WO2012005473A2

WO2012005473A2 - Method for preparing ε-caprolactam by using high-silica nano-plate zeolite

Info

Publication number: WO2012005473A2
Application number: PCT/KR2011/004828
Authority: WO
Inventors: 유룡; 김정남; 박우진
Original assignee: 한국과학기술원
Priority date: 2010-07-05
Filing date: 2011-07-01
Publication date: 2012-01-12
Also published as: KR101180346B1; KR20120003540A; WO2012005473A3

Abstract

The present invention provides a method for preparing ε-caprolactam by using high-silica nano-plate zeolite. According to the present invention, the method prepares ε-caprolactam from cyclohexanone oxime by a gas-phase Beckmann rearrangement, wherein a zeolite material having a multilayered or single plate structure in which a single unit crystal lattice or ten or less lattices are connected to be regularly or irregularly arranged is used as a catalyst. According to the present invention, the method for preparing ε-caprolactam can rapidly increase the productivity of ε-caprolactam by using high-silica nano-plate zeolite having a high oxime conversion rate, high ε-caprolactam selectivity and very slow catalyst inactivation. Further, it is also possible to remarkably reduce known frequent catalyst exchange and regeneration processes, and thus it is possible to prepare ε-caprolactam more economically and efficiently.

Description

[Specifications

[Name of invention]

Manufacturing Method of ε-Caprolactam Using High Silica Nanoplate Zeolite [Technical Field]

The present invention relates to a method for producing ε-caprolactam from cyclonucleanone oxime, and more particularly, from a cyclonucleanone oxime using a high silica nanoplate-shaped zeolite material as a catalyst for gas phase Beckman rearrangement reaction. It relates to a method for producing ε-caprolactam.

[Background technology]

The Beckman cultivation heat reaction of cyclonuxanone oxime is well known as an important industrial process for producing ε-caprolactam, the main raw material of nylon-6.

The existing ε-caprolactam production process converts cyclonucleanone oxime into liquid phase with fuming sulfuric acid as a catalyst. However, the existing processes have raised problems such as the generation of a large amount of ammonium sulfate by-products generated by using sulfuric acid catalysts, vessel corrosion, and safety of use.

Therefore, in order to solve these problems, much research has been conducted on the development of a gas phase Beckman conversion process using a solid acid catalyst instead of sulfuric acid. To date, silica, silica-alumina, boron-silica, solid phosphoric acid, metal oxides and zeolites have been proposed as new catalysts for the Beckman conversion process.

In addition, US Pat. Nos. 4,709,024 and 4,717,769 compare to other catalysts when using a high silica MFI zeolite (silicon / metal element> 500, Η ⁺ -form) as a catalyst. It has been described that the conversion rate of cyclonucleanone oxime and the selectivity of ε-caprolactam are very high. Beckman cultivation heat reaction of cyclonucleanone oxime of this catalyst is a surface or internal defect

It is well known that catalytic activity is caused by weakly acidic silanol groups (Si≡O-H) present in the defect (Bulletin of the Chemical Society of Japan, Vol. 80, 1280-1287, 2007). More specifically, hydrogen-bonded neighboring silanol groups or silanol nests play a critical role in obtaining high ε-caprolactam selectivity and terminal silanol groups on the surface. ) Is known to reduce ε-caprolactam selectivity (Journal of Catalysis, Vol. 186, 12-19, 1999).

U.S. Patent No. 5,212,302 uses a mixture of ammonium nitrate and ammonia water to form hydrogen-bonded silanol groups and simultaneously reduce the amount of terminal silanol groups, thereby increasing the catalytic conversion of ε-caprolactam You can get selectivity It was described.

As described above, the Beckman conversion process of cyclonuclear nonoxime using a conventional high silica zeolite catalyst shows high oxime conversion and ε-caprolactam selectivity. However, myriad micropores (less than 1 nm in diameter) in large crystals of conventional zeolite catalysts (typically 1 μπι or more) lead to slow molecular diffusion, which results in limited catalytic efficiency and short catalyst life in gas phase Beckman conversion processes. It is a cause of having. In particular, the rapid deactivation of the zeolite catalyst requires frequent regeneration and replacement of the catalyst, which is an important factor in increasing the production cost of ε-caprolactam.

On the other hand, Korean Patent No. 10-0613399 discloses that a high silica zeolite catalyst with a nanoparticle size (100-1000 nm) can improve the conversion rate, product selectivity, and catalyst lifetime of cyclonuxanon oxime. ， The performance of the catalyst was not significantly improved compared to the existing catalyst.

