyst filled in the reaction tube 1 (in the case of a vertical reaction tube, on the top of the filled hydrogenation catalyst), for example, glass beads, quartz wool, fibrous It can be formed by filling with stainless steel (SUS). Further, the preheating layer 3 portion of the reaction tube 1 is thinned, or a tube having a thin outer diameter is connected to the reaction tube 1 on which the catalyst layer 2 is formed as a preheating layer 3 site, and this is connected to glass beads, quartz wool, fibrous The preheating layer 3 can also be formed by a method of filling stainless steel (SUS), or a filler such as glass beads is filled if heat exchange with phenol or hydrogen flowing through the reaction tube 1 is sufficient. It can also be set as the preheating layer 3 without.

When glass beads are used, the particle size of the glass beads is approximately 1/10 of the diameter of the reaction tube 1 and depends on the diameter of the reaction tube 1, but for example, a spherical one having a diameter of 1 mm or 2 mm is used. be able to.

Preheating can be performed, for example, by installing a heater 6 outside the preheating layer 3 and external heating.

Cyclohexanone is produced by supplying phenol 7 from the preheating layer 3 side of the hydrogenation device, but the hydrogenation catalyst is reduced in the gas phase or liquid phase before the phenol 7 is supplied.

Examples of the reduction process in the vapor phase include a method using hydrogen as a reducing agent. At that time, the temperature of the catalyst layer 2 is 50 to 500 ° C., preferably 100 to 200 ° C., and the reduction treatment is carried out with an amount of hydrogen and a time sufficient to sufficiently reduce the platinum group metal in the hydrogenation catalyst. . Note that, before supplying hydrogen, an inert gas such as nitrogen or argon is conducted to replace the inside of the reaction system with the inert gas.

As a method for the reduction treatment in the liquid phase, for example, an aqueous solution of 1 to 20% by mass of a reducing agent such as formic acid, an alkali metal salt of formic acid, formalin, hydrazine, or sodium borohydride is used. A method of reducing the platinum group metal in the hydrogenation catalyst at a temperature of ˜100 ° C. can be mentioned.

The raw material phenol 7 can be used regardless of its production method, and there is no problem even in the state of a mixture of phenol and cyclohexanone. For example, phenol obtained by the cumene method can be used, or a mixture of phenol and cyclohexanone obtained by oxidative decomposition of a reduced dimer of benzene described in Patent Document 3 can be used as it is without separation. You can also. The ratio of phenol to cyclohexane is not particularly limited, but the phenol: cyclohexanone ratio (mol%) is preferably 100: 0 to 30:70 from the viewpoint of suppressing the production of by-product cyclohexanol and productivity.

Phenol 7 (or a mixture of phenol and cyclohexanone) as a raw material is heated to 120 ° C. or lower as necessary to be in a liquid state, and is supplied to the preheating layer 3 by a pump such as a plunger pump or a syringe pump.

The flow rate of phenol depends on the reactor, the production scale, and the amount of platinum group metal supported in the hydrogenation catalyst, but the supply rate per weight of the hydrogenation catalyst is 0.2 to 5 kg · kg-cat ⁻¹ · h ^{−. 1} .

The supplied phenol 7 (or a mixture of phenol and cyclohexanone) is heated in the preheating layer, mixed with hydrogen 8 also supplied, and supplied to the catalyst layer 2. As another method, depending on the reaction conditions, a method of passing hydrogen through liquid phenol and sending the vaporized phenol to the preheating layer 3 can be applied.

The amount of hydrogen 8 supplied to the catalyst layer 2 depends on the reactor, the production scale, and the amount of platinum group metal supported in the hydrogenation catalyst, but is 100 to 130,000 L · kg- cat ⁻¹ · h ⁻¹ and heated in the preheating layer 3. A preferable temperature in the preheating layer 3 is 100 to 220 ° C.

The molar ratio of hydrogen to phenol is 2 to 100, preferably 4 to 50.

Phenol and hydrogen react at a temperature of the catalyst layer 2 of 100 to 220 ° C., preferably 140 to 160 ° C., and a pressure of 0 to 1 MPa (gauge pressure or less, G), preferably 0 to 0.3 MPa (G).

