JP4415580B2 - Method for producing lactam compound - Google Patents

Description

比較例３および４より珪素とアルミニウムのＳｉ／Ａｌ（原子比）が２０より小さい場合には、硫黄含有化合物による処理効果が不十分で、ベックマン転位活性の向上が認められない。
【００２９】
【発明の効果】
本発明によれば、安価な複合酸化物触媒を高活性にすることができ、シクロアルカノンオキシム化合物からラクタム化合物を高収率で製造することができ、経済性にも工業的にも有利な製造方法を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a corresponding lactam compound by a Beckmann rearrangement reaction of a cycloalkanone oxime compound. The obtained lactam compound is an important compound as a raw material for nylon.
[0002]
[Prior art]
The rearrangement reaction of a cycloalkanone oxime compound to a lactam compound is known as a Beckmann rearrangement reaction. Specifically, in the industrial production of ε-caprolactam by rearrangement of cyclohexanone oxime, a liquid phase reaction using fuming sulfuric acid as a catalyst is employed. 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, so that a large amount of ammonium sulfate is produced as a by-product, and process problems such as corrosion of the apparatus. Therefore, the development of an efficient rearrangement catalyst is expected.
[0003]
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 the method using a rhenium compound as a catalyst (see, for example, Patent Document 1), 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 2) 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 a zinc zeolite containing zinc as a catalyst (for example, see Patent Document 3), the conversion is 47 mol% and the caprolactam selectivity is 72 mol% (yield 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 or the like is supported on an oxide of a group IV or group III metal such as zirconium oxide, titanium oxide or aluminum oxide (see, for example, Patent Document 4) 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 5) 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 in the presence of a compound having a dielectric constant in the range of 6 to 60 (see, for example, Patent Document 6), 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.
[0004]
[Patent Document 1]
Japanese Patent Laid-Open No. 08-151362 [Patent Document 2]
Japanese Patent Laid-Open No. 09-301952 [Patent Document 3]
JP 2001-19670 A [Patent Document 4]
JP 62-169769 A [Patent Document 5]
JP 09-40641 A [Patent Document 6]
Japanese Patent Laid-Open No. 2001-72657
[Problems to be solved by the invention]
The present invention, when producing a corresponding lactam compound by a Beckmann rearrangement reaction from a cycloalkanone oxime compound in the presence of a composite oxide containing silicon and aluminum,
It is an object of the present invention to provide a method for improving the activity of the composite oxide and producing a lactam compound in a high yield under mild reaction conditions.
[0006]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventor has controlled the atomic ratio of silicon and aluminum (Si / Al) of a composite oxide containing silicon and aluminum, and pretreated with a sulfur-containing compound, Even in the absence of a strong acid, the Beckmann rearrangement reaction of the cycloalkanone oxime compound proceeded efficiently, the amount of by-product oligomers was small, and the corresponding lactam compound was found to be produced advantageously, thus reaching the present invention.
That is,
In producing a corresponding lactam compound by a Beckmann rearrangement reaction from a cycloalkanone oxime compound in the presence of a composite oxide containing silicon and aluminum,
(1) Si / Al (atomic ratio) of silicon and aluminum contained in the composite oxide is 20 or more and treated with a sulfur-containing compound,
This is solved by a method for producing a lactam compound, characterized in that
Preferably,
(2) In the liquid phase
(3) at a reaction temperature of 30 to 350 ° C.
It solves by the manufacturing method of the lactam compound characterized by performing.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
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.
[0008]
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. .
[0009]
The composite oxide containing silicon and aluminum used in the present invention can be produced using silicon, aluminum, an organic solvent, water and, if necessary, a template agent as a raw material. The specific surface area of the composite oxide obtained, is not particularly limited, but is preferably 300 meters ² / g or more, more preferably 600~1200m ² / g, more preferably 700~900m ² / g.
[0010]
As the silicon source of the composite oxide, silicon alkoxide (preferably tetraalkylorthosilicate composed of aliphatic alcohol having 1 to 8 carbon atoms such as tetraethylorthosilicate) is preferably used. Examples of the aluminum source include aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and aluminum hydroxide. Aluminum alkoxide (specifically, aluminum isopropoxide, aluminum ethoxide) is preferable.
[0011]
Examples of the organic solvent include alcohols (preferably, aliphatic alcohols having 1 to 4 carbon atoms such as ethanol, isopropanol, and 1-butanol), ketones (preferably acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and the like having 3 carbon atoms. -8 aliphatic ketones) or the like are used singly or in plural, but alcohol (especially ethanol or isopropanol) is preferred. When using water, there is no restriction | limiting in particular, Deionized water (ion-exchange water, distilled water, etc.) should just be used.
