KR101391571B1 - Catalyst for direct synthesis of methyl acetate by carbonylation of dimethyl ether and preparation thereof - Google Patents

Abstract

The present invention relates to a catalyst for the direct synthesis of methyl acetate by carbonylation reaction of dimethyl ether including ferrierite which is pretreated by 0.1-5 parts by weight of zirconium on the basis of 100 parts by weight of ferrierite and to a method for preparing the same. When carrying out the carbonylation reaction of dimethyl ether using the catalyst of the present invention, by-products can be minimally generated and the selectivity of methyl acetate can be improved. Thus, in a stepwise indirect process of ethanol synthesis in which synthesis gas as a starting material is changed into dimethyl ether and methyl acetate, as the enhancement of the selectivity of methyl acetate by the carbonylation reaction of dimethyl ether is the best contribution to the ethanol yield in the total process, the inactive speed of the catalyst and the conversion to C_1-C_5 hydrocarbons are suppressed at the same time even when the mole ratio of CO to DME is less than 10, and therefore, the ethanol productivity in the entire process can be increased.

Description

[Technical Field] The present invention relates to a catalyst for direct synthesis of methyl acetate by a carbonylation reaction of dimethyl ether,

The present invention relates to a catalyst for direct synthesis of methyl acetate by a carbonylation reaction of dimethyl ether containing perrierite pretreated with zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of perrierite, and a process for producing the same.

As the depletion of petroleum resources, which are fossil fuels on the earth, is becoming more and more common, interest and demand for alternative energy resource development are increasing. Under such circumstances, ethanol has been proposed as an alternative energy source to replace gasoline fuel, which is currently the most popular, and is already being used as a fuel mixture with gasoline in some countries.

Ethanol is used as a raw material or solvent for various chemical substances, and it is expected that the use of fuel mixed with ethanol and gasoline as a clean alternative fuel to reduce the emission of air pollutants will be greatly increased in the future [Licht FO "World Fuel Ethanol, analysis and outlook "(2006). As the demand increases, researches on efficient production of ethanol including alcohol have been actively conducted. However, until now, fermentation process using mainly corn and sugar cane has been known as a commercial production method of ethanol.

However, in the case of the fermentation process, there is a disadvantage that the conversion rate is low and the purification process consumes a large amount of money. Thus, research on the ethanol production through the direct conversion of the catalyst using the syngas has been carried out. However, such direct catalytic conversion of catalysts has a disadvantage in that a high yield of by-products, particularly, a high selectivity to methane and methanol, and a low yield of ethanol and the use of a noble metal catalyst such as rhodium exist, [J. Catal. 261 (2009), 9-16].

Recently, a multi-step synthesis method using synthetic gas as a starting material for intermediates of dimethyl ether (DME) and methyl acetate (MA) has been actively studied as a method for synthesizing ethanol [ Korean Patent Application No. 10-2012-0111536]. In the above process, the synthesis gas can be synthesized directly or indirectly (composed of a methanol synthesis reaction and a dimethyl ether synthesis reaction by dehydration reaction of methanol) by the (R1) reaction, and the dimethyl The ether can synthesize methyl acetate (CH ₃ COOCH ₃ ) by a carbonylation reaction represented by (R 2), and ultimately reacts with ethanol (C ₂ H ₅ OH) can be selectively synthesized. (R3), a major by-product of the reaction of methanol (CH ₃ OH) has the advantage that can be reused in the dimethyl ether synthesis reaction in (R1) reaction.

(R1) DME _{synthesis: 2CO + 4H 2 → CH 3} OCH 3 + H 2 O

2CO + 4H ₂ ? 2CH ₃ OH? CH ₃ OCH ₃ + H ₂ O

(R2) DME carbonylation: CO + CH 3 OCH 3 → CH 3 COOCH 3

_{(R3) MA hydrogenation: CH 3} COOCH 3 + H 2 → CH 3 CH 2 OH + CH 3 OH

In the above reaction, development of a catalyst system for synthesizing methyl acetate, which is an intermediate in the ethanol synthesis reaction, with high selectivity is the most important technical factor and it is necessary to develop a zeolite catalyst for the carbonylation reaction (R2) of dimethyl ether . As a result of the conventional studies, when a mordenite zeolite catalyst and a mordenite zeolite catalyst whose acid sites are controlled by sodium are used as a catalyst system for the carbonylation reaction of dimethyl ether [J. Catal. 245 (2007), 110-123) and copper-supported mordenite zeolite catalysts [Catal. Today, 164 (2011), 425-428) and a study on the use of silver supported mordenite zeolite catalysts (US Patent Application No. 2010/0130771) have been reported.