The desired reaction product can be obtained by cooling and collecting the resulting reaction product from the reaction tube 1 and purifying the collected liquid by, for example, distillation.

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples.

The amount of each component produced in the hydrogenation reaction of phenols was measured by cooling and collecting the obtained reaction solution, and then gas chromatography (manufactured by Shimadzu Corporation, trade name: “GC-2014”, GC column: Analysis was performed using TC-WAX, GC detector (FID), and calculation was performed using diethylene glycol monoethyl ether as an internal standard.

[Example 1]
(Preparation of catalyst A precursor: 0.1Ca-0.05P-SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: CARiACT Q-50, spherical, 1.18-2.36 mm), Ca / Si (mol ratio) = 0.1, P / Si (mol ratio) = 0. A calcium nitrate aqueous solution and a phosphoric acid aqueous solution were impregnated and supported so as to be 05, and dried at 110 ° C. for 12 hours or more. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst A precursor. The BET specific surface area of the catalyst A precursor was 49 m ² / g.

(Measurement of chemical adsorption amount of ammonia and carbon dioxide of catalyst A precursor)
1.5 g of the catalyst A precursor was placed in a glass sample cell and heated at 380 ° C. for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the chemical adsorption amount of ammonia, the pretreated catalyst A precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C (trade name, Yuasa Ionics). Installed).

The catalyst A precursor was kept at 50 ° C. with a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at a total of 20 points) Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst A precursor was 47.1 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemisorption amount of the catalyst A precursor was 6.1 μmol / g.

(Catalyst A: Production of Pd / 0.1Ca-0.05P-SiO ₂ )
The catalyst A precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.5 wt%, and dried at 110 ° C. for 12 hours or longer to obtain catalyst A: Pd / 0.1Ca-0.05P-SiO ₂ . Obtained.

[Example 2]
(Catalyst A: Hydrogenation reaction of phenol with Pd / 0.1Ca-0.05P-SiO ₂ )
Catalyst A: 1 g of Pd / 0.1Ca-0.05P-SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical) were placed on the top. A preheating layer was used. The catalyst layer was heated to 200 ° C., hydrogen gas (26 cc / min) was passed from the top and pretreatment reduction was performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 2) at 140 ° C. and 0 MPa (G). The hydrogenation reaction of phenol was performed by supplying 1) at 2.6 cc / h and hydrogen gas at 26 cc / min.

The collected liquid for 16 h was discarded from the start of the reaction, and then the collected liquid for 1 h was analyzed by gas chromatography. As a result, the conversion rate of the starting phenol was> 99.9%, the selectivity of cyclohexanone was 98.1%, the selectivity of cyclohexanol as a by-product was 1.8%, The selectivity for cyclohexylcyclohexanone was <0.1%.

[Example 3]
(Catalyst A: Hydrogenation reaction of phenol with Pd / 0.1Ca-0.05P-SiO ₂ : life evaluation)
Catalyst A: 1 g of Pd / 0.1Ca-0.05P-SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical) were placed on the top. A preheating layer was used. The catalyst layer is heated to 200 ° C., hydrogen gas (10 cc / min) is circulated from above and pretreatment reduction is performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 2) at 140 ° C. and 0 MPa (G). The hydrogenation reaction of phenol was carried out by continuously supplying 1) at 1.0 cc / h and hydrogen gas at 10 cc / min.

The collected liquid was cut off for 25 h from the start of the reaction, and then sampled every 2 to 5 h for 30 h, and the collected liquid was analyzed by gas chromatography. As a result, the reaction results were stable, and the average value was that the phenol conversion was> 99.9%, the selectivity for cyclohexanone was 97.2%, and the selectivity for cyclohexanol as a by-product. Was 2.6% and the selectivity for 2-cyclohexylcyclohexanone was <0.1%.

Subsequently, the reaction temperature was lowered to 135 ° C., the collected liquid for 15 h was discarded, and then sampling was performed every 2 to 5 h for 60 h, and the collected liquid was analyzed by gas chromatography. As a result, the reaction results were stable, and the average value was that the phenol conversion was> 99.9%, the cyclohexanone selectivity was 98.7%, and the selectivity for the by-product cyclohexanol was Was 1.2% and the selectivity for 2-cyclohexylcyclohexanone was <0.1%.

