KR101603610B1 - Nano-porous sponge or sheet type zeolite catalyst for synthesis of p-xylene from 2.5-dimethylfuran and ethylene - Google Patents

Nano-porous sponge or sheet type zeolite catalyst for synthesis of p-xylene from 2.5-dimethylfuran and ethylene Download PDF

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KR101603610B1
KR101603610B1 KR1020140105501A KR20140105501A KR101603610B1 KR 101603610 B1 KR101603610 B1 KR 101603610B1 KR 1020140105501 A KR1020140105501 A KR 1020140105501A KR 20140105501 A KR20140105501 A KR 20140105501A KR 101603610 B1 KR101603610 B1 KR 101603610B1
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zeolite
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catalyst
xylene
dimethylfuran
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김철웅
정순용
김태완
김상윤
유룡
김정철
김영진
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한국화학연구원
기초과학연구원
한국과학기술원
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Abstract

The present invention relates to a nanoporous sponge or sheet-type zeolite catalyst which is applied to a process for selectively synthesizing para-xylene by cycloaddition and dehydration reaction using 2,5-dimethylfuran and ethylene as starting materials .
The zeolite catalyst of the present invention has a very high specific surface area and allows the mass transfer of the reactant and the product to easily occur in the pore structure and has the advantage of inhibiting the formation of side reactants at the active site, The conversion of furan and the yield of para-xylene are remarkably increased. In particular, it is useful as a catalyst for the synthesis of para-xylene using 2,5-dimethylfuran derived from biomass as a raw material.

Description

Nano-porous sponge or sheet type zeolite catalysts for synthesis of para-xylene from 2,5-dimethylfuran and ethylene in the process of synthesizing para-xylene from 2,5-dimethylfuran and ethylene }

The present invention relates to a nanoporous sponge or sheet-type zeolite catalyst which is applied to a process for selectively synthesizing para-xylene by cycloaddition and dehydration reaction using 2,5-dimethylfuran and ethylene as starting materials .

In recent years, the demand for crude oil produced from fossil raw materials has been steadily increasing, while the number and average size of large oil fields has been remarkably decreasing. Therefore, much efforts are being made to create new markets for the production of chemical materials and basic raw materials using petroleum substitute raw materials as measures to cope with exhaustion of petroleum resources worldwide. Currently, biomass is the most popular oil substitute raw material.

Various methods for producing para-xylene from 2,5-dimethylfuran derived from biomass have been disclosed. [Non-Patent Documents 1, 2 and 3] As a typical method, there is a method of producing para-xylene by cycloaddition and dehydration of 2,5-dimethylfuran and ethylene. In this method, a heterogeneous zeolite catalyst is used as a catalyst. For example, a method using various commercially available zeolite catalysts such as HY-zeolite, MFI zeolite, and beta zeolite is proposed. In the above non-patent documents, it is reported that HY-zeolite increases the yield of para-xylene compared with H-ZSM-5, H-silica-alumina, silicate-I, and Muliite. That is, when CBV 600 (Si / Al 2 = 2.6), CBV 760 (Si / Al 2 = 30) or CBV 780 (Si / Al 2 = 40), which are HY-zeolites having micro pore sizes, It is reported that the reaction characteristics and the selectivity are excellent regardless of the kind of the reaction. It is also reported that beta zeolite CP814C (Si / Al 2 = 38) or CP814E (Si / Al 2 = 25) exhibits superior para-xylene selectivity at 250 ° C compared to HY-zeolite. However, the zeolite catalyst used in this method has a typical zeolite structure with a micro-sized pore structure developed.

In addition, in the reaction using the liquid reaction material, the reaction occurs at the catalytic active sites existing outside and inside the catalyst pores, so that the products produced in the catalyst pores must be easily discharged out of the catalyst pores. When the pore size of the zeolite is too small There is a problem that the produced xylene reacts with ethylene and an alkylaromatic material is produced as a side reaction, thereby lowering the yield of para-xylene. Namely, when 2,5-dimethylfuran in a liquid state is reacted with ethylene under high pressure conditions in the presence of a solvent, a gas phase liquid phase in which ethylene, liquid phase 2,5-dimethylfuran and a solvent and a solid phase catalyst coexist This mixed reaction occurs. In this reaction, mass transfer, in which the liquid phase, 2,5-dimethylfuran, moves to the catalytic active sites in the pores, becomes a very important reaction factor. That is, this reaction is a step in which the liquid phase of 2,5-dimethylfuran reacts with ethylene in the gaseous phase at the reaction active site (acid point) of the zeolite, and when the zeolite catalyst having a micropore size is used, And the p-xylene produced as a result of the reaction can not easily escape out of the pores of the catalyst as a liquid phase and is converted into a side reaction product.

In addition, U.S. Patent No. 7,387,978 discloses activated carbon, silica, alumina, zirconia, and zeolite washed with activated carbon, phosphoric acid or the like as a catalyst for the production of para-xylene using 2,5-dimethylfuran and ethylene, In the figure, activated carbon having a large specific surface area is most suitable. However, the activated carbon has a large specific surface area as compared with other catalysts, but does not have a Bsted acid point acting as an active point in the reaction, thereby increasing the selectivity of para-xylene dehydration from 2,5-dimethylfuran There is a limit to doing this.

