KR101345560B1 - High activity catalysts for epoxidation of dicyclopentadiene and preparation method thereof - Google Patents

Abstract

The present invention is used in the process of preparing a dicyclopentadiene dimer epoxy compound by the epoxidation reaction of the dicyclopentadiene dimer having a large molecular size by the liquid phase oxidation in the presence of hydrogen peroxide and high selectivity to dicyclopentadiene dimer and A high activity heterogeneous catalyst capable of obtaining a dicyclopentadiene dimer epoxy compound in high yield by exhibiting high conversion and a process for producing the same.

Description

High activity catalyst for epoxidation of dicyclopentadiene dimer and preparation method thereof {HIGH ACTIVITY CATALYSTS FOR EPOXIDATION OF DICYCLOPENTADIENE AND PREPARATION METHOD THEREOF}

The present invention relates to a high activity catalyst for epoxidation of dicyclopentadiene dimer and a method for preparing the same, and more particularly, in the process of preparing a dicyclopentadiene dimer epoxy compound by epoxidation of dicyclopentadiene dimer. It relates to a high activity heterogeneous catalyst and a method for preparing the same, which are used to exhibit high selectivity and high conversion rate.

The use of C ₅ fractions in the chemical industry is a very interesting area in terms of waste resources. In particular, cyclopentadiene containing a double bond contained in the oil can be easily oxidized to an acid catalyst or a metal catalyst to prepare an epoxy compound.

Epoxy compounds can be prepared from plastic additives used as stabilizers against heat or light or plasticizers that increase the flexibility and elasticity of lubricating oil additives, polyvinyl chloride (PVC).

In addition, epoxy compounds may be used as raw materials for materials such as alcohols, glycols, alkanoamines, carbonyl compounds, olefin compounds, polymers such as polyesters, polyurethanes, epoxy resins and the like because of the high reactivity of the oxirane ring. It is known that the physical properties of epoxy compounds having high oxirane oxygen values and low iodine values are better.

The epoxidation reaction of cyclopentadiene is influenced by the epoxidation method, catalyst and solvent. The most commonly used method is oxidation by organic peroxides. In situ epoxidation is a commercial process with peroxides produced by the simultaneous injection of acetic acid, formic acid and hydrogen peroxide.

Alkene epoxidation is one of the most important reactions for functionalizing hydrocarbons and epoxy compounds can give functionality quickly. Epoxy compounds are very beneficial intermediates for producing important products such as preservatives, pharmaceuticals, and additives. Their selective synthesis is of interest both academically and industrially.

Industrial production of epoxy compounds from the alkene oxidation reactions uses homogeneous catalysts such as peroxides. However, these methods generate a large amount of waste that pollutes the environment. From the standpoint of sustainable and green technology, heterogeneous catalysts have the advantages of separation of catalysts, reuse of catalysts and high selectivity. Therefore, attention has been paid to the development of a method for producing an epoxy compound that does not generate by-products using oxygen and hydrogen peroxide, which are safe and clean oxidants.

Titanosilicate is known to be the most effective heterogeneous catalyst, and TS-1 catalyst, which is known as a catalyst for producing epoxy compound, is known to exhibit high activity catalytic activity and selectivity in propylene epoxidation reaction using hydrogen peroxide as oxidant. However, the TS-1 catalyst is a ZSM-5 based catalyst and has a disadvantage in that the pore of the catalyst is small, thereby limiting the epoxidation reaction of small sized molecules.

As a prior art of the TS-1 catalyst described above, US Patent No. 6,066,750 discloses a heterogeneous catalyst capable of obtaining propylene oxide at high yield as a catalyst used in a high temperature and high pressure liquid phase process of epoxidizing propylene to propylene oxide. It is starting. The published document discloses the use of a catalyst having a (TiO ₂ / SiO ₂ ) structure and generally referred to as TS-1 as a heterogeneous catalyst used in the process of epoxidizing propylene to propylene oxide.