[Example 4]
(Catalyst A: Hydrogenation reaction of p-cresol with Pd / 0.1Ca-0.05P-SiO ₂ )
Catalyst A: 1 g of Pd / 0.1Ca-0.05P-SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical) were placed on the top. A preheating layer was used. The catalyst layer was heated to 200 ° C., hydrogen gas (10 cc / min) was circulated from the top and subjected to pretreatment reduction, and then a mixture (moles of p-cresol and 4-methylcyclohexanone at 135 ° C. and 0 MPa (G) The hydrogenation reaction of p-cresol was performed by supplying hydrogen gas at a ratio of 1: 1) to 1.0 cc / h and 10 cc / min.

The collected liquid for 14 h was discarded from the start of the reaction, and then the collected liquid for 2 h was analyzed by gas chromatography. As a result, the conversion rate of p-cresol as a starting material was 99.4%, the selectivity of 4-methylcyclohexanone was 98.3%, and the selectivity of 4-methylcyclohexanol as a by-product was 1 0.7%.

[Example 5]
(Preparation of catalyst B precursor: Li—P—SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical, trade name: CARiACT Q-50, spherical, 1.18-2.36 mm), Li / Si (mol ratio) = 0.2, P / Si (mol ratio) = 0. A lithium nitrate aqueous solution and a phosphoric acid aqueous solution were impregnated and supported so as to be 05, and dried at 110 ° C. for 12 hours or longer. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst B precursor. The BET specific surface area of the catalyst B precursor was 53 m ² / g.

(Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst B precursor)
1.5 g of the catalyst B precursor was put into a glass sample cell and heated at 380 ° C. for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the amount of chemisorption of ammonia, the pretreated catalyst B precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C (trade name, Yuasa Ionics). Installed).

The catalyst B precursor was kept at 50 ° C. with a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at a total of 20 points). Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst B precursor was 9.8 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemical adsorption amount of the catalyst B precursor was 0.4 μmol / g.

(Catalyst B: Production of Pd / Li—P—SiO ₂ )
The catalyst B precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.2 wt%, and dried at 110 ° C. for 12 hours or longer to obtain catalyst B: Pd / Li—P—SiO ₂ .

[Example 6]
(Catalyst B: Hydrogenation reaction of phenol with Pd / Li—P—SiO ₂ )
Catalyst B: 1 g of Pd / Li—P—SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical shape) were placed on the top to form a preheating layer. . The catalyst layer was heated to 200 ° C., hydrogen gas (16 cc / min) was passed through the top and subjected to pretreatment reduction, and then at 140 ° C. and 0 MPa (G), a mixture of phenol and cyclohexanone (molar ratio = 1: 1) was supplied at 1.6 cc / h and hydrogen gas was supplied at 16 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 4 hours was cut off from the start of the reaction, and then the collected liquid for 1 hour was analyzed by gas chromatography. As a result, the conversion rate of the starting material phenol was 99.3%, the cyclohexanone selectivity was 98.0%, the byproduct cyclohexanol selectivity was 1.9%, and 2- The selectivity for cyclohexylcyclohexanone was 0.1%.

[Example 7]
(Catalyst C precursor: production of Mg—P—SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: CARiACT Q-50, spherical, 1.18-2.36 mm), Mg / Si (mol ratio) = 0.2, P / Si (mol ratio) = 0. A magnesium nitrate aqueous solution and a phosphoric acid aqueous solution were impregnated and supported so as to be 05, and dried at 110 ° C. for 12 hours or more. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst C precursor. The BET specific surface area of the catalyst C precursor was 59 m ² / g.

(Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst C precursor)
The catalyst C precursor 1.5g was put into the glass sample cell, and it heated at 380 degreeC for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the chemical adsorption amount of ammonia, the pretreated catalyst C precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C (trade name, Yuasa Ionics). Installed).