Detailed description of the invention

[Technical problem]

The present invention is to solve the above-mentioned problems of the prior art, in the production of ε-caprolactam from cyclonucleanone oxime using a gas phase Beckman conversion process, high oxime conversion, high ε-caprolactam selectivity, very slow It is an object of the present invention to provide a method using a high silica nanoplatelet zeolite having a catalyst deactivation characteristic.

Technical Solution

In order to achieve the above object, the present invention, in the method for producing ε-caprolactam from the cyclonuclinon oxime using a gas phase Beckman conversion process, a plate-like structure of one or more unit crystal lattice is arranged Provided is a method for preparing ε-caprolactam from cyclonucleanone oxime using the zeolite material formed as a catalyst.

The plate-like structure refers to a plate-like structure in which the zeolite extends in a plate shape with a unit crystal lattice of 1 or 10 or less in thickness, and the zeolite material is a material formed by regular or irregular arrangement of the plate-like structures of the zeolite. Say Here, the regular arrangement means a structure in which the plate-shaped structures of the zeolite are stacked on top of each other, and the irregular arrangement means a structure in which the plate-shaped structures of the zeolite are stacked in various other forms.

The zeolitic material may itself or delamination, filler It can be used to activate or modify using a post-treatment reaction selected from the group consisting of pillaring, salt aqueous solution treatment, ion exchange, dealumination, metal loading and organic functionalization.

The zeolitic material preferably has a molar ratio of silicon to metal element of at least 500.

Metal elements included in the zeolitic material are, for example, Be, B, Al, Ti, Fe, Ga, V, Cr, Co, Ni, Cu, Zn, Ge, Zr, Nb, Sb, La, Hf and Bi Can be selected from the group consisting of.

The present invention also provides a method for producing ε-caprolactam from cyclonucleanone oxime using a gas phase Beckman conversion process, comprising two or more ammonium functional groups, or one ammonium functional group and one amine functional group. The present invention provides a method for preparing ε-caprolactam from cyclonucleanone oxime using a zeolite material synthesized by adding an organic surfactant to a structural derivative.

The organic surfactant may be used at the same time or each of those represented by the formula (1) or (2).

[Formula 1]

[Formula 2]

Where X is a halogen (CI, Br, I) anion or a hydroxide (OH) anion.

In Formula 1 and Formula 2, C1 is preferably 8 to 22 carbon atoms, C2 is 3 to 6 carbon atoms, and C3 is preferably 1 to 8 carbon atoms.

The zeolitic material may be prepared by completely or partially removing the organic surfactant by calcining or chemical treatment. The zeolite material preferably has a molar ratio of silicon to metal element of at least 500.

The zeolite material may be prepared through a crystallization process selected from the group consisting of, for example, hydrothermal synthesis, microwave heating and dry-gel synthesis.

The present invention also provides a process for preparing ε-caprolactam from cyclonucleanone oxime using a gas phase Beckman conversion process, comprising at least two ammonium functional groups or comprising one ammonium functional group and one amine functional group. It is synthesized by adding organic surfactant as a structural derivative and is selected from the group consisting of delamination, pillaring, base water solution treatment, ion exchange, dealumination, metal loading and organic functionalization. It provides a method for producing ε-caprolactam from cyclonucleanone oxime using a zeolite material that is activated or modified using a catalyst as a catalyst.

[Formula 1]

[Formula 2]

(Wherein X is a halogen (CI, Br, I) anion or a hydroxide (OH) anion, the present invention also removes ε ᅳ caprolactam from the cyclonuclinon oxime described above. Ε-caprolactam prepared using the crude method is provided.

Advantageous Effects

As described above, the present invention provides a method for preparing ε-caprolactam using high silica nanoplatelet zeolite having high yield and long catalyst lifetime in a Beckman conversion process of cyclonucleanone oxime or a post-treated material. To provide. The high silica nanoplatelet zeolite material of the present invention is a significant improvement in the preparation of ε-caprolactam from cyclonuclear oximes compared to conventional zeolites, nanoporous amorphous silica, nanoporous zeolites and their post-treated catalyst materials. Shows catalytic performance. In addition, the performance of such a catalyst can be further improved depending on the synthesis conditions and post-treatment methods of the material.

Therefore, according to the epsilon caprolactam manufacturing method of this invention, productivity of epsilon caprolactam can be improved remarkably. In addition, the existing frequent catalyst replacement and regeneration processes can be greatly reduced, making ε-caprolactam more economical and efficient.

[Brief Description of Drawings]

1 is a premicroscopic scanning micrograph of a high silica nanoplatelet zeolite prepared according to Example 1. FIG.

