KR101949431B1 - Silica supported heteropolyacid catalysts for producing p-xylene and method for manufacturing p-xylene using the smae - Google Patents

Silica supported heteropolyacid catalysts for producing p-xylene and method for manufacturing p-xylene using the smae Download PDF

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KR101949431B1
KR101949431B1 KR1020160146567A KR20160146567A KR101949431B1 KR 101949431 B1 KR101949431 B1 KR 101949431B1 KR 1020160146567 A KR1020160146567 A KR 1020160146567A KR 20160146567 A KR20160146567 A KR 20160146567A KR 101949431 B1 KR101949431 B1 KR 101949431B1
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xylene
catalyst
heteropoly acid
silica
para
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KR20180049984A (en
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제정호
위노토 하르요
서동진
안병성
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한국과학기술연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/247—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by splitting of cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention discloses a heteropoly acid catalyst supported on silica for the production of para-xylene, a process for producing the same, and a process for producing para-xylene using the catalyst. The catalyst has the effect of obtaining a high dimethylfuran conversion rate and a high selectivity of para-xylene from dimethylfuran derived from biomass during a short reaction time when producing p-xylene.

Description

TECHNICAL FIELD The present invention relates to a heteropolyacid catalyst supported on silica, and a method for producing p-xylene using the same, and a method for producing p-xylene using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention discloses a heteropoly acid catalyst supported on silica for the production of para-xylene, a process for producing the same, and a process for producing para-xylene using the catalyst.

Lignocellulose, such as wood and herbal oil, is composed of cellulose, hemicellulose and lignin. Cellulose, which is composed of glucose, is converted to a bioalcohol fuel by a biological process Can be converted into various chemical products. In the case of glucose, various chemical reforming reactions can also be converted into transportation fuels. For example, 5-hydroxymethylfurfural may be obtained through a dehydration reaction, and then converted to 2,5-dimethylfuran by hydrogen deoxygenation.

Since 2,5-dimethylfuran has high octane number and energy density, it is attracting attention as a next-generation transportation fuel replacing bioethanol. In recent years, these 2,5-dimethyl furane have been added to the polymer through the addition cyclization reaction with ethylene to produce polymeric products of polyester, polyethylene terephthalate (PET), packaging resin, There has been reported a technique of switching to LEN. The present inventors have found that H-Beta zeolite and tungstated zirconia, which are commercial catalysts having strong acid sites, have high activity (> 80% yield) in the production of para-xylene, It has been disclosed that silica alumina airgel catalysts with enhanced porosity significantly increase the reaction rate due to rapid mass transfer.

However, a long reaction time (> 24 hr) is required to produce a high yield of para-xylene in the production of paraxylene using conventional H-Beta zeolite, and in the case of silica alumina airgel catalyst having mesopores, Although the reaction time is short (<6 hr), para-xylene selectivity (<70%) is low due to side reactions. Therefore, it is necessary to develop a highly active catalyst capable of producing p-xylene at a high selectivity from a biomass-derived furan compound in a short time.

Korean Patent Publication No. 10-2011-0066933

In one aspect, the present disclosure aims to provide a heteropolyacid catalyst supported on high yield silica for the production of para-xylene.

In another aspect, the present invention aims to provide a process for producing the heteropoly acid catalyst supported on the high-yield silica for the production of para-xylene.

In another aspect, the present disclosure provides a process for preparing para-xylene from dimethylfuran derived from biomass, using the catalyst to obtain high dimethyl furan conversion over a short reaction time and to produce para-xylene with high selectivity The present invention provides a method for providing a plurality of data streams.

In one aspect, the techniques disclosed herein include a silica carrier; And a heteropoly acid supported on the carrier.

In an exemplary embodiment, the silica carrier may be fumed silica or mesoporous silica.

In an exemplary embodiment, the heteropoly acid may comprise tungsten (W).

In an exemplary embodiment, the heteropoly acid has the formula H n XM 12 O 40 , wherein X is the central element of phosphorus (P), silicon (Si), germanium (Ge), or arsenic (As) Tungsten (W), and n may be an integer greater than zero.

In an exemplary embodiment, the heteropoly acid may be at least one selected from the group consisting of 12-tungstophosphoric acid (H 3 PW 12 O 40 ) and 12-tungstosilicic acid (H 4 SiW 12 O 40 ).

In an exemplary embodiment, the heteropoly acid may be supported in an amount of 5 to 20 parts by weight based on 100 parts by weight of the entire carrier.