The catalyst C precursor was kept at 50 ° C. by a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at 20 points in total) Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst C precursor was 40.7 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemical adsorption amount of the catalyst C precursor was 1.0 μmol / g.

(Catalyst C: Production of Pd / Mg—P—SiO ₂ )
The catalyst C precursor was impregnated and supported with an aqueous palladium chloride solution at 0.5 wt%, and dried at 110 ° C. for 12 hours or longer to obtain catalyst C: Pd / Ca—P—SiO ₂ .

[Example 8]
(Catalyst C: Hydrogenation reaction of phenol with Pd / Mg—P—SiO ₂ )
Catalyst C: 1 g of Pd / Mg—P—SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical shape) were placed on the top to form a preheating layer. . The catalyst layer was heated to 200 ° C., hydrogen gas (26 cc / min) was passed from the top and pretreatment reduction was performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 1) at 140 ° C. and 0 MPa (G). ) At 1.0 cc / h and hydrogen gas at 10 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 3 h was discarded from the start of the reaction, and then the collected liquid for 4 h was analyzed by gas chromatography. As a result, the conversion rate of phenol as a starting material was 97.9%, the selectivity of cyclohexanone was 96.7%, the selectivity of cyclohexanol as a by-product was 1.8%, The selectivity for cyclohexylcyclohexanone was 0.6%.

[Example 9]
(Preparation of catalyst D precursor: 0.07Ca-0.05P-SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: CARiACT Q-50, spherical, 1.18-2.36 mm), Ca / Si (mol ratio) = 0.07, P / Si (mol ratio) = 0. A calcium nitrate aqueous solution and a phosphoric acid aqueous solution were impregnated and supported so as to be 05, and dried at 110 ° C. for 12 hours or more. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst D precursor. The BET specific surface area of the catalyst D precursor was 56 m ² / g.

(Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst D precursor)
1.5 g of catalyst D precursor was placed in a glass sample cell and heated at 380 ° C. for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the chemical adsorption amount of ammonia, the pretreated catalyst D precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C type (trade name, Yuasa Ionics). Installed).

The catalyst D precursor was kept at 50 ° C. with a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at 20 points in total) Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst D precursor was 55.7 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemisorption amount of the catalyst D precursor was 4.8 μmol / g.

(Catalyst D: Production of Pd / 0.07Ca-0.05P-SiO ₂ )
The catalyst D precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.5 wt%, and dried at 110 ° C. for 12 hours or more, whereby catalyst D: Pd / 0.07Ca-0.05P-SiO ₂ was obtained. Obtained.

[Example 10]
(Catalyst D: Hydrogenation reaction of phenol with Pd / 0.07Ca-0.05P-SiO ₂ )
Catalyst D: 1 g of Pd / 0.07Ca-0.05P-SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical) were placed on the top. A preheating layer was used. The catalyst layer was heated to 200 ° C., hydrogen gas (26 cc / min) was passed from the top and pretreatment reduction was performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 2) at 140 ° C. and 0 MPa (G). 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 10 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 27 h was discarded from the start of the reaction, and then the collected liquid for 3 h was analyzed by gas chromatography. As a result, the conversion rate of phenol as a starting material was 97.7%, the selectivity of cyclohexanone was 98.2%, the selectivity of cyclohexanol as a by-product was 1.6%, The selectivity for cyclohexylcyclohexanone was <0.1%.

[Example 11]
(Catalyst E precursor: production of 0.2Ca-0.05P-SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical, trade name: CARiACT Q-50, spherical, 1.18-2.36 mm), Ca / Si (mol ratio) = 0.2, P / Si (mol ratio) = 0. A calcium nitrate aqueous solution and a phosphoric acid aqueous solution were impregnated and supported so as to be 05, and dried at 110 ° C. for 12 hours or more. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst E precursor. The BET specific surface area of the catalyst E precursor was 49 m ² / g.

(Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst E precursor)
1.5 g of the catalyst E precursor was placed in a glass sample cell and heated at 380 ° C. for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the amount of chemical adsorption of ammonia, the pre-processed catalyst E precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C (trade name, Yuasa Ionics). Installed).