2 is a transmission electron micrograph of the high silica nanoplatelet zeolite prepared according to Example 1.

3 is a diagram showing an X-ray diffraction pattern of the high silica nanoplatelet zeolite prepared according to Example 1. FIG.

Figure 4 is a view showing the ^ Si MAS NMR spectrum of the high silica nanoplatelet zeolite prepared according to Example 1.

[Form for implementation of invention]

Hereinafter, the present invention will be described in detail. In describing the present invention, detailed descriptions of related well-known configurations or functions will be omitted.

* The terms or words used in this specification and claims are not to be construed as being limited to conventional or dictionary meanings, and should be construed as meanings and concepts consistent with the technical details of the present invention.

The embodiments described in the present specification and the configuration shown in the drawings are preferred embodiments of the present invention, and do not represent all of the technical idea of the present invention. There may be. The present invention relates to a process for producing ε-caprolactam from cyclonucleanone oximes using a gas phase Beckman conversion process. The gaseous Beckman conversion process refers to a method of injecting a cyclonucleanone oxime into a reaction vessel at a temperature of 250 to 500 ^° C. containing a solid catalyst layer, and preparing an epsilon caprolactam from the cyclonucleanone oxime through a gas phase Beckman potential. Using this process can not only produce ε-caprolactam continuously without the catalyst separation process, but also solve the problems such as the generation of a large amount of by-products and vessel corrosion generated in the existing sulfuric acid catalytic process. The catalyst used in the present invention is a zeolite material formed by arranging one or more unit crystal lattice plate-like structures having a thickness of 10 or less. The plate-like structure refers to a plate-like structure in which the zeolite extends in a plate shape with a thickness of one or less unit crystal lattice, and the zeolite material refers to a material formed by regular or irregular arrangement of the plate-like structures of the zeolite. Say. Here, the regularly arranged means a structure in which the plate-shaped structure of the zeolite is stacked on top of one another, and the irregularly arranged means a structure in which the plate-shaped structure of the zeolite is stacked in various other forms.

This nano-plate shaped zeolite material can be synthesized by adding an organic surfactant as a structural derivative to the synthetic composition of the zeolite. Hereinafter, a method of preparing the nano-plate zeolite material will be described in more detail.

Organic-functionalized silica shears are polymerized with other gel shears such as silica or alumina to form organic-inorganic composite gels. At this time, the hydrophobic organic domains are self-assembled between the inorganic domains by non-covalent bonds between organic materials, that is, van der Waals forces, dipole-dipole interactions, and ionic interactions. At this time, depending on the structure or concentration of the organic matter, each gel area is arranged in a regular or complete arrangement.

Subsequently, the nano-sized inorganic gel region stabilized by the organic region has a single unit crystal lattice thickness or 10 single unit crystal lattice stacks depending on the structure of the organic surfactant or the number of ammonium functional groups contained therein through the crystallization process. It is converted into a single or multiple plate-shaped zeolite. At this time, each zeolite Due to the stabilizing effect of organic matter, the growth of zeolite is suppressed and the crystal size

It can be adjusted to a very fine thickness of 10 nm or less. At this time, the crystallization process can be performed through conventional methods such as hydrothermal synthesis, dry-gel synthesis, and microwave synthesis.

The crystallized zeolite can be obtained through conventional methods such as filtration and centrifugation. The material thus obtained may be used as it is or may be selectively or completely removed only from organic matter through firing or other chemical reactions. The organic surfactant used in the present invention is designed to simultaneously form a micro pore structure and a meso pore structure. Generally, a surfactant containing two ammonium functional groups or one ammonium functional group and one amine functional group is used. It consists of a head and a hydrophobic alkyl tail. The organic surfactant may be represented by Formula 1 or 2 below.

[Formula 1]

[Formula 2]

Where X is a halogen (CI, Br, I) anion or a hydroxide (OH) anion. CI, C2 and C3 are each independently substituted or unsubstituted alkyl groups. C3 is also possible in a variety of molecular structures substituted with alkenyl groups or atoms other than carbon on the table. C1 is preferably 8 to 22 carbon atoms, C2 is 3 to 6 carbon atoms, and C3 is preferably 1 to 8 carbon atoms. In the present invention, the organic surfactant is generalized in the order of C1-C2-C3 according to the length of CI, C2, C3 (Eg 22 ᅳ 6-6: C1 is 22 carbon atoms, C2 is 6 carbon atoms, C3 is 6 carbon atoms and consists of two ammonium functional groups; 22-6-0: C1 is 22 carbon atoms, C2 has 6 carbon atoms and consists of one ammonium group and one amine group).

