JP4525418B2 - Sulfated solid acid catalyst and use thereof - Google Patents

Description

  The present invention relates to an environmentally friendly solid acid catalyst having high activity in acid catalyzed reactions and uses thereof.

Conventionally, acid catalysts such as sulfuric acid, aluminum chloride, hydrogen fluoride, and phosphoric acid have been used for acid catalyzed reactions such as alkylation reaction, esterification reaction, and Beckmann rearrangement reaction. However, these acid catalysts are difficult to separate and recover, and there are problems of equipment corrosion and waste acid treatment.
Examples of acid catalysts for solving this problem include single metal oxides such as alumina and titania, composite oxides such as silica-alumina, silica-titania and alumina-boria, ZSM-5, β-zeolite (beta zeolite), and the like. Many solid acid catalysts such as zeolite minerals and clay minerals such as montmorillonite are known (see Non-Patent Document 1, for example). However, since these solid acid catalysts have a relatively weak acid strength, some reaction systems may not exhibit sufficient activity as a solid acid catalyst.
On the other hand, as a solid acid catalyst having strong acidity, after contacting a group IV metal hydroxide or oxide of a periodic table with a sulfate group-containing solution having a 0.01 to 5 molar concentration of 5 to 20 times the weight. There has been proposed a solid acid catalyst which is calcined and sulfated in a temperature range of 350 to 800 ° C. and has an acid strength (H0) higher than −10.6 (for example, see Patent Document 1). However, although this acid catalyst has a strong acid point, since the pore size is not uniform, a shape-selective catalytic reaction utilizing pores, such as that observed in zeolite catalysts and mesoporous catalysts, is expected. I can't do it. Moreover, since the specific surface area is small, the ratio of the IV group metal amount exposed to the surface is small among the total IV group metal amounts constituting the catalyst. This means that only a part of the expensive all group IV metal functions as a catalyst active point, which is not preferable from the viewpoint of effective use of resources, environmental protection, and catalyst cost.
Under these circumstances, in recent years, attempts have been made to highly control the physical properties of solid acid catalysts having strong acid properties. However, as described below, many problems still remain in the catalyst preparation method, and the physical properties have not yet been provided as designed.
For example, a solid acid catalyst in which a high specific surface area mesoporous zeolite is used as a carrier in order to increase the specific surface area and a metal oxide and a sulfate radical are supported thereon has been proposed (see, for example, Patent Document 2). However, this method of supporting an active metal species on a carrier synthesized in advance is easy to prepare, but the active metal species particles may block the pores of the carrier. As a result, the high specific surface area that the carrier originally had is greatly reduced. For example, Patent Document 2 shows that, even when a carrier of about 1200 m ² / g is used, it is drastically reduced to about 300 m ² / g after supporting zirconium hydroxide and sulfate radicals.
In addition, as a method for preparing a solid acid catalyst having a high specific surface area and improved dispersibility of active metal species, attempts have been made to support a sulfate group on a high specific surface area composite oxide (for example, non-patent). Reference 2). However, as non-patent document 2 in the sulfate feed, and using sulfuric acid generally used in sulfation, greatly decreased from the surface area by sulfation process of about 800 m 2 / ^g to about 400 meters 2 / ^g Yes. This preparation method causes a structural change of the high specific surface area composite oxide, and as a result, excellent properties such as high dispersibility and high specific surface area of the active metal species are impaired.

  On the other hand, fuming sulfuric acid is used as an acid catalyst in the industrial production of ε-caprolactam by rearrangement of cyclohexanone oxime. However, in this method, in order to separate and recover ε-caprolactam, it is usually necessary to neutralize a strong acid such as sulfuric acid with ammonia, and a large amount of ammonium sulfate is by-produced. In addition, as described above, there are many process problems such as corrosion of the apparatus, and development of an efficient catalyst for rearrangement is expected.