However, all of the above-mentioned studies have been conducted under unrealistic conditions of CO / DME molar ratio of 45 or more. High dimethyl ether conversion and selectivity to methyl acetate have been reported. However, There is a problem that the selectivity of the C ₁ -C ₅ hydrocarbon due to the decomposition of the dimethyl ether selectively progressing at the strong acid sites on the surface of the zeolite may be increased. As a result, in the present invention, even when the CO / DME molar ratio is as low as 10 or less, Acetate as a catalyst.

Accordingly, it has been confirmed that the production of by-products can be minimized and the selectivity of methyl acetate can be improved by pretreating the ferrierite zeolite catalyst with zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of perrierite, Thereby completing the invention.

The object of the present invention is to provide a catalyst for direct synthesis of methyl acetate by carbonylation reaction of dimethyl ether containing perrierite pretreated with zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of perrierite.

In order to solve the above problems, the present invention provides a catalyst for direct synthesis of methyl acetate by carbonylation reaction of dimethyl ether containing perrierite pretreated with zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of perrierite do.

The present invention also relates to a process for producing zirconium from 0.1 to 5 parts by weight of zirconium relative to 100 parts by weight of ferrierite (step 1) by an ion exchange method or a supporting method, and a step of preparing zirconium precursor And a step (2) of calcining the carbon nanotubes at 300 to 700 ° C. The catalyst for direct synthesis of methyl acetate by the carbonylation reaction of the dimethyl ether is also provided.

Hereinafter, the present invention will be described in detail.

In the present invention, a catalyst suitable for the carbonylation reaction of dimethyl ether using a zeolite catalyst was investigated. A catalyst prepared by treating the surface with a specific metal and controlling the acid sites of the zeolite was used to inhibit the formation of hydrocarbons by side reactions. To improve the selectivity. As a result, experiments were repeated using various metals in order to control the acid sites on the surface of ferrierite by using ferrierite as a zeolite catalyst, and as a result, It was confirmed that the pretreatment with 5 parts by weight of zirconium reduced the selectivity of C ₁ -C ₅ hydrocarbons as a by-product and improved the selectivity to methyl acetate through dimethyl ether carbonylation.

The ferrierite of the present invention can use H-form ferrierite, wherein the zirconium-containing ferrierite is selected from the group consisting of a zirconium nitrate precursor, a zirconium chloride precursor and a zirconium oxychloride precursor as a zirconium precursor Can be produced using one or two of them. The ferrierite of the present invention may have a specific surface area of 200 to 600 m ² / g and a SiO ₂ / Al ₂ O ₃ molar ratio of 10 to 50.

In the present invention, the treatment with 0.1 to 5 parts by weight of zirconium relative to 100 parts by weight of ferrierite leads to a decrease in the selectivity of C ₁ -C ₅ hydrocarbons as a byproduct and an improvement in selectivity to methyl acetate through dimethylether carbonylation . If the content of zirconium exceeds 5 parts by weight with respect to 100 parts by weight of ferrierite, the increase of C ₁ -C ₅ hydrocarbons as a by-product and the selectivity of methanol by dehydration reaction of dimethylether are increased to decrease the selectivity of methyl acetate It is preferable to maintain the content of zirconium at 0.1 to 5 parts by weight with respect to 100 parts by weight of ferrierite.

According to the process for the direct synthesis of methyl acetate by the carbonylation reaction of the dimethyl ether of the present invention, the following two-step catalyst preparation method is followed.

Step 1 is a step of preparing 0.1 to 5 parts by weight of zirconium relative to 100 parts by weight of ferrierite. Specifically, ferrierite and zirconium precursor are dissolved in distilled water or an alcohol solvent (methanol, ethanol and propanol) And 0.1 to 5 parts by weight of zirconium is contained in 100 parts by weight of ferrierite by an ion exchange method or a supporting method.

