CATALYST FOR CARBONYLATION OF DIMETHYL ETHER AND METHOD FOR PREPARING THE SAME

Abstract

Disclosed are a catalyst for carbonylation of dimethyl ether that has high catalyst activity and can be regenerated using a fluidized bed reactor, and a method for preparing the same. The catalyst for carbonylation of dimethyl ether includes a support having a first density; and ferrierite zeolite catalyst particles bound to a surface of the support via a polymer binder and having a second density smaller than the first density.

Claims

1. A catalyst for carbonylation of dimethyl ether, the catalyst comprising: a support having a first density; and ferrierite zeolite catalyst particles bound to a surface of the support via a polymer binder and having a second density smaller than the first density.

2. The catalyst of claim 1, wherein a surface of each of at least some of the ferrierite zeolite catalyst particles is exposed to an outside.

3. The catalyst of claim 1, wherein the catalyst has a core-shell structure in which the ferrierite zeolite catalyst particles are coated on the surface of the support.

4. The catalyst of claim 1, wherein a ratio between a weight of the support and a weight of the ferrierite zeolite catalyst particles is in a range of 2.5:1 to 10:1.

5. The catalyst of claim 1, wherein the polymer binder includes at least one selected from a group consisting of polyethylene glycol (PEG), polyvinyl alcohol (PVA) and methyl cellulose.

6. The catalyst of claim 5, wherein when the polymer binder is polyvinyl alcohol (PVA), a content of the polymer binder is in a range of 9 to 73% by weight, based on a total weight of the support and the ferrierite zeolite catalyst particles.

7. The catalyst of claim 5, wherein when the polymer binder is methyl cellulose, a content of the polymer binder is a range of 15 to 25% by weight, based on a total weight of the support and the ferrierite zeolite catalyst particles.

8. The catalyst of claim 1, wherein the polymer binder has at least one functional group selected from a group consisting of a methoxyl group (CH.sub.3O—), a carboxyl group (—COOH), glycerate (C.sub.3H.sub.5O.sub.4—) and a hydroxyl group (—OH).

9. The catalyst of claim 1, wherein a molecular weight of the polymer binder is in a range of 146000 to 186000 g/mol.

10. The catalyst of claim 1, wherein a molar ratio (Si/Al) as a ratio of a content of silicon to a content of aluminum in the ferrierite zeolite catalyst particle is in a range of 5 to 30.

11. The catalyst of claim 1, wherein a size of the support is in a range of 50 to 150 μm, wherein a size of each of the ferrierite zeolite catalyst particles is in a range of 100 nm to 1 μm.

12. The catalyst of claim 1, wherein the first density is in a range of 750 to 800 kg/m.sup.3.

13. A method for preparing a catalyst for carbonylation of dimethyl ether, the method comprising: mixing a support having a first density, ferrierite zeolite catalyst particles having a second density smaller than the first density, and a polymer binder with each other in a solvent to prepare a mixed solution; drying the mixed solution to prepare a dried mixture; and firing the dried mixture.

14. The method of claim 13, wherein in the firing of the dried mixture, a portion of the polymer binder contained in the dried mixture is decomposed and removed, and the rest thereof remains therein such that a surface of each of at least some of the ferrierite zeolite catalyst particles bound to a surface of the support is exposed to an outside.

15. The method of claim 13, wherein the mixing includes: a first step of mixing the support having the first density and the ferrierite zeolite catalyst particles having the second density smaller than the first density with each other to prepare a mixture; and a second step of adding and mixing the mixture of the support and the ferrierite zeolite catalyst particles to and with a polymer binder solution.

16. The method of claim 15, wherein the polymer binder solution is prepared by dissolving the polymer binder in a solvent for 1 to 6 hours under conditions of pH 6 to 8, and 80 to 100° C.

17. The method of claim 13, wherein in the mixing, a ratio between a weight of the support and a weight of the ferrierite zeolite catalyst particles is in a range of 2.5:1 to 10:1.

18. The method of claim 13, wherein in the mixing, a content of the polymer binder is in a range of 9 to 73% by weight, based on a total weight of the support and the ferrierite zeolite catalyst particles.

19. The method of claim 13, wherein the polymer binder includes at least one selected from a group consisting of polyethylene glycol (PEG), polyvinyl alcohol (PVA) and methyl cellulose.

20. The method of claim 19, wherein when the polymer binder is polyethylene glycol (PEG) or polyvinyl alcohol (PVA), the firing is performed at a temperature of 230 to 550° C. under a nitrogen atmosphere.

21. The method of claim 19, wherein when the polymer binder is methyl cellulose, the firing includes: a first step of performing heat treatment at a temperature of 210 to 250° C. under a nitrogen atmosphere; a second step of performing heat-treatment at a temperature of 230 to 270° C. under a nitrogen atmosphere after the first step; and a third step of performing heat treatment at a temperature of 130 to 170° C. under a nitrogen atmosphere after the second step.

22. The method of claim 13, wherein the polymer binder has at least one functional group selected from a group consisting of a methoxyl group (CH.sub.3O—), a carboxyl group (—COOH), glycerate (C.sub.3H.sub.5O.sub.4—) and a hydroxyl group (—OH).

23. The method of claim 13, wherein a molecular weight of the polymer binder is in a range of 146000 to 186000 g/mol.

24. A method for preparation of methyl acetate, the method comprising performing carbonylation of dimethyl ether using carbon monoxide under presence of the catalyst of claim 1, thereby converting dimethyl ether to methyl acetate.