Accordingly, various studies have been conducted on homogeneous or heterogeneous catalysts regarding the Beckmann rearrangement reaction in a liquid phase not using a sulfuric acid catalyst. However, the homogeneous catalyst is more preferably a heterogeneous catalyst that can be easily separated from the industrial viewpoint because the separation of the catalyst becomes complicated.
Regarding heterogeneous catalysts, a method using a rhenium compound as a catalyst, a method using a beta zeolite containing zinc as a catalyst, palladium on group IV or group III metal oxides such as zirconium oxide, titanium oxide, aluminum oxide, etc. , A method using a catalyst supporting a Group VIII metal such as platinum, rhodium, ruthenium, a method using a zeolite supporting an iminium ion as a catalyst, a compound having a dielectric constant in the range of 6 to 60 in the presence of a solid catalyst. A method of reacting in the coexistence has been proposed.
However, in a method using a rhenium compound as a catalyst (see, for example, Patent Document 3), caprolactam selectivity is extremely low. Furthermore, the reaction temperature is as high as 200 ° C. or higher.
Similarly, a method using a rhenium compound as a catalyst (see, for example, Patent Document 4) has a high conversion rate of 100% and a caprolactam yield of 81.4 mol%. However, since a nitrogen-containing heterocyclic compound such as pyridine is used in combination, the reaction system is complicated. It has become.
In a method using zinc-containing beta zeolite as a catalyst (see, for example, Patent Document 5), the conversion is 47 mol% and the caprolactam selectivity is 72 mol% (yield is 34 mol%) at a reaction temperature of 130 ° C.
A method of using a catalyst in which a group VIII metal such as palladium, platinum, rhodium, ruthenium is supported on an oxide of a group IV or group III metal such as zirconium oxide, titanium oxide, or aluminum oxide as a support (see, for example, Patent Document 6). Although the conversion rate and yield are both high, noble metals such as palladium, platinum, rhodium and ruthenium are also expensive and have large price fluctuations, which are not satisfactory for industrial implementation.
A method using a zeolite carrying iminium ions as a catalyst (see, for example, Patent Document 7) has a complicated catalyst preparation method and a low cyclohexanone oxime conversion rate of 34%.
In the method of reacting in the presence of a solid acid catalyst with a compound having a dielectric constant in the range of 6 to 60 (see, for example, Patent Document 8), the coexistence effect of the compound having a dielectric constant in the range of 6 to 60 is recognized. However, the yield of caprolactam remains low because the catalytic activity of the solid acid catalyst used is insufficient. For example, when dehydrated benzonitrile is used as a compound having a dielectric constant in the range of 6 to 60, the yield of caprolactam is 53% when the solid acid catalyst is beta zeolite, and 33% when the solid acid catalyst is Zn-containing beta zeolite. 61% at the same time, 36% at the SiO ₂ -supported heteropoly acid, and 26% at the Al-containing mesoporous catalyst.

Dictionary of Catalysts (Asakura Shoten) 236 pages Materials Letters 57 (2003) 2572-2579 Japanese Patent Publication No.59-6181 JP 2000-42416 A Japanese Patent Laid-Open No. 08-151362 JP 09-301952 A Japanese Patent Laid-Open No. 2001-19670 JP 62-169769 A Japanese Patent Application Laid-Open No. 09-40641 JP 2001-72657 A

An object of the present invention is to provide a sulfated solid acid catalyst having mesopores that is effective for an acid catalyst reaction.
In particular, when a corresponding lactam compound is produced from a cycloalkanone oxime compound by a Beckmann rearrangement reaction, an object is to provide a catalyst for producing a lactam compound in a high yield under mild reaction conditions.

As a result of intensive studies in view of the above-mentioned problems, the present inventor has found that a complex oxide subjected to sulfation treatment has a hexagonal value in the range of 2θ = 2.0 to 2.5 ° in the X-ray diffraction pattern (Cu—Kα ray). Solid acid catalyst having a peak attributed to d ₁₀₀ of the structure, and a nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 in the nitrogen adsorption isotherm is 20 to 60% of the total adsorption amount Can be achieved.
Further, when this solid acid catalyst is used, the Beckmann rearrangement reaction of the cycloalkanone oxime compound proceeds efficiently and the by-product oligomer is small even in the absence of a strong acid, and the corresponding lactam compound can be produced advantageously.

  By using the catalyst of the present invention, the acid-catalyzed reaction can be efficiently advanced. In particular, a lactam compound can be produced in a high yield from a cycloalkanone oxime compound.