Further, in order to solve the disadvantage of a zeolite catalyst having a micro-sized pore structure, a method of producing para-xylene from biomass-derived 2,5-dimethylfuran using mesoporous zeolite was proposed by the present inventors There is also a patent application. [Korean Patent Application 10-2013-0039745]. In this method, para-xylene was produced with a yield of 60% or higher using a mesoporous HY-zeolite catalyst having an average pore size of 2 to 50 nm.

The inventors of the present invention have studied to develop a catalyst for the production of para-xylene having a higher yield than the above-mentioned methods. As a result, it has been confirmed that the use of a nanoporous sponge or a zeolite catalyst in the form of a sheet can significantly increase the selectivity of para-xylene compared with the conventional catalyst.

None of the reports reported to date disclose the use of nanoporous sponges or zeolites in the form of sheets as catalysts in the reaction for the production of para-xylene from 2,5-dimethylfuran.

Patent Document 1: U.S. Patent No. 7,387,978 Patent Document 2: Korean Patent Application No. 10-2013-0039745

Non-Patent Document 1: C. Luke Williams et al., ACS Catal, 2, (2012), 935-939 Non-Patent Document 2: J. N. Chheda, Y. Roman-Leshkov and J. A. Dumesic, Green Chem., 9, (2007) 342350 Non-Patent Document 3: Chun-Chih Chang et al., Green Chemistry, 16, (2014), 585-588

It is an object of the present invention to provide a novel catalyst to be used in the reaction for selectively producing para-xylene using 2,5-dimethylfuran.

In order to solve the above problems, the present invention is a catalyst applied to a process for selectively synthesizing para-xylene by cycloaddition and dehydration using 2,5-dimethylfuran and ethylene as starting materials, The present invention provides a zeolite catalyst in the form of nanoporous sponges or sheets with significantly improved specific surface area compared to bulk-zeolite.

Further, the present invention provides a method for producing para-xylene by liquid phase reaction of 2,5-dimethylfuran derived from biomass and ethylene under the condition that the zeolite catalyst and the solvent are present.

The nano-porous sponge or sheet-type zeolite of the present invention is applied to a process for selectively producing para-xylene from 2,5-dimethylfuran simultaneously in a reactor in which a Diels-Alder cyclization addition reaction and a dehydration reaction occur simultaneously in the reactor Exhibit excellent catalytic activity.

Further, since the zeolite catalyst according to the present invention has nano-sized pores, compared with commercial zeolite catalysts having pores of known micro size, it is possible to produce para-xylene using biomass-derived 2,5- To improve the conversion of 2,5-dimethylfuran and the yield of p-xylene produced.

In addition, since the zeolite catalyst of the present invention has a much larger specific surface area than that of the conventional bulk zeolite catalyst, the acid sites are well developed, and mass transfer of the reactants and products occurs easily on the surface of the catalyst, And the selectivity of para-xylene is greatly increased.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart sequentially showing an example of a process for producing a nanoporous sponge-type BEA zeolite catalyst as a zeolite catalyst representing the present invention. FIG.
(B) nanoporous sponge-type and bulk MRE zeolites, (c) nanoporous sponge-type and bulk-type MTW zeolites, (d) nanoporous sheet type, and Nitrogen adsorption-desorption curves for each of the bulk MFI zeolites.
(B) a nanoporous sponge type and bulk MRE zeolite; (c) a nanoporous sponge type and bulk type MTW zeolite; (d) a nanoporous sheet type; and ≪ / RTI > shows a powder X-ray diffraction pattern for each of the bulk MFI zeolites.
FIG. 4 is a graph showing the results of (a) nanoporous sponge type beta zeolite, (b) nanoporous sponge type MRE zeolite, (c) nanoporous sponge type MTW zeolite, (d) nanoporous sheet type and bulk MFI zeolite TEM photograph.
(B) nano-porous sponge and bulk MRE zeolites, (c) nanoporous sponge-type and bulk-type MTW zeolites, (d) nanoporous sheet type, and SEM photographs of each of the bulk MFI zeolites.

The present invention relates to a zeolite in the form of nanoporous sponges or sheets, which is used as a catalyst in the process of selectively synthesizing para-xylene using 2,5-dimethylfuran and ethylene as starting materials.

It is more preferable that 2,5-dimethylfuran is 2,5-dimethylfuran derived from biomass in view of environmental friendliness.

 The process for the preparation of para-xylene by the reaction of 2,5-dimethylfuran with ethylene consists of a two-step reaction in terms of the reaction mechanism. The first step is a Diels-Alder cycloaddition reaction, and the second step is a dehydration reaction. The first cyclisation reaction takes place in the confinement where contact between the reactants occurs in the pores and the second dehydration reaction takes place at the Bronsted acid site. Therefore, the zeolite catalyst having the micropores of 1 nm or less and the Brensted acid sites simultaneously becomes active. However, in the case of 2,5-dimethylfuran and the product para-xylene used as the raw material, the molecular size is similar to that of the zeolite, so that the mass transfer of the molecules is not easy. As a result, a side reaction product is generated at the reaction active site, so that the selectivity of the reaction is lowered, and the activity of the reaction is lowered by blocking these active sites. Therefore, the present invention is characterized in that a nano-porous sponge and a zeolite in the form of a sheet are specifically manufactured and used as means for solving such problems.