25. The method of claim 24, wherein the performing of the carbonylation of dimethyl ether using carbon monoxide under presence of the catalyst, thereby converting dimethyl ether to methyl acetate includes reacting a mixed gas containing carbon monoxide and dimethyl ether in a fluidized bed reactor at a temperature of 200 to 240° C.

26. A method for regenerating a catalyst, the method comprising treating a deactivated catalyst with carbon monoxide-containing gas in a fluidized bed reactor, thereby regenerating the catalyst, wherein the catalyst includes the catalyst of claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0048] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0049] FIG. 1 shows SEM analysis images of catalysts according to Present Examples and Comparative Examples of the present disclosure.

[0050] FIG. 2 shows the results of X-ray diffraction analysis of catalysts according to Present Examples and Comparative Examples of the present disclosure.

[0051] FIG. 3 shows results of TPD analysis using ammonia of catalysts according to Present Examples and Comparative Examples of the present disclosure.

[0052] FIGS. 4A and 4B are graphs respectively showing dimethyl ether conversions and methyl acetate selectivity in carbonylation using catalysts according to Present Examples and Comparative Examples of the present disclosure.

[0053] FIGS. 5A to 5C are graphs showing TGA analysis results of catalysts according to Present Examples of the present disclosure.

DETAILED DESCRIPTIONS

[0054] Descriptions and details of well-known steps and elements are omitted for simplicity of the description. Furthermore, in the following detailed description of the present disclosure, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be understood that the present disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail so as not to unnecessarily obscure aspects of the present disclosure. Examples of various embodiments are illustrated and described further below. It will be understood that the description herein is not intended to limit the claims to the specific embodiments described. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the present disclosure as defined by the appended claims.

[0055] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present disclosure. As used herein, the singular forms “a” and “an” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises”, “comprising”, “includes”, and “including” when used in this specification, specify the presence of the stated features, integers, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, operations, elements, components, and/or portions thereof.

[0056] Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

Catalyst for Carbonylation of Dimethyl Ether

[0057] A catalyst for carbonylation of dimethyl ether according to one embodiment of the present disclosure includes a support having a first density, and ferrierite zeolite catalyst particles bonded to a surface of the support via a polymer binder and having a second density smaller than the first density.

[0058] The support having the first density means the support having a density set such that the support can flow in a fluidized bed reactor. For example, a commercial FCC (fluid catalytic cracking) catalyst having a density of 750 to 800 kg/m.sup.3 may be used as the support. That is, the support has the density set such that the support may flow in the fluidized bed reactor. Thus, when the catalyst according to the present disclosure is deactivated, the catalyst may be regenerated in the fluidized bed reactor.

[0059] In one embodiment, a size of the support may be in a range of 50 to 150 μm, preferably in a range of 75 to 95 μm.

[0060] The ferrierite zeolite catalyst particles act as active materials for carbonylation of dimethyl ether, are bonded to the surface of the support via the polymer binder and have a second density smaller than that of the support. In this regard, a molar ratio (Si/Al) between a content of silicon and a content of aluminum in the ferrierite zeolite catalyst particle is preferably in a range of 5 to 30. Further, the ferrierite zeolite catalyst particles may include commercially available ferrierite zeolite catalyst particles, or H-form ferrierite that is synthesized by a known seed synthesis method and then is subjected to ion exchange.

[0061] In one embodiment, a size of each of the ferrierite zeolite catalyst particles may be in a range of 100 nm and 1 μm, preferably in a range of 200 and 400 nm.

[0062] Further, a ratio between a size of the support and a size of the ferrierite zeolite catalyst particle may be in a range of 150:1 to 500:1, preferably 275:1.

[0063] In one embodiment, a surface of each of at least some of the ferrierite zeolite catalyst particles may be exposed to an outside. Increase in the exposed area of the ferrierite zeolite catalyst particles may improve the catalyst activity.

[0064] In one embodiment, the catalyst according to the present disclosure may have a core-shell structure in which the ferrierite zeolite catalyst particles are coated on the surface of the support. Therefore, when the catalyst according to the present disclosure is used for carbonylation of dimethyl ether, deactivation of the catalyst may be prevented due to the core-shell structure, and coke production may be suppressed.

[0065] Further, the catalyst according to the present disclosure may be regenerated in a fluidized bed reactor, and the regenerated catalyst may be reused. Thus, process continuity may be increased and thus production of methyl acetate may be increased.

[0066] The polymer binder may be a material for binding the ferrierite zeolite catalyst particles to the surface of the support, and may be preferably a water-soluble polymer or a polymer having a functional group capable of binding to the ferrierite zeolite catalyst particles.

[0067] In one embodiment, the polymer binder may include at least one selected from polyethylene glycol (PEG), polyvinyl alcohol (PVA) and methyl cellulose. Specifically, a viscosity of the polyethylene glycol (PEG) may be preferably in a range of 114 to 142 mPa.Math.s, a viscosity of the polyvinyl alcohol (PVA) may be preferably in a range of 35 to 55 mPa.Math.s, and a viscosity of the methyl cellulose may be preferably in a range of 12 to 8000 cP.