In step 1, the reaction temperature is preferably 150 to 300 DEG C and the reaction pressure is preferably 5 to 30 bar. When the reaction temperature is lower than 150 ° C., the reaction activity is decreased and the conversion of dimethyl ether is lowered. When the reaction temperature is higher than 300 ° C., the production of hydrocarbon, which is a byproduct, increases and the selectivity of methyl acetate decreases. Lt; / RTI >

As the zirconium precursor, one or two selected from the group consisting of a zirconium nitrate precursor, a zirconium chloride precursor, and a zirconium oxychloride precursor can be used.

Step 2 is a step of calcining the prepared ferrierite pretreated with zirconium at a temperature of 300 ° C to 700 ° C. The zirconium-containing zirconium- The ferrierite catalyst is calcined in an air atmosphere of 300 ° C to 700 ° C to properly adjust the acid point on the surface of the ferrierite.

When the calcination temperature is less than 300 ° C., the zirconium precursor is present on the surface of the periaritride and affects the acid sites, thereby decreasing the reactivity. When the calcination temperature is higher than 700 ° C., It is preferable to prepare the catalyst in the above calcination temperature range.

The catalyst comprising ferrierite pretreated with zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the ferrierite produced by the above-mentioned method has improved stability, and thus, in the carbonylation reaction of dimethyl ether, The selectivity of acetate can be improved.

Carbonylation of dimethyl ether using a catalyst comprising ferrierite pretreated with zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the ferrierite of the present invention minimizes the formation of byproducts, Can be improved.

Therefore, the improvement in the selectivity of methyl acetate by the carbonylation reaction of dimethyl ether in the step-wise ethanol indirect synthesis process using dimethyl ether and methyl acetate as the starting material of the synthesis gas contributes the greatest to the ethanol yield in the whole process , And even when the CO / DME molar ratio is as low as 10 or less, the rate of inactivation of the catalyst can be suppressed and the conversion to C ₁ -C ₅ hydrocarbons can be suppressed, so that the productivity of ethanol in the whole process can be increased.

Fig. 1 shows conversion ratios of dimethyl ether according to reaction times in Examples 1, 4 and 7 and Comparative Example 2. Fig.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are intended to illustrate the present invention, and the scope of the present invention is not limited by these examples.

Manufacturing example  One: Perrier Light  Preparation of Catalyst

The ferrierite of NH ₃ -form was calcined at 500 ° C for 3 hours as a catalyst for synthesizing methyl acetate by methylation of methyl ether, and H-form ferrierite (SiO ₂ / Al ₂ O ₃ = 20, specific surface area = 400 m ² / g). The catalyst at this time was designated as FER.

Example  1: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used. In order to control the acid sites on the surface, zirconium (IV) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite, It was prepared in; (zirconium (IV) oxychloride octahydrate ZrOCl 2 · 8H 2 O) ion exchange method (ion exchange method) the ferrierite zeolite (1.0g) that contained 0.50 weight using a zirconium oxychloride precursor.

The ion exchange was carried out at 70 ° C. for 3 hours, followed by washing and drying at 100 ° C. for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C. to prepare Zr-ferrierite. Was expressed as Zr-FER (0.50) -IE.

Example  2: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a zirconium (IV) oxychloride precursor (ZrOCl ₂ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite 8H ₂ O; using a zirconium (IV) oxychloride octahydrate) that contained 1.0 parts by weight of zirconium was produced ferrierite zeolite (1.0g) as an ion exchange method.

The ion exchange was carried out at 70 ° C. for 3 hours, followed by washing and drying at 100 ° C. for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C. to prepare Zr-ferrierite. (1.0) -IE. ≪ / RTI >

Example  3: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a zirconium (IV) oxychloride precursor (ZrOCl ₂ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite 8H ₂ O; zirconium (IV) oxychloride octahydrate) was used to prepare 1.0 g of ferrierite zeolite by ion exchange so as to contain 2.0 weight of zirconium.

The ion exchange was carried out at 70 ° C. for 3 hours, followed by washing and drying at 100 ° C. for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C. to prepare Zr-ferrierite. Was labeled with Zr-FER (2.0) -IE.