The nanoporous sponge-type zeolite catalyst of the present invention has a crystal thickness of about 4 to 6 nm, and the nanoporous sheet-type zeolite catalyst has a crystal thickness of about 2 to 7 nm, preferably about 2 to 4 nm.

In addition, the nanoporous sponge or sheet-type zeolite catalyst of the present invention has a BET specific surface area of 380 to 850 m 2 / g, a specific surface area several tens times larger than that of conventional commercial zeolite, and a very large amount of Bronsted There are acid points.

In addition, the nanoporous sponge or sheet-type zeolite catalyst of the present invention has a mesoporous structure having a uniform pore size with an average pore size of about 2 to 7 nm, preferably about 4 nm, 2,5-Dimethylfuran and the product paraxylene are suitable for migration, so that the reactants easily diffuse within the catalyst to facilitate contact with the catalyst, and the product can be easily removed from the catalyst and converted to the side reaction can do.

The method of preparing the nanoporous sponge or sheet-type zeolite catalyst according to the present invention will be described in more detail as follows.

A method for producing a nanoporous sponge type or sheet type zeolite catalyst according to the present invention comprises:

I) mixing a silica source, an alumina source and a template agent, and then gelling the amorphous silica aluminum mixed gel;

Ii) crystallizing the gel into zeolite crystals in the form of a sponge or sheet;

Iii) washing, drying and calcining the zeolite crystals; And

Iv) ion exchanging the calcined zeolite; .

Hereinafter, the method for producing the nanoporous sponge type or sheet type zeolite according to the present invention will be described in more detail with respect to each step.

The step i) is a step of mixing and gelling the raw materials. That is, the raw material is mixed and aged to form an amorphous silica aluminum mixed gel.

As the raw material, a silica source, an alumina source, and a template agent may be used. The silica source and the alumina source are generally used in the art, and there is no particular limitation on the kind thereof. Specific examples of the silica source include at least one selected from tetraethylorthosilicate, silica sol, silica gel, sodium silicate, and fumed silica. Specific examples of the alumina source include aluminum alkoxide, sodium aluminate (NaAlO 2 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), aluminum chloride (AlCl 3 ), boehmite, aluminum hydroxide (Al 3 ), and the like can be used. In addition, the framework structure of the zeolite produced by the present invention is beta, MRE, MTW, MFI and the like, and the production method of these zeolites is described in Science 333 (2011) 328-332; ACS Catal. 3 (2013) 192-195), and the like.

In the present invention, an organic surfactant composed of a head portion containing an ammonium functional group and a tail of a hydrophobic alkyl is used as a template as shown in Formula 1 below.

[Chemical Formula 1]

Figure 112014076906467-pat00001

(Wherein C1 is a substituted or unsubstituted alkyl group having 10 to 25 carbon atoms, C2 is a substituted or unsubstituted alkyl group having 3 to 6 carbon atoms,

Figure 112014076906467-pat00002
ego; C3 is a substituted or unsubstituted alkyl group having 5 to 25 carbon atoms; and n is an integer of 1 to 10 as the number of repetitions of the ammonium group,

The template shown in the above formula (1) is specially designed for producing a nanoporous sponge or sheet-like zeolite. After forming a micelle (surfactant micel), it interacts with a silica source and an alumina source to form a zeolite . In addition, the pore structure and the mesoporous structure of the zeolite can be formed at the same time by selecting the casting agent.

Representative examples of the main agent used in the present invention are as follows. The crystal structure and thickness of the zeolite are determined by the selection of the main agent, and the number of ammonium (N + ) is increased, so that the thickness of the nodule structure can be thickened.

C 22 H 45 -N + (CH 3) 2 - [C 6 H 12 -N + (CH 3) 2 -CH 2 - (C 6 H 4) -CH 2 -N + (CH 3) 2] 2 - C 6 H 12 -N + (CH 3 ) 2 -C 22 H 45 (weak to C 22 -6 N);

C 16 H 33 -N + (CH 3 ) 2 -C 6 H 12 -N + (CH 3 ) 2 -C 6 H 12 (weak in C 16 -6-6 );

C 22 H 45 -N + (CH 3) 2 - [C 6 H 12 -N + (CH 3) 2] 3 -N + (CH 3) 2 -C 6 H 12 (C 22-6-6-6 -6 ).

The step ii) is a step of crystallizing the gel to form a zeolite crystal in the form of a sponge or a sheet. Specifically by injecting an amorphous silica aluminum mixed gel into a high pressure reactor and heating at a temperature of 120 ° C to 180 ° C for 3 to 5 days.

The step iii) is a step of obtaining the crystallized zeolite by a conventional method such as filtration and centrifugation, and then washing, drying and calcining to remove organic substances including the crude zeolite.

The washing is a process in which the zeolite crystals are repeatedly washed with distilled water several times until the pH of the zeolite crystals becomes neutral. The drying is carried out at a temperature of 100 ° C to 150 ° C for 10 to 20 hours to completely remove residual moisture. The calcination may be carried out at a temperature of 550 ° C to 600 ° C and an air atmosphere for 3 to 6 hours. The above filtration, washing, drying and calcination methods are not particularly limited in the present invention.

The step iv) is a step of ion-exchanging the calcined zeolite. The zeolite prepared through steps i) to iii) is prepared in the form of a cation by the acid or base used in the sol-gel process. For example, a sodium cation (Na + ) is bonded to a zeolite terminal. A sodium cation (Na + ) can be replaced with a hydrogen cation (H + ) through ion exchange.

