JP2007222758A - CATALYST FOR PRODUCING epsilon-CAPROLACTAM, ITS MANUFACTURING METHOD AND PRODUCTION METHOD OF epsilon-CAPROLACTAM USING CATALYST - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing ε-caprolactam capable of keeping good activity over a long period of time without regeneration in the gaseous phase Beckman rearrangement reaction of cyclohexanone oxime, its manufacturing method and an ε-caprolactam producing method using the catalyst. <P>SOLUTION: The catalyst for producing ε-caprolactam is based on pentasyl type zeolite and characterized in that the volume of pores with a radius of 0.3 μm or above is 0.05 mL/g or above and the cumulated volume of pores is 0.60 mL/g or above. The catalyst for producing ε-caprolactam is manufactured by mixing a pore imparting agent with a catalyst powder comprising pentasyl type zeolite and the obtained mixture is molded and baked before subjected to ion exchange treatment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a catalyst for producing ε-caprolactam useful for gas phase Beckmann rearrangement of cyclohexanone oxime, a method for producing the same, and a method for producing ε-caprolactam using the same.

  Conventionally, as a method for producing ε-caprolactam, a method in which cyclohexanone oxime is subjected to gas phase Beckmann rearrangement in the presence of a solid acid catalyst is known. For example, a method using a boron oxide-containing fluidized bed catalyst (see Patent Document 1), a method using a high silica-containing zeolite as a catalyst (see Patent Document 2), a method using a tungsten-containing solid catalyst (see Patent Document 3), a zeolite and A method using a solid acid catalyst obtained by firing a crystalline clay mineral and a specific inorganic oxide and / or oxide-forming compound (silica, silica alumina, alumina, etc.) has been proposed (see Patent Document 4).

JP-A-53-37686 Japanese Patent Laid-Open No. 57-139062 JP 2002-145853 A WO2002 / 064560

  However, in general, in the gas phase Beckmann rearrangement reaction, as the reaction proceeds, the carbonaceous material is deposited on the solid acid catalyst to be used, so that the active sites are covered with the carbonaceous material and the activity gradually decreases. was there. It is known that in order to regenerate a solid catalyst that is covered with a carbonaceous material and has reduced activity, the carbonaceous material may be oxidized and removed with an oxygen-containing gas. Therefore, until now, in accordance with the timing when the catalyst activity decreases, a regeneration operation has been performed in which the oxygen-containing gas is sent to the catalyst layer to oxidize and remove the carbonaceous material to recover the catalyst activity. However, when ε-caprolactam is continuously produced industrially, the reaction must be interrupted every time the regeneration operation is performed, which is a factor that greatly impairs productivity.

  Therefore, in the industrial production process of ε-caprolactam, there has been a demand for a catalyst that can maintain good activity over a long period of time without performing regeneration in order to reduce the number of regeneration operations as much as possible. In addition, it was difficult to satisfy this with the catalyst for producing ε-caprolactam.

  Accordingly, an object of the present invention is to provide a catalyst for producing ε-caprolactam capable of maintaining good activity over a long period of time without performing regeneration in the gas phase Beckmann rearrangement reaction of cyclohexanone oxime, and a method for producing the same, and the use thereof. It is in providing the manufacturing method of (epsilon) -caprolactam.

  As a result of intensive studies to solve the above problems, the present inventors have determined that a gas phase Beckmann rearrangement of cyclohexanone oxime is possible if it is a catalyst based on pentasil-type zeolite and designed to have a specific pore structure. To obtain a catalyst having a high cyclohexanone oxime conversion rate and high cyclohexanone oxime conversion over a long period of time without regeneration in the reaction, and to obtain a catalyst having the specific pore structure described above, the catalyst powder must be finely divided. It has been found that the pore-imparting agent may be mixed and molded, and the present invention has been completed.

