Ortho-alkylation reaction catalyst, ortho-alkylation reaction extrusion molding catalyst and method for preparing ortho-alkylation reaction product by using ortho-alkylation reaction catalyst and ortho-alkylation reaction extrusion molding catalyst

Abstract

The invention relates to an ortho-alkylation reaction catalyst, an ortho-alkylation reaction extrusion molding catalyst and a method for preparing an ortho-alkylation reaction product by using the ortho-alkylation reaction extrusion molding catalyst, and particularly relates to a method for preparing an ortho-alkylation reaction product by using the ortho-alkylation reaction extrusion molding catalyst. The present invention relates to an ortho-alkylation reaction catalyst and an ortho-alkylation reaction extrusion molding catalyst for obtaining an ortho-alkylation reaction product with high selectivity and conversion rate, and a method for preparing an ortho-alkylation reaction product using the same.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0058310 filed in the Korean Intellectual Property Office on May 12, 2022, and Korean Patent Application No. 10-2023-0055405 filed in the Korean Intellectual Property Office on April 27, 2023, the disclosures of which are incorporated herein by reference in their entirety.

[0003] The present invention relates to an ortho-alkylation reaction catalyst, an ortho-alkylation reaction extrusion-molded catalyst, and a method for preparing an ortho-alkylation reaction product using the same. More specifically, the present invention relates to an ortho-alkylation reaction catalyst and an ortho-alkylation reaction extrusion-molded catalyst, which can maximally reduce the material diffusion resistance of the catalyst in the ortho-alkylation reaction of phenolic compounds, thereby obtaining an ortho-alkylation reaction product with high selectivity and conversion rate, and a method for preparing an ortho-alkylation reaction product using the same. Background Art

[0004] Alkylated hydroxyaromatic compounds have a variety of applications and are usually prepared by the gas phase reaction of phenol and methanol. In addition, further alkylation reactions can be used to prepare compounds of various structures, which are easy to use in high-performance thermoplastic products.

[0005] This further alkylation reaction is usually carried out in the presence of a magnesium compound, and various studies have been conducted to optimize the performance of magnesium-based catalysts.

[0006] In alkylation reactions, magnesium-based catalysts are required to have high activity, long activity life, and high selectivity for the desired reaction products. Most alkylation catalysts used in the past produce large amounts of para-alkylated products, but various studies have been conducted to obtain more useful ortho-alkylated products in high yields.

[0007] However, conventional techniques further use a combination of a co-catalyst compound and a magnesium-based catalyst, change the composition of the catalyst, or change the reaction conditions. Conventional techniques have the problem of difficulty in obtaining an ortho-alkylated product at a desired level with high selectivity and high yield.

[0008] Therefore, in ortho-alkylation reactions, there is a need to develop catalysts that are improved in terms of catalyst selectivity, catalyst activity, yield, cost reduction, and overall productivity.

[0009] Meanwhile, for alkylation reactions, a small amount of powdered catalyst can be used at the laboratory level, but in order to mass-produce the catalyst and apply it to a commercially available fixed-bed reactor, the catalyst must be properly shaped to fit the reactor in consideration of the pressure drop during the reaction.

[0010] Generally, the commonly used methods in catalyst molding methods are extrusion molding and tablet molding. Tablet molding can produce precise molded body shapes, but the equipment is expensive and the unit production cost is high, which significantly reduces the economic benefits. On the other hand, extrusion molding is currently a widely used molding method due to its simple equipment and relatively low unit production cost. However, since molding the catalyst affects the internal / external material diffusion resistance, this will lead to a decrease in the activity of the molded catalyst. Therefore, various studies are needed to minimize the decrease in activity. Summary of the invention

[0011]

Technical issues

[0012] An object of the present disclosure is to provide an ortho-alkylation reaction catalyst and an ortho-alkylation reaction extrusion catalyst, which can achieve excellent conversion rate and yield in the preparation of a selective ortho-alkylation reaction product.

[0013] Another object of the present disclosure is to provide an ortho-alkylation reaction catalyst and an ortho-alkylation reaction extruded molded catalyst, which can achieve uniform catalytic activity inside and outside the molded catalyst without reducing the activity.

[0014] Another object of the present invention is to provide a method for preparing an ortho-alkylation reaction product using the catalyst.

[0015]

Technical solution

[0016] In order to achieve the above object, the present invention provides an ortho-alkylation reaction catalyst, which comprises:

[0017] It has a bimodal pore structure and a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide.

[0018] The present invention also provides an ortho-alkylation reaction extrusion molding catalyst, which comprises magnesium oxide, and

[0019] It includes macropores with diameters ranging from 50nm to 10,000nm and mesopores with diameters ranging from 2nm to 50nm.

[0020] The BET surface area is 45 m 2 / g to 180m 2 / g.

[0021] The invention also provides a method for preparing the ortho-alkylation reaction catalyst.

[0022] Specifically, the present invention provides a method for preparing an ortho-alkylation reaction catalyst, which comprises:

[0023] Step 1: Preparation of a nanostructured nanostructured nanostructure with a bimodal pore structure and a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide, an organic binder and a solvent; and

[0024] Step 2, extruding the mixture into a mold.

[0025] The present invention also provides an ortho-alkylation reaction composition, which comprises: the ortho-alkylation reaction catalyst or the ortho-alkylation reaction extrusion molding catalyst, and a monomer composition comprising a meta-alkyl-substituted phenolic monomer.

[0026] The present invention also provides a method for preparing an ortho-alkylation reaction product, which comprises:

[0027] The step of subjecting the monomer composition containing the meta-alkyl-substituted phenolic monomer to an alkylation reaction in the presence of the ortho-alkylation reaction catalyst or the ortho-alkylation reaction extrusion molding catalyst.

[0028]

Beneficial Effects

[0029] The ortho-alkylation reaction catalyst according to the present disclosure exhibits high catalytic activity by using magnesium oxide having specific physical properties and pore structure, and when the ortho-alkylation reaction product is prepared using the catalyst, it exhibits significantly high selectivity and conversion rate.

[0030] The ortho-alkylation reaction catalyst according to the present disclosure exhibits high catalytic activity itself without using a separate co-catalyst or additional additives, and when the ortho-alkylation reaction product is prepared using the catalyst, it exhibits significantly high selectivity and conversion rate.

[0031] The ortho-alkylation reaction extrusion-molded catalyst according to the present disclosure exhibits high catalytic activity, and when the ortho-alkylation reaction product is prepared using the catalyst, it exhibits significantly high selectivity and conversion rate.