The ion exchange method is also carried out by a conventional method. After the ion exchange, the zeolite catalyst of the present invention is prepared by washing, drying and calcining in the same manner as in the step iii).

Para-xylene is selectively prepared from 2,5-dimethylfuran by using the zeolite catalyst prepared through the above-described production method. Specifically, 2,5-dimethylfuran is mixed with a solvent, and then a zeolite catalyst is added to the solution. Then, while maintaining the temperature of the reactor at 280 to 330 ° C, the pressure of the reactor was maintained at 50 to 60 atm while injecting ethylene gas into the reactor. The reaction was allowed to proceed while maintaining the above reaction temperature and reaction pressure to prepare para-xylene. As the reaction solvent, aliphatic or aromatic hydrocarbons having 5 to 12 carbon atoms such as n-hexane and n-heptane can be used.

When the reaction was carried out in the presence of a nanoporous sponge type or sheet type zeolite catalyst according to the present invention, the conversion of 2,5-dimethylfuran was 83.7% or more and the selectivity of para-xylene was 67.2% or more.

The present invention will now be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

[Preparation Example] Preparation of catalyst

Preparation Example 1. Preparation of beta zeolite catalyst in nanoporous sponge form

Beta-zeolite in the form of nanoporous sponge was prepared on the basis of the process drawing shown in Fig.

That is, the organic templating agent surfactant C 22 -6N [C 22 H 45 -N + (CH 3) 2 -C 6 H 12 -N + (CH 3) 2 -CH 2 - (C 6 H 4) -CH 2 -N + (CH 3 ) 2 -C 6 H 12 -N + (CH 3 ) 2 -CH 2 - (C 6 H 4 ) -CH 2 -N + (CH 3 ) 2 -C 6 H 12 -N + (CH 3 ) 2 -C 22 H 45 ] (Br - ) 2 (Cl - ) 4 ] was used. The masterbatch, sodium aluminate, sodium hydroxide, and distilled water were placed in a polypropylene container and stirred at 60 ° C for 2 hours. Then, tetraethyl orthosilicate was added and vigorously shaken, followed by further stirring for 6 hours. The mixed solution, which had been stirred, was gelled with amorphous silica aluminum mixed gel having a white color. In this connection, the composition of the mixed solution is 1 C 22 -6N: 30 SiO 2 : 1 Al 2 O 3: 3.34 Na 2 O: H 2 O molar ratio was prepared in 1070.

In order to crystallize the amorphous silica-aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at a temperature of 140 ° C for 5 days to form zeolite crystals. The prepared zeolite crystals were cooled to room temperature and then filtered to separate into an aqueous solution layer and a solid matter layer. The separated zeolite crystals were washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at a temperature of 100 ° C for 12 hours, and the dried zeolite was calcined for 4 hours in an air atmosphere at a temperature of 580 ° C. The calcined zeolite exists in the Na-BEA form with sodium (Na) attached at the terminal end, and the zeolite is ion-exchanged using 1M NH 4 NO 3 aqueous solution to prepare zeolite in the form of H-BEA. At this time, the ion exchange was performed by repeating the process of immersing zeolite in 1M NH 4 NO 3 aqueous solution at a temperature of 25 ° C and stirring for 30 minutes three times, and the zeolite subjected to ion exchange was neutralized And then dried at 100 ° C for 12 hours, and calcined at 580 ° C for 4 hours in an air atmosphere to prepare a zeolite.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. According to the above results, it can be confirmed that the prepared zeolite is a nano-porous sponge-like beta zeolite and has an average crystal thickness of 4 nm and a specific surface area of 850 m 2 / g.

Comparative Preparation Example 1. Preparation of bulk beta zeolite catalyst

The structural derivative used in the present invention is tetraethylammonium hydroxide. The structural derivative is transparently mixed with sodium chloride, potassium chloride and distilled water. After the addition of fumed silica, the mixture was vigorously shaken and stirred for 2 hours. Sodium hydroxide, sodium aluminate and distilled water were mixed and mixed, followed by stirring at room temperature for 2 hours. After the stirring was completed, the mixed solution was gelled with a white amorphous silica aluminum mixed gel. The composition of the mixed solution was 25 TEAOH: 50 SiO 2 : 1.66 Al 2 O 3 : 0.4 NaOH: 0.9 NaCl: 2.0 KCl: 1070 H 2 O molar ratio.

In order to crystallize the amorphous silica-aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at a temperature of 140 ° C for 5 days to form zeolite crystals. The prepared zeolite crystals were cooled to room temperature and then filtered to separate into an aqueous solution layer and a solid matter layer. The separated zeolite crystals were washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at a temperature of 100 ° C for 12 hours, and the dried zeolite was calcined for 4 hours in an air atmosphere at a temperature of 580 ° C. The calcined zeolite exists in the Na-BEA form with sodium (Na) attached at the terminal end, and the zeolite is ion-exchanged using 1M NH 4 NO 3 aqueous solution to prepare zeolite in the form of H-BEA. At this time, the ion exchange was carried out by immersing zeolite in 1M NH 4 NO 3 aqueous solution at a temperature of 25 ° C and stirring for 30 minutes three times, and the zeolite subjected to the ion exchange had a pH of neutral , Followed by drying at a temperature of 100 ° C for 12 hours. The zeolite was calcined in an air atmosphere at 580 ° C for 4 hours to prepare a zeolite.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. From the above results, it can be confirmed that the prepared zeolite is a bulk type beta zeolite having a specific surface area of 450 m 2 / g.