In another aspect, the technique disclosed in this specification is a method for producing a catalyst for producing para-xylene, comprising the steps of: preparing a mixed solution by dissolving heteropoly acid in an alcohol solvent; Impregnating the mixed solution with a silica carrier; And calcining the impregnated silica support. The present invention also provides a method for producing a catalyst for producing para-xylene.

In an exemplary embodiment, the heteropoly acid may be a hydrate of heteropoly acid.

In an exemplary embodiment, the alcohol solvent may be an alcohol solvent having 1 to 6 carbon atoms.

In an exemplary embodiment, the alcohol solvent may be an ethanol solvent.

In an exemplary embodiment, the heteropoly acid may be dissolved in an alcohol solvent at an initial volume of infiltration point of the silica carrier.

In an exemplary embodiment, the method may comprise drying the impregnated silica carrier in an air atmosphere prior to calcination.

In an exemplary embodiment, the firing process may be carried out at a temperature of 100 to 350 DEG C under an air atmosphere.

In another aspect, the technology disclosed herein provides a process for preparing paraxylene by reacting dimethylfuran with ethylene in the presence of the catalyst for the production of para-xylene and an organic solvent.

In an exemplary embodiment, the reaction temperature may be 200-300 &lt; 0 &gt; C.

In an exemplary embodiment, the reaction time can be from 1 to 8 hours.

In one aspect, the technique disclosed herein is effective to provide a heteropoly acid catalyst supported on high yield silica for the production of para-xylene.

In another aspect, the technique disclosed in this specification has an effect of providing a method for producing the heteropoly acid catalyst supported on the high-yield silica for producing para-xylene.

In another aspect, the technique disclosed herein is a method for preparing para-xylene from dimethylfuran derived from biomass, using the catalyst to obtain high dimethyl furan conversion over a short reaction time, There is an effect of providing a method of manufacturing Rhen.

Figure 1 schematically illustrates the conversion pathway of 2,5-dimethylfuran to para-xylene.
FIG. 2 shows the results of production of para-xylene according to the catalyst in an experimental example of the present invention (PX: para-xylene, Rates: PX production rate).
FIG. 3 shows the results of comparing the activity of a bulk heteropoly acid catalyst with a silica-supported heteropolyacid catalyst in one experimental example of the present specification.
4 is a photograph of a product solution obtained after a dimethylfuran conversion reaction using a Bulk heteropoly acid catalyst and a silica-supported heteropoly acid catalyst in an experimental example of this specification (Comparative Example 1 (A), Example 1 (B), Comparative Example 2 (C), Example 2 (D)).
FIG. 5 shows the results of comparing the activities of the heteropoly acid catalysts carried on various carriers in one experimental example of the present specification.
6 shows the effect of the weight ratio of heteropoly acid carried on the silica carrier on the catalytic activity in one experimental example of the present specification.
Fig. 7 shows the effect of the surface area of the silica support on the catalytic activity in the experimental example of this specification ((A) 1 hour reaction result (B) 6 hour reaction result).
FIG. 8 shows the effect of the calcination temperature of the catalyst on the catalyst activity in one experimental example of the present specification.
FIG. 9 shows the XRD analysis of the effect of the calcination temperature of the catalyst on the catalyst activity in the experimental example of the present specification.
10 shows the effect of the reaction temperature on the yield of para-xylene in the dimethylfuran conversion reaction in an experimental example of this specification.
11 shows the results of comparing the activity of a zeolite catalyst and a silica-supported heteropolyacid catalyst in an experimental example of the present specification.
12 shows the results of comparing the activity of heteropoly acid catalysts of the molybdenum series and the tungsten series in one experimental example of the present specification.

Hereinafter, the present invention will be described in detail.

In one aspect, the techniques disclosed herein include a silica carrier; And a heteropoly acid supported on the carrier.

The catalyst may be used in a process for preparing para-xylene from biomass-derived dimethylfuran.

In an exemplary embodiment, the silica carrier may be fumed silica or mesoporous silica.

In an exemplary embodiment, the mesoporous silica may be MCM-41 or SBA-15.

Heteropoly acid is a coordination element of tungsten (W), molybdenum (Mo), vanadium (V), niobium (Nb) and the like and phosphorus (P), silicon (Si), germanium (Ge), arsenic B), cobalt (Co), etc., are central elements. In an exemplary embodiment, the heteropoly acid may be a Keggin structure having the formula H n XM 12 O 40 , where X is a central element and M is And n is an integer greater than zero.