[0068] In one embodiment, the polymer binder may be a polymer binder including a functional group including at least one selected from a methoxyl group (CH.sub.3O—), a carboxyl group (—COOH), a glycerate (C.sub.3H.sub.5O.sub.4—) and a hydroxyl group (—OH) as a functional group capable of binding to the ferrierite zeolite catalyst particles. When the polymer binder including the exemplified functional group is contained in the catalyst, the number of the ferrierite zeolite catalyst particles that may be bound to the support via the same amount of the polymer binder may be increased, thereby increasing the catalyst activity.

[0069] In one embodiment, a molecular weight of the polymer binder is preferably in a range of 146000 to 186000 g/mol. When the molecular weight of the polymer binder is in a range of 146000 to 186000 g/mol, as a chain length of the polymer binder increases, the number of the ferrierite zeolite catalyst particles that may be bound to the support via the same amount of the polymer binder may increase, thereby increasing the catalyst activity.

[0070] In one example, in the catalyst according to the present disclosure, a weight ratio between a content of the support and a content of the ferrierite zeolite catalyst particles is preferably in a range of 2.5:1 to 10:1. When the weight ratio (support/ferrierite zeolite catalyst particles) is smaller than 2.5:1, there is an excessive amount of ferrierite zeolite catalysts such that agglomeration occurs between the ferrierites rather than a uniform coating thereof occurs, thereby resulting in uneven coating. When the ratio exceeds 10:1, there is a problem in that an amount of the active material is too small and the catalyst reaction occurs insignificantly.

[0071] Further, in the catalyst according to the present disclosure, when the polymer binder is polyvinyl alcohol (PVA), a content of the polymer binder may be in a range of 9 to 73% by weight, preferably, of 50 to 60% by weight, based on a total weight of the support and the ferrierite zeolite catalyst particles. When the content of the polymer binder is smaller than 9% by weight based on the total weight of the support and the ferrierite zeolite catalyst particles, the ferrierite zeolite particles are not entirely coated on the support due to an insufficient amount of the binder relative to the catalyst and are partially removed from the support so that the catalyst activity is reduced. When the content exceeds 73 wt%, an exposed area of the ferrierite zeolite catalyst particles is reduced, so that the catalyst activity is reduced.

[0072] In another example, when the polymer binder is methyl cellulose, a content of the polymer binder is preferably in a range of 15 to 25% by weight of the total weight of the support and the ferrierite zeolite catalyst particles. When the content of the polymer binder is smaller than 15% by weight based on the total weight of the support and the ferrierite zeolite catalyst particles, the ferrierite zeolite particles are not entirely coated on the support due to an insufficient amount of the binder relative to the catalyst and are partially removed from the support so that the catalyst activity is reduced. When the content exceeds 25 wt %, an exposed area of the ferrierite zeolite catalyst particles is reduced, so that the catalyst activity is reduced.

[0073] As described above, in the catalyst according to the present disclosure, the content of each of the support, the ferrierite zeolite catalyst particles, and the polymer binder may be controlled to an appropriate range such that the ferrierite zeolite catalyst particles are uniformly coated on the surface of the support while maintains crystallinity thereof. Thus, the catalyst according to the present disclosure may exhibit high activity in a conversion reaction from dimethyl ether to methyl acetate, and the deactivated catalyst may be regenerated in the fluidized bed reactor and then reused.

[0074] Further, since the catalyst according to the present disclosure has the core-shell structure and is present in a form of a particle, deactivation thereof may be prevented, and coke deposition during the catalyst reaction may be suppressed, thereby enabling a stable process.

Method for Preparing Catalyst for Carbonylation of Dimethyl Ether

[0075] A method for preparing a catalyst according to one embodiment of the present disclosure includes mixing a support having a first density, ferrierite zeolite catalyst particles having a second density smaller than the first density, and a polymer binder with each other in a solvent to prepare a mixture in S100, drying the mixture in S200, and firing the dried mixture in S300.

[0076] In one embodiment, S100 may include a first step S110 of mixing the support having a first density and the ferrierite zeolite catalyst particles having a second density smaller than the first density with each other, and a second step S120 of adding and mixing a mixture of the support and the ferrierite zeolite catalyst particles to and with a polymer binder solution.

[0077] The polymer binder solution in S120 may be prepared by dissolving the polymer binder in a solvent for 1 to 6 hours under conditions of pH 6 to 8 and 80 to 100° C. Under the above conditions, the polymer binder may be sufficiently dissolved in the solvent.

[0078] In S100, a weight ratio of the support and the ferrierite zeolite catalyst particles to be mixed with each other is preferably in a range of 2.5:1 to 10:1. When the weight ratio (support/ferrierite zeolite catalyst particles) is smaller than 2.5:1, there is an excessive amount of ferrierite zeolite catalysts such that agglomeration occurs between the ferrierites rather than a uniform coating thereof occurs, thereby resulting in uneven coating. When the ratio exceeds 10:1, there is a problem in that an amount of the active material is too small and the catalyst reaction occurs insignificantly.

[0079] Further, the content of the polymer binder to be added thereto is preferably in a range of 9 to 73% by weight of the total weight of the support and the ferrierite zeolite catalyst particles. When the content of the polymer binder is smaller than 9% by weight based on the total weight of the support and the ferrierite zeolite catalyst particles, the ferrierite zeolite particles are not entirely coated on the support due to an insufficient amount of the binder relative to the catalyst and are partially removed from the support so that the catalyst activity is reduced. When the content exceeds 73 wt %, an exposed area of the ferrierite zeolite catalyst particles is reduced, so that the catalyst activity is reduced.