Preparation Example 2. Preparation of nanoporous sponge MRE zeolite catalyst

The casting agent organic surfactant C 22 -6 N according to the present invention was used, and the above-mentioned masterbatch, sodium aluminate, sodium hydroxide and distilled water were placed in a polypropylene container and stirred at 60 ° C for 2 hours. After adding tetraethyl orthosilicate, the mixture was vigorously shaken and stirred for 6 hours. After the stirring was completed, the mixed solution was gelled with a white amorphous silica aluminum mixed gel. The composition of the mixed solution was 1.67 C 22 -6 N: 100 SiO 2 : 0.5 Al 2 O 3 : 13 Na 2 O: 3000 H 2 O in a molar ratio.

In order to crystallize the amorphous silica aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at a temperature of 150 ° C. for 3 days to form zeolite crystals. The prepared zeolite crystals were cooled to room temperature and then filtered to separate into an aqueous solution layer and a solid matter layer. The separated zeolite crystals were washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at a temperature of 100 ° C for 12 hours, and the dried zeolite was calcined for 4 hours in an air atmosphere at a temperature of 580 ° C. The calcined zeolite exists in the form of Na-MRE with sodium (Na) attached at the terminal end, and zeolite in the form of H-MRE was prepared by ion-exchanging the zeolite with 1M NH 4 NO 3 aqueous solution. At this time, the ion exchange was performed by repeating the process of immersing zeolite in 1M NH 4 NO 3 aqueous solution at a temperature of 25 ° C and stirring for 30 minutes three times, and the zeolite subjected to ion exchange was neutralized And then dried at 100 ° C for 12 hours, and calcined at 580 ° C for 4 hours in an air atmosphere to prepare a zeolite.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. According to the above results, it can be confirmed that the prepared zeolite is a nanoporous sponge type MRE zeolite having an average crystal thickness of 4 nm and a specific surface area of 380 m 2 / g.

Comparative Preparation Example 2. Preparation of Bulk MRE Zeolite Catalyst

The structural derivative used in the present invention was hexamethonium bromide (HMBr), which was transparently mixed with the structural derivative, sodium aluminate, sodium hydroxide and distilled water. Colloidal silica (Ludox AS-40) was added thereto, followed by stirring at room temperature for 3 hours. After the stirring was completed, the mixed solution was gelled with a white amorphous silica aluminum mixed gel. The composition of the mixed solution was 2.3 HMBr: 100 SiO 2 : 1 Al 2 O 3 : 8.5 Na 2 O: 2000 H 2 O molar ratio.

In order to crystallize the amorphous silica aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at 160 ° C. for 5 days to form zeolite crystals. The prepared zeolite crystals were cooled to room temperature and then filtered to separate into an aqueous solution layer and a solid matter layer. The separated zeolite crystals were washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at a temperature of 100 ° C for 12 hours, and the dried zeolite was calcined for 4 hours in an air atmosphere at a temperature of 580 ° C. The calcined zeolite exists in the form of Na-MRE with sodium (Na) attached at the terminal end, and zeolite in the form of H-MRE was prepared by ion-exchanging the zeolite with 1M NH 4 NO 3 aqueous solution. At this time, the ion exchange was carried out by immersing zeolite in 1M NH 4 NO 3 aqueous solution at a temperature of 25 ° C and stirring for 30 minutes three times, and the zeolite subjected to the ion exchange had a pH of neutral , Followed by drying at a temperature of 100 ° C for 12 hours. The zeolite was calcined in an air atmosphere at 580 ° C for 4 hours to prepare a zeolite.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. From the above results, it can be confirmed that the prepared zeolite is a bulk MRE zeolite having a specific surface area of 160 m 2 / g.

Production Example 3. Preparation of nanoporous sponge MTW zeolite catalyst

The casting agent organic surfactant C 22 -6 N according to the present invention was used, and the above-mentioned masterbatch, sodium aluminate, sodium hydroxide and distilled water were placed in a polypropylene container and stirred at 60 ° C for 2 hours. After adding tetraethyl orthosilicate, the mixture was vigorously shaken and stirred for 6 hours. After the stirring was completed, the mixed solution was gelled with a white amorphous silica aluminum mixed gel. The composition of the mixed solution was 3.33 C 22 -6 N: 100 SiO 2 : 1 Al 2 O 3 : 13 Na 2 O: 4500 H 2 O molar ratio.

In order to crystallize the amorphous silica aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at a temperature of 150 ° C. for 3 days to form zeolite crystals. The zeolite crystals were cooled to room temperature and then separated by filtration into an aqueous solution layer and a solid layer. The separated zeolite crystals were washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at a temperature of 100 ° C for 12 hours, and the dried zeolite was calcined for 4 hours in an air atmosphere at a temperature of 580 ° C. The calcined zeolite is in the form of Na-MTW with sodium (Na) attached at the terminal end, and zeolite in the form of H-MTW was prepared by ion-exchanging the zeolite with 1M NH 4 NO 3 aqueous solution. At this time, the ion exchange was carried out three times by immersing zeolite in 1 M NH 4 NO 3 aqueous solution at a temperature of 25 ° C. and stirring for 30 minutes. The zeolite subjected to ion exchange was neutralized until the pH became neutral After thoroughly washing, it was dried at a temperature of 100 ° C for 12 hours, and calcined in air atmosphere at 580 ° C for 4 hours to prepare a zeolite.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. According to the above results, it can be confirmed that the prepared zeolite is a nanoporous sponge type MTW zeolite having an average crystal thickness of 4 nm and a specific surface area of 470 m 2 / g.