[0032] In addition, the ortho-alkylation reaction extruded molded catalyst according to the present disclosure includes appropriately formed macropores and mesopores and has a suitable BET specific surface area, thereby providing an ortho-alkylation reaction extruded molded catalyst that can minimize the material diffusion resistance of the catalyst and achieve uniform and excellent catalytic activity inside and outside the molded catalyst without reducing the activity.

[0033] The ortho-alkylation reaction extrusion molding catalyst according to the present disclosure is prepared by using a combination of magnesium oxide, an organic binder and a solvent having specific physical properties, so it itself exhibits high catalytic activity without the need to use a separate co-catalyst or additional additives. When the catalyst is used to prepare an ortho-alkylation reaction product, it exhibits very high selectivity and conversion rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 : is a graph showing the selectivity of reaction products prepared using the ortho-alkylation reaction catalysts of Examples and Comparative Examples of the present disclosure.

[0035] Figure 2 is an XDR chart of the ortho-alkylation reaction catalysts of the Examples and Comparative Examples of the present disclosure.

[0036] Figure 3 is a graph showing pore distribution of ortho-alkylation reaction catalysts according to Examples and Comparative Examples of the present disclosure based on N2 adsorption-desorption analysis.

[0037] Figure 4 1 is a graph showing the relationship between the conversion rate and the selectivity according to the catalyst type in the ortho-alkylation reaction extrusion molding catalysts of the Examples and Comparative Examples of the present disclosure.

[0038] Figure 5 : is a graph showing the relationship between conversion and selectivity according to the type / content of the binder in the ortho-alkylation reaction extrusion catalyst of the embodiment of the present disclosure.

[0039] Figure 6 is a graph showing the relationship between pore diameter and pore volume for types of shaped catalysts according to Examples and Comparative Examples of the present disclosure. DETAILED DESCRIPTION

[0040] Although the present disclosure may have various forms and various modifications may be made thereto, specific examples will be illustrated and explained in detail below. However, it is not intended to limit the present disclosure to a specific disclosure, and it should be understood that the present disclosure includes all modifications, equivalents or substitutions that do not depart from the spirit and technical scope of the present disclosure.

[0041] The technical terms used herein are only used to explain the exemplary embodiments and are not intended to limit the scope of the present disclosure. The singular forms "a", "an" and "the" are intended to include the plural forms, unless the context clearly indicates otherwise. It should be understood that the terms "comprising", "including", "having" and the like are used herein to specify the presence of stated features, steps, components or combinations thereof, but do not exclude the presence or addition of one or more other features, steps, components or combinations thereof.

[0042] Additionally, when used in the context of forming or configuring an element, the term "on" or "over" means referring to the formation or configuration of one element directly on another element or an element being additionally formed or configured between two layers or on a body or substrate.

[0043] 1. Ortho-alkylation catalyst

[0044] (A. Ortho-alkylation catalyst)

[0045] Magnesium-based catalysts commonly used in alkylation reactions are required to have high activity, long activity life, and high selectivity for the desired reaction products. Most alkylation catalysts used in the past produce large amounts of para-alkylated products, but various studies have been conducted to obtain more useful ortho-alkylated products in high yields.

[0046] Specifically, recently, various techniques have been developed to further use a combination of a co-catalyst compound and a magnesium-based catalyst, change the composition of the catalyst, or change the reaction conditions. However, these techniques have the problem that it is difficult to obtain an ortho-alkylated product with a high selectivity and yield at the expected level.

[0047] In addition, the present inventors have confirmed that, in order to solve these problems, the BET specific surface area and the pore structure of the magnesium oxide catalyst are set within a specific range, thereby achieving significantly high catalytic activity in the alkylation reaction. The present inventors have found that the ortho-alkylation reaction catalyst according to the present disclosure exhibits excellent catalytic activity by a single catalyst even without further using a co-catalyst or adjusting the reaction conditions, and when the ortho-alkylation reaction product is prepared using the catalyst, very high selectivity and conversion can be exhibited, thereby completing the present invention.

[0048] The ortho-alkylation reaction catalyst according to an embodiment of the present disclosure comprises a catalyst having a bimodal pore structure and a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide.

[0049] Generally speaking, the catalytic activity of a catalyst is determined by the reaction conditions or the acid-base properties of the catalyst. In the alkylation reaction of a meta-alkyl-substituted phenolic monomer, if the catalyst has a basic property, it will vertically adsorb the reactants and favor ortho-C-alkylation (see structural formula (a) below). Therefore, the ortho-alkylation reaction catalyst according to the present disclosure contains a magnesium oxide (MgO) component.

[0050]

[0051] Magnesium oxide has a bimodal pore structure, specifically a mesopore bimodal shape, which is conducive to the diffusion of reactants, so that the reaction can be carried out efficiently. In addition, by simultaneously satisfying the above-mentioned specific range of BET surface area, it has excellent catalytic activity in ortho-alkylation reactions and can show high selectivity, conversion rate and yield.

[0052] Generally, the larger the BET surface area, the more active sites the catalyst has, but in the case of a single-peak shape, even if the BET surface area increases, diffusion of reactants is not smooth, which makes it difficult to carry out the reaction to a desired extent.

[0053] Preferably, in the bimodal pore structure, the diameter of the first pore may be 2nm to 10nm, and the diameter of the second pore may be 10nm to 50nm. More preferably, the diameter of the first pore may be 4nm to 8nm, and the diameter of the second pore may be 20nm to 45nm or 35nm to 45nm. The bimodal pore structure having a diameter within the above range makes it possible to exhibit the desired excellent catalytic activity, improved selectivity, conversion rate and yield.

[0054] The magnesium oxide satisfies a BET specific surface area of ​​100 m 2 / g to 180m 2 / g, there are many reactive sites and a large specific surface area, so the catalytic activity is excellent. At the same time, as mentioned above, magnesium oxide has a bimodal pore structure, which is also conducive to the diffusion of reactants, so that the reaction can be carried out effectively. As a result, magnesium oxide has excellent catalytic activity in ortho-alkylation reactions and can show improved selectivity, conversion rate and yield. When the BET specific surface area is less than 100m 2 / g, the number of active sites is significantly reduced, the conversion rate of the reactants is reduced, and it is difficult to achieve the desired activity. In addition, when the BET specific surface area exceeds 180m 2 / g, the number of reaction active sites increases, but the first pores are mainly formed, the diffusion of reactants / products is not smooth, and it is difficult to obtain high activity.