In one exemplary embodiment, the heteropoly acid comprises tungsten (W) to yield a high yield of para-xylene over a short reaction time.

In an exemplary embodiment, the heteropoly acid has the formula H n XM 12 O 40 , wherein X is the central element of phosphorus (P), silicon (Si), germanium (Ge), or arsenic (As) Tungsten (W), and n may be an integer greater than zero.

In an exemplary embodiment, the heteropoly acid may be at least one selected from the group consisting of 12-tungstophosphoric acid (H 3 PW 12 O 40 ) and 12-tungstosilicic acid (H 4 SiW 12 O 40 ).

In an exemplary embodiment, the heteropoly acid may be supported in an amount of 5 to 20 parts by weight based on 100 parts by weight of the entire carrier. In another aspect, the heteropolyacid is present in an amount of at least 5 parts by weight, at least 6 parts by weight, at least 7 parts by weight, at least 8 parts by weight, at least 9 parts by weight, at least 10 parts by weight, at least 11 parts by weight, at least 12 parts by weight, Not less than 13 parts by weight, not less than 14 parts by weight or not less than 15 parts by weight but not more than 20 parts by weight, not more than 19 parts by weight, not more than 18 parts by weight, not more than 17 parts by weight, not more than 16 parts by weight or not more than 15 parts by weight , It is possible to obtain p-xylene having a high degree of dimethylfuran conversion and high selectivity during a short reaction time to produce para-xylene having a high yield.

In another aspect, the present invention provides a process for producing the catalyst for producing para-xylene, comprising the steps of: preparing a mixed solution by dissolving heteropoly acid in an alcohol solvent; Impregnating the mixed solution with a silica carrier; And calcining the impregnated silica support. The present invention also provides a method for producing a catalyst for producing para-xylene.

In an exemplary embodiment, the heteropoly acid may be a hydrate of heteropoly acid.

In an exemplary embodiment, the alcohol solvent can be used for an alcohol of 1 to 6 carbon atoms per day.

In an exemplary embodiment, the alcohol solvent may be ethanol for daily use.

In an exemplary embodiment, the heteropoly acid may be dissolved in an alcohol solvent at an initial volume of infiltration point of the silica carrier.

In one exemplary embodiment, the method may comprise drying the impregnated silica carrier in an air atmosphere prior to calcination.

In an exemplary embodiment, the firing process may be carried out at a temperature of 100 to 350 DEG C under an air atmosphere. In another aspect, the firing process may be performed at a temperature of 100 ° C or higher, 150 ° C or higher, 200 ° C or higher, 250 ° C or higher or 300 ° C or higher and 350 ° C or lower, 340 ° C or lower, 330 ° C or lower, Or 300 ° C or less, p-xylene having a high degree of dimethyl furan conversion and high selectivity can be obtained during a short reaction time, and thus a high yield of para-xylene can be produced.

In another aspect, the present invention provides a method for producing para-xylene by reacting dimethylfuran with ethylene in the presence of the catalyst for producing p-xylene and an organic solvent.

The method can produce para-xylene in a reactor through 1) addition cyclization reaction with ethylene from 2,5-dimethylfuran (DMF) and 2) dehydration reaction.

In an exemplary embodiment, the reaction temperature may be 200-300 &lt; 0 &gt; C. In another aspect, the reaction temperature is at least 200 ° C, at least 225 ° C, at least 250 ° C, or at least 275 ° C but no greater than 300 ° C, no greater than 295 ° C, no greater than 290 ° C, no greater than 285 ° C, no greater than 280 ° C, It is preferable to increase the production yield of the phenol.

In an exemplary embodiment, the reaction time can be from 1 to 8 hours, or from 1 to 6 hours, or from 1 to 4 hours.

In an exemplary embodiment, the reaction may be with an initial ethylene pressure condition of 20 to 30 bar.

In an exemplary embodiment, the organic solvent may be polar aprotic organic solvents.

In an exemplary embodiment, the polar aprotic organic solvent may be one or more selected from the group consisting of 1,4-dioxane and tetrahydrofuran.

The catalyst disclosed in this specification can obtain a high dimethyl furan conversion rate and a high selectivity of para-xylene for a short reaction time of 6 hours or less in the production of para-xylene from dimethylfuran derived from biomass.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Examples 1-11.