[0080] In one embodiment, the polymer binder solution in which the polymer binder is dissolved in the solvent may be mixed with the support and the ferrierite zeolite catalyst particles. Alternatively, the polymer binder in a powder form may be mixed with the support and the ferrierite zeolite catalyst particles in a solvent. In this regard, the solvent is preferably distilled water. However, the present disclosure is not limited thereto.

[0081] In one example, the polymer binder preferably includes any at least one selected from polyethylene glycol (PEG), polyvinyl alcohol (PVA) and methyl cellulose. Specifically, the viscosity of the polyethylene glycol (PEG) is preferably in a range of 114 to 142 mPa.Math.s, the viscosity of the polyvinyl alcohol (PVA) is preferably in a range of 35 to 55 mPa.Math.s, and the viscosity of the methyl cellulose is preferably in a range of 12 to 8000 cP.

[0082] In one embodiment, when the polymer binder is polyethylene glycol (PEG) or polyvinyl alcohol (PVA), S300 may be performed at a temperature of 230 to 550° C. under a nitrogen atmosphere. Thus, a portion of the polymer binder contained in the dried mixture is decomposed and removed, and the remaining portion thereof remains. Thus, the catalyst in which a surface of each of at least some of the ferrierite zeolite catalyst particles bonded to the support surface is exposed to an outside may be prepared.

[0083] In one embodiment, when the polymer binder is methyl cellulose, S300 may include a first step of performing heat treatment at a temperature of 210 to 250° C. under a nitrogen atmosphere, a second step of performing heat treatment at a temperature of 230 to 270° C. under a nitrogen atmosphere after the first step, and a third step of performing heat-treatment at a temperature of 130 to 170° C. under a nitrogen atmosphere after the second step. Each of the first, second and third steps may be performed for 3 hours.

[0084] During the firing, a portion of the polymer binder contained in the dried mixture is decomposed and removed, and the remaining portion thereof remains, so that the catalyst in which the surface of each of at least some of the ferrierite zeolite catalyst particles bonded to the support surface is exposed to the outside may be prepared.

[0085] In one embodiment, the polymer binder may be a polymer binder including a functional group including at least one selected from a methoxyl group (CH.sub.3O—), a carboxyl group (—COOH), a glycerate (C.sub.3H.sub.5O.sub.4—) and a hydroxyl group (—OH) as a functional group capable of binding to the ferrierite zeolite catalyst particles. When the polymer binder including the exemplified functional group is contained in the catalyst, the number of the ferrierite zeolite catalyst particles that may be bound to the support via the same amount of the polymer binder may be increased, thereby increasing the catalyst activity.

[0086] In one embodiment, a molecular weight of the polymer binder is preferably in a range of 146000 to 186000 g/mol. When the molecular weight of the polymer binder is in a range of 146000 to 186000 g/mol, as a chain length of the polymer binder increases, the number of the ferrierite zeolite catalyst particles that may be bound to the support via the same amount of the polymer binder may increase, thereby increasing the catalyst activity.

[0087] According to the method for preparing the catalyst according to the present disclosure, during the preparation, the content of each of the support, the ferrierite zeolite catalyst particles, and the polymer binder may be controlled to an appropriate range such that the ferrierite zeolite catalyst particles may be successfully bound to the surface of the support, and a portion of the polymer binder may remain via the firing process. Thus, the catalyst may be prepared in which the surface of each of at least some of the ferrierite zeolite catalyst particles bound to the support surface is exposed to the outside.

[0088] The method for preparing the catalyst according to the present disclosure is economical and has a fast synthesis rate because the method does not use a special mechanical apparatus, which is not the case in a conventional method for preparing a catalyst for a fluidized bed in which a density is controlled using extrusion, compression, and spraying.

Method for Preparing Methyl Acetate

[0089] A method for preparing methyl acetate according to one embodiment of the present disclosure may include performing carbonylation of dimethyl ether using carbon monoxide under presence of the catalyst according to the present disclosure, thereby converting dimethyl ether to methyl acetate.

[0090] In one embodiment, converting dimethyl ether to methyl acetate may include reacting a mixed gas containing carbon monoxide and dimethyl ether at a temperature of 200 to 240° C. in a fluidized bed reactor. For example, the mixed gas may be a mixed gas containing carbon monoxide: dimethyl ether: nitrogen at 4.5:90:5.5 mol %.

[0091] Further, before the carbonylation, a pretreatment process of removing foreign substances such as water molecules present in the catalyst according to the present disclosure may be performed by raising a temperature of the catalyst to 500° C. under a nitrogen gas atmosphere and then maintaining the catalyst for 1 hour.

[0092] In one example, the carbonylation may be performed for 15 to 19 hours at a reaction temperature of 200 to 240° C. and a pressure of 10 to 30 bar. When the reaction is carried out within the temperature and pressure ranges, a reaction rate and selectivity of methyl acetate may be improved.

Method for Regenerating Catalyst

[0093] According to the present disclosure, after the carbonylation, a deactivated catalyst is injected into a fluidized bed reactor, and a carbon monoxide-containing gas is added thereto to regenerate the catalyst. Since the catalyst according to the present disclosure includes the support having a density set such that the support can flow in the fluidized bed reactor, the catalyst may be regenerated while the support flows in the fluidized bed reactor.

[0094] Hereinafter, preparation and characteristics of the catalyst according to the present disclosure will be described in more detail based on specific Examples.