The catalyst E precursor was kept at 50 ° C. with a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at a total of 20 points) Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst E precursor was 91.7 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemisorption amount of the catalyst E precursor was 7.5 μmol / g.

(Catalyst E: Production of Pd / 0.2Ca-0.05P-SiO ₂ )
The catalyst E precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.2 wt%, and dried at 110 ° C. for 12 hours or longer to obtain catalyst E: Pd / 0.2Ca-0.05P-SiO ₂ . Obtained.

[Example 12]
(Catalyst E: Hydrogenation reaction of phenol with Pd / 0.2Ca-0.05P-SiO ₂ )
Catalyst E: 1 g of Pd / 0.2Ca-0.05P-SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical) were placed on the top. A preheating layer was used. The catalyst layer was heated to 200 ° C., hydrogen gas (26 cc / min) was passed from the top and pretreatment reduction was performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 2) at 140 ° C. and 0 MPa (G). 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 10 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 8 hours was cut off from the start of the reaction, and then the collected liquid for 3 hours was analyzed by gas chromatography. As a result, the conversion rate of phenol as a starting material was 96.7%, the selectivity of cyclohexanone was 98.3%, the selectivity of cyclohexanol as a by-product was 1.6%, The selectivity for cyclohexylcyclohexanone was 0.1%.

[Example 13]
(Preparation of catalyst F precursor: 0.3Ca-0.05P-SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: CARiACT Q-50, spherical, 1.18-2.36 mm), Ca / Si (mol ratio) = 0.3, P / Si (mol ratio) = 0. A calcium nitrate aqueous solution and a phosphoric acid aqueous solution were impregnated and supported so as to be 05, and dried at 110 ° C. for 12 hours or more. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst F precursor. The BET specific surface area of the catalyst F precursor was 41 m ² / g.

(Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst F precursor)
The catalyst F precursor 1.5g was put into the glass sample cell, and it heated at 380 degreeC for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the amount of chemical adsorption of ammonia, the pretreated catalyst F precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C (trade name, Yuasa Ionics). Installed).

The catalyst F precursor was kept at 50 ° C. by a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at a total of 20 points) Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst F precursor was 89.8 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemisorption amount of the catalyst F precursor was 13.2 μmol / g.

(Catalyst F: Production of Pd / 0.3Ca-0.05P-SiO ₂ )
The catalyst F precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.5 wt%, and dried at 110 ° C. for 12 hours or longer, whereby catalyst F: Pd / 0.3Ca-0.05P-SiO ₂ was obtained. Obtained.

[Example 14]
(Catalyst F: Hydrogenation reaction of phenol with Pd / 0.3Ca-0.05P-SiO ₂ )
Catalyst F: 1 g of Pd / 0.3Ca-0.05P-SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical) were placed on the top. A preheating layer was used. The catalyst layer was heated to 200 ° C., hydrogen gas (26 cc / min) was passed from the top and pretreatment reduction was performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 3) at 135 ° C. and 0 MPa (G). 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 10 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 70 h was discarded from the start of the reaction, and then the collected liquid for 2 h was analyzed by gas chromatography. As a result, the conversion rate of phenol as a starting material was 96.5%, the selectivity of cyclohexanone was 95.2%, the selectivity of cyclohexanol as a by-product was 4.6%, The selectivity for cyclohexylcyclohexanone was <0.1%.

[Comparative Example 1]
(Hydrogenation reaction of phenol with Pd—Na / Al ₂ O ₃ 1)
Aluminum oxide (Al ₂ O ₃ : manufactured by Sumitomo Chemical Co., Ltd., spherical) was impregnated and supported with sodium acetate so as to be 2 wt%, dried at 110 ° C., and then calcined at 500 ° C. for 3 h, and 2% Na / Al ₂ O ₃ was obtained. Thereafter, a palladium nitrate aqueous solution was impregnated and supported on 2% Na / Al ₂ O ₃ so as to be 0.05 wt%, dried at 110 ° C. for 12 hours or more, then fired at 450 ° C. for 3 h, and 0.05 wt%. Pd-2% Na / Al ₂ O ₃ was obtained.