[0055] Preferably, the BET specific surface area of ​​magnesium oxide can be 130 m 2 / g to 180m 2 / g, more preferably 130m 2 / g to 150m 2 / g, and within the above range, excellent catalytic activity can be achieved without the above problems, which is preferred.

[0056] The ortho-alkylation reaction catalyst may have a particle shape, and preferably, it may have a particle size of about 212 μm to 425 μm. Within the above particle size range, excellent catalytic activity may be achieved, which is preferred.

[0057] (B. Ortho-alkylation reaction extrusion molding catalyst)

[0058] Meanwhile, for alkylation reactions, a small amount of powdered catalyst can be used at the laboratory level, but in order to mass-produce the catalyst and apply it to a commercially available fixed-bed reactor, the catalyst must be properly molded to fit the reactor in consideration of the pressure drop during the reaction. The most commonly used methods for molding catalysts are extrusion molding and tableting. Tablet molding can produce precise molded body shapes, but the equipment is expensive and the unit production cost is high, significantly reducing the economic benefits. On the other hand, extrusion molding is currently a widely used molding method due to its simple equipment and relatively low unit production cost. However, since the extrusion molding of the catalyst affects the internal / external material diffusion resistance, this may lead to the problem of reduced activity of the prepared extrusion-molded catalyst.

[0059] Therefore, in order to solve these problems, the present inventors have derived the main factors affecting the catalytic activity of the molded catalyst when preparing the molded catalyst by extrusion molding. Specifically, the present inventors have confirmed that, as described above, magnesium oxide having a specific pore structure is used, while appropriately molding large-size pores and medium-size pores in the final catalyst to achieve a suitable BET specific surface area, thereby minimizing the influence on the internal / external material diffusion resistance and achieving uniform catalytic activity in the prepared extrusion-molded catalyst, thereby completing the present invention.

[0060] In addition, the present inventors have confirmed that, for an extruded catalyst prepared by including a specific magnesium oxide, when the catalyst satisfies an appropriate pore distribution and BET specific surface area, a significantly high catalytic activity can be achieved in an alkylation reaction. In this regard, the present inventors have found that the ortho-alkylation reaction catalyst according to the present disclosure exhibits excellent catalytic activity by a single catalyst even without further using a co-catalyst or adjusting reaction conditions, and when the ortho-alkylation reaction product is prepared using the catalyst, very high selectivity and conversion can be exhibited, thereby completing the present invention.

[0061] The ortho-alkylation reaction extrusion molding catalyst according to an embodiment of the present disclosure comprises magnesium oxide, and macropores having a diameter of 50 nm to 10,000 nm and mesopores having a diameter of 2 nm to 50 nm, wherein the BET surface area satisfies 45 m 2 / g to 180m 2 / g.

[0062] As mentioned above, the catalytic activity of the catalyst is generally determined by the reaction conditions or the acid-base properties of the catalyst. Therefore, the ortho-alkylation reaction extrusion molding catalyst according to the present disclosure includes a magnesium oxide (MgO) component, so that the catalyst has alkaline properties, vertically adsorbs reactants, and is conducive to ortho-C alkylation (see structural formula (a) above).

[0063] The catalyst is prepared using magnesium oxide having a bimodal pore structure, wherein the magnesium oxide used in the preparation step specifically has a bimodal shape of mesopores, thereby facilitating the diffusion of reactants and enabling the reaction to proceed effectively. As a result, the magnesium oxide has excellent catalytic activity in ortho-alkylation reactions and can exhibit high selectivity, conversion rate and yield.

[0064] The ortho-alkylation reaction extrusion catalyst comprises macropores with diameters ranging from 50 nm to 10,000 nm and mesopores with diameters ranging from 2 nm to 50 nm.

[0065] In this way, macropores and mesopores are appropriately formed to minimize the material diffusion resistance of the catalyst, which makes it possible to achieve uniform and excellent catalytic activity inside and outside the shaped catalyst without reducing the activity.

[0066] Based on the total mixed volume of macropores and mesopores, the content of macropores in the ortho-alkylation reaction extrusion molding catalyst can be 1 to 10 volume %, preferably 1 to 9 volume %, 2 to 10 volume %, 2 to 9 volume % or 2 to 5 volume %. When the content is within the above range, the material diffusion resistance of the molding catalyst can be minimized, so this is preferred.

[0067] Based on the total mixed volume of macropores and mesopores, the mesopore content of the ortho-alkylation reaction extrusion molding catalyst can be 90 to 99 volume %, preferably 90 to 98 volume %, 91 to 98 volume % or 95 to 98 volume %. When the content is within the above range, the molded catalyst is suitable for achieving excellent catalytic activity without reducing activity.

[0068] The method for measuring the pore size and pore volume distribution of the catalyst will be described in more detail in the experimental examples described below.

[0069] The BET specific surface area of ​​the extruded catalyst for ortho-alkylation reaction is 45 m 2 / g to 180m 2 / g.

[0070] The catalyst has appropriately formed macropores and mesopores while exhibiting a specific range of BET specific surface area values, which can minimize the material diffusion resistance of the catalyst, thereby achieving uniform and excellent catalytic activity inside and outside the formed catalyst without reducing the activity.

[0071] Preferably, the BET specific surface area can be 45 m 2 / g to 150m 2 / g, 45m 2 / g to 130m 2 / g, or 60m 2 / g to 130m 2 / g, and when the specific surface area is within the above range, the material diffusion resistance of the molded catalyst can be minimized, which is preferred. The method for measuring the BET specific surface area of ​​the catalyst will be described in more detail in the experimental examples described below.

[0072] At the same time, the pore distribution and BET specific surface area of ​​the catalyst can be preferably achieved by combining an organic binder and a solvent with magnesium oxide having specific physical properties. This will be described in more detail in the preparation method section.

[0073] The ortho-alkylation reaction extrusion catalyst may meet the size of 0.5 mm to 6.0 mm, and uniform and excellent catalytic activity may be achieved within this range. More preferably, the size of the catalyst may be 1.0 mm to 3.0 mm or 1.2 to 2.0 mm. If the size of the catalyst is too small outside the above range, a large pressure drop may occur during the alkylation reaction, which may be problematic, and if the catalyst size is too large outside the above range, there may be a reduction in catalytic activity.

[0074] The size of the catalyst can be controlled by the diameter of the extrusion die used in the final extrusion step of the manufacturing process.

[0075] Typically, the shape of the extruded catalyst is realized as a cylinder by an extrusion die, wherein the ratio between the diameter of the circular cross-section of the cylinder and the length of the cylinder of the extruded catalyst according to the present disclosure may be 1:1 (±0.1).