That is, the present invention has the following configuration.
(1) The main component is pentasil-type zeolite, the pore volume having a radius of 0.3 μm or more is 0.05 mL / g or more, and the cumulative pore volume is 0.60 mL / g or more. -Catalyst for caprolactam production.
(2) The catalyst for producing ε-caprolactam according to the above (1), wherein the pore volume having a radius of 0.3 μm or more is 0.25 mL / g or more and the cumulative pore volume is 0.90 mL / g or more.
(3) The catalyst for producing ε-caprolactam according to (1), which is a ring-shaped or cylindrical pellet having an outer diameter of 3 to 5 mm, an inner diameter of 1 to 2 mm, and a length of 1 to 10 mm.
(4) The catalyst for producing ε-caprolactam according to any one of (1) to (3), wherein the pentasil-type zeolite is a porous crystal containing silicon (Si) and oxygen as essential components.
(5) The ε-caprolactam production according to (4), wherein the pentasil-type zeolite contains a metal element (Me) other than silicon in an atomic ratio with silicon (Si) of Si / Me ≧ 500. Catalyst.

(6) A method for producing a catalyst for producing ε-caprolactam as described in (1) to (5) above, wherein a pore-imparting agent is mixed with catalyst powder comprising pentasil-type zeolite, and the mixture is molded. A method for producing a catalyst for producing ε-caprolactam, which is calcined and then subjected to an ion exchange treatment.
(7) A swellable substance that swells by water absorption is used as the pore imparting agent, and the pore imparting agent is mixed at a ratio of 1 to 30 parts by weight with respect to 100 parts by weight of the catalyst powder. A method for producing a catalyst for producing ε-caprolactam.
(8) The method for producing a catalyst for producing ε-caprolactam according to (7), wherein the swellable substance has an average particle diameter of 1 to 500 μm.
(9) A non-swellable substance that does not swell even if it absorbs water is used as the pore imparting agent, and the pore imparting agent is mixed at a ratio of 10 to 120 parts by weight with respect to 100 parts by weight of the catalyst powder. ) -Caprolactam production catalyst described in the above.
(10) The method for producing a catalyst for producing ε-caprolactam according to (9), wherein the non-swellable substance has an average particle diameter of 1 to 40 μm.

(11) In the method for producing ε-caprolactam by a reaction in which cyclohexanone oxime undergoes gas phase Beckmann rearrangement in the presence of a catalyst, the catalyst for producing ε-caprolactam according to any one of (1) to (5) above is used as the catalyst. The manufacturing method of the epsilon caprolactam characterized by using.
(12) The method for producing ε-caprolactam according to (11), wherein the reaction is carried out in a fixed bed reactor.

  According to the present invention, there is provided a catalyst for producing ε-caprolactam capable of maintaining good activity over a long period of time without regenerating when producing ε-caprolactam by gas phase Beckmann rearrangement reaction of cyclohexanone oxime. The catalyst has an effect that ε-caprolactam can be produced from cyclohexanone oxime with high conversion and high productivity.

[Catalyst for ε-caprolactam production]
In the catalyst for producing ε-caprolactam of the present invention (hereinafter abbreviated and sometimes referred to as “the catalyst of the present invention”), it is important that the main component is a pentasil-type zeolite.

  The pentasil-type zeolite is a porous crystal that contains silicon (Si), oxygen, and essential components, and may contain a metal element (Me) other than silicon as necessary. Examples of metal elements (Me) other than silicon include aluminum, gallium, iron, boron, zirconium, chromium, beryllium, cobalt, lanthanum, glutanium, titaniumnium, hafnium, vanadium, nickel, antimony, bismuth, copper, niobium, and the like. Is mentioned. These metal elements (Me) may be only one kind or two or more kinds. As specific examples of the pentasil type zeolite, ZSM-5 type, ZSM-11 type and the like are particularly preferable.

  In the catalyst of the present invention, when the pentasil-type zeolite also contains a metal element (Me) other than silicon, the atomic ratio of silicon (Si) to the metal element (Me) other than silicon is Si / Me ≧ 500. It is preferable that When the atomic ratio Si / Me is less than 500, sufficient catalytic activity cannot be obtained, and there is a possibility that both the conversion rate and the selectivity are lowered.