Ammonium functional groups can be expanded to two or more, preferably 2 to 5. Too many ammonium functional groups thicken the skeleton thickness of the crystal, resulting in low efficiency of the catalyst.

By controlling the structure of the organic surfactant or the number of ammonium or amine functional groups, the number of single unit crystal lattice included in a single plate-like structure can be controlled.

In preparing the zeolite, the mole ratio of silicon to metal is preferably 500 or more, and the silica raw material is conventionally free of impurities such as fumed silica, colloidal silica, and organosilicon compounds. Silica materials can be used. Metal elements include Be, B, Al, Ti, Fe, Ga, V, Cr, Co, Ni, Cu, Zn, Ge, Zr, Nb, Sb, La, Hf, Bi. Crystallization of the zeolite is preferably carried out for 1 to 30 days at 100 to 200 ^° C through hydrothennal synthesis, dry-gel, microwave synthesis, and more preferably. Preferably it is carried out at 130 to 150 ^° C for 3 to 15 days. If the reaction temperature is low or the reaction time is short, the crystallinity of the zeolite is poor and the catalytic performance is poor. If the reaction temperature is too high, the crystallization and the decomposition reaction of the surfactant occur simultaneously, so that the nano-plate zeolite and the existing large zeolite crystals together It is mixed, and the performance as a catalyst is reduced.

The synthesized zeolite is preferably subjected to filter recovery, washing and drying using an aspirator, and then firing the organic surfactant under air or nitrogen at 300 to 700 ^° C. More preferably, 400 to 500 ° C. It is advantageous to fire at C under air or nitrogen. Low firing temperatures do not completely remove organic surfactants, and too high calcined silver leads to dehydroxylation reactions of silanol groups, thereby reducing the activity and selectivity of the catalyst.

The microporous structure of the zeolite can be any zeolite structure that can be induced by an organic surfactant, preferably pentasil zeolite, and in its case is also preferably a codename designated by the MFK International Zeolite Association. The above zeolite can be peeled, peeled, and replaced with silver. Conventional post-treatment of tablets, bases, silanizations and acid treatments can be used. However, without any aftertreatment, the nano-plate zeolites show superior catalytic activity, selectivity, and lifetime compared to other silica catalysts.

The present inventors have variously characterized zeolite obtained by powder X-ray diffraction method, nitrogen adsorption method, SEM (scanning electron microscope), TEM (transmission electron microscope), ¾1 MAS NMR, FT-IR, ICP-AES, etc. The result is a high silica nanostructure with a very large specific surface area (> 600 m ² g ^"1 ), large pore volume (> 1.0 cm ³ g ^{" 1} ), and a large amount of silanol groups ^ Si MAS NMR from Q3 / Q4-0.25) It was confirmed that the plate-like zeolite was synthesized. In particular, the zeolite catalyst shows very high catalytic activity, selectivity, and lifetime despite the fact that the FT-IR analysis shows that the terminal surface silanol groups are known to have very low selectivity of ε-caprolactam. It means that the orientation and acidity of the group is different from that of other zeolites. Highly catalytically active hydrogen bonding through the synthesis conditions of the zeolite (preferably, the amount of surfactant, control of hydrothermal synthesis time, ρΗ of the synthetic gel, etc.) and various post-treatment processes (typically ammonium nitrate and ammonia water treatment) The formed silanol group can be further formed to further improve the conversion rate of cyclonucleanone oxime.

The Beckman rearrangement conversion reaction of the cyclonucleanone oxime using the above-mentioned zeolite catalyst can be suitably performed under gas phase conditions in a fixed bed or a fluidized bed, and the reaction temperature is generally preferably performed ^at 250 to 500 ^° C., More preferably, it is good to set it to 300 ~ 380 ° C. When the reaction temperature is low, the conversion rate of cyclonucleanone oxime is low and the activity of the catalyst is also fast. Too high a decrease in selectivity of ε-caprolactam by the side reactions. The reaction pressure is typically between 0.005 and 0.5 MPa, preferably between 0.005 and 0.2 MPa. Space velocity (WHSV) of cyclohexanone hex oxime is 0.1 ~ 30 h ^"1, preferably preferably in the 0.2 ~ 10 h ^1. Cyclo hex oxime is a block such as a sole or nitrogen, Helms, argon and carbon dioxide, It can be supplied together with an active gas, and more preferably, a solution in which cyclonucleanone oxime is dissolved in C1-C8 alcohols, benzene, toluene, acetonitrile and the like and mixed with the above inert gas is supplied. Preferred examples are provided to aid the understanding of the invention, but the following examples are merely illustrative of the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It goes without saying that modifications fall within the scope of the appended claims Example 1: High silica nanoplatelet agent with single unit crystal lattice thickness Beckman conversion reaction of cyclonuxanon oxime with light

1) Preparation of high silica nanoplatelet zeolite with single unit crystal lattice thickness

C1 has 16 carbon atoms, C2 has 6 carbon atoms, C3 has 6 carbon atoms, and an organic surfactant consisting of two ammonium functional groups and two hydroxyl anions (OH-) (hereinafter, 16-6- 6) was mixed with tetraethyl orthorsilicate (TEOS) and distilled water to prepare a mixed gel. The molar composition of the synthetic gel was as follows.