[0076] Therefore, the size of the extruded catalyst may refer to the diameter of the circular cross section of the cylinder and / or the length of the cylinder. Preferably, both the circular cross section and the length of the cylinder satisfy the above ranges.

[0077] The specific method of measuring the catalyst size will be described in more detail in the experimental examples described below.

[0078] 2. Method for preparing ortho-alkylation reaction extrusion molding catalyst

[0079] According to another embodiment of the present invention, a method for preparing an ortho-alkylation reaction extrusion molding catalyst is provided, comprising the following steps as the above-mentioned method for preparing an ortho-alkylation reaction extrusion molding catalyst (B).

[0080] Specifically, the method comprises the step of preparing a nanostructured nanostructured nanostructure having a bimodal pore structure and a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide, an organic binder and a solvent; and step 2: extruding the mixture.

[0081] Hereinafter, each step will be described in detail.

[0082] Step 1: Steps to prepare the mixture

[0083] First, a nanostructured nanostructured nanostructure with a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide, an organic binder and a solvent.

[0084] The magnesium oxide may be applied in the same manner as described for the ortho-alkylation extruded catalyst.

[0085] Preferably, the magnesium oxide has a bimodal pore structure, specifically, a bimodal shape in the mesopore range, which is beneficial to the diffusion of reactants and enables the reaction to proceed efficiently. This allows excellent catalytic activity in ortho-alkylation reactions and exhibits high selectivity, conversion rate and yield.

[0086] Generally, the larger the BET surface area, the more active sites the catalyst has, but in the case of a single-peak shape, even if the BET surface area increases, diffusion of reactants is not smooth, which makes it difficult to carry out the reaction to a desired extent.

[0087] Preferably, in the bimodal pore structure, the diameter of the first pore may be 2nm to 10nm, and the diameter of the second pore may be 10nm to 50nm. More preferably, the diameter of the first pore may be 4nm to 8nm, and the diameter of the second pore may be 20nm to 45nm or 35nm to 45nm. The bimodal pore structure having a diameter within the above range makes it possible to exhibit the desired excellent catalytic activity, improved selectivity, conversion rate and yield.

[0088] The magnesium oxide satisfies a BET specific surface area of ​​100 m 2 / g to 180m 2 / g, there are many reactive sites and a large specific surface area, so the catalytic activity is excellent. At the same time, as mentioned above, magnesium oxide has a bimodal pore structure, which is also conducive to the diffusion of reactants, so that the reaction can be carried out effectively. As a result, magnesium oxide has excellent catalytic activity in ortho-alkylation reactions and can show improved selectivity, conversion rate and yield. When the BET specific surface area is less than 100m 2 / g, the number of active sites is significantly reduced, the conversion rate of the reactants is reduced, and it is difficult to achieve the desired activity. In addition, when the BET specific surface area exceeds 180m 2 / g, the number of reaction active sites increases, but the first pores are mainly formed, the diffusion of reactants / products is not smooth, and it is difficult to obtain high activity.

[0089] Preferably, the BET specific surface area of ​​magnesium oxide can be 130 m2 / g to 180m 2 / g, more preferably 130m 2 / g to 150m 2 / g, and within the above range, excellent catalytic activity can be achieved without the above problems, which is preferred.

[0090] The organic binder is a component that uniformly binds magnesium oxide during the preparation of the molded catalyst to make the preparation of the catalyst easier, and particularly plays an important role in forming appropriate pores inside the catalyst by baking during the preparation of the extrusion molded catalyst, thereby achieving uniformity of catalyst activity. When magnesium oxide having the above-mentioned specific physical properties is used alone, the ease of catalyst preparation may be reduced, and the formation of the desired pores may be slightly difficult, but if magnesium oxide is used in combination, more excellent catalyst activity can be uniformly achieved, which is preferred.

[0091] Specific examples of the organic binder include methylcellulose, carboxymethylcellulose, ethylene glycol, polyethylene glycol, polyphenylene ether, glycerol and propylene glycol, which can be used alone or in combination of two or more. More preferably, methylcellulose, carboxymethylcellulose, polyethylene glycol (PEG 20000 or PEG 400) can be used.

[0092] The content of the organic binder may be 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, 0.1 to 10 parts by weight, or 1 to 5 parts by weight, based on 100 parts by weight of magnesium oxide. Using the organic binder within the above range is suitable for achieving the above effects.

[0093] The solvent is used to knead the mixture uniformly and facilitate extrusion when producing an extrusion molded product.

[0094] Specific examples of solvents include water, alcohols, etc., which can be used alone or in combination of two or more. More preferably, water can be used. Water can be distilled water, ion exchange water or high purity water (such as deionized water (DIW)). When water contains impurities, the impurities may adhere to the catalyst and reduce the activity of the catalyst, so ultrapure water, etc. are preferably used. In the case of alcohol, primary alcohols above C3 can be used.

[0095] Based on 100 parts by weight of magnesium oxide, the content of the solvent may be 50 to 200 parts by weight, preferably 80 to 150 parts by weight or 100 to 120 parts by weight. The mixture mixed in the above ratio may preferably be in the form of a paste. In this case, an extrusion molding process may be easily performed, which is preferred.

[0096] At the same time, according to an embodiment of the present disclosure, additional additives may be optionally used in the mixture, for example, a lubricant may be used so that the final shaped catalyst can be prepared uniformly or without pulverization during the preparation process. Specific examples of lubricants include, but are not limited to, magnesium stearate, aluminum stearate, graphite, and the like.

[0097] In addition, other additives used in the art may be used without particular limitation within the range not impairing the desired physical properties.

[0098] Step 2: Extrusion step

[0099] Next, the method includes step 2 of extruding the mixture.

[0100] Generally, the tablet molding used in the catalyst molding method can produce a precise shape of the molded body, but the equipment is expensive, the unit cost of production is high, and the economic benefit is significantly reduced. On the other hand, extrusion molding is a widely used molding method at present because of its simple equipment and relatively low unit cost of production. However, when the catalyst is molded, it may affect the internal / external material diffusion resistance, which may lead to a decrease in the activity of the molded catalyst. However, in the present disclosure, magnesium oxide, an organic binder and a solvent with specific physical properties are used in combination as described above, so that an extrusion-molded catalyst with high activity and no such problems can be prepared, and at the same time, the uniformity of the catalyst inside and outside is obtained.