Example  4: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a zirconium (IV) oxychloride precursor (ZrOCl ₂ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite 8H ₂ O; zirconium (IV) oxychloride octahydrate) was used to prepare 1.0 g of ferrierite zeolite by ion exchange to contain 2.5 weight of zirconium.

The ion exchange was carried out at 70 ° C. for 3 hours, followed by washing and drying at 100 ° C. for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C. to prepare Zr-ferrierite. Was labeled Zr-FER (2.5) -IE.

Example  5: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a zirconium (IV) oxychloride precursor (ZrOCl ₂ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite 8H ₂ O; zirconium (IV) using an oxychloride octahydrate) was prepared using a ferrierite zeolite (3.0g) method (impregnation) carrying thereon to contain 0.5 weight zirconium.

The zirconium support was carried out at 70 ° C for 3 hours, followed by removal of the solvent in a rotary evaporator at 70 ° C and drying at 100 ° C for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C to remove Zr - Ferrierite was prepared and the catalyst was designated Zr-FER (0.5) -IMP.

Example  6: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a zirconium (IV) oxychloride precursor (ZrOCl ₂ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite 8H ₂ O; that using zirconium (IV) oxychloride octahydrate) containing 2.0 parts by weight of zirconium was prepared using ferrierite zeolite (3.0g) method (impregnation) carrying thereon.

The zirconium support was carried out at 70 ° C for 3 hours, followed by removal of the solvent in a rotary evaporator at 70 ° C and drying at 100 ° C for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C to remove Zr - Ferrierite was prepared and the catalyst was designated Zr-FER (2.0) -IMP.

Example  7: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a zirconium (IV) oxychloride precursor (ZrOCl ₂ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite _{8H 2 O; zirconium (IV)} oxychloride octahydrate using a) was prepared using the carrying ferrierite zeolite (3.0g) that contained 5.0 parts by weight of zirconium method (impregnation).

The zirconium support was carried out at 70 ° C for 3 hours, followed by removal of the solvent in a rotary evaporator at 70 ° C and drying at 100 ° C for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C to remove Zr - Ferrierite was prepared and the catalyst was designated Zr-FER (5.0) -IMP.

Example  8: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used and the zirconium (IV) oxynitrate precursor (ZrO 2) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite (3.0 g) was impregnated so as to contain 0.5 weight of zirconium by using zirconium (IV) oxynitrate dihydrate (NO ₃ ) ₂ · 2H ₂ O.

The zirconium support was carried out at 70 ° C for 3 hours, followed by removal of the solvent in a rotary evaporator at 70 ° C and drying at 100 ° C for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C to remove Zr - Ferrierite was prepared and the catalyst was designated ZrN-FER (0.5) -IMP.

Example  9: as zirconium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used and the zirconium (IV) oxynitrate precursor (ZrO 2) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite _{NO 3) 2 · 2H 2 O} ; was prepared using a zirconium (IV) such that the zirconium containing 2.0 wt carrying a ferrierite zeolite (3.0g) method using a oxynitrate dihydrate) (impregnation).

The zirconium support was carried out at 70 ° C for 3 hours, followed by removal of the solvent in a rotary evaporator at 70 ° C and drying at 100 ° C for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C to remove Zr - Ferrierite was prepared and the catalyst was designated ZrN-FER (2.0) -IMP.

Comparative Example  1: as potassium Preprocessed Perrier Light  Preparation of Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a potassium (II) carbonate precursor (K ₂ CO ₃ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite ; Potassium (II) carbonate) was used to prepare 1.0 g of ferrierite zeolite containing 1.0 weight of potassium metal by the ion exchange method.

The ion exchange was carried out at 70 ° C. for 3 hours, followed by washing and drying at 100 ° C. for 12 hours or more, followed by firing in an air atmosphere at 500 ° C. to prepare K-ferrierite, Was expressed as K-FER (0.5) -IE.

Comparative Example  2: Preparation of mordenite catalyst

Mordenite of NH ₃ -form was calcined at 500 ° C for 3 hours as a catalyst for synthesizing methyl acetate by the carbonylation reaction of methyl ether to obtain H-form mordenite (SiO ₂ / Al ₂ O ₃ = 20, specific surface area = 400 m ² / g). The catalyst at this time was designated as MOR.