[0012]
The template agent may or may not be used, but is preferably used from the viewpoints of increasing the specific surface area, improving the dispersibility of the metal, and forming an appropriate reaction field. When used, since the pore diameter varies depending on the molecular size of the template, it can be appropriately selected according to the required pore diameter. As the template agent, alkylamines, alkylammonium salts and the like are preferably used.
Among the template agents, primary alkylamines are preferable from the viewpoint of production cost. Among them, primary alkylamines having 6 to 20 carbon atoms are preferable, and primary alkylamines having 8 to 20 carbon atoms may give mesopores to the porous body. Since it is possible, it is more preferable.
Specific examples of the alkylamine include primary alkylamines (preferably those having 8 to 20 carbon atoms such as dodecylamine and hexadecylamine), secondary alkylamines (preferably N-methylhexylamine and the like). A main chain having 6 to 20 carbon atoms, an N-alkyl group having 1 to 6 carbon atoms), a tertiary alkylamine (preferably, N, N-dimethyldodecylamine or the like having 8 to 20 carbon atoms in the main chain, N-alkyl group having 1 to 6 carbon atoms) and alkyl ammonium salts include alkyl ammonium halides having 8 to 20 carbon atoms such as dodecyltrimethylammonium bromide and cetyltrimethylammonium bromide.
[0013]
The composite oxide containing silicon and aluminum of the present invention can be produced, for example, by the following procedure, but is not limited thereto.
In addition, Si / Al (atomic ratio) is 20 or more, preferably 25 ≦ Si / Al (atomic ratio) ≦ 500, and more preferably 30 ≦ Si / Al (atomic ratio) ≦ 100.
When Si / Al (atomic ratio) is smaller than 20, it is not preferable because the Beckmann rearrangement activity cannot be improved even if it is treated with a sulfur-containing compound.
(1) Preparation of liquid mixture 1: 1 mol of a silicon source and 1 to 20 times mol of an organic solvent with respect to the silicon source are mixed, and an aluminum source is added thereto so as to have a predetermined Si / Al (atomic ratio). And stir at 50 to 100 ° C. for 10 minutes to 5 hours.
The resulting solution is referred to as “mixed solution 1”.
(2) Preparation of liquid mixture 2: 0.1 to 10 times mol of the template agent and 10 to 50 times mol of water are mixed with the silicon source. The resulting mixed liquid is referred to as “mixed liquid 2”.
(3) Gel formation and aging: Mixture 1 is added to Mixture 2 and vigorously stirred at 0-50 ° C. (0 to 150 ° C. in the case of hydrothermal synthesis) for 10 minutes to 5 hours to form a gel. Thereafter, aging is carried out in the same temperature range for 12 to 400 hours. The white solid obtained by filtration is then washed with water and ethanol and dried at 80-120 ° C.
(4) Detemplaterization treatment (firing): The solid after drying is 0.1 to 20 ° C./min (preferably 0) in the air or in an inert gas atmosphere (preferably while circulating air or an inert gas). The temperature is increased to a predetermined temperature at 5 to 5 ° C./min), the temperature and the time are selected in the range of 400 to 900 ° C. and 10 minutes to 4 hours, and the baking is performed until the template agent is removed. Thereby, a composite oxide is obtained.
[0014]
In the present invention, it is necessary to perform treatment by bringing a sulfur-containing compound into contact with the complex oxide after gel formation or aging after the gel obtained by setting the atomic ratio of silicon and aluminum to 20 or more. Preferably, the composite oxide is contact-treated with a sulfur-containing compound.
Examples of the sulfur-containing compounds _{e.g., H 2 SO 4, (NH} 4) 2 SO 4, SO 2, SO 3, S n O n (n = 5~8), H 2 SO 3, H 2 S 2 O n ( n = 3 to 7), FSO ₃ H, CF ₃ SO ₃ H, ClSO ₃ H, SO ₂ Cl ₂ may be mentioned, and H ₂ SO ₄ , (NH ₄ ) ₂ SO ₄ and SO ₂ are preferable.
The treatment method is not particularly limited, and an impregnation method, a vapor phase method, a vapor deposition method (CVD method), or the like can be applied.