[0101] The extrusion molding process can generally be performed by using a screw type extruder and a piston type extruder, but preferably, can be performed by using a single piston extruder, and in this case, an extrusion molding catalyst having a low moisture content and a high compression ratio under high pressure can be prepared. In this case, the extrusion process can be performed by a die of a specific diameter, but is not limited thereto.

[0102] The average diameter of the extrusion die used can be appropriately adjusted according to the desired diameter range of the final shaped catalyst.

[0103] Additional steps: drying and baking steps

[0104] In one embodiment of the present disclosure, the method may further include drying and baking steps after extrusion molding.

[0105] The process conditions of the drying and baking steps may be applicable to processes commonly used in the art without any specific limitation.

[0106] Specifically, the temperature at which the drying step is performed is not particularly limited, but the drying may be, for example, 80°C to 120°C, preferably 90°C to 110°C.

[0107] The time for performing the drying step is not particularly limited, but can be performed, for example, for 1 hour to 13 hours, preferably 3 hours to 8 hours, or 4 hours to 6 hours.

[0108] The temperature at which the baking step is performed is not particularly limited, but the baking may be performed, for example, at 300°C to 600°C, preferably 400°C to 550°C.

[0109] The baking step is performed for a period of time that is not particularly limited, but is performed for a suitable period of time or longer to remove the organic binder and solvent in the mixture and to form desired pores in the catalyst. Preferably, the baking may be performed for 1 to 9 hours, or 3 to 6 hours.

[0110] The catalyst produced by the above-mentioned method for preparing the ortho-alkylation reaction extrusion molding catalyst adopts a combination of magnesium oxide, organic binder and solvent with specific physical properties, thereby achieving uniform and excellent catalytic activity inside and outside the molded catalyst without reducing the activity.

[0111] 3. Ortho-alkylation reaction composition

[0112] According to one embodiment of the present disclosure, the ortho-alkylation reaction composition comprises: the ortho-alkylation reaction catalyst (A) or the ortho-alkylation reaction extrusion molding catalyst (B) mentioned above, and a monomer composition comprising a meta-alkyl-substituted phenolic monomer.

[0113] The ortho-alkylation catalyst (A) comprises a catalyst having a bimodal pore structure and a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide. In this regard, the above contents are all applicable to the catalyst. Specifically, magnesium oxide has a bimodal pore structure, especially a bimodal shape with mesopores, which makes the diffusion of reactants smooth, so that the reaction can be carried out effectively. In addition, by simultaneously satisfying the above-mentioned specific range of BET surface area, it has excellent catalytic activity in ortho-alkylation reaction and can show high selectivity and conversion rate.

[0114] In addition, the ortho-alkylation reaction extrusion molding catalyst (B) contains magnesium oxide, includes macropores having a diameter of 50 nm to 10,000 nm and mesopores having a diameter of 2 nm to 50 nm, and has a BET surface area of ​​45 m 2 / g to 180m 2 / g. In this regard, the above contents are all applicable to the catalyst. Specifically, the extruded catalyst has the above-mentioned macropores and mesopores appropriately formed to minimize the material diffusion resistance of the catalyst, thereby achieving uniform and excellent catalytic activity inside and outside the molded catalyst without reducing the activity.

[0115] In addition, the magnesium oxide contained in the ortho-alkylation reaction extrusion molding catalyst has a bimodal pore structure, specifically, it has a bimodal shape of mesopores, which is conducive to the diffusion of reactants, so that the reaction can be carried out efficiently. In addition, by simultaneously satisfying the above-mentioned specific range of BET surface area, it is possible to have excellent catalytic activity in the ortho-alkylation reaction and exhibit high selectivity and conversion rate.

[0116] In the monomer composition, the meta-alkyl-substituted phenolic monomer may be meta-cresol.

[0117] In addition to the meta-alkyl-substituted phenolic monomer, the monomer composition also contains alkanol and distilled water (DI water), wherein the alkyl group can be introduced by reaction with the alkanol, and distilled water is used at the same time to suppress the decomposition reaction of the alkanol, which is preferred. The alkanol can preferably be methanol.

[0118] The monomer composition may preferably contain a phenolic monomer:alkanol:distilled water in a ratio of 1:3 to 10:1 to 5 parts by weight, more preferably 1:4 to 6:1 to 3 parts by weight. In this case, if the content of the alkanol is in a small amount exceeding the above range, the alkylating agent (reagent) will be reduced, and the conversion rate will be reduced. If the content of the distilled water is in a small amount exceeding the above range, the effect of suppressing the decomposition reaction of the alkanol will be reduced, and if the content of the alkanol or distilled water is in an excessive amount exceeding the above range, the phenolic monomer may be competitively adsorbed to the catalyst active site, resulting in a problem of reduced reactivity.

[0119] When the content is within the above range, it is preferably possible to prepare an ortho-alkylation reaction product with desired selectivity and conversion.

[0120] 4. Preparation method of ortho-alkylation reaction product

[0121] According to one embodiment of the present disclosure, the preparation method of the ortho-alkylation reaction product comprises: in the presence of the above-mentioned ortho-alkylation reaction catalyst (A) or the ortho-alkylation reaction extrusion molding catalyst (B), a monomer composition containing a meta-alkyl-substituted phenolic monomer is subjected to an alkylation reaction. Specifically, the method for preparing the ortho-alkylation reaction product can be carried out using an ortho-alkylation reaction composition containing the above-mentioned ortho-alkylation reaction catalyst or the ortho-alkylation reaction extrusion molding catalyst. The details of the catalyst and the reaction composition can be similarly applied to all of the above.

[0122] Specifically, by containing the above-mentioned ortho-alkylation reaction catalyst (A) or ortho-alkylation reaction extrusion molded catalyst B, uniform and excellent catalytic activity can be achieved inside and outside of the molded catalyst without reducing the activity.

[0123] In the method for preparing the ortho-alkylation reaction product, the monomer composition can be similarly applied to all of the above. Specifically, the monomer composition can be a meta-alkyl-substituted phenolic monomer, such as meta-cresol. By using a reaction composition comprising the above-mentioned extrusion molding catalyst, the method for preparing the ortho-alkylation reaction product can show high selectivity and conversion rate of the desired ortho-alkylation reaction product.

[0124] The ortho-alkylation reaction product may be, for example, at least one selected from the group consisting of 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 3,4-dimethylphenol and tetramethylphenol, and may be prepared by selectively replacing the ortho-alkyl group in m-cresol through the following multi-step reaction.