Hereinafter, the present invention will be described in detail.
The sulfation treatment of the present invention is a step of treating a composite oxide with sulfate ions or sulfur trioxide, and the sulfation treatment agent to be used is not particularly limited as long as it contains sulfur. As these sulfur-containing compounds, for _{example, SO 2, SO 3, S} n O n (n = 5~8), H 2 SO 4, _{oleum, (NH 4) 2 SO 4} , H 2 SO 3, H 2 _{S 2 O n (n = 3~7} ), FSO 3 H, CF 3 SO 3 H, ClSO 3 H, SOCl 2, SO 2 Cl 2, metal sulfates Tiso _4, and the like. These may be used alone or in combination.
Among these compounds, a gas compound at room temperature can be used as sulfur trioxide by oxidation as it is or after dilution into an inert gas, oxidation or thermal decomposition, or thermal decomposition. A compound that is solid or liquid at room temperature can be used as it is or after being vaporized or thermally decomposed. When vaporized or thermally decomposed, it can be used as sulfur trioxide as it is or diluted to an inert gas or oxidized.
Preferably, sulfur trioxide (SO ₃ ) obtained by oxidizing gaseous sulfur dioxide (SO ₂ ) at normal temperature is used. In the case of sulfur dioxide, for example, diluted with an inert gas or the like can be used.
Sulfur dioxide is usually oxidized with oxygen, but an oxidizing agent such as ozone or peroxide can also be used.
The oxygen oxidation is not particularly limited, and those diluted with pure oxygen, air, inert gas, or the like can be used. However, any of them having a low water content is preferable. Specifically, the moisture content of the introduced gas is preferably controlled to 1000 ppm or less, more preferably 100 ppm, even more preferably 10 ppm or less, and most preferably 1 ppm or less.
The oxidation catalyst is not particularly limited as long as it is a catalyst having an ability to oxidize sulfur dioxide. For example, a catalyst containing one or more of vanadium, copper, iron, cobalt, and nickel can be preferably used. Vanadium is preferred.
Because of their role, these oxidation catalysts are usually filled in the upstream portion of the composite oxide.

Composite oxide prior to treatment sulfated for use in the present invention, a peak attributed to _{d 100} of hexagonal structure in the range of 2 [Theta] = 2.0 to 2.5 ° in X-ray diffraction pattern (Cu-K [alpha line) Can be used as long as a large amount of nitrogen adsorption is observed in the range of P / P ₀ = 0.2 to 0.6 of the nitrogen adsorption isotherm. For example, what introduce | transduced the metal into the porous oxide which has hexagonal structures, such as HMS and MCM-41, is mentioned.
The specific surface area is not particularly limited, but is preferably greater than 500 meters ² / g, more preferably 600 meters ² / g or more, more preferably 800~1200m ² / g.

The elements constituting the composite oxide are specifically selected from the group consisting of group numbers according to groups 4 to 14 (according to the IUPAC inorganic chemical nomenclature revised in 1989 using a serial number of 1-18 as the group number) 1 type or more (however, except carbon) is mentioned.
As at least one element selected from Group 4-14, Group 4 titanium, zirconium, hafnium, Group 5 vanadium, neobium, tantalum, Group 6 chromium, molybdenum, tungsten, Group 7 manganese, rhenium, Group 8 Iron, ruthenium, osmium, group 9 cobalt, rhodium, iridium, group 10 nickel, palladium, platinum, group 11 copper, silver, gold, group 12 zinc, cadmium, mercury, group 13 boron, aluminum, Examples include gallium, indium, thallium, group 14 silicon, germanium, tin, and lead. Titanium, zirconium, zinc, boron, aluminum, gallium, indium, thallium, germanium, tin, lead and silicon are preferable. More preferred are zirconium, aluminum, gallium and silicon.
There is no problem even if these elements are used in a mixture of two or more, or even three or more.

  The form of sulfation treatment for the composite oxide is not particularly limited. For example, sulfur trioxide may be contacted directly in the gas phase. Alternatively, the gas phase contact may be performed in the presence of sulfur dioxide (or a sulfur-containing compound), oxygen, and the above-described oxidation catalyst. As an example of the gas phase contact method, the lower part of the quartz tube is filled with a composite oxide, and the upper part thereof is filled with an oxidation catalyst, and a gas containing sulfur dioxide (or a sulfur-containing compound) and oxygen The gas phase contact is performed at a temperature of 800 ° C., preferably 200 to 700 ° C., within a range of 10 minutes to 1000 hours. In this case, the gas is circulated from the upper layer portion toward the lower layer portion. The concentration of sulfur trioxide produced in the gas is not particularly limited, but the total sulfur-containing compound supply amount is preferably 0.1 mmol to 100 mol with respect to 1 g of the composite oxide. The oxygen concentration is not particularly limited, but is preferably 0.1 to 1000 times the molar amount of the gaseous sulfur-containing compound.