100 SiO ₂ : 10 16-6-6 Organic surfactant: 6000 H ₂ O

After the mixed gel was stirred at room temperature for 2 hours, the final mixture was placed in a stainless autoclave and reacted with stirring (60 rpm) at 140 ° C. for 6 days. At this time, the pH of the synthetic gel is 12. After reaction, the product was filtered using an aspirator and washed several times with distilled water. The resulting product was dried thoroughly in Aubon 120 ° C, and then fired in a 500 ° C furnace (2 hours) while blowing air.

1 is a scanning electron micrograph of the high silica nanoplatelet zeolite prepared according to Example 1, Figure 2 is a transmission electron micrograph of the high silica nanoplatelet zeolite prepared according to Example 1, Figure 3 Is a diagram showing the X-ray diffraction pattern of the high silica nanoplatelet zeolite prepared according to Example 1, Figure 4 is a diagram showing the ^¾ Si9SAS NSR spectrum of the high silica nanoplatelet zeolite prepared according to Example 1 . The scanning electron micrograph of FIG. 1 shows that the zeolite was crystal-grown in the form of a plate-like structure having a thickness of 20 to 50 ran. The transmission electron micrograph of FIG. 2 shows that the zeolite crystals are very thin on the b-axis of crystals and wide on the ac plane of the crystals. In particular, the thickness of the crystals on the b-axis is about 2 nm. Corresponds to the single unit cell size of the MFI zeolite structure. In addition, powder X-ray diffraction analysis confirmed that the synthesized material had a structure of MFI zeolite. However, only the diffraction pattern corresponding to WI diffraction was clearly seen due to the very thin skeleton thickness on the b-axis (FIG. 3). The Si MAS NMR spectrum (Fig. 4) of this material showed two peaks corresponding to the Q ³ (O≡Si_OH) and Q ⁴ (OSi) configuration of Si, and the ratio of Q ³ representing the amount of silane groups was It was 0.4: 1 compared with Q <^4> . After firing, the Si / Al ratio of the synthesized material was 3,800, and the specific surface area was 680 mg. The total pore volume was 1.3 cm ³ g ^"1 . 2) Beckman conversion reaction of cyclonuclinon oxime

The calcined zeolite catalyst was molded into a size of 14-20 mesh, and 0.1 g of catalyst and 2 g of quartz sand (14-20 mesh) were mixed well, followed by quartz reaction (40 cm in length, Inside diameter was 1.3 cm). The catalyst was pretreated at 500 ^° C. for 2 hours under air flow (50 mL / min) and the reaction temperature was adjusted to 320 ^° C. At the same temperature, high purity nitrogen (99.999%) was added to the reaction vessel at 60 mL / min, and after sufficient stabilization, cyclohexanone oxime solution (10 wt%) dissolved in ethanol was subjected to high performance liquid chromatography (HPLC). A pump was used to inject the reaction at a rate of 0.06 mL per minute. At this time, the space velocity (WHSV) of cyclonucleanone oxime is 3 h ^_1 . The reactions were collected after liquefaction through a condenser (0 ^° C) every hour, and either a FID-attached gas chromatography (column: HP—innowax, 30 m length) or a gas chromatography with a mass spectrometer was attached. The analysis was carried out. The reaction results are shown in Table 1.

Table 1

Comparative Example 1: Comparison with Existing High Silica Zeolite

Existing high silica zeolite catalysts were prepared with reference to Document 1 of US Pat. No. 5,212,302. 10% tetrapropylammonium hydroxide (tetrapropylammoni-umhydroxide, TPAOH), TEOS, ethanol (Ε1ΌΗ) was mixed to prepare a mixed gel. The molar composition of the synthetic gel was as follows.

100 SiO ₂ : 23 TPAOH: 970 EtOH: 2340 H ₂ 0

The mixed gel was stirred at room temperature for 2 hours, then the final mixture was placed in a stainless autoclave and reacted with stirring (400 rpm) at 105 ^° C. for 4 days. After reaction, the solid product is separated and centrifuged and washed repeatedly. The resulting product was dried in 120 ° C. Aubon and then calcined in a 500 ° C. furnace for 2 hours while blowing air.