[0125]

[0126] The alkylation reaction may be preferably performed at 350° C. to 550° C., more preferably 350° C. to 550° C. In this case, if the temperature is lower than 350° C., the alkylation reaction may not be sufficiently activated, and if the temperature exceeds 550° C., a large amount of byproducts are generated due to excessive reaction.

[0127] The alkylation reaction can be carried out under inert conditions, for example, in the presence of an inert carrier gas. As the inert carrier gas, nitrogen, helium, neon, argon, etc. can be used, and nitrogen can be preferably used.

[0128] The nitrogen flow rate is not particularly limited, but is preferably 5 to 70 cc / min, 10 to 50 cc / min, or 15 to 40 cc / min. By conducting the reaction under the above conditions, an ortho-alkylation reaction product can be prepared with desired selectivity and conversion, which is preferred.

[0129] Meanwhile, before the monomer composition is introduced into the alkylation reaction, a step of raising and maintaining the inside of the reactor to an activation temperature for catalyst activation may be performed, and the temperature range may be the same as the reaction temperature. The time for catalyst activation is not particularly limited, but may be about 30 minutes to 1 hour.

[0130] The alkylation reaction can preferably be carried out using a continuous flow gas phase reactor. In this case, the monomer composition can be heated to 0.5 hr. -1 Up to 2.0hr -1 The reaction is carried out while being injected into a continuous flow gas phase reactor at a liquid hourly space velocity (LHSV) of 1.5 %. At this time, if the space velocity range is deviated from, the reactants may not be fully activated at the catalytic active sites, making it difficult to obtain the product smoothly, and the activity or selectivity of the catalyst may decrease, thereby reducing the amount of the product.

[0131] By conducting the reaction under the above-mentioned conditions, an ortho-alkylation reaction product can be prepared with desired selectivity and conversion, which is preferred.

[0132] The operation and effects of the present invention will be described in more detail below through specific examples. However, these examples are presented for illustrative purposes only, and the scope of the present disclosure is not limited thereby.

[0133] [Example 1 and Comparative Example 1: Ortho-Alkylation Reaction Using Ortho-Alkylation Reaction Catalyst (A)]

[0134] Example 1-1

[0135] The alkylation reaction of m-cresol was carried out using a continuous flow gas phase reactor. First, a magnesium oxide component (MgO-1, crystal structure: MgO) having the physical properties shown in Table 1 was prepared into a granular shape (212-425 um), and 1 g of the catalyst was loaded into a stainless steel tubular reactor with a diameter of 1 / 2 inch and a length of 50 cm, which was then installed in the main furnace.

[0136] Then, a mass flow controller (MFC) was used to flow N2 as a carrier gas (37.5cc / min), and the inside of the reactor was heated to the activation temperature (450°C) for catalyst activation and maintained for 1 hour. Then, a monomer composition (12.5mg / min, m-cresol: methanol: deionized water = 1:5:1, LHSV 0.75 / h) was introduced and evaporated through a preheater (250°C). The reaction composition comprising the catalyst and the monomer composition was introduced into the reactor, and then an alkylation reaction (450°C, maintained at normal pressure) was carried out for 5 hours to obtain a reaction product.

[0137] The products during the reaction were collected in liquid form (using IPA (isopropyl alcohol) as a solvent) for analysis.

[0138] Example 1-2 and Comparative Examples 1-1 to 1-9

[0139] An alkylation reaction was carried out in the same manner as in Example 1-1, except that the magnesium oxide component was changed as shown in Table 1 below, to obtain a reaction product.

[0140] [Experimental Example 1-1: Physical Property Analysis of Ortho-Alkylation Catalyst (A)]

[0141] (1) XRD analysis

[0142] The crystal structure of the catalyst used in the examples and comparative examples was confirmed by XRD analysis, and the crystallite size was calculated by the Scherrer formula using the maximum peak of the XRD spectrum. The results are shown in Tables 1 and Figure 2 shown.

[0143] In this case, K = 0.89 (the shape factor of the average crystallite), (wavelength of Cu Kα), and FWHM represents the full width at half maximum of the peak, and θ = maximum peak position.

[0144] (2) N2 adsorption-desorption analysis

[0145] The catalysts used in Examples and Comparative Examples were analyzed by N2 adsorption-desorption analysis to confirm the BET (Brunauer-Emmett-Teller) surface area, pore volume and size distribution.

[0146] The BET surface area was calculated using the adsorption value P / P0 = 0.05-0.3, and the pore volume and size distribution were calculated using the desorption value. The results are shown in Table 1 and Figure 3 .

[0147] [Table 1]

[0148]

[0149]

[0150] [Experimental Example 1-2: Analysis of ortho-alkylation reaction products]

[0151] The liquid collected from the reaction products prepared in Example 1 and Comparative Example 1 was analyzed using a gas chromatography (GC) apparatus equipped with a flame ionization detector (FID). Based on the GC result values, the conversion rate of m-cresol and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated using the following mathematical formulas 1 and 2, and the results are shown in Table 2 below.

[0152] The target product is defined as the final product 2,3,6-TMP, as well as the intermediate materials 2,5-DMP and 2,3-DMP, which can be further reacted to obtain the final product.

[0153] [Mathematical formula 1]

[0154]

[0155] [Mathematical formula 2]

[0156]

[0157] [Table 2]

[0158]

[0159] From the experimental data in Table 2, it can be seen that the catalyst comprising magnesium oxide having specific physical properties and pore structure of the present disclosure is confirmed to exhibit high catalytic activity even by a single catalyst, and when the catalyst is used to prepare an ortho-alkylation reaction product, it can exhibit very high selectivity and conversion rate.

[0160] [Example 2 and Comparative Example 2: Ortho-Alkylation Reaction Extrusion Molding Catalyst (B)]

[0161] Example 2-1. Preparation of extrudate catalyst (Preparation of extrusion molding catalyst)

[0162] 50 g of magnesium oxide (MgO powder, crystallite size 9 nm, BET surface area: 144.4 m 2 / g, total pore volume: 0.72cm 3 / g, pore size: 6,40nm), 1g organic binder (methyl cellulose) and 60g distilled water are placed in a mixing bowl and mixed evenly to make a paste. When the paste is completed, it is extruded through a 2mm diameter die using a single piston extruder catalyst molding device. The noodle shapes extruded from the single piston extruder are evenly spread on a tray.

[0163] Next, after drying at 100° C. for 4 hours using a convection oven, the dried extruded catalyst was cut into 2 mm intervals and baked at 450° C. for 6 hours using a muffle furnace to prepare a magnesium-based extruded catalyst (A-1).