A 1 / 2-inch stainless steel (SUS) tube was filled with 1.0 g of 0.05 wt% Pd-2% Na / Al ₂ O ₃ , and 10 g of glass beads were placed on the top to form a preheated layer. The catalyst layer is heated to 200 ° C., hydrogen gas (13 cc / min) is circulated from the upper portion and pretreatment reduction is performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 2) at 140 ° C. and 0 MPa (G). 1) was supplied at 0.5 cc / h and hydrogen gas was supplied at 13 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 8 hours was cut off from the start of the reaction, and then the collected liquid for 1 hour was analyzed by gas chromatography. As a result, the conversion rate of phenol as a starting material was 99.4%, the selectivity of cyclohexanone was 90.3%, the selectivity of cyclohexanol as a by-product was 0.7%, The selectivity for cyclohexylcyclohexanone was 8.7%.

[Comparative Example 2]
(Phenol hydrogenation reaction 2 with Pd—Na / Al ₂ O ₃ )
Aluminum oxide (Al ₂ O ₃ : made by N.E. Chemcat, cylindrical shape) was crushed and powdered, impregnated with sodium acetate so as to be 2 wt%, dried at 110 ° C. for 12 hours or more, and then 500 Firing at 3 ° C. for 3 h gave 2% Na / Al ₂ O ₃ . Thereafter, a palladium nitrate aqueous solution is impregnated and supported on 2% Na / Al ₂ O ₃ so as to be 0.1 wt%, dried at 110 ° C. for 12 hours or more, and then calcined at 450 ° C. for 3 h. Pd-2% Na / Al ₂ O ₃ was obtained.

A 1/2 inch stainless steel (SUS) tube was filled with a mixture of 0.13 g of 0.1 wt% Pd-2% Na / Al ₂ O ₃ and 0.37 g of 2% Na / Al ₂ O _3. Then, 10 g of glass beads were put on the top to form a preheated layer. The catalyst layer was heated to 200 ° C., hydrogen gas (25 cc / min) was passed from the top to perform pretreatment reduction, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 160 ° C., 0 MPa (G)). 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 25 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 1 h was discarded from the start of the reaction, and then the collected liquid for 1 h was analyzed by gas chromatography. As a result, the conversion of phenol as a starting material was 99.8%, the selectivity of cyclohexanone was 89.1%, the selectivity of cyclohexanol as a by-product was 10.3%, The selectivity for cyclohexylcyclohexanone was 0.6%.

[Comparative Example 3]
_{(Pd-Na / Al 2 O} 3 phenol hydrogenation reaction 3 by)
Aluminum oxide (Al ₂ O ₃ : made by N.E. Chemcat, cylindrical shape) was crushed and powdered, impregnated with sodium acetate so as to be 2 wt%, dried at 110 ° C. for 12 hours or more, and then 500 Firing at 3 ° C. for 3 h gave 2% Na / Al ₂ O ₃ . Thereafter, a palladium nitrate aqueous solution was impregnated and supported on 2% Na / Al ₂ O ₃ so as to be 0.05 wt%, dried at 110 ° C. for 12 hours or more, then fired at 450 ° C. for 3 h, and 0.05 wt%. Pd-2% Na / Al ₂ O ₃ was obtained.

A 1 / 2-inch stainless steel (SUS) tube was filled with 1.3 g of 0.05 wt% Pd-2% Na / Al ₂ O ₃ , and 10 g of glass beads were placed on the top to form a preheating layer. The catalyst layer was heated to 200 ° C., hydrogen gas (25 cc / min) was passed from the top to perform pretreatment reduction, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 160 ° C., 0 MPa (G)). 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 25 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 1 h was discarded from the start of the reaction, and then the collected liquid for 1 h was analyzed by gas chromatography. As a result, the conversion rate of the starting phenol was> 99.9%, the selectivity of cyclohexanone was 93.1%, the selectivity of the by-product cyclohexanol was 5.1%, 2 The selectivity for -cyclohexylcyclohexanone was 1.8%.