EXAMPLES

Preparation of Catalyst for Carbonylation of Dimethyl Ether

Present Example 1: Preparation of FCC@CFER=10:1 (PVA, 54.5%) Catalyst

[0095] 10 g of support (commercial fluidized bed (FCC) catalyst) and 1 g of commercial ferrierite zeolite catalyst particles were mixed with each other via physical agitation.

[0096] Further, 6 g of PVA having a viscosity of 35 to 55 mPa.Math.s was sufficiently dissolved in distilled water at pH 6 to 8 and 80 to 100° C. for 1 hour to prepare a polymer binder solution.

[0097] Thereafter, a mixture of the support and the ferrierite zeolite catalyst particles was added to the polymer binder solution, and stirring of the mixed solution was executed for 6 hours. The resulting mixed solution was dried in an oven at 110° C. for 24 hours.

[0098] Next, the dried mixture was fired at 550° C. for 3 hours under a nitrogen atmosphere to prepare the catalyst (Present Example 1, FCC@CFER=10:1 (PVA, 54.5%)) according to the present disclosure).

Present Examples 2 to 3

[0099] The same process as the preparation process of the catalyst according to Present Example 1 was performed except that each of 9.167 g and 7.857 g of the support was used, and the weight ratio of the support and the ferrierite zeolite catalyst particles was changed to each of 5:1 and 2.5:1. Thus, we obtained a catalyst of FCC@CFER=5:1 (PVA, 54.5%) in Present Example 2 and a catalyst of FCC@CFER=2.5:1 (PVA, 54.5%) in Present Example 3.

Present Examples 4 to 5

[0100] The same process as the preparation process of the catalyst according to Present Example 1 was performed except that PEG was used as the polymer binder. Thus, a catalyst of Present Example 4 (FCC@CFER=10:1 (PEG, 54.5%) was obtained.

[0101] Further, the same process as the preparation process of the catalyst according to Present Example 3 was performed except that PEG was used as the polymer binder. Thus, a catalyst of Present Example 5 FCC@CFER=2.5:1 (PEG, 54.5%) was obtained.

Present Example 6: Preparation of Layer/FCC@CFER=10:1 (Methyl Cellulose, 36%) Catalyst

[0102] 10 g of support (commercial fluidized bed (FCC) catalyst) and 1 g of commercial ferrierite zeolite catalyst particles were mixed with each other via physical agitation.

[0103] Then, 4 g of methyl cellulose having a viscosity of 15 cp and a mixture of the support and the ferrierite zeolite catalyst particles were sieved and laminated with each other, and a resulting mixture was dried in an oven at 110° C. for 24 hours.

[0104] Next, the dried mixture was fired for 3 hours at a temperature at each of 230° C., 250° C. and 150° C. under a nitrogen atmosphere, and thus a catalyst according to the present disclosure (Present Example 6, Layer/FCC@CFER=10:1 (Methyl cellulose), 36%)) was prepared.

Present Examples 7 to 8

[0105] The same process as the preparation process of the catalyst according to Present Example 6 was performed except that each of 9.167 g and 7.857 g of the support was used, and the weight ratio of the support and the ferrierite zeolite catalyst particles was changed to each of 5:1 and 2.5:1. Thus, a catalyst of Present Example 7 (Layer/FCC@CFER=5:1 (Methyl cellulose, 36%)), and a catalyst of Present Example 8 (Layer/FCC@CFER=2.5:1 (Methyl cellulose, 36%)) were obtained.

Present Example 9: Preparation of FCC@CFER=10:1 (Methyl Cellulose, 36%) Catalyst

[0106] 10 g of the support (commercial fluidized bed (FCC) catalyst) and 1 g of commercial ferrierite zeolite catalyst particles were mixed with each other via physical agitation.

[0107] Further, 4 g of methyl cellulose having a viscosity of 15 cp was sufficiently dissolved in distilled water at pH 6 to 8 and 80 to 100° C. for 1 hour to prepare a polymer binder solution.

[0108] Thereafter, a mixture of the support and the ferrierite zeolite catalyst particles was added to the polymer binder solution, and stirring of the mixed solution was continued for 6 hours. The resulting mixed solution was dried in an oven at 110° C. for 24 hours.

[0109] Next, the dried mixture was fired for 3 hours at a temperature at each of 230° C., 250° C. and 150° C. under a nitrogen atmosphere, and thus a catalyst according to the present disclosure (Present Example 9, FCC@CFER=10:1 (Methyl cellulose, 36%)) was prepared.

Present Examples 10 to 11

[0110] The same process as the preparation process of the catalyst according to Present Example 9 was performed except that each of 9.167 g and 7.857 g of the support was used, and a weight ratio of the support and the ferrierite zeolite catalyst particles was changed to each of 5:1 and 2.5:1. Thus , a catalyst (FCC@CFER=5:1 (Methyl cellulose, 36%)) of Present Example 10 and a catalyst (FCC@CFER=2.5:1 (Methyl cellulose, 36%)) of Present Example 11 were obtained.

Present Examples 12 to 14

[0111] The same process as the preparation process of the catalyst according to Present Example 9 was performed except that instead of the commercial ferrierite zeolite catalyst particles, H-form ferrierite zeolite catalyst particles (NSFER (0.2), where 0.2 denotes an amount of nanosheet ferrierite as a seed) synthesized using seed synthesis and subjected to ion exchange were used, and 5 g of the support (commercial fluidized bed (FCC) catalyst) and 0.5 g of nanosheet ferrierite were used. Thus, a catalyst (FCC@NSFER (0.2)=10:1 (Methyl cellulose, 73%)) of Present Example 12 was obtained.