[0164] Comparative Example 2-1. Preparation of Tableted Catalyst

[0165] First, magnesium oxide (MgO powder, crystallite size: 9 nm, BET surface area: 144.4 m 2 / g, total pore volume: 0.72cm 3 / g, pore size: 6,40nm) was tableted into a disc shape, and then pulverized to prepare granules with a suitable particle size and provide fluidity. 10 wt% of an organic binder (PPO, polyphenylene ether) and 1 wt% of a lubricant (magnesium stearate) were mixed into the prepared granules, and a single rotary tableting catalyst molding device was used to produce a tablet with a diameter of 2.4 mm.

[0166] Next, the dried pelletized catalyst was dried in a convection oven at 100° C. for 4 hours, and then baked in a muffle furnace at 450° C. for 1 hour, thereby completing a magnesium-based pelletized catalyst (B-1).

[0167] Examples 2-2 to 2-8

[0168] The same procedure was performed in the same manner as in Example 1-1, except that the components and contents of the binder resin and the solvent used in Example 1-1 were changed as shown in Table 3 below.

[0169] [Table 3]

[0170]

[0171]

[0172] [Experimental Example 2-1: Analysis of ortho-alkylation reaction extrusion molding catalyst (B)]

[0173] (1) BET specific surface area analysis

[0174] The catalysts of Example 1 and Comparative Example 1 were subjected to nitrogen adsorption / desorption analysis experiments. The isothermal adsorption curves and the amount of adsorbed nitrogen at standard temperature and pressure were measured according to the BET (Brunauer Emmett Teller) calculation formula to determine the BET specific surface area value. The results are shown in Table 4.

[0175] The average diameter of the catalyst in the form of extrudates refers to the diameter of the circular cross-section of a cylindrical catalyst produced by a die mounted on a single piston extruder, and the average diameter of the catalyst in the form of tablets refers to the diameter of the circular cross-section of a cylindrical catalyst produced by a punch mounted on a rotary tablet press.

[0176] [Table 4]

[0177] category Size (average diameter) / shape <![CDATA[BET specific surface area (m 2 / g)]]> Example 2-1 (A-1) 2mm / extrudate 77.86 Example 2-2 (A-2) 1.2mm / extrudate 60.32 Example 2-3 (A-3) 2mm / extrudate 129.82 Example 2-4 (A-4) 2mm / extrudate 129.42 Example 2-5 (A-5) 2mm / extrudate 71.87 Example 2-6 (A-6) 2mm / extrudate 131.17 Example 2-7 (A-7) 2mm / extrudate 45.09 Example 2-8 (A-8) 2mm / extrudate 83.71 Comparative Example 2-1 (B-1) 2.4mm / tablet 82.40

[0178] (2) Hg porosity analysis

[0179] The pore structures of the large and medium regions of the catalysts of Example 2-1 and Comparative Example 2-1 were confirmed by Hg porosity. The results are shown in Tables 5 and Figure 6 shown.

[0180] [Table 5]

[0181]

[0182]

[0183] *It refers to the ratio of the total mixed volume of macropores and mesopores

[0184] From Tables 4, 5 and Figure 4It can be seen that it has been confirmed that in order to minimize the decrease in activity due to the diffusion resistance of the internal / external materials, it is necessary to prepare the extruded catalyst by extrusion using appropriate organic binders and solvents as limited in the present disclosure, thereby forming appropriate pores ranging from medium to large while having an appropriate range of BET surface area.

[0185] By achieving corresponding pore distribution and BET surface area values, the material diffusion resistance during the alkylation reaction can be minimized, thereby exhibiting high conversion and selectivity, which will be described in more detail in Experimental Example 2-2.

[0186] [Example 3 and Comparative Example 3: Ortho-Alkylation Reaction Using Ortho-Alkylation Reaction Extrusion Molding Catalyst (B)]

[0187] Example 3-1: Preparation of alkylation product of m-cresol

[0188] The alkylation reaction of m-cresol was carried out by a continuous flow gas phase reactor. First, 1 g of the formed catalyst of Example 1-1 having the physical properties of Table 1 was loaded into a stainless steel tubular reactor of 1 / 2 inch diameter x 50 cm length, and then installed in the main furnace.

[0189] Then, a mass flow controller (MFC) was used to flow N2 as a carrier gas (37.5cc / min), and the inside of the reactor was heated to the activation temperature (450°C) to activate the catalyst and maintained for 1 hour. Then, the monomer composition (12.5mg / min, m-cresol:methanol:DI water=1:5:1, LHSV 0.75 / h) was evaporated by a preheater (250°C) and then introduced. The reaction composition containing the catalyst and the monomer composition was introduced into the reactor, and then an alkylation reaction (450°C, maintained at normal pressure) was carried out for 5 hours to obtain a reaction product.

[0190] The products during the reaction were collected in liquid form (using IPA (isopropyl alcohol) as solvent) for analysis.

[0191] Examples 3-2 to 3-8, Comparative Example 3-1

[0192] The catalyst was subjected to an alkylation reaction in the same manner as in Example 3-1, except that the catalysts of Examples 2-2 to 2-8 and Comparative Example 2-1 in Table 3 were used instead of the catalyst of Example 2-1, thereby obtaining a reaction product.

[0193] [Experimental Example 3-2: Analysis of ortho-alkylation reaction products]

[0194] (3-2-1) Analysis of reaction products according to catalyst type

[0195] The liquid collected from the reaction products prepared in Example 3 and Comparative Example 3 was analyzed using a gas chromatograph (GC) equipped with a hydrogen flame ionization detector (FID). Based on the GC result values, the conversion rate of m-cresol and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP, tetramethylphenol) were calculated using the following mathematical formulas 1 and 2. The results are shown in Table 6. Figure 4 (catalyst type (size / shape)) and Figure 5 (Type / amount of binder used in catalyst preparation).

[0196] The target product is defined as the final product 2,3,6-TMP, as well as the intermediate materials 2,5-DMP and 2,3-DMP, which can be further reacted to obtain the final product.

[0197] [Mathematical formula 1]

[0198]

[0199] [Mathematical formula 2]

[0200]

[0201] [Table 6]

[0202]

[0203] From the experimental data in Table 6, it can be seen that when the extruded catalyst according to the present disclosure is used, it is confirmed that even if a single catalyst is used, it exhibits high catalytic activity, and when such a catalyst is used to prepare an ortho-alkylation reaction product, very high selectivity and conversion can be exhibited.