The specific surface area of the synthesized material is 340 m ² g ^_1 and the total pore volume is 0.22 cm ^{3 1} . Powder X-ray diffraction analysis confirmed that the synthesized material was MFI zeolite. The Si / Al ratio of the synthesized material is 2,050. Electron micrographs showed that the crystal size of the synthesized material was about 200 nm.

The calcined conventional zeolite catalyst was carried out in the same manner as the Beckman conversion reaction process of the cyclonucleanone oxime of Example 1. The reaction results are shown in Table 2.

Table 2

Comparative Example 2: Comparison with Nanoporous Amorphous Silica

Existing nanoporous amorphous silica catalysts were prepared with reference to the Journal of American Chemical Society, Vol. 127, 7601-7610, 2005. Three-block co-polymer polymer P123 (Εθ2οΡθ7οΕθ2ο, molecular weight = 5,800), η_butanol (BuOH), TEOS, and hydrochloric acid (HC1) were mixed to prepare a mixed gel. The molar composition of the synthetic gel was as follows.

0.017 P123: 1.0 TEOS: 1.31 BuOH: 1.83 HC1: 195 H ₂ O

After the mixed gel was stirred at 35 ^° C. for 1 day, the final mixture was placed in a stainless autoclave and reacted at 130 ^° C. without stirring for 1 day. After reaction, the solid product was separated and dried without washing. The dried product was washed at room temperature with ethane using a single hydrochloric acid solution and calcined for 2 hours in a furnace at 500 ^° C while blowing air to remove the polymer.

The specific surface area of the synthesized material was 750 m ² g ^-1 , the total pore volume included 0.92 cm ³ g ^"1 , and a very uniform mesopore size (7 nm). Low angle powder X-ray diffraction analysis It was confirmed that the synthesized material had a cubic Idid mesoporous structure, and the high-angle powder X-ray diffraction results showed that the amorphous silica had no specific microporous structure. It was.

The calcined conventional nanoporous catalyst was carried out in the same manner as the Beckman conversion reaction process of the cyclonucleanone oxime of Example 1. The reaction results are shown in Table 3.

Table 3

Comparative Example 3: Comparison with Nanoporous High Silica Zeolite

Existing nanoporous high silica zeolite catalysts were prepared with reference to the synthesis method of the reference (Journal of American Chemical Society, Vol. 122, 7116-7117, 2000). In the comparative example of the present invention, instead of the carbon black of the literature, the structure-regulated nanoporous carbon (Journal of Materials Chemistry, 16, 1445, 2006) was used as the solid mold. A mixed gel was prepared by mixing 20% TPAOH solution, TEOS, ethanol (EtOH) and nanoporous carbon. The molar composition of the synthetic gel was as follows.

100 SiO ₂ : 25 TPAOH: 940 H ₂ O: 900 carbon

The final mixture was placed in a stainless autoclave and reacted at 170 ^° C. without stirring for 6 days. After reaction, the product was filtered using an aspirator and washed several times with distilled water. The obtained product was dried in 120 ° C Aubon, and then fired in a 600 ^° C furnace for 12 hours while blowing air.

The specific surface area of the synthesized material was 430 m ² g— ¹ , the total pore volume included 0.52 cm ³ g ^“1 , and a very uniform mesopore size (8 nm). Low angle powder X-ray diffraction analysis It was confirmed that the synthesized material had a regular cubic mesoporous structure, and the elevation of the powder X-ray diffraction showed that it had a MFI type zeolite structure.

The calcined conventional nanoporous catalyst was carried out in the same manner as the Beckman conversion reaction process of the cyclonucleanone oxime of Example 1. The reaction results are shown in Table 4.

TABLE 4

Comparative Example 4 Comparison with Existing High Silica Zeolite Post-treated with Ammonium Nitrate (1 g) The comparative high silica zeolite catalyst of Comparative Example 1 (1 g) was repeated three times at 60 ^° C. for 6 hours at 1 M NH ₄ NO ₃ solution (20 mL). After the treatment, it was carried out in the same manner as the Beckman conversion reaction process of the cyclonucleanone oxime of Example 1. The reaction results are shown in Table 5.