  The average particle size of the pentasil-type zeolite is not particularly limited, but is preferably 1 to 60 μm, more preferably 3 to 30 μm. If the average particle size of the pentasil-type zeolite is too large, sufficient strength as a molded article may not be obtained. On the other hand, if it is too small, the handleability tends to be inferior.

  The catalyst for producing ε-caprolactam of the present invention has pores, the pore volume having a radius of 0.3 μm or more is 0.05 mL / g or more, and the cumulative pore volume is 0.60 mL / g or more. This is very important. Preferably, the pore volume having a radius of 0.3 μm or more is 0.25 mL / g or more, and the cumulative pore volume is 0.90 mL / g or more. By having such a specific pore structure, the catalyst of the present invention maintains good activity over a long period of time without regeneration. When the pore volume having a radius of 0.3 μm or more is less than 0.05 mL / g, a sufficient conversion rate cannot be obtained. On the other hand, if the cumulative pore volume is less than 0.60 mL / g, the carbonaceous material tends to deposit on the solid acid catalyst, and good activity cannot be maintained unless it is frequently regenerated.

  The catalyst of the present invention is preferably a ring-shaped or cylindrical pellet having an outer diameter of 3 to 5 mm, an inner diameter of 1 to 2 mm, and a length of 1 to 10 mm, from the viewpoint of easy filling of the reaction tube. . If the catalyst is too small, the pressure loss in the reaction tube tends to increase. On the other hand, if the catalyst is too large, the reaction tube may not be filled with a predetermined amount of catalyst.

[Method for producing catalyst for producing ε-caprolactam]
In the method for producing a catalyst of the present invention, a pore-imparting agent is mixed with catalyst powder made of pentasil-type zeolite, the mixture is molded, calcined, and then subjected to ion exchange treatment. According to such a method, the catalyst of the present invention described above can be easily obtained.

  The catalyst powder made of pentasil-type zeolite can be obtained, for example, by hydrothermal synthesis using tetraethylorthosilicate and tetra-n-propylammonium hydroxide aqueous solution as raw materials, and the resulting solid is filtered, dried and calcined. it can. Here, the hydrothermal synthesis is usually carried out in an autoclave while stirring at a temperature of 100 to 200 ° C. Drying or calcination is usually performed at a temperature of 100 to 600 ° C. Of course, the pentasil-type zeolite powder can be obtained by methods other than those described above.

  The pore-imparting agent is not particularly limited as long as it can form pores by mixing and forming and then disappearing by firing, and it does not affect the catalyst activity. , Inorganic salts such as ammonium nitrate, ammonium sulfate, ammonium carbonate, polysaccharides such as cereal, starch, cellulose, resins such as methacrylic resin, polyethylene, polypropylene, nylon, polyacrylic acid soda, polyethylene oxide copolymer, N-vinylacetamide And water-absorbing resins such as isobutylene-maleic anhydride and hydrocarbons such as naphthalene. These pore imparting agents may be used alone or in combination of two or more.

  The aforementioned pore-imparting agents are roughly classified into a swellable substance that swells by absorbing water such as a water-absorbing resin, and a non-swellable substance that does not swell when absorbed by water such as crystalline cellulose fine particles.

When the swellable substance is used as the pore imparting agent, the amount used is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the catalyst powder. More preferably, it is 2 to 20 parts by weight with respect to 100 parts by weight of the catalyst powder. If the amount of the pore-imparting agent, which is a swellable substance, is too smaller than the above range, pores having a radius of 0.3 μm or more are not easily formed, and a sufficient conversion rate may not be obtained. If the amount is too much, the strength of the catalyst molded body may be lowered.
The swellable material preferably has an average particle size of 1 to 500 μm. More preferably, it is 10-300 micrometers. If the average particle size of the swellable material is too smaller than the above range, pores having a radius of 0.3 μm or more are difficult to be formed, and a sufficient conversion rate may not be obtained. In addition, the strength of the catalyst molded body may be reduced. Moreover, the water absorption capacity | capacitance of this swellable substance is 10-1000 times normally by weight ratio, and it is more preferable that it is 20-50 times.