[0204] It was confirmed that in Comparative Example 3-1, it was difficult to achieve a desired level of catalytic activity by using a tablet-molded catalyst, and therefore, the conversion rate and the like were lowered compared to the Examples.

[0205] (3-2-2) Analysis of products according to reaction conditions

[0206] Example 4: Variation of reaction temperature

[0207] The alkylation reaction was carried out in the same manner as in Example 3-1, except that the methylation reaction temperature was increased from 400°C to 450°C by 10°C every 3 hours. The conversion rate of m-cresol and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated according to the method of Experimental Example 3-2, and the results are shown in Table 7 below.

[0208] Example 5: Variation of carrier gas flow rate

[0209] The alkylation reaction was carried out in the same manner as in Example 3-1, except that the carrier gas flow rate was 18.7 cc / min. The conversion rate of m-cresol and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated according to the method of the above Experimental Example 3-2. The results are shown in Table 7 below.

[0210] Example 6: Changes in the amount of methanol injected

[0211] The alkylation reaction was carried out in the same manner as in Example 3-1, except that m-cresol:methanol:DI water=1:4:1 (11.1 mg / min, LHSV 0.666 / h) and m-cresol:methanol:DI water=1:3:1 (9.7 mg / min, LHSV 0.582 / h) were injected as the liquid mixture containing the reactants in Example 3-1. The conversion rate of m-cresol and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated according to the method of the above Experimental Example 3-2. The results are shown in Table 7 below.

[0212] [Table 7]

[0213]

[0214]

[0215] It can be seen from the experimental data in Table 7 that the methylation reaction temperature starts at 400°C and increases by 10°C every 3 hours to 450°C, and the catalytic performance increases with the reaction.

[0216] It can be confirmed that Example 5, in which the nitrogen input amount is varied, has an influence on the contact time (GHSV, gas hourly space velocity) between the catalyst and the reactants.

[0217] It can be confirmed that Example 6, in which the ratio of the introduced feeds was changed, has an influence on the ratio of m-cresol, the reactants, and methanol as the alkylation medium.

Claims

1. An ortho-alkylation reaction catalyst comprising: It has a bimodal pore structure and a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide.

2. The ortho-alkylation reaction catalyst according to claim 1, wherein In the bimodal pore structure, The diameter of the first pore is 2 nm to 10 nm, and The diameter of the second pore is 10 nm to 50 nm.

3. The ortho-alkylation catalyst according to claim 1, wherein: The BET surface area is 130 m 2 / g to 180m 2 / g.

4. An ortho-alkylation reaction extrusion molding catalyst, Contains magnesium oxide, and It includes macropores with diameters ranging from 50nm to 10,000nm and mesopores with diameters ranging from 2nm to 50nm. The BET surface area is 45 m 2 / g to 180m 2 / g.

5. The ortho-alkylation reaction extrusion molding catalyst according to claim 1, wherein: Based on the total mixed volume of the macropores and the mesopores, The content of the macropores is 1 to 10 volume %, and The content of the mesopores is 90 to 99 volume %.

6. The ortho-alkylation reaction extrusion molding catalyst according to claim 1, wherein: The size of the extruded catalyst is 0.5 mm to 6.0 mm.

7. A method for preparing the catalyst according to claim 4, comprising: Step 1: Preparation of a nanostructured nanostructured nanostructure with a bimodal pore structure and a BET surface area of ​​100 m 2 / g to 180m 2 / g of magnesium oxide, an organic binder and a solvent; and Step 2, extruding the mixture into a mold.

8. The method for preparing a catalyst according to claim 7, wherein the bimodal pore structure comprises: a first hole having a diameter of 2 nm to 10 nm, and The second pore has a diameter of 10 nm to 50 nm.

9. The method for preparing a catalyst according to claim 7, wherein: Based on 100 parts by weight of magnesium oxide, The content of the organic binder resin is 0.1 to 20 parts by weight, and The content of the solvent is 50 to 200 parts by weight.

10. The method for preparing a catalyst according to claim 7, wherein: The organic binder includes at least one selected from the group consisting of methyl cellulose, carboxymethyl cellulose, ethylene glycol, polyethylene glycol, polyphenylene ether, glycerin, and propylene glycol.

11. The method for preparing a catalyst according to claim 7, wherein: The solvent is alcohol, water or a mixture thereof.

12. The method for preparing a catalyst according to claim 7, wherein: The solvent is water.

13. The method for preparing a catalyst according to claim 7, wherein: The extrusion molding in step 2 is performed by using a single piston extruder.

14. The method for preparing the catalyst according to claim 7, It also includes drying and baking after the extrusion molding in step 2.

15. The method for preparing a catalyst according to claim 14, wherein: The drying is performed at 80°C to 120°C.

16. The method for preparing a catalyst according to claim 14, wherein: The baking is performed at 300°C to 600°C.

17. An ortho-alkylation reaction composition, comprising the ortho-alkylation reaction catalyst according to claim 1 or the ortho-alkylation reaction extrusion molding catalyst according to claim 4, and a monomer composition containing a meta-alkyl-substituted phenolic monomer.

18. The ortho-alkylation reaction composition according to claim 17, wherein: The meta-alkyl-substituted phenolic monomer is meta-cresol.

19. The ortho-alkylation reaction composition according to claim 17, wherein: The monomer composition also includes an alkanol and distilled water.

20. The ortho-alkylation reaction composition according to claim 19, wherein: The monomer composition comprises a phenolic monomer:alkanol:distilled water in a ratio of 1:3 to 10:1 to 5 parts by weight.

21. A method for preparing an ortho-alkylation reaction product, comprising: In the presence of the ortho-alkylation reaction catalyst according to claim 1 or the ortho-alkylation reaction extrusion molding catalyst according to claim 4, a monomer composition containing a meta-alkyl-substituted phenolic monomer is subjected to an alkylation reaction.

22. The method for preparing an ortho-alkylation reaction product according to claim 21, wherein: The alkylation reaction is carried out at 350 to 550°C.

23. The method for preparing an ortho-alkylation reaction product according to claim 21, wherein: The alkylation reaction is carried out in a continuous flow gas phase reactor.

24. The method for preparing an ortho-alkylation reaction product according to claim 23, wherein: The monomer composition was stirred for 0.5 hr. -1 Up to 2.0hr -1 The liquid hourly space velocity (LHSV) of 1.5 wt% was injected into the continuous flow gas phase reactor.

25. The method for preparing an ortho-alkylation reaction product according to claim 21, wherein: The ortho-alkylation reaction product is at least one selected from 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 3,4-dimethylphenol and tetramethylphenol.

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