Comparative Example  3: ZSM Preparation of -5 type zeolite catalyst

ZSM-5 zeolite (ZSM-5 zeolite) of NH ₃ -form was calcined at 500 ° C for 3 hours as a catalyst for synthesizing methyl acetate by methylation of methyl ether, -5 Zeolite, SiO ₂ / Al ₂ O ₃ = 20, specific surface area = 400 m ² / g). The catalyst at this time was designated as ZSM5.

Comparative Example  4: as zirconium Preprocessed Perrier Light  By the carbonylation reaction of the dimethyl ether involved Methyl acetate  Preparation of Direct Synthesis Catalyst

The H-form ferrierite prepared in the same manner as in Preparation Example 1 was used, and a zirconium (IV) oxychloride precursor (ZrOCl ₂ ) was prepared by using tertiary distilled water as a solvent on the basis of 100 weight of ferrierite zeolite _{8H 2 O; zirconium (IV)} oxychloride octahydrate) was prepared so that the zirconium-containing metal of 10.0 parts by weight using a ferrierite zeolite (3.0g) to incipient wetness technique (impregnation) using a.

The zirconium support was carried out at 70 ° C for 3 hours, followed by removal of the solvent in a rotary evaporator at 70 ° C and drying at 100 ° C for 12 hours or more, followed by calcination in an air atmosphere at 500 ° C to remove Zr - Ferrierite was prepared and the catalyst was designated Zr-FER (10.0) -IMP.

Experimental Example  1: Activity verification experiment

For the activity test of the catalyst prepared in Preparation Example 1, a methyl acetate synthesis reaction was carried out by a carbonylation reaction of methyl ether using an average of 60 mesh size and 0.2 g of catalyst. Before starting the reaction, the mixture was treated under a hydrogen atmosphere at 300 ° C for 5 hours, and then reacted with dimethyl ether: carbon monoxide: nitrogen at a reaction temperature of 220 ° C and a reaction pressure of 20 kg / cm 2 at a space velocity of 2000 L / kg cat / The molar ratio was fixed at a ratio of 5: 45: 50 and reactants were injected into the reactor for reaction for 15 hours or more. The reaction results are shown in Table 1, in which the steady-state dimethyl ether conversion and the selectivities of methyl acetate, methanol and by-products were averaged between 12 hours and 15 hours of the reaction.

Experimental Example  2: Activation Verification Experiment

In order to verify the reaction activity of the catalysts prepared in Examples 1 to 10, activity verification tests were carried out under the same conditions as in Experimental Example 1 using the catalysts prepared in Examples 1 to 10. The reaction results are shown in Table 1, in which the steady-state dimethyl ether conversion and the selectivities of methyl acetate, methanol and by-products were averaged between 12 hours and 15 hours of the reaction.

Comparative Experimental Example  1: Activity verification experiment

In order to verify the reaction activity of the catalysts prepared in Comparative Examples 1 to 4, activity verification tests were carried out under the same conditions as in Experimental Example 1 using the catalysts prepared in Comparative Examples 1 to 4. The reaction results are shown in Table 1, in which the steady-state dimethyl ether conversion and the selectivities of methyl acetate, methanol and by-products were averaged between 12 hours and 15 hours of the reaction.

Experiment result

division Catalyst name DME conversion (mol%) Carbon selectivity ^*
[MA / MeOH / CH ₄ / by-products; MA yield (%) Production Example 1 FER 11.2 77.6 / 13.1 / 4.6 / 4.6 8.7 Example 1 Zr-FER (0.5) -IE 9.0 75.9 / 17.1 / 4.7 / 2.2 6.8 Example 2 Zr-FER (1.0) -IE 8.7 70.5 / 22.3 / 5.1 / 2.1 6.1 Example 3 Zr-FER (2.0) -IE 8.6 71.0 / 22.7 / 4.5 / 1.9 6.1 Example 4 Zr-FER (2.5) -IE 9.0 69.5 / 23.3 / 5.3 / 2.0 6.3 Example 5 Zr-FER (0.5) -IMP 12.9 84.7 / 7.0 / 4.6 / 3.7 10.9 Example 6 Zr-FER (2.0) -IMP 12.6 85.6 / 7.4 / 3.0 / 4.0 10.7 Example 7 Zr-FER (5.0) -IMP 10.1 82.4 / 1.1 / 12.0 / 4.5 8.8 Example 8 ZrN-FER (0.5) -IMP 12.4 85.0 / 8.1 / 4.8 / 2.1 10.5 Example 9 ZrN-FER (2.0) -IMP 12.0 87.5 / 7.5 / 3.0 / 2.0 10.5 Comparative Example 1 K-FER (0.5) -IE 3.6 34.8 / 39.1 / 4.7 / 21.3 1.3 Comparative Example 2 MOR 12.3 5.9 / 40.1 / 5.3 / 48.7 0.7 Comparative Example 3 ZSM5 17.6 8.5 / 33.8 / 7.1 / 50.6 1.5 Comparative Example 4 Zr-FER (10.0) -IMP 8.7 65.7 / 19.5 / 10.3 / 4.6 5.8 ^* MA: methyl acetate, MeOH: methanol, the by-products are mainly C ₁ -C ₅ hydrocarbons