Phosphotungstic acid hydrate (H 3 PW 12 O 40 ⋅ xH 2 O, HPW, reagent grade) and Silicotungstic acid hydrate (H 4 SiW 12 O 40 ⋅ xH 2 O, HSiW ≥99.9%) are purchased from Sigma-Aldrich and used Respectively. Fumed silica (SiO 2 , 99.8%), a catalyst carrier, was prepared by mixing samples with four different surface areas (SA = 85-115 m 2 / g, 175-225 m 2 / g, 300-350 m 2 / 350-420 m 2 / g) was purchased from Alfa Aesar and used.

First, 15 wt% of HPW based on the weight of silica carrier (1 g) was dissolved in ethanol of initial silica impregnation point volume, and HPW / ethanol solution was slowly impregnated into silica. After completion of the impregnation, the HPW was slowly dried in the air for 24 hours so that the HPW could be evenly distributed in the silica pores, and then calcined in a drying oven at 100 DEG C for 24 hours. Finally, a 15 wt% HPW supported silica (SA = 175-225 m 2 / g, Example 1, 15% HPW / SiO 2 ) catalyst was prepared.

15% HSiW / SiO 2 (SA = 175-225 m 2 / g, Example 2) The catalyst was also prepared in the same manner as above using HSiW as a precursor.

In addition, 5% HSiW / SiO 2 (Example 3), 10% HSiW (SiO 2 ) and the like were prepared in the same manner as above except that the weight ratio of HSiW was adjusted to 5-20% by weight based on the silica carrier (SA = 175-225 m 2 / g) / SiO 2 (Example 4), 20% HSiW / SiO 2 (Example 5) catalyst.

In order to investigate the effect of the silica surface area on the catalytic activity, 15% HSiW / SiO 2 (SA = 85-115 m 2) having 15% by weight of HSiW supported on a silica support having various surface areas / g, Example 6), 15% HSiW / SiO 2 (SA = 300-350 m 2 / g, Example 7), 15% HSiW / SiO 2 (SA = 350-420 m 2 / ) Catalyst.

Finally, in order to investigate the effect of the catalyst firing temperature on the catalytic activity, 15% HSiW / SiO 2 (SA = 175-225 m 2 / g, Example 2) 15% HSiW / SiO 2 (calcination at 300 ° C, Example 9), 15% HSiW / SiO 2 (calcination at 400 ° C, Example 10) and 15% HSiW / SiO 2 (calcination at 500 ° C) , Example 11) catalyst.

Comparative Examples 1 to 14

Phosphotungstic acid hydrate (H 3 PW 12 O 40 ⋅ xH 2 O, HPW, reagent grade) purchased from Sigma-Aldrich and Silicotungstic acid hydrate (H 4 SiW 12 O 40 ⋅ xH 2 O, HSiW ≥99.9% Lt; 0 &gt; C to prepare Bulk HPW (Comparative Example 1) catalyst and Bulk HSiW (Comparative Example 2) catalyst.

The alumina carrier (Al 2 O 3 , γ-phase, 99.97%) and zirconia carrier (ZrO 2 ) were purchased from Alfa Aesar and Titania carrier (TiO 2 , ≥99.5%, P25) were purchased from PlasmaChem. 15 wt% of HPW and HSiW based on the weight of the carrier were loaded on each metal oxide carrier by the initial impregnation method using ethanol as a solvent and dried at room temperature for 24 hours, Lt; / RTI &gt; The prepared catalysts were 15% HPW / Al 2 O 3 (Comparative Example 3), 15% HPW / TiO 2 (Comparative Example 4), 15% HPW / ZrO 2 (Comparative Example 5), 15% HSiW / Al 2 O 3 (Comparative Example 6), 15% HSiW / TiO 2 (Comparative Example 7) and 15% HSiW / ZrO 2 (Comparative Example 8).

Commercial H-Beta and H-ZSM-5 were purchased from Zeolyst Company for comparison with the heteropoly acid supported catalyst. The experimental zeolite catalysts were H-BEA-25 (Si / Al = 12.5, Comparative Example 9), H-BEA-38 (Si / Al = 19, Comparative Example 10) 15, Comparative Example 11). In addition, silica alumina airgel catalysts with wide specific surface area and mesopores were prepared by sol-gel method and supercritical CO 2 drying. The prepared airgel catalyst was named SAA-57 (Si / Al = 1, Comparative Example 12).