Meanwhile, catalysts such as Ti-Beta and mesoporous titanosilicates have been developed to overcome the limitation of the particle size of the TS-1 catalyst. Indeed, these materials showed effective catalytic activity in cyclododecene, cyclohexene, and derivatives of cyclohexane, which are larger in size than the TS-1 catalyst. Nevertheless, the presence of a weak acid point of Ti-Beta, the amorphous nature, and the hydrophilic properties of strong mesoporous materials can cause a decrease in reactivity and selectivity when hydrogen peroxide is used as an oxidant.

In order to solve the above problems, the present inventors have repeatedly studied to obtain the epoxidation reaction of a material having a large molecular size with high selectivity and yield, and as a result, a heterogeneous catalyst completed by replacing titanium with a large pore size zeolite. The present invention has been completed by discovering that it can provide a very good selectivity and yield for epoxidation of large molecular size materials such as dicyclopentadiene dimer.

Accordingly, an object of the present invention is to use a dicyclopentadiene epoxy compound in the process of preparing a dicyclopentadiene dimer epoxy compound by oxidizing a liquid having a large molecular size, in particular dicyclopentadiene dimer by liquid phase oxidation in the presence of hydrogen peroxide, The present invention provides a heterogeneous catalyst capable of exhibiting high selectivity and high conversion rate for diene dimers and a method for preparing the same.

In order to achieve the above object, the present invention is a heterogeneous catalyst used in the process of preparing a dicyclopentadiene dimer epoxy compound by the epoxidation reaction of dicyclopentadiene dimer, acid-treated zeolite molecular sieve and the zeolite Provided is a catalyst for the epoxidation reaction of dicyclopentadiene dimer comprising titanium exchanged with aluminum of molecular sieve.

In addition, the present invention is a method for producing a heterogeneous catalyst used in the process of preparing a dicyclopentadiene dimer epoxy compound by the epoxidation reaction of dicyclopentadiene dimer, the zeolite molecular sieve is immersed in an acidic solution and stirred Dicyclopenta comprising an acid treatment step (S1) and adding the acid treated zeolite molecular sieve and titanium precursor to an alcoholic solvent and stirring to exchange titanium with aluminum of the acid treated zeolite molecular sieve (S2). Provided is a method for producing a catalyst for epoxidation reaction of diene dimer.

In general, zeolites are defined as crystalline aluminosilicate materials in which uniform micropores (0.3 <diameter <2 nm) in the molecular size region are regularly arranged, including zeolites and similar materials There are various types. Among the various types of zeolites, zeolites having large pore sizes, such as zeolite X, zeolite Y, zeolite Beta, zeolite A, mordenite, and the like, can be used without limitation.

In one aspect of the invention, it is preferable to use a zeolite H-Y molecular sieve having a pore size of 7 to 9 mm 3 as the zeolite Y molecular sieve.

As a method for acid-treating the zeolite molecular sieve, a conventional organic acid or inorganic acid may be used. Preferably, 0.5M hydrochloric acid aqueous solution may be used as an acid solution, but is not limited thereto.

The process for acid treatment of the zeolite molecular sieve is preferably carried out by immersion in an acidic solution and stirred for 2 to 3 hours at 70 ~ 80 ℃.

Thereafter, the acid-treated zeolite molecular sieve is filtered and dried, and then added to an alcoholic solvent with a titanium precursor and stirred to replace titanium with aluminum of the acid-treated zeolite molecular sieve, followed by washing, drying and calcining. To prepare a catalyst for the epoxidation reaction of dicyclopentadiene dimer.

 The invention is a heterogeneous system that can exhibit high selectivity and high conversion for large molecular size dicyclopentadiene dimers used in the process of preparing dicyclopentadiene dimer epoxy compounds by epoxidation of dicyclopentadiene dimers. By providing a catalyst, the dicyclopentadiene dimer epoxy compound can be obtained in high yield.