Since the composite oxide (which may be in the form of oxide or hydroxide) before contact treatment with sulfur trioxide in the gas phase may be attached with water or organic matter, it may be pre-treated in the air. Alternatively, it can be fired in an inert gas atmosphere (preferably while circulating air or an inert gas).
In addition, in order to remove the sulfur-containing compounds weakly physically adsorbed on the catalyst surface of the composite oxide subjected to the sulfation treatment, calcination is performed in the air or in an inert gas atmosphere (preferably while circulating air or an inert gas) as a post-treatment. It is preferable. The firing temperature and firing time for the pre-treatment and post-treatment are not particularly limited and can be selected depending on the case, but are preferably 100 to 800 ° C. and 1 minute to 100 hours.

The solid acid catalyst of the present invention thus obtained is a composite oxide obtained by calcination after sulfation treatment, and 2θ = 2.0 to 2.5 ° in an X-ray diffraction pattern (Cu—Kα ray). range holds peak assigned to _{d 100} of hexagonal structure, the nitrogen adsorption amount in the range of _P / _P 0 = _0.2~0.6 in nitrogen adsorption isotherm 20 to 60% of the total adsorption amount of Is.
Note that the range of P / P ₀ = 0.2 to 0.6 suggests the presence of mesopores.
The specific surface area of the composite oxide was fired also, preferably greater than 500 meters ² / g, more preferably 600 meters ² / g or more, more preferably holding the 800~1200m ² / g.
Moreover, as sulfur content, less than 5 weight% is enough, Preferably, it is 1-4 weight%.
Even if outside the above range of physical properties, the catalytic action is not particularly affected, but if it is within the above range, it is economical and efficient.
The solid acid catalyst having such physical properties can be effectively used for various catalytic reactions.

  For example, it can be used for reactions such as alkylation, acylation, oligomerization, isomerization, hydration, dehydration, etherification, esterification, hydrogenolysis, nitration of organic compounds, rearrangement, especially from cycloalkanone oxime compounds It is effectively used as a catalyst in producing the corresponding lactam compound by Beckmann rearrangement reaction.

The cycloalkanone oxime compound used in the present invention is preferably a cyclic aliphatic hydrocarbon oxime compound having 5 to 12 carbon atoms. Specific examples include cyclopentanone oxime, cyclohexanone oxime, cycloheptanone oxime, cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cycloundecanone oxime, and cyclododecanone oxime. Cyclohexanone oxime and cyclododecanone oxime are preferable.
These cycloalkanone oximes can also be used in the form of salts. As a salt, it is used in hydrochloride or sulfate.
These cycloalkanone oxime compounds may be used alone or in combination of two or more.

  Specific examples of the corresponding lactam compound obtained in the present invention include valerolactam from cyclopentanone oxime, caprolactam from cyclohexanone oxime, enantolactam from cycloheptanone oxime, and laurolactam from cyclododecanone oxime. .

The Beckmann rearrangement reaction of the present invention is not particularly limited and is carried out by a gas phase reaction, trickle reaction and liquid phase reaction, and is preferably a liquid phase reaction.
In the liquid phase reaction, it is not always necessary to use a solvent. Specific examples in the case of using a solvent include nitrile compounds such as benzonitrile, acetonitrile, propionitrile, butyronitrile, capronitrile, adiponitrile, and tolunitrile, and aromatic hydrocarbon compounds such as benzene, toluene, xylene, mesitylene, and methoxybenzene. Aliphatic hydrocarbon compounds such as n-hexane, n-heptane, n-octane and n-dodecane, ester compounds such as dimethyl phthalate, dibutyl phthalate and dimethyl malonate, benzyl alcohol, cyclohexanol, isopropyl alcohol, isobutyl Alcohol compounds such as alcohol, aldehyde compounds such as acetaldehyde and benzaldehyde, ketone compounds such as diethyl ketone, methyl ethyl ketone and cyclohexanone, diethylene glycol dimethyl Ether compounds such as ethers, etc. can be mentioned halogen-containing hydrocarbon compounds such as chlorobenzene, it can be used as a mixture even these alone. Nitrile compounds are preferred. The amount of these solvents used is not particularly limited, but is 0.1 to 10000 times by weight, preferably 1 to 1000 times by weight, more preferably 2 to 100 times by weight, more than the cycloalkanone oxime compound. Preferably it is 3-50 weight times.