Comparative Preparation Example 3. Preparation of Bulk MTW Zeolite Catalyst

The structural derivative used in the present invention was methyltriethylammonium chloride (MTEACl), and the above structural derivative and distilled water were mixed. Sodium silicate solution, aluminum nitrate solution and sulfuric acid solution were mixed and stirred at room temperature for 6 hours. After the stirring was completed, the mixed solution was gelled with a white amorphous silica aluminum mixed gel. In this connection, the composition of the mixed solution is 20 MTEACl: 100 SiO 2: 1 Al 2 O 3: 30 Na 2 O: 17 H 2 SO 4: H 2 O molar ratio was prepared in 5000.

In order to crystallize the amorphous silica aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at 160 ° C. for 5 days to form zeolite crystals. The prepared zeolite crystals were cooled to room temperature and then filtered to separate into an aqueous solution layer and a solid matter layer. The separated zeolite crystals were washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at a temperature of 100 ° C for 12 hours, and the dried zeolite was calcined for 4 hours in an air atmosphere at a temperature of 580 ° C. The calcined zeolite is in the form of Na-MTW with sodium (Na) attached at the terminal end, and zeolite in the form of H-MTW was prepared by ion-exchanging the zeolite with 1M NH 4 NO 3 aqueous solution. At this time, the ion exchange was carried out by immersing zeolite in 1M NH 4 NO 3 aqueous solution at a temperature of 25 ° C and stirring for 30 minutes three times, and the zeolite subjected to the ion exchange had a pH of neutral , Followed by drying at a temperature of 100 ° C for 12 hours. The zeolite was calcined in an air atmosphere at 580 ° C for 4 hours to prepare a zeolite.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. From the above results, it can be confirmed that the produced zeolite is a bulk type MTW zeolite and has a specific surface area of 280 m 2 / g.

Production Example 4. Preparation of nanoporous sheet type MFI zeolite catalyst having a crystal thickness of 2.5 nm

A mold-less organic surfactant (C 16-6-6 Br 2 ) was used, and the above-mentioned syringe , sodium silicate and distilled water were placed in a polypropylene container and stirred at 60 ° C for 12 hours. After addition of sodium aluminate and distilled water, the mixture was further stirred for 12 hours, sulfuric acid and distilled water were added, and the mixture was stirred for 12 hours. After the stirring was completed, the mixed solution was gelled with a white amorphous silica aluminum mixed gel. The composition of the mixed solution was 7.5 C 16-6-6 Br 2 : 100 SiO 2 : 1 Al 2 O 3 : 29.89 Na 2 O: 23.23 H 2 SO 4 : 4000 H 2 O molar ratio.

To crystallize the amorphous silica-aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at a temperature of 150 ° C for 5 days to form zeolite crystals. The prepared zeolite crystals were cooled to room temperature and then centrifuged to separate into an aqueous solution layer and a solid matter layer. The separated zeolite crystals were washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at 100 ° C. for 12 hours, and the dried zeolite was calcined in an air atmosphere at a temperature of 550 ° C. for 4 hours. The calcined zeolite was in the form of Na-ZSM-5 with sodium (Na) attached at the terminal end and zeolite in the form of H-ZSM-5 was prepared by ion exchange of zeolite with 1N NH 4 NO 3 . The ion exchange was carried out by immersing the zeolite with 1M NH 4 NO 3 at 25 ° C and stirring the mixture for 30 minutes three times. The zeolite subjected to ion exchange was neutralized until the pH became neutral After thoroughly washing, it was dried at a temperature of 100 ° C for 12 hours, and calcined in an air atmosphere of 550 ° C for 4 hours to prepare a zeolite.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. According to the above results, it can be confirmed that the prepared zeolite is MFI zeolite in the form of nanoporous sheet and has an average thickness of 2.5 nm and a specific surface area of 650 m 2 / g.

Production Example 5. Preparation of nano-porous sheet type MFI zeolite catalyst having a crystal thickness of 6.0 nm

An organic surfactant (C 22-6-6-6-6 Br 2 ) was used as a template and the composition of the mixed solution was 2.5 C 22-6-6-6-6 Br 2 : 100 SiO 2 : 1 Al 2 O 3 : 29.89 Na 2 O: 19.57 H 2 SO 4 : 4000 H 2 O molar ratio. The zeolite produced by the above method was a nano-porous sheet type MFI zeolite having an average crystal thickness of 6.0 nm and a specific surface area of 600 m 2 / g.

Comparative Preparation Example 4. Preparation of bulk MFI zeolite catalyst

Aluminum sulfate octadecahydrate and distilled water were injected into the mixture to make a transparent mixture. After addition of tetraethyl orthosilicate, stirring was continued until the solution became a colorless transparent solution in white color. The composition of the mixed solution was 30 TPAOH: 100 SiO 2 : 1 Al 2 O 3 : 6000 H 2 O molar ratio.