When the non-swellable substance is used as the pore imparting agent, the amount used is preferably 10 to 120 parts by weight with respect to 100 parts by weight of the catalyst powder. More preferably, it is 20-100 weight part with respect to 100 weight part of catalyst powder. If the amount of the pore-imparting agent, which is a non-swellable substance, is too smaller than the above range, pores having a radius of 0.3 μm or more are hardly formed, and a sufficient conversion rate may not be obtained. When it is more than the range, the strength of the catalyst molded body may be lowered.
The average particle diameter of the non-swellable substance is preferably 1 to 40 μm. More preferably, it is 6-10 micrometers. If the average particle size of the non-swellable material is too smaller than the above range, pores having a radius of 0.3 μm or more are not easily formed, and a sufficient conversion rate may not be obtained. And there exists a possibility that the intensity | strength of a catalyst molded object may fall.

  The apparatus used for mixing the pore-imparting agent with the catalyst powder is not particularly limited. For example, a ball mill, a vibration mill, a V-type mixer, a concrete mixer, a Ladige mixer, a Nauter mixer, a ribbon mixer An omni mixer or the like can be used.

  Molding is usually performed by extrusion molding or the like. Extrusion molding is a method of mixing powder and molding aids such as water, making it into a clay with a kneader, etc., and then extruding with a die of a predetermined shape, and as an extruder used for extrusion molding For example, there are a mold, a uniaxial vacuum extruder, a biaxial vacuum extruder, a cylindrical granulator, and the like.

  In molding, for example, additives such as methyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyethylene oxide, and waxes may be added as necessary. Furthermore, it can be molded by adding glass fiber, quartz fiber, alumina fiber, silica alumina fiber, silicon carbide whisker, silicon nitride whisker, silica sol, alumina sol, titania sol and the like.

It is preferable to perform the firing usually at a temperature of 100 to 600 ° C. The firing time may be appropriately set according to the firing temperature and the like, and is not particularly limited, but is usually preferably 10 hours to 100 hours.
The apparatus used for firing is not particularly limited as long as it can heat the molded body. For example, a hot-air circulating firing furnace, a stationary firing furnace, a tunnel furnace, a rotary kiln, a far infrared furnace, a microwave heating furnace Etc. can be used.

  The ion exchange treatment can usually be performed by placing the fired molded body together with an alkaline liquid such as aqueous ammonia in an autoclave and stirring. At this time, the pH of the alkaline liquid is preferably preferably 9 to 14, and the temperature of the alkaline liquid is preferably 50 to 100 ° C. The ion exchange treatment time (stirring time) is usually preferably 1 to 24 hours. The ion exchange treatment may be repeated by replacing the alkaline solution, and the number of ion exchange treatments is usually preferably 1 to 4 times.

  After the ion exchange treatment, if necessary, filtration and washing are repeated until the pH of the washing water becomes neutral, followed by drying to obtain the catalyst of the present invention. At this time, although the number of times of filtration and washing depends on the pH of the alkaline liquid used in the ion exchange treatment, it is usually preferably 1 to 4 times. The drying temperature is usually preferably 100 to 200 ° C.

[Method of producing ε-caprolactam]
In the production method of ε-caprolactam of the present invention, ε-caprolactam is obtained by a reaction of cyclohexanone oxime in the gas phase Beckmann rearrangement in the presence of the catalyst of the present invention described above (hereinafter also referred to as “Beckmann rearrangement reaction”). It is a manufacturing method. Specifically, the Beckmann rearrangement reaction is a reaction in which cyclohexanone oxime is isomerized to ε-caprolactam.

  In the method for producing ε-caprolactam of the present invention, the Beckmann rearrangement reaction is preferably performed in a fixed bed reactor. This is because the catalyst of the present invention described above is more effective in a fixed bed type reaction.