In order to compare the activity of heteropoly acid with metal group, molybdenum type Phosphomolybdic acid hydrate (H 3 PMo 12 O 40 ⋅ xH 2 O, HPMo, reagent grade) and Silicomolybdic acid hydrate (H 4 SiMo 12 O 40 ⋅ xH 2 O , HSiMo) were respectively purchased from Sigma-Aldrich and then supported on a silica carrier in the same manner as in the above examples. The prepared catalyst was 15% HPMo / SiO 2 (Comparative Example 13) and 15% HSiMo / SiO 2 (Comparative Example 14).

Experimental Example 1. Preparation of para-xylene using a catalyst

A high-pressure autoclave equipped with a 160 mL impeller was used for the conversion of dimethylfuran to para-xylene. 0.15 g of each of the catalysts of Examples 1 and 2 and Comparative Examples 1 to 12 was introduced, and 3.90 mL of 2,5-dimethylfuran mixed with 30 mL of 1,4-dioxane as a solvent 98% purity, from Alfa Aesar) was charged to the reactor. Then, the air contained in the reactor was exhausted with nitrogen, the ethylene gas was filled up to 20 bar, the impeller was operated at 350 rpm, and the reaction temperature was increased to 250 ° C while stirring. After reaching the reaction temperature, the reaction was maintained for 1 hour, and the reaction products were analyzed by GC. The experimental results are shown in Fig.

As a result, it was confirmed that Bulk HPW (Comparative Example 1) and HSiW (Comparative Example 2) exhibited high activity in the conversion of dimethylfuran and the production rate of paraxylene in the activity results of the initial reaction for 1 hour. (Al 2 O 3 , TiO 2 , ZrO 2 ) which is different from 15% HPW / SiO 2 (Example 1) and 15% HSiW / SiO 2 (Example 2) in the case of the carrier- supported heteropolyacid catalyst, Showed significantly higher activity in para-xylene selectivity and production rate than the catalysts of Comparative Examples 3 to 8 carried on the catalyst. Among the silica alumina-based aerogels and zeolite catalysts, H-BEA-25 (Comparative Example 9) showed the highest para-xylene production rate, while Examples 1 and 2 catalysts showed comparably high activity in Comparative Example 9 gave.

Experimental Example 2. Comparison of activity of bulk heteropolyacid with silica-supported heteropoly acid

In the same manner as in Experimental Example 1, 0.15 g of each of the catalysts prepared in Comparative Examples 1 and 2 and Examples 1 and 2 was injected, and the dimethylfuran conversion reaction was carried out. The reaction was carried out at a reaction temperature of 250 ° C. and an initial ethylene pressure of 20 bar for 6 hours. The reaction products were analyzed by GC.

Bulk heteropoly acid not supported on the carrier Comparative Example 1-2 After the reaction of the catalyst of Example 1-2 carried on the silica carrier and the activity of the catalyst after 6 hours of the reaction was carried out, Showed better para-xylene selectivity (see Figure 3). In particular, when the carbon balance of the whole products is calculated, the catalyst of Comparative Example 1-2 shows a low value of 68% to 58%, and oligomers that are not observed by GC due to the side reaction are formed, I can see that it has been lost a lot. In addition, as shown in the photographs of the products obtained after the reaction in FIG. 4, in the case of the catalyst of Comparative Example 1-2, the product solution turned black and proved that the lost carbon atoms were converted into heavy oligomers.

Experimental Example  3. Various On the carrier Supported Heteropoly acid  Comparison of catalyst activity

In the same manner as in Experimental Example 1, 0.15 g of each of the catalysts prepared in Examples 1 and 2 and Comparative Examples 3 to 8 was introduced, and a dimethylfuran conversion reaction was carried out. The reaction was carried out at a reaction temperature of 250 ° C and an initial ethylene pressure of 30 bar for 6 hours. The reaction products were analyzed by GC.

As a result, the catalyst activity with the same tendency as the reaction result during the initial 1 hour was also observed in the reaction results for 6 hours (see FIG. 5). The catalysts of Examples 1 and 2, which are heteropolyacid catalysts supported on a silica support, exhibited significantly higher dimetifuran conversion and p-xylene selectivity than the catalysts of Comparative Examples 3 to 8 supported on alumina, titania and zirconia. On the other hand, when Example 1 and Example 2 were compared, the HSiW heteropolyacid catalyst of Example 2 exhibited superior activity in dimethylfuran conversion and p-xylene selectivity.