Hereinafter, the manufacturing method of the catalyst for epoxidation reaction of the dicyclopentadiene dimer of this invention is demonstrated concretely.

First, the zeolite molecular sieve is immersed in an acidic solution and acidified by stirring (step S1).

In the present invention, step S1 is a pretreatment step for dissolving aluminum in the zeolite molecular sieve and replacing it with titanium, and acid treatment is performed by dipping and stirring the zeolite molecular sieve in an acidic solution.

In the preparation of the catalyst for epoxidation reaction of the dicyclopentadiene dimer of the present invention, zeolites having a large pore size, for example, a pore size of 7 GPa or more, can be used without limitation, and in particular, zeolite Y molecular sieves can be used. Preferably, zeolite HY molecular sieves having a pore size of 7 to 9 mm 3 can be used.

The acidic solution for acid treatment of the zeolite molecular sieve may be used without limitation, organic or inorganic acid, preferably 0.5M hydrochloric acid aqueous solution, but is not limited thereto.

In one embodiment of the present invention, the step S1 is preferably carried out by immersing the zeolite H-Y molecular sieve having a pore size of 8 에 in 0.5M hydrochloric acid aqueous solution and then stirred at 70 ~ 80 ℃ for 2 to 3 hours.

When the zeolite H-Y molecular sieve is immersed in 0.5M hydrochloric acid solution in the step S1 and then acid treated at 70 to 80 ° C. for more than 3 hours, the structure of a part of the zeolite H-Y molecular sieve may be destroyed.

After the acid treatment of the zeolite molecular sieve in step S1, it may be further filtered and dried.

Next, the acid-treated zeolite molecular sieve and titanium precursor are added to the alcohol solvent to replace titanium with aluminum of the acid-treated zeolite molecular sieve (step S2).

In step S2, the zeolite molecular sieve and the titanium precursor acid-treated in step S1 are added to the alcohol solvent and stirred to replace aluminum and titanium of the zeolite molecular sieve.

Titanium precursors include metal salts such as halides containing titanium metal elements, titanium metal nitrates, titanium metal sulfates, titanium metal acetates, titanium metal carbonyls, titanium metal alkoxides, Or hydrates thereof. Preferably, titanium metal alkoxide may be used, for example titanium butoxide (Ti (OBu) ₄ ) may be used, but is not limited thereto.

As the alcohol solvent used in the present invention, anhydrous alcohols such as ethanol anhydride may be used to remove H ₂ O, etc. in the zeolite molecular sieve, but are not necessarily limited thereto.

Thereafter, ion-exchanged titanium is applied to the acid-treated zeolite molecular sieve, followed by washing with anhydrous ethanol and the like, drying, and calcining at 350 to 450 ° C., preferably 400 ° C. to further dicyclopentadiene dimer. To prepare a catalyst for the epoxidation reaction.

The catalyst for epoxidation reaction of the dicyclopentadiene dimer of the present invention prepared as described above is prepared by replacing the acid-treated zeolite molecular sieve with titanium, and the titanium exchanged in the skeleton of the zeolite molecular sieve into a tetrahedral structure. It is formed to improve the catalytic reaction activity can exhibit a high selectivity and a high conversion rate for macromolecules such as dicyclopentadiene dimer.

The catalyst for the epoxidation reaction of the dicyclopentadiene dimer prepared according to the present invention in the process of producing a dicyclopentadiene dimer epoxy compound by epoxidation of the dicyclopentadiene dimer represented by Scheme 1 in the presence of hydrogen peroxide It can be used as a heterogeneous catalyst.

[Reaction Scheme 1]

The catalyst for epoxidation of dicyclopentadiene dimer according to the present invention has a larger pore size in the molecular sieve than the conventional TS-1 catalyst, Ti-Beta catalyst, etc. It can exhibit high selectivity and high conversion for clopentadiene dimer.