  Cyclohexanone oxime used as a raw material may be used in a vapor (gaseous) or liquid form. For example, when the reaction is carried out in a fixed bed reactor, usually, vapor (gaseous) cyclohexanone oxime may be introduced into a fixed bed reactor equipped with a catalyst layer maintained at the reaction temperature.

  In the Beckmann rearrangement reaction, the reaction temperature is usually preferably 250 to 450 ° C, more preferably 300 to 400 ° C. The reaction pressure is usually preferably 10 kPa to 0.5 MPa, more preferably 50 kPa to 0.3 MPa.

The space velocity in the reactor (fixed bed reactor) of cyclohexanone oxime used as a raw material is usually preferably WHSV (weight space velocity), preferably 0.1 h ^{−1 to} 20 h ⁻¹ , more preferably 0.2 h ⁻¹ to It is selected from the range of 10 h ⁻¹ (that is, the supply rate of cyclohexanone oxime per kg of the catalyst is preferably 0.1 to 20 kg / h, more preferably 0.2 to 10 kg / h).

  In the Beckmann rearrangement reaction, a lower alcohol having 1 to 6 carbon atoms can coexist with cyclohexanone oxime in the reaction system. Thereby, the effect of improving the selectivity of ε-caprolactam or extending the catalyst life can be expected. Examples of the lower alcohol having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, n-amyl alcohol, n-hexanol and the like. Among these, methanol and ethanol are preferably used. These lower alcohols may be used alone or in combination of two or more. When the lower alcohol is allowed to coexist, the amount is usually 0.1 to 20 times, more preferably 0.2 to 10 times by weight with respect to cyclohexanone oxime.

  When the cyclohexanone oxime is introduced into the reactor, it is advantageous to allow water to coexist. In this case, the amount of coexisting water is preferably 2.5 mol times or less with respect to cyclohexanone oxime.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to a following example.
In addition, the measuring method of the physical-property value shown in an Example and a comparative example is as follows.

  <Crystalline phase> After pulverizing the catalyst powder sample in a mortar for 5 minutes, it was analyzed with an X-ray diffractometer (“RINT-2100V” manufactured by Rigaku Corporation), and the crystal phase was determined from the peak data of the obtained X-ray diffraction spectrum. Identified.

  <Silicon (Si) / Metal element other than silicon (Me) atomic ratio> The catalyst powder sample was dissolved in an acid after being alkali-melted and analyzed by an ICP emission spectroscope ("SPS4000" manufactured by SII Nanotechnology). Thus, the silicon (Si) content in the catalyst powder sample was determined. On the other hand, the catalyst powder sample is treated with hydrofluoric acid, then melted in an alkali, dissolved in an acid, analyzed by the same ICP emission spectroscopic device as described above, and a metal element other than silicon in the catalyst powder sample (Me ) Content was determined. Then, the respective contents of Si and Me were divided by the respective atomic weights to calculate the atomic ratio (Si / Me).

  <Pore volume> The obtained catalyst (catalyst molded body) was dried in a hot air circulation dryer at 120 ° C. for 4 hours in a solid state. Thereafter, the pore distribution of the sample was measured by a mercury intrusion method using a pore distribution measuring device (“Autopore III9420 type” manufactured by MICROMERITICS). Then, the cumulative pore volume and the cumulative pore volume from the cumulative pore distribution curve in which the horizontal axis is the pore radius and the vertical axis is the cumulative pore volume obtained by sequentially accumulating the volume from the largest to the smallest pore radius, The pore volume with a radius of 0.3 μm or more was determined.