In order to crystallize the predominantly silica-aluminum mixed gel, the gel was injected into a high-pressure reactor and heated at 170 ° C for 3 days to form zeolite crystals. The prepared zeolite crystals were cooled to room temperature, separated into an aqueous solution layer and a solid layer, and washed with distilled water until the pH of the separated zeolite crystals became neutral.

The washed zeolite was then placed in a dryer and dried at 120 ° C. for 12 hours. The dried zeolite was calcined in an air atmosphere at a temperature of 550 ° C. for 4 hours.

The results of the nitrogen adsorption-desorption experiment for the zeolite prepared by the above method are shown in FIG. 2, the powder X-ray diffraction analysis and the TEM photograph are shown in FIGS. 3 and 4, and the SEM photograph is shown in FIG. According to the above results, it can be confirmed that the produced zeolite is a bulk MFI zeolite having a specific surface area of 280 m 2 / g.

[Examples] Preparation of para-xylene

Example 1. Preparation of para-xylene using nanoporous sponge beta zeolite

The reactor system was a high pressure autoclave equipped with a 250 mL impeller and the reaction temperature was kept constant by interlocking with an external heater with a PID controller. 11 g (12.5 mL) of 2,5-dimethylfuran (99.5% purity, manufactured by Aros Organics) was injected into the reactor, and n-heptane as a solvent was added thereto in the volume ratio of 2,5-dimethylfuran to 3 times , 0.5 g of the catalyst prepared in Preparation Example 1 was injected into the reactor, and the reactor was agitated at 500 rpm. The reactor was evacuated with air using nitrogen, and the temperature of the reactor was maintained at a reaction temperature of 300 ° C. Subsequently, while the ethylene gas was fed into the reactor, the reaction was continued while injecting the reactor pressure at a constant pressure of 57 atm. Paraxylene was prepared, and the product was analyzed by gas chromatography (GC).

The column used for the GC analysis was an Echipi-Innoax (HP-INNOWAX), and the analysis was carried out under the conditions of maintaining the initial temperature at 70 ° C for 30 minutes, the temperature elevation temperature at 15 ° C / min and the final temperature at 220 ° C for 5 minutes, As a standard material, n-tridecane was injected to quantitatively analyze each product.

The conversion of 2,5-dimethylfuran was calculated based on the amount of 2,5-dimethylfuran in the product after the reaction with the introduced 2,5-dimethylfuran, and the selectivity of para- It was calculated by the amount occupied by paraxylene as a whole. The conversion of 2,5-dimethylfuran and the selectivity of para-xylene according to the method of Example 1 were calculated, and the results are shown in Table 1 below.

Comparative Examples 1 and 2. Preparation of para-xylene using bulk beta zeolite and commercial bulk beta zeolite

A p-xylene production process was carried out by the method of Example 1 above. As the catalyst used, Comparative Example 1 used the Belk-Beta zeolite shown in Comparative Preparation Example 1, and Comparative Example 2 used commercial bulk-beta zeolite (Zeolite Co., CP811-300). The conversion of 2,5-dimethylfuran and the selectivity of p-xylene according to the methods of Comparative Examples 1 and 2 were calculated. The results are shown in Table 1 below.


division

Type of catalyst used
Dimethylfuran
Conversion Rate
(%)
Para-xylene
Selectivity of
(%)
Example 1 Production Example 1 Nanoporous sponge type beta zeolite (Si / Al = 15) 98.5 81.8 Comparative Example 1 Comparative Preparation Example 1 Bulk Beta Zeolite
(Si / Al = 15)
10.9 16.1
Comparative Example 2 Commercial Bulk-Beta Zeolite Bulk type beta zeolite (Si / Al = 180) 27.6 34.4

According to the above Table 1, the method using the nano-porous sponge type beta zeolite catalyst (Example 1) of the present invention is superior to the method using the bulk type beta zeolite catalysts (Comparative Examples 1 and 2) - dimethylfuran conversion and para-xylene selectivity were all excellent.

Example 2 and Comparative Example 3. Preparation of para-xylene using nanoporous sponge-type MRE zeolite and bulk MRE zeolite

A p-xylene production process was carried out by the method of Example 1 above. As the catalyst used in Example 2, the nanoporous sponge type MRE zeolite catalyst prepared in Preparation Example 2 was used and in Comparative Example 3, the bulk type MRE zeolite catalyst prepared in Comparative Preparation Example 2 was used. The conversion of 2,5-dimethylfuran according to the method of Example 2 or Comparative Example 3 and the selectivity of p-xylene were calculated. The results are shown in Table 2 below.

division Type of catalyst used Dimethylfuran
Conversion Rate
(%)
Para-xylene
Selectivity of
(%)
Example 2 Production Example 2 Nanoporous sponge type MRE
Zeolite
(NSP-MRE, Si / Al = 100)
83.7 67.2
Comparative Example 3 Comparative Production Example 2 Bulk type MRE zeolite
(Si / Al = 100)
41.2 4.6

According to the above Table 2, the method using the nanoporous sponge type MRE zeolite catalyst according to the present invention (Example 2) is superior to the method using the bulk MRE zeolite catalyst (Comparative Example 3) The conversion and para-xylene selectivity were both excellent.