  Although the usage-amount of the solid acid catalyst manufactured by the above-mentioned method is not specifically limited, 0.000001-10 weight times can be used with respect to a cycloalkanone oxime compound.

The Beckmann rearrangement reaction in the liquid phase, which is a preferred form of the present invention, is usually performed by introducing a cycloalkanone oxime compound and a solid acid catalyst into a suitable solvent and then heating. The reaction is usually carried out in the presence of air or a gas inert to the rearrangement reaction, preferably in the presence of a gas inert to the rearrangement reaction. Examples of the gas inert to the rearrangement reaction include nitrogen, helium, and argon. Reaction temperature is 30-350 degreeC normally, Preferably it is 50-250 degreeC, More preferably, it implements at 60-200 degreeC. The reaction pressure is not particularly limited, and the reaction is performed under normal pressure or under pressure.
If the rearrangement reaction temperature is too low, the reaction hardly proceeds. On the other hand, when the reaction temperature is too high, side reaction proceeds and the yield of the desired lactam decreases, which is not preferable.
The reaction format may be either a batch reaction or a continuous flow reaction, and may be carried out in any of a suspended bed, a fixed bed, and a fluidized bed. The reaction time or residence time varies depending on the reaction conditions, but is carried out in 1 minute to 24 hours.

  The obtained lactam compound is separated and purified by crystallization, distillation operation or the like.

(Example of composite oxide synthesis)
Next, a method for synthesizing the composite oxide used in the present invention will be described.
The component oxide atomic ratio of the composite oxide was determined by ICP analysis using an ICP-AES measuring device (ICAP-575II type; manufactured by Nippon Jarrell-Ash), and the specific surface area was measured by a high-speed specific surface area / pore size distribution measuring device (NOVA- 1200; manufactured by Yuasa Ionics Co., Ltd.) BET specific surface area measurement by nitrogen adsorption (pretreatment at 120 ° C. under vacuum for 30 minutes), X-ray diffraction pattern (Cu-Kα ray) was determined by powder X-ray diffractometer (RAD-RX) : Manufactured by Rigaku Denki Co., Ltd.).

(Composite oxide synthesis example 1)
200 mmol of tetraethylorthosilicate and 10 mmol of 70 wt% zirconium propoxide / propanol solution were mixed and stirred at room temperature for 1 minute. The obtained solution (1) was added to a mixed solution (2) of 60 mmol of dodecylamine, 1.3 mol of ethanol and 7.2 mol of water and vigorously stirred at room temperature for 1 hour. The resulting white gel was aged at room temperature for 113 hours, then the white solid was collected by filtration, washed with water and ethanol, and dried at 105 ° C. for 24 hours. Next, the temperature was raised from room temperature to 600 ° C. at a rate of 5 ° C./min in the air, followed by firing at 600 ° C. for 1 hour.
From the BET specific surface area measurement by nitrogen adsorption, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 27% of the total adsorption amount. Further, the BET specific surface area was 993 m ² / g. Further, from the X-ray diffraction measurement (Cu-K [alpha line), a sharp diffraction peak assigned to d ₁₀₀ characteristic hexagonal structure porous body having a hexagonal pores in the vicinity of 2 [Theta] = 2.3 ° was observed From this, it was confirmed that the obtained composite oxide was a mesoporous material having hexagonal pores. FIG. 1 shows a nitrogen adsorption isotherm, and FIG. 2 shows an X-ray diffraction pattern (sometimes referred to as an XRD spectrum). When this composite oxide was analyzed by ICP, it was Si / Zr (atomic ratio) = 16. Hereinafter, this is abbreviated as Zr-MS-16.