The method for preparing a dicyclopentadiene dimer epoxy compound using the catalyst for epoxidation reaction of the dicyclopentadiene dimer of the present invention may be carried out by a conventional epoxidation reaction method. In one aspect of the invention, the dicyclopentadiene dimer epoxy compound is added to a dicyclopentadiene dimer and the heterogeneous catalyst of the present invention in a solvent such as methanol in the presence of hydrogen peroxide in a reactor, such as a batch reactor, and reacts the same. Can be obtained. Specifically, 1 to 10 parts by weight of the heterogeneous catalyst of the present invention is preferably added to 100 parts by weight of dicyclopentadiene dimer, and the reaction may be performed at a temperature of 30 to 100 ° C. for 1 to 5 hours. In the present invention, the dicyclopentadiene dimer epoxy compound may be obtained by performing the epoxy reaction by the liquid phase oxidation in a high conversion rate of about 70% or more, preferably about 80% or more.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention. It is obvious to those who have knowledge. It is therefore intended that such variations and modifications fall within the scope of the appended claims.

[Example]

Example  One

5 g of zeolite H-Y720 (manufactured by ZEOLYST) and 100 ml of 0.5 M HCl aqueous solution were added thereto, followed by acid treatment by stirring at a temperature of 70 to 80 ° C. for 3 hours, and filtering the solid portion to dryness. The dried solid was added 10 g of titanium butoxide in 100 ml anhydrous ethanol for 30 minutes and stirred at 80 ° C. for 4 hours. The solid portion was filtered off, washed with anhydrous ethanol and dried. The dried solid was calcined at a temperature of 400 ° C. to prepare a Ti-HY720 catalyst containing titanium, and SiO ₂ / Al ₂ O ₃ and surface area of the catalyst were measured and shown in the following [Table 1].

Example 2

Zeolite HY760 (ZEOLYST Co., Ltd.), except for using 5g to to Example 1 were prepared by the same way as in the Ti-HY760 catalyst containing titanium, measuring the SiO ₂ / Al ₂ O ₃ and the surface area of the catalyst [ Table 1].

Example  3

A Ti-HY780 catalyst containing titanium was prepared in the same manner as in Example 1 except that 5 g of zeolite H-Y780 (manufactured by ZEOLYST) was used, and SiO ₂ / Al ₂ O ₃ and the surface area of the catalyst were measured and then [ Table 1].

Comparative Example  One

Ti-USY was prepared using zeolite HUSY manufactured by ZEOLYST in order to compare with Examples 1-3. 5 g of zeolite HUSY (manufactured by ZEOLYST) and 100 ml of 0.5 M HCl aqueous solution were added thereto, followed by acid treatment with stirring at a temperature of 70 to 80 ° C. for 3 hours, and the solid portion was filtered and dried. The dried solid was added 10 g of titanium butoxide in 100 ml anhydrous ethanol for 30 minutes and stirred at 80 ° C. for 4 hours. The solid portion was filtered off, washed with anhydrous ethanol and dried. The dried solid was calcined at a temperature of 400 ° C. to prepare a Ti-USY catalyst containing titanium, and SiO ₂ / Al ₂ O ₃ and the surface area of the catalyst were measured and shown in the following [Table 1].

Comparative Example  2

TS-1 was prepared for comparison with Examples 1-3. 10 g of tetraethylsilicate, 0.5 g of tetrabutyl ortitanate and 3.6 g of tetrapropyl ammonium hydroxide were dissolved in 100 g of distilled water, followed by stirring for 3 days at 170 ^° C. in a high pressure reactor coated with Teflon. The crystallized solid was filtered, dried at 120 ^° C. for 12 hours, and calcined at 550 ^° C. to prepare TS-1. SiO ₂ / Al ₂ O ₃ and the surface area of the prepared catalyst were measured and shown in the following [Table 1].