[Comparative Example 4]
(Catalyst G precursor: production method of P-SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: CARiACT Q-50, spherical, 1.18-2.36 mm) is impregnated and supported with an aqueous phosphoric acid solution so that P / Si (mol ratio) = 0.05. , And dried at 110 ° C. for 12 hours or longer. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst G precursor. The BET specific surface area of the catalyst G precursor was 56 m ² / g.

(Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst G precursor)
The catalyst G precursor 1.5g was put into the glass sample cell, and it heated at 380 degreeC for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the chemical adsorption amount of ammonia, the pretreated catalyst G precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C (trade name, Yuasa Ionics). Installed).

The catalyst G precursor was kept at 50 ° C. with a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at 20 points in total) Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst G precursor was 134 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemisorption amount of the catalyst G precursor was <0.1 μmol / g.

(Catalyst G: Production of Pd / P—SiO ₂ )
The catalyst G precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.2 wt%, and dried at 110 ° C. for 12 hours or longer to obtain catalyst G: Pd / P—SiO ₂ .

[Comparative Example 5]
(Catalyst G: Hydrogenation reaction of phenol with Pd / P—SiO ₂ )
Catalyst G: 1 g of Pd / P—SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical shape) were placed on the top to form a preheated layer. The catalyst layer was heated to 200 ° C., hydrogen gas (16 cc / min) was passed through the top and subjected to pretreatment reduction, and then at 140 ° C. and 0 MPa (G), a mixture of phenol and cyclohexanone (molar ratio = 1: 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 10 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 5 h was discarded from the start of the reaction, and then the collected liquid for 1 h was analyzed by gas chromatography. As a result, the conversion of phenol as a starting material was 5.2%, the selectivity of cyclohexanone was 83.8%, the by-product cyclohexanol was <0.1%, and 2-cyclohexylcyclohexanone. The selectivity of was 16.1%.

[Comparative Example 6]
(Catalyst H precursor: process for producing Ca-SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: CARiACT Q-50, spherical, 1.18-2.36 mm) is impregnated and supported with an aqueous calcium nitrate solution so that Ca / Si (mol ratio) = 0.1. , And dried at 110 ° C. for 12 hours or longer. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst H precursor.

(Catalyst H: Production of Pd / Ca—SiO ₂ )
The catalyst H precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.5 wt%, and dried at 110 ° C. for 12 hours or longer to obtain catalyst H: Pd / Ca—SiO ₂ .

[Comparative Example 7]
(Catalyst H: Hydrogenation reaction of phenol with Pd / Ca—SiO ₂ )
Catalyst H: 1 g of Pd / Ca—SiO ₂ was filled in a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical shape) were placed on the top to form a preheated layer. The catalyst layer was heated to 200 ° C., hydrogen gas (16 cc / min) was passed through the top and subjected to pretreatment reduction, and then at 140 ° C. and 0 MPa (G), a mixture of phenol and cyclohexanone (molar ratio = 1: 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 10 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 5 h was discarded from the start of the reaction, and then the collected liquid for 1 h was analyzed by gas chromatography. As a result, the conversion rate of phenol as a starting material was 99.9%, the selectivity of cyclohexanone was 88.0%, the selectivity of cyclohexanol as a by-product was 11.6%, The selectivity for cyclohexylcyclohexanone was 0.4%.

[Comparative Example 8]
(Catalyst I precursor: production of 0.01Ca-0.05P-SiO ₂ )
SiO ₂ (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: CARiACT Q-50, spherical, 1.18-2.36 mm), Ca / Si (mol ratio) = 0.01, P / Si (mol ratio) = 0. A calcium nitrate aqueous solution and a phosphoric acid aqueous solution were impregnated and supported so as to be 05, and dried at 110 ° C. for 12 hours or more. Thereafter, it was calcined at 600 ° C. for 3 hours in an air atmosphere to obtain a catalyst I precursor. The BET specific surface area of the catalyst I precursor was 53 m ² / g.

(Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst I precursor)
1.5 g of the catalyst I precursor was placed in a glass sample cell and heated at 380 ° C. for 2 h at 4 Pa or less (pretreatment). Next, in order to measure the amount of chemical adsorption of ammonia, the pretreated catalyst I precursor is used as a sample cell in a high-performance, fully automatic gas adsorption amount measurement device Autosorb-1-C (trade name, Yuasa Ionics). Installed).