For example, in the case of the impregnation method, the composite oxide is introduced into a predetermined amount of the treatment agent (although not particularly limited, but preferably 0.1 to 50 times the molar amount relative to zirconium), filtered, and then dried at 80 to 120 ° C. The obtained dried product is predetermined at 0.1 to 20 ° C./min (preferably 0.5 to 5 ° C./min) in the air or in an inert gas atmosphere (preferably while allowing air or inert gas to flow). The temperature is raised to 120 to 700 ° C. (preferably 200 to 700 ° C.), and the temperature and time are selected in the range of 10 minutes to 10 hours, followed by firing. If the calcination temperature is too high, the dislocation activity and yield decrease, which is not preferable.
[0015]
Although the usage-amount of the complex oxide processed with the sulfur containing compound is not specifically limited, 0.000001-10 weight times can be used with respect to a cycloalkanone oxime compound.
[0016]
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. Although the usage-amount of these solvents is not specifically limited, 0.1-10000 weight times can be used with respect to a cycloalkanone oxime compound.
[0017]
The Beckmann rearrangement reaction in the liquid phase, which is a preferred form of the present invention, is usually carried out by introducing a complex oxide containing a cycloalkanone oxime compound, silicon and zirconium 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. The reaction temperature is generally 30 to 350 ° C, preferably 50 to 250 ° C, more preferably 60 to 200 ° C. 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.
[0018]
The obtained lactam compound is separated and purified by crystallization, distillation operation or the like.
[0019]
【Example】
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.
Si / Al (atomic ratio) and sulfur content were determined by ICP analysis using an ICP-AES measuring device (ICAP-575II type; manufactured by Nippon Jarrell-Ash). X-ray diffraction pattern (Cu-Kα ray) was determined by powder X-ray diffractometer by BET specific surface area measurement by nitrogen adsorption using a device (NOVA-1200; manufactured by Yuasa Ionics Co., Ltd.). (RAD-RX: manufactured by Rigaku Corporation) was used for measurement. The conversion rate of the cycloalkanone oxime compound and the yield of the lactam compound were calculated by analyzing the reaction solution using liquid chromatography.
[0020]
Example 1
(Preparation of catalyst)
200 mmol of tetraethylorthosilicate, 1.3 mol of ethanol and 200 mmol of isopropanol were mixed, and 6.7 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 nitrogen adsorption isotherm by X-ray diffraction measurement (Cu-Kα ray) and nitrogen adsorption measurement, it was confirmed that the obtained composite oxide was a mesoporous material. The specific surface area was 836 m ² / g. When this composite oxide was analyzed by ICP, it was Si / Al (atomic ratio) = 30. Hereinafter, this is abbreviated as Al-MS-30.
2 g of the Al-MS-30 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. Hereinafter, this is abbreviated as SO ₄ ²⁻ / Al-MS-30. ICP analysis of the sulfur content of this composite oxide was 1.3% by weight.
(Synthesis of lactam by Beckmann rearrangement reaction)
In a 50 ml glass flask, 0.05 g of SO ₄ ²⁻ / Al-MS-30 previously dried at 100 ° C. under reduced pressure, 2.5 mmol of cyclododecanone oxime subjected to reduced pressure drying at 50 ° C. for 12 hours, 5.0 g of nitrile was charged and reacted at 90 ° C. for 4 hours. As a result, the conversion of cyclododecanone oxime was 96.4 mol%, and the yield of laurolactam was 93.1 mol%.
[0021]
Comparative Example 1
(Synthesis of lactam by Beckmann rearrangement reaction)
The same procedure as in Example 1 was performed except that the catalyst was changed to Al-MS-30. As a result, the conversion of cyclododecanone oxime was 56.9 mol%, and the yield of laurolactam was 54.6 mol%.
[0022]
Example 2
(Catalyst adjustment)
A composite oxide was prepared in the same manner as in Example 1 except that aluminum isopropoxide was changed to 2.0 mmol. The obtained composite oxide was Si / Al (atomic ratio) = 103, and was confirmed to be a mesoporous material by X-ray diffraction measurement (Cu—Kα ray). The specific surface area was 988 m ² / g. Hereinafter, this is abbreviated as Al-MS-103. Al-MS-103 was treated with a 1N H ₂ SO ₄ aqueous solution in the same manner as in Example 1. Hereinafter, this is abbreviated as SO ₄ ²⁻ / Al-MS-103.