Experimental Example  4. Silica On the carrier Supported Heteropoly  Effect of weight ratio on catalyst activity

0.15 g each of the catalysts loaded with various weights (5-20%) of HSiW prepared in Examples 2 to 5 were injected, and the catalytic reaction was carried out in the same manner as in Experimental Example 1. The reaction was carried out at a reaction temperature of 250 ° C and an initial ethylene pressure of 30 bar for 6 hours. The reaction products were analyzed by GC.

As a result, it was found that the conversion of dimethylfuran and the yield of para-xylene were greatly changed according to the HSiW content (see FIG. 6). The increase in HSiW content from 5% to 15% resulted in a linear increase in dimethyfuran conversion and para-xylene yield, while the increase in digestifuran conversion and p-xylene yield again at 20% Could know. Overall, the highest para-xylene yield of 80% was obtained with the 15% by weight Example 2 catalyst.

Experimental Example 5. Effect of the surface area of the silica carrier on the catalytic activity

0.15 g of HSiW-supported catalysts were loaded into the silica supports having various surface areas (SA = 85-420 m 2 / g) prepared in Examples 2 and 6 to 8, respectively. Respectively. The reaction was carried out at a reaction temperature of 250 ° C and an initial ethylene pressure of 30 bar for 1 hour to 6 hours, and the reaction products were analyzed by GC.

As a result, the effect of the surface area of the silica carrier on the activity of the catalyst was considerably small (see FIG. 7). A similar level of dimethyl furan conversion and para-xylene selectivity was observed in the catalysts of Examples 2 and 6 to 8, regardless of the change in silica surface area in both the initial 1 hour reaction and the 6 hour reaction.

Experimental Example 6 Effect of Catalyst Firing Temperature on Catalytic Activity

0.15 g of the 15% HSiW / SiO 2 catalyst pretreated at the various calcination temperatures of 100-500 ° C. prepared in Examples 2 and 9 to 11 were injected and the catalytic reaction was carried out in the same manner as in Experimental Example 1. The reaction was carried out at a reaction temperature of 250 ° C and an initial ethylene pressure of 30 bar for 1 hour. The reaction products were analyzed by GC.

As a result, the dimethylfuran conversion and para-xylene selectivity were found to be greatly influenced by the calcination temperature of the catalyst (see FIG. 8). Specifically, although the catalyst exhibited excellent activity in the production of para-xylene at a calcination temperature of 100 to 300 ° C, the activity greatly decreased at a calcination temperature of 400 ° C, and almost lost catalytic activity at a calcination temperature of 500 ° C I could see the fact. Therefore, it is important to keep the catalyst firing temperature between 100 and 350 ° C.

On the other hand, according to the XRD analysis, it was found that the Keggin structure of the heteropoly acid was well maintained by showing diffraction peaks at 10.3 °, 25.3 ° and 34.8 ° 2θ in Example 2 calcined at 100 ° C Reference). On the other hand, in the case of Example 9 calcined at 300 ° C, no such Keggin structure-related diffraction peaks appeared at all because the large HSiW clusters were highly dispersed by cleavage into small particles by heat treatment. In the case of Example 11 calcined at 500 ° C, new diffraction peaks appeared at 22-25 °, 33-35 ° and 42 ° 2θ due to the high heat temperature of the heteropolyacid crystal structure and formation of bulk tungsten oxide It is thought that it is because it did. Therefore, it is necessary to calcine the catalyst at a low temperature of 400 ° C or less in order to maintain the high activity without collapsing the Keggin structure that maintains the strong acid character of HSiW.

Experimental Example 7 Effect of Reaction Temperature on Production of Paraxylene

0.15 g of the 15% HSiW / SiO 2 (SA = 300-350 m 2 / g) catalyst prepared in Example 7 was introduced into the reactor, and a catalytic reaction was carried out in the same manner as in Experimental Example 1. The reaction was carried out for 6 hours while changing the reaction temperature from 200 ° C to 300 ° C while keeping the initial ethylene pressure at 30 bar. The reaction products were analyzed by GC.

As a result, it was found that the dimethylfuran conversion and the para-xylene yield were linearly increased as the reaction temperature was increased from 200 ° C to 275 ° C (see FIG. 10). However, when the reaction temperature was increased to 300 ° C, the yield of para-xylene began to decrease again. Finally, the highest dimethyl furan conversion and para-xylene yield were obtained at 275 ° C.