Example 3 and Comparative Example 4. Preparation of para-xylene using nanoporous sponge-type MTW zeolite and bulk-type MTW zeolite

A p-xylene production process was carried out by the method of Example 1 above. As the used catalyst, the nanoporous sponge type MTW zeolite catalyst prepared in Preparation Example 3 was used in Example 3, and the bulk MTW zeolite catalyst prepared in Comparative Preparation Example 2 was used in Comparative Example 4. The conversion of 2,5-dimethylfuran according to the method of Example 3 or Comparative Example 4 and the selectivity of para-xylene were calculated. The results are shown in Table 3 below.

division Type of catalyst used Dimethylfuran
Conversion Rate
(%)
Para-xylene
Selectivity of
(%)
Example 3 Production Example 3 Nanoporous sponge type MTW
Zeolite
(NSP-MTW, Si / Al = 100)
95.1 71.0
Comparative Example 4 Comparative Production Example 3 Bulk MTW Zeolite
(Si / Al = 100)
13.6 29.6

According to the above Table 3, the method using the nanoporous sponge type MTW zeolite catalyst according to the present invention (Example 3) is superior to the method using the bulk type MTW zeolite catalyst (Comparative Example 4) The conversion and para-xylene selectivity were both excellent.

Examples 4 to 5 and Comparative Example 5. Preparation of para-xylene using nanosheet MFI zeolite and bulk MFI zeolite

A p-xylene production process was carried out by the method of Example 1 above. The nanosheet-type MFI zeolite catalyst prepared in Production Example 4 and Production Example 5 was used in Examples 4 and 5, and the bulk MFI zeolite catalyst prepared in Comparative Preparation Example 4 was used in Comparative Example 5 . The conversion of 2,5-dimethylfuran and the selectivity of para-xylene according to the methods of Examples 4 to 5 and Comparative Example 5 were calculated, and the results are shown in Table 4 below.

division Type of catalyst used Dimethylfuran
Conversion Rate
(%)
Para-xylene
Selectivity
(%)
Example 4 Production Example 4 Nanosheet type MFI zeolite (Si / Al = 100, thickness 2.5 nm) 98.5 81.8 Example 5 Production Example 5 Nano sheet type MFI zeolite (Si / Al = 100, thickness 6.0 nm) 89.3 70.9 Comparative Example 5 Comparative Production Example 4 Bulk MFI zeolite
(Si / Al = 100)
2.3 0.0

According to the above Table 4, the method using the nanosheet type MFI zeolite catalyst according to the present invention (Examples 4 and 5) is superior to the method using the bulk MFI zeolite catalyst (Comparative Example 5) And p-xylene selectivity were both excellent. Further, it can be confirmed that the thickness of the zeolite crystal has a great influence on the catalytic activity.

Claims (8)

  1. The catalyst is applied as a catalyst in the process of selectively synthesizing para-xylene using 2,5-dimethylfuran and ethylene as starting materials, and has a BET specific surface area of 380 to 850 m 2 / g and an average pore size of 2 to 7 nm Nanoporous sponge or zeolite catalyst in sheet form with mesoporous.
  2. The method according to claim 1,
    Wherein the 2,5-dimethylfuran is derived from a biomass.
  3. The method according to claim 1,
    Beta, MRE, MTW, and MFI.
  4. delete
  5. The method according to claim 1,
    Wherein the nanoporous sponge-type zeolite has an average thickness of 4 to 6 nm, and the nanoporous sheet-type zeolite has an average thickness of 2 to 7 nm.
  6. The process according to claim 1, wherein the zeolite catalyst
    a) mixing a silica source, an alumina source and a casting agent represented by the following formula (1), and then gelling the mixture with an amorphous silica aluminum mixed gel;
    b) crystallizing the gel into zeolite crystals in the form of a sponge or a sheet;
    c) washing, drying and calcining the zeolite crystals; And
    d) ion exchanging the calcined zeolite; ≪ RTI ID = 0.0 > zeolite < / RTI > catalyst.
    [Chemical Formula 1]
    Figure 112014076906467-pat00003

    (Wherein C1 is a substituted or unsubstituted alkyl group having 10 to 25 carbon atoms, C2 is a substituted or unsubstituted alkyl group having 3 to 6 carbon atoms,
    Figure 112014076906467-pat00004
    ego; C3 is a substituted or unsubstituted alkyl group having 5 to 25 carbon atoms; and n is an integer of 1 to 10 as the number of repetitions of the ammonium group,
  7. The method according to claim 6,
    The mold material represented by the above formula (1)
    C 22 H 45 -N + (CH 3) 2 - [C 6 H 12 -N + (CH 3) 2 -CH 2 - (C 6 H 4) -CH 2] 2 -N + (CH 3) 2 - C 6 H 12 -N + (CH 3 ) 2 -C 22 H 45 ;
    C 16 H 33 -N + (CH 3 ) 2 -C 6 H 12 -N + (CH 3 ) 2 -C 6 H 12 ; And
    C 22 H 45 -N + (CH 3 ) 2 - [C 6 H 12 -N + (CH 3 ) 2 ] 3 -N + (CH 3 ) 2 -C 6 H 12 ; ≪ RTI ID = 0.0 > zeolite < / RTI >
  8. A method for producing para-xylene by reacting 2,5-dimethylfuran derived from biomass with ethylene under the condition that the zeolite catalyst and the solvent of any one of claims 1 to 3 and 5 to 7 are present Way.
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