[0112] Further, the same process as the preparation process of the catalyst according to Present Example 12 was performed except that 4.58 g and 3.93 g of the support and 0.917 g and 1.57 g of the nanosheet ferrierite were used, respectively. Thus, a catalyst (FCC@NSFER(0.2)=5:1 (Methyl cellulose, 73%)) of Present Example 13, and a catalyst of FCC@NSFER (0.2)=2.5:1 (Methyl cellulose, 73%)) of Present Example 14 were obtained.

Present Example 15

[0113] The same process as the preparation process of the catalyst according to Present Example 3 was performed except that 8.8 g of PVA was used as the polymer binder. Thus, a catalyst (FCC@CFER=2.5:1 (PVA, 80%)) of Present Example 15 was obtained.

Present Example 16

[0114] A commercial ferrierite zeolite catalyst particle (VFER) was prepared.

Present Example 17

[0115] H-form ferrierite zeolite catalyst particles (NSFER (0.2), where 0.2 denotes an amount of nanosheet ferrierite as a seed) synthesized using seed synthesis and subjected to ion exchange were prepared.

Present Example 18: Preparation of FCC@CFER=2.5:1 (Methyl Cellulose, 18%, 130-150-50) Catalyst

[0116] A dried mixture was obtained in the same manner as in Present Example 11 except that 2 g of methyl cellulose having a viscosity of 8000 cp was used. Then, the dried mixture was fired for 3 hours at a temperature of each of 130° C., 150° C. and 50° C. under a nitrogen atmosphere. Thus, a catalyst according to the present disclosure (Present Example 18, FCC@CFER=2.5:1 (Methyl cellulose, 18%), 130-150-50)) was prepared.

Present Example 19

[0117] The same process as the preparation process of the catalyst according to Present Example 18 was performed except that the firing temperature was changed to 430° C., 450° C. and 350° C. Thus, a catalyst (FCC@CFER=2.5:1 of (Methyl cellulose, 18%, 430-450-350)) of Present Example 19 was obtained.

Present Examples 20 to 23

[0118] The same process as the preparation process of the catalyst according to Present Example 1 was performed except that PVA having a viscosity of 35 to 55 mPa.Math.s was used at a content of each of 9 wt %, 27 wt %, 54.5 wt %, and 90 wt %, based on a total weight of the support and the ferrierite zeolite catalyst particles. Thus, a catalyst (FCC@CFER=10:1 (PVA, 9%, 550)) of Present Example 20, a catalyst (FCC@CFER=10:1 (PVA, 27%, 550)) of Present Example 21, a catalyst (FCC@CFER=10:1 (PVA, 54.5%, 550)) of Present Example 22, and a catalyst (FCC@CFER=10:1 (PVA, 90%, 550)) of Present Example 23 were obtained.

Present Example 24: Preparation of FCC@CFER=5:1 (PVA,18%,250) Catalyst

[0119] A dried mixture was prepared in the same manner as in Present Example 2, except that PVA having a viscosity of 11.6 to 15.4 mPa.Math.s was used at a content of 18% by weight, based on a total weight of the support and the ferrierite zeolite catalyst particles. Thereafter, the dried mixture was fired at 250° C. for 3 hours under a nitrogen atmosphere to prepare a catalyst (Present Example 24, FCC@CFER=5:1 (PVA, 18%, 250)) according to the present disclosure.

Present Examples 25 to 26

[0120] The same process as the preparation process of the catalyst according to Present Example 24 was performed except that the firing temperature was changed to 650° C. and 750° C. Thus, a catalyst (FCC@CFER=5:1 (PVA, 18%, 650)) of Present Example 26, and a catalyst (FCC@CFER=5:1 (PVA, 18%, 750)) of Present Example 26 were prepared.

Comparative Example 1

[0121] A commercial fluidized bed (FCC) catalyst was prepared.

Structure Analysis of Catalyst

[0122] SEM analysis and X-ray diffraction analysis were performed to identify structures of catalysts prepared according to Present Examples and Comparative Examples of the present disclosure. Results thereof are shown in FIGS. 1 and 2, respectively.

[0123] Referring to FIG. 1, it may be identified that in each of the catalysts (Present Examples 1 to 5, Present Example 7, and Present Example 10) according to Present Examples of the present disclosure, the ferrierite zeolite catalyst particles are present on the surface of the support. Further, it may be observed that each of the catalysts (Present Examples 1 to 5, Present Example 7, and Present Example 10) according to Present Examples of the present disclosure has a core-shell structure in which the ferrierite zeolite catalyst particles are coated on the support surface, and an intrinsic structure of the ferrierite is not changed.

[0124] Further, referring to FIG. 2 as the result of X-ray diffraction analysis, it may be identified that in the catalyst according to each of Present Examples 1 to 5, an intrinsic skeletal structure of the ferrierite is maintained.

Analysis of Acid Site of Catalyst

[0125] In order to analyze an acid site of each of the catalysts prepared according to the Present examples of the present disclosure, TPD analysis (NH.sub.3-TPD) was performed using ammonia as a basic material, and results are shown in FIG. 3 and Table 1. In this regard, a peak corresponding to a strong acid in the TPD analysis result is classified as a Brønsted acid site, while the remaining acid site is classified as a Lewis acid site or defect site.