(Example 1-1)
(Preparation of catalyst powder)
A 5 L stainless steel autoclave was charged with 500 g of tetraethyl orthosilicate (Al content of 10 ppm or less), 1120 g of 10% tetra-n-propylammonium hydroxide aqueous solution and 1070 g of ethanol, and stirred vigorously for 120 minutes. The pH of the mixed solution was 13. After closing the autoclave lid, hydrothermal synthesis was carried out for 96 hours while stirring at a rotational speed of 400 rpm or more while keeping the internal temperature at 105 ° C. During this time, the internal pressure of the autoclave reached 0.2 to 0.3 MPa. The pH at the end of hydrothermal synthesis was 11.8. The white solid was separated by filtration, and then continuously washed with distilled water until the pH of the filtrate reached about 7, to obtain 300 g of a slurry having a solid concentration of 40%. 300 g of the resulting slurry was filtered, dried and fired to obtain a powdery white solid.

  As a result of analyzing the obtained powdery white solid by X-ray diffraction, it was identified as a pentasil-type zeolite. Moreover, as a result of analyzing this powdery white solid by atomic absorption spectrometry, the Al content was 3 ppm and the Si / Al atomic ratio was 147000.

  Next, this powdery white solid was supplied to a small collision plate jet mill (“CO-JET” manufactured by Seishin Enterprise Co., Ltd.) at a speed of 125 g / min with a vibrating loss-in-weight feeder, and a grinding nozzle pressure of 0.49 MPa, Crushing was performed under the condition of a pusher nozzle pressure of 0.54 MPa to obtain 100 g of catalyst powder.

[Mixing and forming of pore-imparting agent]
To 100 parts by weight of the obtained catalyst powder, 40 parts by weight of crystalline cellulose (“Avicel PH-M06” manufactured by Asahi Kasei Chemicals Co., Ltd., component: methylcellulose, average particle diameter: 8 μm) as a pore-imparting agent, and crystals as a molding aid 3 parts by weight of functional cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., “Metroze 90SH-4000”, component: hydroxypropylmethylcellulose, average particle size 80 μm) for 3 minutes using an omnimixer, and further added 85 parts by weight of water and 3 Mixed for minutes. The obtained mixture was kneaded with a kneader and then filled into a mold having an outer diameter of 5 mm and a die having a pin having a diameter of 2 mm at the center. This mold was pressurized with a compression tester to obtain an extruded product having an outer diameter of 5 mm and an inner diameter of 2 mm. This extrudate was cut to a length of 5 mm with a piano wire during extrusion. The obtained extrudate was allowed to stand for 24 hours or more at room temperature and dried to obtain 100 g of an extrudate dried product.

[Baking]
100 g of the obtained extrusion-dried product was baked at 500 to 530 ° C. for 6 hours under the flow of a mixed gas of nitrogen and air (volume ratio of 1: 1) to obtain 70 g of a baked product.

[Ion exchange treatment]
70 g of the obtained baked product was placed in an autoclave together with 200 g of aqueous ammonia having a pH of 11.5 prepared from 28 wt% aqueous ammonia and distilled water, stirred at 90 ° C. for 1 hour, and then decanted to remove the aqueous ammonia. . After performing this alkali treatment operation three times in total, the catalyst (1) was obtained by filtration, washing with water and drying (120 ° C. × 16 hours).

  As a result of measuring the pore distribution of the obtained catalyst (1), the cumulative pore volume was 0.88 mL / g, and the pore volume having a radius of 0.3 μm or more was 0.08 mL / g. The cumulative pore distribution curve obtained by the measurement is shown in FIG.

(Example 1-2)
Instead of 40 parts by weight of crystalline cellulose ("Avicel PH-M06" manufactured by Asahi Kasei Chemicals Co., Ltd., component: methylcellulose, average particle size 8 µm) in Example 1-1 [mixing and forming of pore imparting agent] Amount of water to be added after mixing for 3 minutes using an omni mixer using 16 parts by weight of a functional resin (“Aqua Coke TWB” manufactured by Sumitomo Seika, component: polyethylene oxide copolymer, average particle size 140 μm) A catalyst (2) was obtained in the same manner as in Example 1-1 except that the amount was changed from 160 parts to 160 parts by weight.

  As a result of measuring the pore distribution of the obtained catalyst (2), the cumulative pore volume was 1.17 mL / g, and the pore volume having a radius of 0.3 μm or more was 0.57 mL / g. The cumulative pore distribution curve obtained by the measurement is shown in FIG.