(Composite oxide synthesis example 2)
200 mmol of tetraethylorthosilicate, 1.3 mol of ethanol and 200 mmol of isopropanol were mixed, 4.0 mmol of gallium nitrate was added thereto, and the mixture was stirred at room temperature for 20 minutes. The obtained mixed liquid (1) was added to a mixed liquid (2) of 60 mmol of dodecylamine and 7.2 mol of water and vigorously stirred at room temperature for 1 hour. The resulting white gel was aged at room temperature for 113 hours, then the white solid was collected by filtration, washed with water and ethanol, and dried at 105 ° C. for 24 hours. Next, the temperature was raised from room temperature to 600 ° C. at a rate of 5 ° C./min in the air, followed by firing at 600 ° C. for 1 hour.
From the BET specific surface area measurement by nitrogen adsorption, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 30% of the total adsorption amount. The BET specific surface area was 921 m ² / g. Furthermore, X-ray diffraction measurement (Cu-Kα ray) confirmed that the obtained composite oxide was a mesoporous material having hexagonal pores. The nitrogen adsorption isotherm is shown in FIG. 3, and the X-ray diffraction pattern is shown in FIG. From ICP analysis, it was Si / Ga (atomic ratio) = 50. Hereinafter, this is abbreviated as Ga-MS-50.

(Composite oxide synthesis example 3)
200 mmol of tetraethylorthosilicate, 1.3 mol of ethanol and 200 mmol of isopropanol were mixed, and 4.0 mmol of aluminum isopropoxide was added thereto, followed by stirring at 70 ° C. for 20 minutes. The obtained mixed liquid (1) was added to a mixed liquid (2) of 60 mmol of dodecylamine and 7.2 mol of water and vigorously stirred at room temperature for 1 hour. The resulting white gel was aged at room temperature for 113 hours, then the white solid was collected by filtration, washed with water and ethanol, and dried at 105 ° C. for 24 hours. Next, the temperature was raised from room temperature to 600 ° C. at a rate of 5 ° C./min in the air, followed by firing at 600 ° C. for 1 hour.
From the BET specific surface area measurement by nitrogen adsorption, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 35% of the total adsorption amount. The BET specific surface area was 1020 m ² / g. Furthermore, X-ray diffraction measurement (Cu-Kα ray) confirmed that the obtained composite oxide was a mesoporous material having hexagonal pores. The nitrogen adsorption isotherm is shown in FIG. 5, and the X-ray diffraction pattern is shown in FIG. From ICP analysis, it was Si / Al (atomic ratio) = 50. Hereinafter, this is abbreviated as Al-MS-50.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to a following example.
In addition, the sulfur content of the solid acid catalyst was measured using a fully automatic fluorescent X-ray analyzer (PW-2400 type: manufactured by PHILIPS). The conversion rate of the cycloalkanone oxime compound and the yield of the lactam compound were calculated by analyzing the reaction solution by liquid chromatography.

Example 1
The lower layer of the quartz glass tube is filled with 0.6 g of Zr-MS-16 (composite oxide) and the upper layer is filled with 8 g of 7 wt% vanadium pentoxide / silica catalyst (oxidation catalyst), and nitrogen-based 5000 ppm SO ₂ gas at 40 ml / min. And a mixed gas of G2 grade pure air (JFP product standard) at 100 ml / min for 18 hours at 420 ° C. In addition, baking was performed at 600 ° C. for 30 minutes under an air (100 ml / min) air flow as a pretreatment and for 1 hour at 420 ° C. under an air (100 ml / min) air flow as a post-treatment.
When the obtained solid acid catalyst was analyzed, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 27% of the total adsorption amount from the BET specific surface area measurement by nitrogen adsorption. . The BET specific surface area was 828 m ² / g. Further, from the X-ray diffraction measurement (Cu-K [alpha line), a sharp diffraction peak assigned to d ₁₀₀ characteristic hexagonal structure porous body having a hexagonal pores in the vicinity of 2 [Theta] = 2.3 ° was observed From this, it was confirmed that the mesopores were retained. A nitrogen adsorption isotherm is shown in FIG. 7, and an X-ray diffraction pattern is shown in FIG. The sulfur content of the catalyst was 2.2% by weight. Hereinafter, this is abbreviated as Zr-MS-16-SO ₃ .
The mixed gas (exhaust gas) after contact with the composite oxide was brought into contact with water for 1 hour, and sulfate ions and sulfite ions contained in the water were analyzed by ion chromatography. 0.058 mmol and 0.019 mmol were detected.
Zr-MS-16-SO _{3 (} 0.05 g), cyclododecanone oxime (2.5 mmol) and benzonitrile (5.0 g) that had been dried under reduced pressure for 12 hours at 50 ° C. were charged into a 50 ml glass flask and reacted at 90 ° C. for 4 hours. Went. As a result, the conversion of cyclododecanone oxime was 89.6 mol%, and the yield of laurolactam was 83.0 mol%.