TABLE-US-00001 TABLE 1 M(220 S(400 to to 400° C.) 485° C.) W(~220° C.) (mmol/ (mmol/ Examples Zeolite catalyst (mmol/gcat) gcat) gcat) Present FCC@CFER = 10:1 0.072 0.072 0.064 Example 1 (PVA, 54.5%) Present FCC@CFER = 5:1 0.09 0.088 0.134 Example 2 (PVA, 54.5%) Present FCC@CFER = 2.5:1 0.165 0.108 0.121 Example 3 (PVA, 54.5%) Present FCC@CFER = 10:1 0.094 0.049 0.098 Example 4 (PEG, 54.5%) Present FCC@CFER = 2.5:1 0.195 0.134 0.148 Example 5 (PEG, 54.5%) Present FCC@CFER = 10:1 0.133 0.058 0.042 Example 9 (Methyl cellulose, 36%) Present FCC@CFER = 5:1 0.098 0.059 0.053 Example 10 (Methyl cellulose, 36%) Present FCC@CFER = 2.5:1 0.127 0.092 0.062 Example 11 (Methyl cellulose, 36%) Present VFER 0.757 0.199 0.163 Example16 Comparative FCC 0.028 0.064 — Example 3

[0126] Referring to Table 1, it may be identified that the FCC catalyst as the support has no acid site, and thus has no activity in the reaction. It may be observed that as the content of the ferrierite zeolite coated on the support increases, the number of acid sites increases. Therefore, the number of acid sites may be adjusted based on an amount of the coating, and thus, the reactivity or activity may also be selectively changed.

Carbonylation of Dimethyl Ether

Present Examples 1-1 to 1-15, and Present Examples 1-18 to 1-26

[0127] A pretreatment process in which each of the catalysts prepared according to Present Examples 1 to 15 and Present Examples 18 to 26 was heated to 500° C. under a nitrogen gas atmosphere and maintained for 1 hour to remove foreign substances such as water molecules present in the catalyst was performed. After the pretreatment, 2 g of catalyst was introduced into the reactor, and a mixed gas containing dimethyl ether:carbon monoxide:nitrogen at 4.5:90:5.5 mol % was injected into the reactor and flowed therein at a reaction pressure of 20 kg/cm.sup.3, a space velocity of 500 L/kgcat/h, and a reaction temperature of 220° C. Thus, carbonylation was carried out for 17 hours.

Present Examples 1-16 and 1-17, and Comparative Example 1-1

[0128] A pretreatment process in which each of the catalysts of Present Examples 16 to 17 and Comparative Example 1 was heated to 500° C. under a nitrogen gas atmosphere and maintained for 1 hour to remove foreign substances such as water molecules present in the catalyst was performed. After the pretreatment, 0.4 g of catalyst was introduced into the reactor, and a mixed gas containing dimethyl ether:carbon monoxide:nitrogen at 4.5:90:5.5 mol % was injected into the reactor and flowed therein at a reaction pressure of 20 kg/cm3, a space velocity of 2000 L/kgcat/h, and a temperature of 220° C. Thus, carbonylation was carried out for 17 hours.

[0129] A composition of a product from the reaction was analyzed using gas chromatography. Dimethyl ether conversion (mol %), methyl acetate selectivity (mol %), and deactivation rate (mol %/h) were calculated using the analysis results. The deactivation rate is defined as an average change rate from a time corresponding to a maximum conversion rate to a last time. Specific reaction results are shown in Table 2 and FIG. 4A and FIG. 4B.

TABLE-US-00002 TABLE 2 Con- Selectivity Deactiv- version [MA/ ation [DME] MeOH] rate Examples Zeolite catalyst (Mol %) (Mol %) (Mol %/h) Present FCC@CFER = 4.3 79.2 0.02 Example 10:1(PVA, 54.5%) 1-1 Present FCC@CFER = 5.0 57.4 0.06 Example 5:1 (PVA, 54.5%) 1-2 Present FCC@CFER = 14.2 97.6 0.12 Example 2.5:1(PVA, 54.5%) 1-3 Present FCC@CFER = 6.2 61.8 0.07 Example 10:1 (PEG, 54.5%) 1-4 Present FCC@CFER = 16.4 83.7 0.18 Example 2.5:1(PEG, 54.5%) 1-5 Present layer/FCC@CFER = 5.8 73 0.05 Example 10:1 (Methyl 1-6 cellulose, 36%) Present Layer/FCC@CFER = 5:1 5.9 79 0.04 Example 1-7 (Methyl cellulose, 36%) Present Layer/FCC@CFER = 2.5:1 18.9 100 0.1 Example (Methyl cellulose, 36%) 1-8 Present FCC@CFER = 10:1 6.6 100.0 0.05 Example (Methyl cellulose, 36%) 1-9 Present FCC@CFER = 5:1 10.6 100.0 0.07 Example (Methyl cellulose, 36%) 1-10 Present FCC@CFER = 2.5:1 11.0 94.0 0.04 Example (Methyl cellulose, 36%) 1-11 Present FCC@NSFER(0.2) = 10:1 2.1 83.9 0.01 Example (Methyl cellulose, 73%) 1-12 Present FCC@NSFER(0.2) = 5:1 18.0 100.0 0.22 Example (Methyl cellulose, 73%) 1-13 Present FCC@NSFER(0.2) = 2.5:1 18.9 97.3 0.2 Example (Methyl cellulose, 73%) 1-14 Present FCC@CFER = 2.5:1 0 0 0 Example (PVA, 80%) 1-15 Present VFER 28.3 100 0.17 Example 1-16 Present NSFER(0.2) 24.0 89.9 0.45 Example 1-17 Present FCC@CFER = 2.5:1 12.5 100 0.09 Example (Methyl cellulose, 18%, 1-18 130-150-50) Present FCC@CFER = 28.8 100 0.6 Example 2.5:1 (Methyl 1-19 cellulose,18%, 430-450-350) Present FCC@CFER = 7.0 59.7 0.08 Example 10:1(PVA, 9%, 550) 1-20 Present FCC@CFER = 3.1 72.3 0 Example 10:1(PVA, 27%, 550) 1-21 Present FCC@CFER = 4.3 79.2 0.02 Example 10:1(PVA, 54.5%, 550) 1-22 Present FCC@CFER = 2.8 64.2 0.02 Example 10:1(PVA, 90%, 550) 1-23 Present FCC@CFER = 0.9 37.8 0.08 Example 5:1(PVA, 18%, 250) 1-24 Present FCC@CFER = 2.1 32.8 0.08 Example 5:1(PVA, 18%, 650) 1-25 Present FCC@CFER = 2.5 34.75 0.1 Example 5:1(PVA, 18%, 750) 1-26 Com- FCC 1.5 33.6 0.02 parative Example 1-1