(Synthesis of lactam by Beckmann rearrangement reaction)
The same procedure as in Example 1 was performed except that the catalyst was changed to SO ₄ ²⁻ / Al-MS-103. As a result, the conversion of cyclododecanone oxime was 58.1 mol%, and the yield of laurolactam was 56.5 mol%.
[0023]
Comparative Example 2
(Synthesis of lactam by Beckmann rearrangement reaction)
The same procedure as in Example 1 was performed except that the catalyst was changed to Al-MS-103. As a result, the conversion of cyclododecanone oxime was 27.5 mol%, and the yield of laurolactam was 21.4 mol%.
[0024]
Comparative Example 3
(Catalyst adjustment)
200 mmol of tetraethylorthosilicate, 1.3 mol of ethanol and 200 mmol of isopropanol were mixed, and 20.0 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, under a nitrogen stream of 100 ml / min, the temperature was raised from room temperature to 400 ° C. at 5 ° C./min and calcined at 400 ° C. for 4 hours. The obtained composite oxide was Si / Al (atomic ratio) = 10, and was confirmed to be a mesoporous material by X-ray diffraction measurement (Cu—Kα ray). The specific surface area was 1233 m ² / g. Hereinafter, this is abbreviated as Al-MS-10. Al-MS-10 was treated with a 1 N H ₂ SO ₄ aqueous solution in the same manner as in Example 1. Hereinafter, this is abbreviated as SO ₄ ²⁻ / Al-MS-10.
(Synthesis of lactam by Beckmann rearrangement reaction)
The same procedure as in Example 1 was performed except that the catalyst was changed to SO ₄ ²⁻ / Al-MS-10. As a result, the conversion of cyclododecanone oxime was 30.6 mol%, and the yield of laurolactam was 24.3 mol%.
[0025]
Comparative Example 4
(Synthesis of lactam by Beckmann rearrangement reaction)
The same procedure as in Example 1 was performed except that the catalyst was changed to Al-MS-10. As a result, the conversion of cyclododecanone oxime was 51.2 mol%, and the yield of laurolactam was 49.7 mol%.
[0026]
Comparative Example 5
A composite oxide was prepared in the same manner as in Example 1 except that aluminum isopropoxide was changed to 13.3 mmol. The obtained composite oxide was Si / Al (atomic ratio) = 15, and was confirmed to be a mesoporous material by X-ray diffraction measurement (Cu—Kα ray). The specific surface area was 920 m ² / g. Hereinafter, this is abbreviated as Al-MS-15. Al-MS-15 was treated with a 1 N H ₂ SO ₄ aqueous solution in the same manner as in Example 1. Hereinafter, this is abbreviated as SO ₄ ²⁻ / Al-MS-15.
(Synthesis of lactam by Beckmann rearrangement reaction)
The same procedure as in Example 1 was performed except that the catalyst was changed to SO ₄ ²⁻ / Al-MS-15. As a result, the conversion of cyclododecanone oxime was 47.8 mol%, and the yield of laurolactam was 46.0 mol%.
[0027]
Comparative Example 6
(Synthesis of lactam by Beckmann rearrangement reaction)
The same procedure as in Example 1 was performed except that the catalyst was changed to Al-MS-15. As a result, the conversion of cyclododecanone oxime was 55.3 mol%, and the yield of laurolactam was 53.4 mol%.
[0028]
As described above, Examples 1 and 2 and Comparative Examples 1 to 4 are collectively shown in Table 1.
[Table 1]

When the Si / Al (atomic ratio) of silicon and aluminum is smaller than 20 from Comparative Examples 3 and 4, the treatment effect by the sulfur-containing compound is insufficient, and the Beckmann rearrangement activity is not improved.
[0029]
【The invention's effect】
According to the present invention, an inexpensive composite oxide catalyst can be made highly active, and a lactam compound can be produced in a high yield from a cycloalkanone oxime compound, which is economically and industrially advantageous. A manufacturing method can be provided.

Claims (2)

In producing a corresponding lactam compound by a Beckmann rearrangement reaction from a cycloalkanone oxime compound in the presence of a composite oxide containing silicon and aluminum,
(1) Si / Al (atomic ratio) of silicon and aluminum contained in the composite oxide is 30 ≦ Si / Al (atomic ratio) ≦ 103 , the specific surface area is 600 to 1200 m ² / g, and H ₂ SO ₄ Processed in
A process for producing a lactam compound, characterized in that Reaction (2) in liquid phase,
(3) at a reaction temperature of 30 to 350 ° C.
The method for producing a lactam compound according to claim 1, wherein the method is carried out.