The catalyst I precursor was kept at 50 ° C. with a heater, and ammonia gas was gradually introduced from the vacuum state into the sample cell, and the adsorption amount (ie, the absolute amount from 5.3 kPa to 5.3 kPa at 106.7 kPa at a total of 20 points) Measure the total adsorption amount of the chemical adsorption amount and the physical adsorption amount (measurement temperature: 50 ° C., thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical Including both adsorption and physical adsorption).

Thereafter, the physically adsorbed ammonia is removed by exhausting in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) is measured again at a total of 20 points from 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa, A physical adsorption isotherm was created. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of the catalyst I precursor was 148 μmol / g.

Also, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the carbon dioxide chemisorption amount of the catalyst I precursor was <0.1 μmol / g.

(Catalyst I: Production of Pd / 0.01Ca-0.05P-SiO ₂ )
The catalyst I precursor was impregnated with and supported by an aqueous palladium chloride solution at 0.5 wt%, and dried at 110 ° C. for 12 hours or longer to obtain catalyst I: Pd / 0.01Ca-0.05P-SiO ₂ . Obtained.

[Comparative Example 9]
(Catalyst I: Hydrogenation reaction of phenol with Pd / 0.01Ca-0.05P-SiO ₂ )
Catalyst I: 1 g of Pd / 0.01Ca-0.05P-SiO ₂ was filled into a 1/2 inch stainless steel (SUS) tube, and 10 g of glass beads (diameter 1 mm, spherical) were placed on the top. A preheating layer was used. The catalyst layer was heated to 200 ° C., hydrogen gas (26 cc / min) was passed from the top and pretreatment reduction was performed, and then a mixture of phenol and cyclohexanone (molar ratio = 1: 2) at 140 ° C. and 0 MPa (G). 1) was supplied at 1.0 cc / h and hydrogen gas was supplied at 10 cc / min to carry out a hydrogenation reaction of phenol.

The collected liquid for 2 hours was discarded from the start of the reaction, and then the collected liquid for 1 h was analyzed by gas chromatography. As a result, the conversion rate of phenol as a starting material was 21.9%, the selectivity of cyclohexanone was 95.9%, the selectivity of cyclohexanol as a by-product was 0.1%, The selectivity for cyclohexyl cyclohexanone was 4.0%.

1 reaction tube 2 catalyst layer 3 preheating layer 4 quartz wool 5 bottom plate 6 heater 7 phenol 8 hydrogen

Claims (7)

1. A hydrogenation catalyst in which a platinum group metal is supported on a catalyst precursor containing phosphorus and an alkali metal and / or an alkaline earth metal on a carrier,
   A hydrogenation catalyst having an ammonia chemisorption amount of the catalyst precursor at 50 ° C. of 100 μmol / g or less.
2. 2. The hydrogenation catalyst according to claim 1, wherein a chemical adsorption amount of carbon dioxide at 50 ° C. of the catalyst precursor is 15 μmol / g or less.
3. The hydrogenation catalyst according to claim 1 or 2, wherein the carrier is at least one of silica, alumina, silica alumina, zirconia and activated carbon.
4. The hydrogenation catalyst according to any one of claims 1 to 3, which is a hydrogenation catalyst of phenol or a derivative thereof.
5. The hydrogenation catalyst according to claim 4, wherein the phenol or a derivative thereof is represented by the following formula (1).
   

   

   [In the formula (1), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a hydroxy group, a phenol group, a phenyl group, a C1-C10 alkyl group or a C1-C10 An alkoxy group; ]
6. A method for producing a hydrogenation catalyst according to any one of claims 1 to 5,
   Mixing an alkali metal and / or alkaline earth metal source, water, carrier and phosphorus source;
   Calcination after evaporating the water to obtain a catalyst precursor;
   And a step of supporting a platinum group metal on the catalyst precursor.
7. A process for producing cyclohexanone or a derivative thereof, in which phenol or a derivative thereof is hydrogenated using the hydrogenation catalyst according to claim 4 or 5.

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