Catalyst Activity Based on Content of Each of Support, Ferrierite Zeolite Catalyst Particles, and Polymer Binder

[0130] Referring to Table 2, it may be identified that the dimethyl ether conversion of each of the catalysts of Present Examples 1-1 to 1-14 varies based on the weight content of the added ferrierite zeolite catalyst particles. As described above, the reactivity or activity of the catalyst may be controlled by appropriately adjusting the content of each of the support, the ferrierite zeolite catalyst particles, and the polymer binder.

[0131] To the contrary, in Present Example 1-15 where the content of the polymer binder exceeds 73% by weight based on the total weight of the support and the ferrierite zeolite catalyst particles, the ferrierite zeolite catalyst particles may not bind to the support surface, resulting in no catalyst reactivity or activity.

[0132] Therefore, in order for the catalyst according to the present disclosure to exhibit high activity, the weight ratio of the support and the ferrierite zeolite catalyst particles may be in a range of 2.5:1 to 10:1, and the content of the polymer binder may be in a range of 9 to 73% by weight based on the total weight of the support and the ferrierite zeolite catalyst particles.

[0133] Further, it may be identified from Tables 1 and 2 that as an amount of the ferrierite zeolite catalyst particles coated on the support surface increases while the above defined content range is satisfied, the number of the acid sites that play an important role in DME carbonylation may increase, resulting in high reactivity or activity.

Optimal Content of Polymer Binder Remaining in Entirety of Catalyst

[0134] Using the Table 2 and FIGS. 5A to 5C showing the results of TGA analysis, a content of the polymer binder remaining in the catalyst after the firing was identified.

[0135] First, it may be identified that in a catalyst of Present Example 2 and a catalyst of each of Present Examples 20 to 23, when the content of the added binder is 54 wt %, 50 to 60% of the polymer binder remains after the firing at an optimum temperature, and in this case, the reactivity or activity of the catalyst has a maximal level. This is because, when the content of the residual binder is too high, the exposed area of the ferrierite particles is reduced and thus the catalyst activity decreases, whereas when the content of the residual binder is too low, the catalyst activity decreases because the number of ferrierite particles bound to the support decreases.

[0136] Further, it may be identified that in Present Examples 6 to Present Example 14 using the methyl cellulose polymer binder, the reactivity or activity of the catalyst is excellent when the content of the remaining polymer binder is about 20%.

Catalyst Activity Based on Viscosity (Molecular Weight) of Polymer Binder

[0137] Using Table 2 and FIGS. 5A to 5C showing the results of TGA analysis, the catalyst activity based on a viscosity of the polymer binder was identified.

[0138] First, each of the catalysts of Present Examples 24 to 26 using PVA with a short polymer chain exhibits lower reactivity or activity than that of each of the catalysts of Present Example 2 and Present Examples 20 to 23 using PVA with a longer polymer chain.

[0139] Further, when methyl cellulose is used as the polymer binder, the catalyst of each of Present Examples 18 to 19 having methyl cellulose having a long polymer chain exhibits better reactivity or activity, compared to the catalyst of each of Examples 6 to 14 having methyl cellulose having a short polymer chain.

[0140] This is because as the chain length of the polymer binder increases (that is, as the viscosity (molecular weight) thereof increases), the number of ferrierite particles that may be bound to the support at the same amount of the binder may increase.

[0141] A scope of protection of the present disclosure should be construed by the scope of the claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present disclosure. Although the embodiments of the present disclosure have been described in more detail with reference to the accompanying drawings, the present disclosure is not necessarily limited to these embodiments. The present disclosure may be implemented in various modified manners within the scope not departing from the technical idea of the present disclosure. Accordingly, the embodiments disclosed in the present disclosure are not intended to limit the technical idea of the present disclosure, but to describe the present disclosure. the scope of the technical idea of the present disclosure is not limited by the embodiments. Therefore, it should be understood that the embodiments as described above are illustrative and non-limiting in all respects. The scope of protection of the present disclosure should be interpreted by the claims, and all technical ideas within the scope of the present disclosure should be interpreted as being included in the scope of the present disclosure.