TABLE 5

Comparative Example 5: Comparison with Existing High Silica Zeolites Post-treated with Ammonium Nitrate and Ammonia Water

Referring to US Pat. No. 5,212,302, the existing high silica zeolite catalyst of Comparative Example 1 was post-treated with a mixed solution of ammonium nitrate and ammonia water. 1 g of zeolite was mixed with 1 g of ammonia water (25 wt%) and 3 g of ammonium nitrate solution (7.5 wt%), and then placed in a sealed plastic bottle and stirred at 90 ° C for 1 hour. The obtained product was filtered, washed and dried, and was carried out in the same manner as the Beckman conversion reaction process of cyclonuclinon oxime of Example 1. However, 500 ° C pretreatment was not performed. The reaction results are shown in Table 6.

Table 6

Example 2: Beckman Conversion of Nanonuclear Zeolites to Cyclonucleosanone Oximes

The hydrothermal synthesis time carried out in Example 1 was increased to 6 days (Sample A), 9 days (Sample Β), 15 days (Sample _ C), and the Beckman conversion reaction characteristics were confirmed. Except for the small bed temperature 600 ^° C. was the same as in Example 1. The calcined zeolite catalyst was carried out in the same manner as in the Beckman conversion reaction process of cyclonuclinon oxime of Example 1. The reaction results are shown in Table 7.

[Table 7]

Example 3: Beckman conversion reaction of cyclonucleoside oxime of nanoplatelet zeolite according to synthetic gel ρΗ

After addition of sulfuric acid to adjust the ρΗ of the synthetic gel of Example 1 to 10, a nano-plate zeolite was prepared (Sample D). The molar composition of the final synthetic gel was as follows. 100 SiO ₂ : 1016-6-6 Organic Surfactant: 6000 H ₂ 0: 3 H ₂ S0 ₄

All other manufacturing procedures were the same as in Example 1, except that the firing temperature was performed at 600 ^° C. The Beckman conversion reaction process of the calcined zeolite catalyst was carried out in the same manner as the Beckman conversion reaction process of cyclonuclinon oxime of Example 1 except that the reaction temperature was 370 ° C. and the space velocity WHSV was 8 h ^_1 . The reaction results are shown in Table 8 in comparison with Sample A (Example 2).

[Table 8]

Example 4 Beckman Conversion of Cyclonusanone Oxime of Nanoplate Zeolite with Amount of Surfactant

While adjusting the amount of the surfactant of Example 1, a nano-plate zeolite was prepared. The molar composition of each synthetic gel was as follows.

(Sample Ε) 100 SiO ₂ : 716-6-6 Organic surfactant: 6000 H ₂ O

(Sample F) 100 SiO ₂ : 1516-6-6 Organic Surfactant: 6000 H ₂ O

All other manufacturing procedures were the same as in Example 1. The calcined zeolite catalyst was carried out in the same manner as the Beckman conversion reaction process of the cyclonucleanone oxime of Example 1. The reaction results are shown in Table 9.

[Table 9]

Example 5 Beckman's Conversion of Cyclonucleoxan Oxime of Nanoplate Zeolite with Silica Pillaring

22-6-6 organic surfactants other than 16-6-6 organic surfactants (Example 1) (C1 has 22 carbon atoms, C2 has 6 carbon atoms, C3 has 6 carbon atoms) Using to prepare a nano-plate type zeolite in the same manner as in Example 1, was carried out silica filler. 5 g of TEOS was added to 1 g of the nanoplatelet zeolite before firing, and the mixture was stirred in a sealed plastic bottle at room temperature for 12 hours. After the completion of reaction, the obtained material was filtered without washing, dried at room temperature, 20 g of distilled water was added thereto, heated at 100 ^° C. for 12 hours, then obtained through filtration and washed with distilled water. After drying at 110 ^° C to remove the organic surfactant through a calcination process at 600 ^° C for 4 hours. It was confirmed by electron microscopic analysis that an amorphous silica column was formed between the plate of the zeolite and the plate thus obtained.

The calcined zeolite catalyst was carried out in the same manner as the Beckman conversion reaction process of cyclonucleanone oxime of Example 3, and the reaction results before (sample G) and after (sample H) are shown in Table 10.

TABLE 10

Example 6: Beckman conversion reaction of cyclonucleanone oxime of nanoplate-shaped zeolite after-treatment with ammonium nitrate and ammonia water

The catalyst of Example 2 (Sample A) was worked up with a mixed solution of ammonium nitrate and ammonia water, and the process was carried out in the same manner as in Comparative Example 5. The catalyst thus obtained was carried out in the same manner as in the Beckman conversion reaction process of cyclohexanone oxime of Comparative Example 5. The reaction results are shown in Table 11.