Experimental Example 8. Comparison of activity of zeolite catalyst and silica-supported heteropolyacid catalyst

Catalysts were prepared in the same manner as in Experimental Example 1, except that 0.15 g of each of the catalysts prepared in Example 2 and Comparative Example 9 was injected into the reactor. The reaction was carried out at a reaction temperature of 250 ° C and an initial ethylene pressure of 30 bar for 1 hour to 12 hours, and the reaction products were analyzed by GC.

As a result, the catalyst of Example 2 and the catalyst of Comparative Example 9 exhibited a similar rate of dimethylfuran conversion at the initial stage of the reaction, but the catalyst of Example 2 was remarkably superior in terms of para-xylene selectivity and yield in terms of time (See FIG. 11). Particularly, in the case of Example 2, the para-xylene yield reached 80% after 6 hours of reaction, while in Comparative Example 9, 60% yield of para-xylene was produced during the same time. Further, even when the reaction time of the catalyst of Comparative Example 9 was increased to 12 hours, the yield of para-xylene remained at about 68%. Thus, it can be seen that the catalyst of Example 2 selectively produces para-xylene at a faster rate.

Experimental Example 9. Comparison of catalytic activity of heteropoly acid between molybdenum series and tungsten series

The catalysts prepared in Examples 1 and 2 and Comparative Examples 13 and 14 were injected into the reactor in an amount of 0.15 g, respectively, and catalytic reactions were carried out in the same manner as in Experimental Example 1. The reaction was carried out at a reaction temperature of 250 ° C and an initial ethylene pressure of 30 bar for 6 hours. The reaction products were analyzed by GC.

As a result, it was found that the catalyst of Example 1-2, which is a tungsten-based heteropolyacid catalyst, was significantly superior to the molybdenum-based catalyst of Comparative Example 13-14 in dimethylfuran conversion and para-xylene selectivity (see FIG. 12). Therefore, it has been found that the specific heteropoly acid catalyst group containing tungsten is more advantageous for the production of para-xylene.

Having described specific portions of the present invention in detail, it will be apparent to those skilled in the art that this specific description is only a preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (16)

As a catalyst for producing para-xylene,
Silica carriers; And
And a heteropoly acid supported on the carrier,
Wherein the heteropoly acid has the formula H n XM 12 O 40 wherein X is a central element of phosphorus (P) or silicon (Si), M is a coordination element comprising tungsten (W), and n is an integer greater than 0 Lt;
The heteropoly acid is supported in an amount of 10 to 20 parts by weight based on 100 parts by weight of the entire carrier,
Wherein the catalyst produces para-xylene from dimethylfuran.
The method according to claim 1,
Wherein the silica carrier is fumed silica or mesoporous silica.
delete delete The method according to claim 1,
Wherein the heteropoly acid is 12-tungstosilicic acid (H 4 SiW 12 O 40 ).
The method according to claim 1,
Wherein the heteropoly acid is supported in an amount of 14 to 16 parts by weight based on 100 parts by weight of the whole carrier.
A process for producing a catalyst for producing paraxylene according to any one of claims 1, 2, 5 and 6,
Dissolving heteropoly acid in an alcohol solvent to prepare a mixed solution;
Impregnating the mixed solution with a silica carrier; And
And calcining the impregnated silica support. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
8. The method of claim 7,
Wherein the heteropoly acid is a hydrate of heteropoly acid.
8. The method of claim 7,
Wherein the alcohol solvent is an alcohol solvent having 1 to 6 carbon atoms.
10. The method of claim 9,
Wherein the alcohol solvent is an ethanol solvent.
8. The method of claim 7,
Wherein the heteropoly acid is dissolved in an alcohol solvent having an initial volume of the initial impregnation point of the silica carrier.
8. The method of claim 7,
The method includes the step of drying the impregnated silica carrier in an air atmosphere before calcination.
8. The method of claim 7,
Wherein the calcination step is carried out at a temperature of 100 to 350 DEG C under an air atmosphere.
A process for producing para-xylene by reacting dimethylfuran with ethylene in the presence of an organic solvent and a catalyst for the production of para-xylene according to any one of claims 1, 2, 5, and 6.
15. The method of claim 14,
Wherein the reaction temperature is 200 to 300 占 폚.
15. The method of claim 14,
Wherein the reaction time is 1 to 8 hours.
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