Comparing Preparation 1 and Comparative Examples 2 and 3, H-ferrierite zeolite exhibited the best conversion and selectivity among the zeolites under the given reaction conditions (CO / DME = 9, 220 ° C, 20 bar) .

In addition, the reaction was carried out in the same manner as in Examples 1 to 4 by using a catalyst in which zirconium was contained in various contents by using an ion exchange method using ferrierite zeolite, and as a result, the production of by-products C ₁ -C ₅ was suppressed A better catalytic activity could be confirmed.

In the case of Examples 5 to 9, a catalyst containing zirconium in various contents was prepared by changing the production method to the supported method by the ion exchange method. In this case, more excellent activity could be confirmed. Also as shown in Examples 8 and 9, in the same catalyst preparation method, the zirconium (IV) oxycitrate precursor (ZrO (NO ₃ ) ₂ .2H ₂ O; zirconium (IV) oxynitrate dihydrate) (ZrCl ₂ O · 8H ₂ O; zirconium (IV) oxychloride octahydrate), the selectivity to methyl acetate was better.

However, as in Comparative Example 1, in the case of pretreating with potassium to control the acid sites on the surface of ferrierite, the formation of byproducts was rather increased, and when zirconium content exceeded the range suggested by the present invention On the Zr-FER (10.0) -IMP catalyst of Comparative Example 4, a decrease in selectivity to MA and an increase in the production of by-products were observed.

Therefore, as shown in Examples 1 to 9, it was confirmed that when the content of zirconium was 0.1 to 5 parts by weight based on 100 parts by weight of ferrierite, the selectivity of methyl acetate by dimethylether carbonylation was excellent.

From the above results, it is found that ferrierite is suitable for the carbonylation reaction of dimethyl ether in zeolite, and when the acidic surface of the surface is treated with a specific content by using a zirconium precursor, the production inhibition and stability of by- .

Claims (6)

A catalyst for direct synthesis of methyl acetate by carbonylation reaction of dimethyl ether containing perrierite pretreated with zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of ferrierite. The method according to claim 1, wherein the ferrierite is a H-form ferrierite having a SiO ₂ / Al ₂ O ₃ molar ratio of 10 to 50. catalyst. The method according to claim 1, wherein the ferrierite containing zirconium is produced by using one or two selected from the group consisting of a zirconium nitrate precursor, a zirconium chloride precursor and a zirconium oxychloride precursor as a zirconium precursor Catalyst for Direct Synthesis of Methyl Acetate by Carbonylation of Dimethyl Ether. The process according to claim 1, wherein the ferrierite has a specific surface area of 200 to 600 m ² / g and a molar ratio of SiO ₂ / Al ₂ O ₃ of 10 to 50. Catalyst for direct synthesis of acetate. Preparing a zirconium precursor so as to contain zirconium in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of ferrierite by an ion exchange method or a supporting method (step 1); And
(Step 2) calcining the prepared ferrierite pretreated with zirconium at 300 ° C to 700 ° C.
A process for producing a catalyst for direct synthesis of methyl acetate by carbonylation reaction of dimethyl ether according to any one of claims 1 to 4. 6. The process for the direct synthesis of methyl acetate according to claim 5, wherein the reaction temperature of step 1 is 150 to 300 DEG C and the reaction pressure is 5 to 30 bar. Gt;

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