Table 11

Example 7: Beckman Conversion of Cyclonucleanone Oximes Using Nanoplate Zeolites Post-treated with (CH ₃ ) ₃ SiCl

The catalyst of Example 2 (Sample A) was worked up using trimethyl silane chloride ((C¾) ₃ SiCl, TMSC1). 1 g of zeolite catalyst was added to 1.9 g of TMSC1 and 100 mL of toluene solution and then refluxed with stirring at 110 ^° C. for 3 hours. After the reaction was completed, the mixture was filtered through a filter and washed several times with toluene and acetone. After drying at 80 ° C. for 2 hours, the catalyst thus obtained was replaced with cyclone nucleus of Comparative Example 5. The same procedure was followed as for Beckman's conversion reaction. Return results

It is shown in 12.

Table 12

Claims

[Range of request]

[Claim 1]

From Cyclonucleanone Oximes Using a Vapor Beckman Conversion Process

In the method for producing ε-caprolactam,

A method for producing ε-caprolactam from a cyclonucleone oxime using a zeolite material formed by arranging plate structures having a unit crystal lattice of one or ten or less thicknesses as a catalyst.

[Claim 2]

In that U term,

The zeolitic material is activated or modified using a post treatment reaction selected from the group consisting of delamination, pillaring, base water solution treatment, ion exchange, dealumination, metal loading and organic functionalization. A method of producing ε-caprolactam from a cyclonucleosanone oxime.

[Claim 3]

The method of claim 1,

And wherein said zeolitic material has a molar ratio of silicon to metal element of at least 500.

[Claim 4]

The method of claim 1,

Metal elements included in the zeolitic material are Be, B, Al, Ti, Fe, Ga, V, Cr, Co, Ni, Cu, Zn, Ge, Zr, Nb, Sb, La, Hf and Bi A method for producing ε-caprolactam from cyclonuclinonone oxime, characterized in that it is selected.

[Claim 5]

From cyclonucleanone oxime according to any one of claims 1 to 4

ε—caprolactam prepared using a method for producing caprolactam.

[Claim 6]

From Cyclonucleanone Oximes Using a Vapor Beckman Conversion Process

In the method for producing ε-caprolactam, Ε-capro from cyclonucleanone oxime using a zeolite material which is synthesized by adding an organic surfactant comprising two or more ammonium functional groups or containing one ammonium functional group and one amine functional group as a structural derivative Process for preparing lactam.

[Claim 7]

The method of claim 16,

The organic surfactant is a method for producing _ε -caprolactam from cyclonesananone oxime, characterized in that represented by the formula (1) or (2).

[Formula 1]

[Formula 2]

Where X is a halogen (CI, Br, I) anion or a hydroxide (this) anion.)

[Claim 8]

The method according to claim 7,

In Formula 1 and Formula 2, C1 is 8 to 22 carbon atoms, C2 is 3 to 6 carbon atoms, C3 is 1 to 8 carbon atoms, characterized in that for preparing ε—caprolactam from cyclohexanone oxime Way.

[Claim 9]

The method of claim 6,

The zeolite material is prepared by completely or partially removing the organic surfactant by calcining or chemical treatment. To prepare ε-caprolactam.

[Claim 10]

The method of claim 6,

[Claim 11]

The method of claim 6,

Metal elements included in the zeolitic material are Be, B, Al, Ti, Fe, Ga, V, Cr, Co, Ni, Cu, Zn, Ge, Zr, Nb, Sb, La, Hf and Bi A process for producing ε-caprolactam from cyclonuclinon oximes which is selected.

[Claim 12]

According to claim 16,

The zeolitic material is cyclonuxanon oxime, characterized in that is prepared through a crystallization process selected from the group consisting of hydrothermal synthesis, microwave heating and dry-gel synthesis Method for preparing ε-caprolactam from

[Claim 13]

An epsilon caprolactam manufactured using the method of manufacturing an epsilon caprolactam from the cyclonucleanone oxime according to any one of claims 6 to 12.

[Claim 14]

Gas phase Beckman conversion process from cyclonuxanon oxime

In the method for producing ε-caprolactam,

Synthesized by adding organic surfactants containing at least two ammonium functional groups or containing one ammonium functional group and one amine functional group as structural derivatives, delamination, pillaring, aqueous solution treatment, and silver exchange , Ε-caprolactam from cyclonuxanonone oxime using a zeolite material that is activated or modified using a post-treatment reaction selected from the group consisting of dealumination, metal loading and organic functionalization . [Claim 15]

The method of claim 14,

The organic surfactant is a method for producing _ε -caprolactam from clonuxanone oxime, characterized in that represented by the formula (1) or (2).

[Formula 1]

C1 C2 C3

XX ^"

[Formula 2]

X ^"

Where X is a halogen (CI, Br, I) anion or a hydroxide (OH) anion.