(Example 1-3)
In Example 1-1 [Mixing and shaping of pore-imparting agent], the amount of crystalline cellulose (“Avicel PH-M06” manufactured by Asahi Kasei Chemicals Corporation, component: methylcellulose, average particle size 8 μm) was changed from 40 parts by weight to 90 parts by weight. The amount of crystalline cellulose (“Metrozu 90SH-4000” manufactured by Shin-Etsu Chemical Co., Ltd., component: hydroxypropylmethylcellulose, average particle size 80 μm) as a molding aid was changed from 3 parts by weight to 3.3 parts by weight. In Example 1-1, except that 141 parts by weight of the slurry obtained in [Preparation of catalyst powder] was used instead of 85 parts by weight of water added after mixing for 3 minutes using an omni mixer. In the same manner as described, a catalyst (3) was obtained.

  As a result of measuring the pore distribution of the obtained catalyst (3), the cumulative pore volume was 1.82 mL / g, and the pore volume having a radius of 0.3 μm or more was 0.94 mL / g. The cumulative pore distribution curve obtained by the measurement is shown in FIG.

(Example 1-4)
Instead of 40 parts by weight of crystalline cellulose ("Avicel PH-M06" manufactured by Asahi Kasei Chemicals Co., Ltd., component: methyl cellulose, average particle size 8 μm) in Example 1-1 [Mixing and shaping of pore imparting agent] Using 90 parts by weight of resin (“Kemisnow MX-150”, manufactured by Soken Chemical Co., Ltd., component: polymethyl methacrylate, average particle size: 1.4 μm) and mixing for 3 minutes using an omni mixer, the amount of water added is 85% by weight. A catalyst (4) was obtained in the same manner as in Example 1-1 except that the amount was changed from 66 parts to 66 parts by weight.

  As a result of measuring the pore distribution of the obtained catalyst (4), the cumulative pore volume was 1.75 mL / g, and the pore volume having a radius of 0.3 μm or more was 0.48 mL / g. The cumulative pore distribution curve obtained by the measurement is shown in FIG.

(Example 1-5)
In Example 1-1 [mixing and forming of pore-imparting agent], crystalline cellulose ("Avicel PH-M06" manufactured by Asahi Kasei Chemicals Co., Ltd., component: methylcellulose, average particle size of 8 μm) was replaced by 40 parts by weight. Using 10 parts by weight of N-vinylacetamide (manufactured by Showa Denko KK, average particle size 13.2 μm), the amount of water added after mixing for 3 minutes using an omni mixer was changed from 85 parts by weight to 140 parts by weight. Except for this, a catalyst (5) was obtained in the same manner as in the method described in Example 1-1.

  As a result of measuring the pore distribution of the obtained catalyst (5), the cumulative pore volume was 0.82 mL / g, and the pore volume having a radius of 0.3 μm or more was 0.06 mL / g. The cumulative pore distribution curve obtained by the measurement is shown in FIG.

(Examples 2-1 to 2-5)
Using the catalysts (1) to (5) obtained in Examples 1-1 to 1-5, a Beckmann rearrangement reaction of cyclohexanone oxime was performed on each. That is, a fixed bed flow type reactor was used, and a catalyst layer was formed by filling 2.0 g of the catalyst into a quartz glass reaction tube having an inner diameter of 2 cm. Nitrogen 1.16 L / h was passed through the reaction tube, the temperature of the reaction tube was set to 350 ° C., and pre-heat treatment was performed for 1 hour. Next, with the nitrogen 1.16 L / h being circulated, the temperature of the reaction tube was raised to 365 ° C., and a mixture of cyclohexanone oxime / methanol = 1 / 1.3 (weight ratio) was 23 g / h (cyclohexanone oxime WHSV = The reaction was carried out at the same temperature by supplying the reaction tube at a supply rate of 5 h ⁻¹ ).