Test Example 1 Epoxidation of Dicyclopentadiene Dimer Using Catalyst

10 wt% of the catalyst in Examples 1 to 3 and Comparative Examples 1 and 2, 80 wt% of dicyclopentadiene dimer, and 10 wt% of hydrogen peroxide were added together with methanol to a batch reactor and reacted at 50 ° C. for 5 hours. The epoxidation reaction of dicyclopentadiene dimer was performed. Thereafter, the conversion rate of the dicyclopentadiene dimer epoxy compound prepared by the epoxidation reaction was measured and shown in the following [Table 1].

division SiO ₂ / Al ₂ O ₃ Surface area (m ² / g) Conversion Rate (%) Example 1 30 780 90.1 Example 2 60 720 78.0 Example 3 80 780 85.8 Comparative Example 1 5 690 68.2 Comparative Example 2 30 500 51.1

Referring to [Table 1], it was confirmed that the catalysts of Examples 1 to 3 prepared according to the present invention showed a higher conversion rate for the dicyclopentadiene dimer epoxy compound than the comparative examples.

Test Example 2 Epoxidation of Dicyclopentadiene Dimer Using Various Molecular Sieve Catalysts Containing Titanium

After the molecular sieve catalyst containing the known titanium was reacted under the same conditions as in Test Example 1, the conversion was measured and shown in the following [Table 2].

division % Conversion for epoxy compounds Ti / Al ₂ O ₃ 2.7 Ti / zeolite Y 5.1 TiCl ₃ 0.5 TS-2 42.3 Ti-Beta 35.1

Referring to Table 2, it was confirmed that even if the catalyst simply contains titanium, it could not exhibit high conversion for the dicyclopentadiene dimer epoxy compound.

Claims (10)

As a method for producing a heterogeneous catalyst used in the process of preparing a dicyclopentadiene dimer epoxy compound by the epoxidation reaction of dicyclopentadiene dimer,
Acid-treating the macroporous zeolite molecular sieve of 7 Pa or more (S1) and agitating the acid-treated zeolite molecular sieve and titanium precursor to exchange aluminum of the acid-treated zeolite molecular sieve with titanium (S2); ,
In step (S2), the acid-treated zeolite molecular sieve and titanium precursor are stirred under anhydrous alcoholic solvent,
The catalyst is a method for producing a catalyst for the epoxidation reaction of dicyclopentadiene dimer, characterized in that the metal of the macromolecular zeolite molecular sieve of 7 Å or more exchanged with titanium. The method of claim 1, wherein the zeolite molecular sieve is selected from zeolite Y, zeolite X, zeolite A or zeolite Beta. The method for preparing a catalyst for epoxidation reaction of dicyclopentadiene dimer according to claim 1, wherein the step (S1) is followed by filtration and drying. The method of claim 1, wherein the titanium precursor is a titanium alkoxide. The catalyst for epoxidation of dicyclopentadiene dimer according to claim 1, further comprising the step of exchanging aluminum of the zeolite molecular sieve with titanium, followed by washing with water, drying and calcining at 350 to 450 ° C. Manufacturing method. As a heterogeneous catalyst used in the process of preparing a dicyclopentadiene dimer epoxy compound by the epoxidation reaction of a dicyclopentadiene dimer,
The catalyst is a catalyst for epoxidation of dicyclopentadiene dimer having a structure in which the metal of the macromolecular zeolite molecular sieve of 7 Pa or more is exchanged with titanium, and prepared by the method according to claim 1. The catalyst for epoxidation of dicyclopentadiene dimer according to claim 6, wherein the zeolite molecular sieve is selected from zeolite Y, zeolite X, zeolite A or zeolite Beta. The catalyst for epoxidation of dicyclopentadiene dimer according to claim 6 or 7, wherein the zeolite molecular sieve is zeolite H-Y having a pore size of 7 to 9 mm 3. 8. The epoxidation reaction of the dicyclopentadiene dimer according to claim 6 or 7, wherein the heterogeneous catalyst is selected from Ti-zeolite Beta, Ti-zeolite X, Ti-zeolite Y or Ti-zeolite A. Catalyst.
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