Comparative Example 1
2 g of Zr-MS-16 was immersed in 10 ml of 1N H ₂ SO ₄ aqueous solution, filtered, and dried at 105 ° C. for 24 hours. The dried product was heated in air from room temperature to 400 ° C. at a rate of 5 ° C./min and calcined at 400 ° C. for 3 hours.
When the obtained solid acid catalyst was analyzed, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 17% of the total adsorption amount from the BET specific surface area measurement by nitrogen adsorption. . The BET specific surface area was 579 m ² / g. The nitrogen adsorption isotherm is shown in FIG. Hereinafter, this is abbreviated as Zr-MS-16-H ₂ SO ₄ .
The reaction was conducted in the same manner as in Example 1 using Zr-MS-16-H ₂ SO ₄ . As a result, the conversion of cyclododecanone oxime was 66.8 mol%, and the yield of laurolactam was 60.2 mol%.

Comparative Example 2
The reaction was conducted in the same manner as in Example 1 except that the catalyst was changed to Zr-MS-16. As a result, the conversion of cyclododecanone oxime was 26.1 mol%, and the yield of laurolactam was 19.3 mol%.

Example 2
A catalyst was prepared in the same manner as in Example 1 except that the composite oxide was changed to Ga-MS-50.
When the obtained solid acid catalyst was analyzed, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 30% of the total adsorption amount from the BET specific surface area measurement by nitrogen adsorption. . The BET specific surface area was 830 m ² / g. Further, from the X-ray diffraction measurement (Cu-K [alpha line), a sharp diffraction peak assigned to d ₁₀₀ characteristic hexagonal structure porous body having a hexagonal pores in the vicinity of 2 [Theta] = 2.3 ° was observed From this, it was confirmed that the mesopores were retained. A nitrogen adsorption isotherm is shown in FIG. 9, and an X-ray diffraction pattern is shown in FIG. The sulfur content of the catalyst was 2.1% by weight. Hereinafter, this is abbreviated as Ga-MS-50-SO ₃ .
Using _{Ga-MS-50-SO 3} , it was reacted in the same manner as in Example 1. As a result, the conversion of cyclododecanone oxime was 97.8 mol%, and the yield of laurolactam was 93.3 mol%.

Comparative Example 3
A catalyst was prepared in the same manner as in Comparative Example 1 except that the composite oxide was changed to Ga-MS-50.
When the obtained solid acid catalyst was analyzed, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 19% of the total adsorption amount from the BET specific surface area measurement by nitrogen adsorption. . Further, the BET specific surface area was 851 m ² / g. The nitrogen adsorption isotherm is shown in FIG. Hereinafter, this is abbreviated as Ga-MS-50-H ₂ SO ₄ .
Using _{Ga-MS-50-H 2} SO 4, reaction was performed in the same manner as in Example 1. As a result, the conversion of cyclododecanone oxime was 55.3 mol%, and the yield of laurolactam was 48.2 mol%.

Comparative Example 4
The reaction was performed in the same manner as in Example 1 except that the catalyst was changed to Ga-MS-50. As a result, the conversion of cyclododecanone oxime was 18.7 mol%, and the yield of laurolactam was 12.3 mol%.

Example 3
A catalyst was prepared in the same manner as in Example 1 except that the composite oxide was changed to Al-MS-50.
When the obtained solid acid catalyst was analyzed, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 30% of the total adsorption amount from the BET specific surface area measurement by nitrogen adsorption. . Further, the BET specific surface area was 900 m ² / g. Further, from the X-ray diffraction measurement (Cu-K [alpha line), a sharp diffraction peak assigned to d ₁₀₀ characteristic hexagonal structure porous body having a hexagonal pores in the vicinity of 2 [Theta] = 2.3 ° was observed From this, it was confirmed that the mesopores were retained. The nitrogen adsorption isotherm is shown in FIG. 11, and the X-ray diffraction pattern is shown in FIG. The sulfur content of the catalyst was 2.0% by weight. Hereinafter, this is abbreviated as Al-MS-50-SO ₃ .
With _{Al-MS-50-SO 3} , it was reacted in the same manner as in Example 1. As a result, the conversion of cyclododecanone oxime was 90.9 mol%, and the yield of laurolactam was 86.4 mol%.