  After feeding the cyclohexanone oxime / methanol mixture to the reaction tube, immediately sample for 15 minutes (this is the “initial” sample), and then sample for 15 minutes after the start of the feed (this is “after 12 hours”). Samples), cyclohexanone oxime and ε-caprolactam were analyzed by gas chromatography, and the conversion of cyclohexanone oxime and the selectivity of ε-caprolactam were determined as follows. That is, the conversion ratio of cyclohexanone oxime and the selectivity of ε-caprolactam are respectively determined by assuming that the number of moles of cyclohexanone oxime supplied is X, the number of moles of unreacted cyclohexanone oxime is Y, and the number of moles of ε-caprolactam produced is Z. It was calculated by the following formula. The results are shown in Table 1.

Conversion of cyclohexanone oxime (%) = [(XY) / X] × 100
Selectivity of ε-caprolactam (%) = [Z / (XY)] × 100

It is a graph which shows the cumulative pore distribution curve of the catalyst (1) obtained in Example 1-1. It is a graph which shows the cumulative pore distribution curve of the catalyst (2) obtained in Example 1-2. It is a graph which shows the cumulative pore distribution curve of the catalyst (3) obtained in Example 1-3. It is a graph which shows the cumulative pore distribution curve of the catalyst (4) obtained in Example 1-4. It is a graph which shows the cumulative pore distribution curve of the catalyst (5) obtained in Example 1-5.

Claims (12)

  Production of ε-caprolactam, wherein the main component is pentasil-type zeolite, the pore volume having a radius of 0.3 μm or more is 0.05 mL / g or more, and the cumulative pore volume is 0.60 mL / g or more. Catalyst.   The catalyst for producing ε-caprolactam according to claim 1, wherein the pore volume having a radius of 0.3 µm or more is 0.25 mL / g or more and the cumulative pore volume is 0.90 mL / g or more.   The catalyst for producing ε-caprolactam according to claim 1, which is a ring-shaped or cylindrical pellet having an outer diameter of 3 to 5 mm, an inner diameter of 1 to 2 mm, and a length of 1 to 10 mm.   The catalyst for producing ε-caprolactam according to any one of claims 1 to 3, wherein the pentasil-type zeolite is a porous crystal body containing silicon (Si) and oxygen as essential components.   5. The catalyst for producing ε-caprolactam according to claim 4, wherein the pentasil-type zeolite contains a metal element (Me) other than silicon in a range in which an atomic ratio with silicon (Si) is Si / Me ≧ 500.   A method for producing a catalyst for producing ε-caprolactam according to any one of claims 1 to 5, wherein a pore-imparting agent is mixed with a catalyst powder made of pentasil-type zeolite, the mixture is molded, calcined, and then ionized. A method for producing a catalyst for producing ε-caprolactam, characterized by performing an exchange treatment.   The ε-caprolactam production according to claim 6, wherein a swellable substance that swells by water absorption is used as the pore imparting agent, and the pore imparting agent is mixed in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of the catalyst powder. For producing a catalyst.   The method for producing a catalyst for producing ε-caprolactam according to claim 7, wherein the swellable substance has an average particle diameter of 1 to 500 µm.   The epsilon according to claim 6, wherein a non-swellable substance that does not swell even when water is absorbed is used as the pore imparting agent, and the pore imparting agent is mixed at a ratio of 10 to 120 parts by weight with respect to 100 parts by weight of the catalyst powder. -The manufacturing method of the catalyst for caprolactam manufacture.   The method for producing a catalyst for producing ε-caprolactam according to claim 9, wherein the non-swellable substance has an average particle diameter of 1 to 40 µm.   In the method for producing ε-caprolactam by a reaction in which cyclohexanone oxime undergoes gas phase Beckmann rearrangement in the presence of a catalyst, the catalyst for producing ε-caprolactam according to any one of claims 1 to 5 is used as the catalyst. To produce ε-caprolactam. The method for producing ε-caprolactam according to claim 11, wherein the reaction is carried out in a fixed bed reactor.

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