Comparative Example 5
A catalyst was prepared in the same manner as in Comparative Example 1 except that the oxide was changed to Al-MS-50.
When the obtained solid acid catalyst was analyzed, from the measurement of the BET specific surface area by nitrogen adsorption, the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 was 14% of the total adsorption amount. . Moreover, the BET specific surface area was 879 m < ² > / g. The nitrogen adsorption isotherm is shown in FIG. Hereinafter, this product is referred to as _{Al-MS-50-H 2} SO 4.
With _{Al-MS-50-H 2} SO 4, reaction was performed in the same manner as in Example 1. As a result, the conversion of cyclododecanone oxime was 33.4 mol%, and the yield of laurolactam was 32.0 mol%.

Comparative Example 6
The reaction was performed in the same manner as in Example 1 except that the catalyst was changed to Al-MS-50. As a result, the conversion of cyclododecanone oxime was 27.9 mol%, and the yield of laurolactam was 27.3 mol%.

Comparative Example 7
A catalyst was prepared in the same manner as in Example 1 except that the 7 wt% vanadium pentoxide / silica catalyst was not charged.
The physical properties of the obtained catalyst were the same as in Example 1.
As a result of conducting the Beckmann rearrangement reaction using the prepared catalyst, the conversion of cyclododecanone oxime was 18.5 mol%, and the yield of laurolactam was 14.8 mol%.
In the absence of an oxidation catalyst, it was found that SO ₂ could not be oxidized to SO ₃ and the function as a solid acid catalyst was not expressed.

  Examples 1 to 3 and Comparative Examples 1 to 6 are collectively shown in Table 1.

The nitrogen adsorption isotherm of Zr-MS-16 is shown. It shows the XRD spectrum of Zr-MS-16 and _{Zr-MS-16-SO 3} . The nitrogen adsorption isotherm of Ga-MS-50 is shown. It shows the XRD spectrum of Ga-MS-50 and _{Ga-MS-50-SO 3} . The nitrogen adsorption isotherm of Al-MS-50 is shown. It shows the XRD spectra of Al-MS-50 and _{Al-MS-50-SO 3} . ₃ shows a nitrogen adsorption isotherm of Zr-MS-16-SO ₃ . The nitrogen adsorption isotherm of Zr-MS-16-H ₂ SO ₄ is shown. The nitrogen adsorption isotherm of Ga-MS-50-SO ₃ is shown. It shows the nitrogen adsorption isotherms of the _{Ga-MS-50-H 2} SO 4. ₃ shows a nitrogen adsorption isotherm of Al-MS-50-SO ₃ . ₃ shows a nitrogen adsorption isotherm of Al-MS-16-H ₂ SO ₄ .

Claims (10)

In composite oxide was subjected to sulfuric acid treatment, has a peak assigned to _{d 100} range to hexagonal structure of the 2 [Theta] = 2.0 to 2.5 ° in X-ray diffraction pattern (Cu-K [alpha line), nitrogen A solid acid catalyst in which the nitrogen adsorption amount in the range of P / P ₀ = 0.2 to 0.6 on the adsorption isotherm is 20 to 60% of the total adsorption amount. The solid acid catalyst according to claim 1, wherein the specific surface area exceeds 500 m ² / g.   The solid acid catalyst according to claim 1 or 2, wherein the sulfur content is less than 5% by weight.   The composite oxide is one or more elements selected from the group consisting of group numbers according to groups 4 to 14 (according to IUPAC inorganic chemical nomenclature revised in 1989 using a serial number of 1-18 as the group number), The solid acid catalyst according to any one of claims 1 to 3, wherein the solid acid catalyst is excluded.   A solid acid catalyst, wherein the elements according to claim 4 are zirconium, aluminum, gallium and silicon.   The solid acid catalyst according to any one of claims 1 to 5, wherein the sulfation treatment is brought into contact with a gas containing sulfur trioxide.   Use of the solid acid catalyst according to any one of claims 1 to 6 in an acid catalyzed reaction.   The manufacturing method of the lactam compound characterized by manufacturing the corresponding lactam compound by a Beckmann rearrangement reaction from a cycloalkanone oxime compound in presence of the solid acid catalyst of any one of Claims 1-6. Reaction (1) in liquid phase,
(2) at a reaction temperature of 30 to 350 ° C.
The method for producing a lactam compound according to claim 8, wherein the method is carried out.   The method for producing a lactam compound according to any one of claims 8 to 9, wherein the cycloalkanone oxime compound is cyclododecanone oxime and / or cyclohexanone oxime.

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