Ortho-alkylation reaction catalyst, ortho-alkylation reaction extrusion catalyst, and method for producing ortho-alkylation reaction products using the same.

Abstract

The present invention relates to an ortho-alkylation catalyst, an extrusion-molded ortho-alkylation catalyst, and a method for producing an ortho-alkylation product using the same. More specifically, the present invention relates to an ortho-alkylation catalyst, an extrusion-molded ortho-alkylation catalyst, and a method for producing an ortho-alkylation product using the same, which can minimize the material diffusion resistance of the catalyst in the ortho-alkylation reaction of a phenolic compound, thereby obtaining an ortho-alkylation product with high selectivity and conversion rate.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority rights based on Korean Patent Application No. 10-2022-0058310 dated May 12, 2022, and Korean Patent Application No. 10-2023-0055405 dated April 27, 2023, and all content disclosed in the documents of said Korean patent applications is incorporated herein by reference.

[0002] The present invention relates to an ortho-alkylation reaction catalyst, an ortho-alkylation reaction extrusion catalyst, and a method for producing an ortho-alkylation reaction product using the same. More specifically, the present invention relates to an ortho-alkylation reaction catalyst, an ortho-alkylation reaction extrusion catalyst, and a method for producing an ortho-alkylation reaction product using the same, which minimize the material diffusion resistance of the catalyst in the ortho-alkylation reaction of phenolic compounds, thereby enabling the production of ortho-alkylation reaction products with high selectivity and conversion rate. [Background technology]

[0003] Alkylated hydroxyaromatic compounds have a wide range of applications and are typically produced by the gas-phase reaction of phenol and methanol. Furthermore, compounds with diverse structures can be generated through additional alkylation reactions, which are easily applicable to high-performance thermoplastic products and other applications.

[0004] Such additional alkylation reactions are typically carried out in the presence of magnesium-based compounds, and various studies are being conducted to optimize the performance of magnesium-based catalysts.

[0005] In alkylation reactions, magnesium-based catalysts are required to have high activity, a long activity lifetime, and high selectivity for the desired reaction product. Most alkylation catalysts used in the past produced large quantities of para-alkylated products, but various studies are being conducted to obtain ortho-alkylated products, which are more useful, in high yield.

[0006] However, the conventional techniques involve using an additional cocatalyst compound in combination with a magnesium-based catalyst, changing the composition of the catalyst, or changing the reaction conditions. There is a problem in the conventional techniques that it is difficult to obtain ortho-alkylation products with high selectivity and yield to the desired extent.

[0007] Therefore, in the ortho-alkylation reaction, there is a need to develop a catalyst improved in terms of catalyst selectivity, catalyst activity, production yield, cost reduction, and overall productivity.

[0008] On the other hand, for the alkylation reaction, although it is possible to use a small amount of catalyst in powder form at the laboratory level, in order to produce the catalyst in large quantities and apply it to a commercial fixed-bed reactor, the catalyst must be appropriately shaped to fit the reactor considering the pressure drop during the reaction.

[0009] The methods most commonly used in the normal catalyst shaping method are extrusion shaping and tablet shaping. Tablet shaping can produce an accurate shaped body, but the equipment is expensive and the manufacturing unit price is high, so the economic efficiency is significantly reduced. On the contrary, extrusion shaping is a frequently used shaping method because the equipment is simple and the manufacturing unit price is relatively low. However, when the catalyst is shaped, it may affect the internal / external mass transfer resistance, and thus the activity of the produced shaped catalyst may decrease. Therefore, various studies are needed to minimize the activity decrease.

Summary of the Invention

Problems to be Solved by the Invention

[0010] An object of the present invention is to provide an ortho-alkylation reaction catalyst and an ortho-alkylation reaction extrusion-shaped catalyst that can achieve excellent conversion rates and yields in the production of selective ortho-alkylation reaction products.

[0011] Another object of the present invention is to provide an ortho-alkylation reaction catalyst and an ortho-alkylation reaction extrusion-molded catalyst capable of realizing uniform catalytic activity inside and outside a catalyst molded without reduction in activity.

[0012] Another object of the present invention relates to a method for producing an ortho-alkylation reaction product using the catalyst.

Means for Solving the Problems

[0013] To solve the above problems, the present invention provides an ortho-alkylation reaction catalyst containing magnesium oxide having a bimodal pore structure and a BET specific surface area of 100 m / g to 180 m 2 / g. 2

[0014] Further, the present invention provides an ortho-alkylation reaction extrusion-molded catalyst containing magnesium oxide, including macropores having a diameter of 50 nm to 10,000 nm and mesopores having a diameter of 2 nm to 50 nm, and having a BET specific surface area of 45 m / g to 180 m 2 / g. 2

[0015] Further, the present invention provides a method for producing the ortho-alkylation reaction extrusion-molded catalyst.

[0016] Specifically, the present invention provides a method for producing an ortho-alkylation reaction extrusion-molded catalyst, including: a first step of producing a mixture of magnesium oxide having a bimodal pore structure and a BET specific surface area of 100 m 2 / g to 180 m 2 / g, an organic binder, and a solvent; and a second step of extrusion-molding the mixture.

[0017] Further, the present invention provides The present invention provides an ortho-alkylation reaction composition comprising the ortho-alkylation reaction catalyst or the ortho-alkylation reaction extrusion catalyst and a monomer composition comprising a meta-alkyl-substituted phenol monomer.

[0018] Furthermore, the present invention is The present invention provides a method for producing an ortho-alkylation reaction product, comprising the alkylation reaction of a monomer composition containing a meta-alkyl-substituted phenolic monomer in the presence of the ortho-alkylation reaction catalyst or the ortho-alkylation reaction extrusion catalyst. [Effects of the Invention]

[0019] The ortho-alkylation reaction catalyst according to the present invention exhibits high catalytic activity by using magnesium oxide having specific physical properties and porosity structure, and when used to produce ortho-alkylation reaction products, it shows remarkably high selectivity and conversion rate.

[0020] The ortho-alkylation reaction catalyst according to the present invention exhibits high catalytic activity on its own, without the use of a separate co-catalyst or additional additives, and when used to produce ortho-alkylation reaction products, it shows remarkably high selectivity and conversion rate.

[0021] The ortho-alkylation reaction extrusion catalyst according to the present invention exhibits high catalytic activity, and when used to produce ortho-alkylation reaction products, it shows remarkably high selectivity and conversion rate.

[0022] Furthermore, the ortho-alkylation reaction extrusion catalyst according to the present invention provides an ortho-alkylation reaction extrusion catalyst that minimizes the material diffusion resistance of the catalyst by appropriately forming macropores and mesopores and having an appropriate BET specific surface area, thereby enabling uniform and excellent catalytic activity both inside and outside the molded catalyst without any reduction in activity.

[0023] The ortho-alkylation reaction extrusion catalyst according to the present invention is manufactured using a combination of magnesium oxide with specific physical properties, an organic binder, and a solvent. It exhibits high catalytic activity on its own, without the use of a separate co-catalyst or additional additives, and when used to produce ortho-alkylation reaction products, it shows remarkably high selectivity and conversion rates. [Brief explanation of the drawing]

[0024] [Figure 1] This graph shows the selectivity of reaction products produced using the ortho-alkylation reaction catalysts of the present invention in examples and comparative examples. [Figure 2] This is an XDR graph of the ortho-alkylation reaction catalysts of the examples and comparative examples of the present invention. [Figure 3] This graph shows the pore distribution of ortho-alkylation reaction catalysts in examples and comparative examples of the present invention, as determined by N2 adsorption-desorption analysis. [Figure 4] This graph shows the conversion rate versus selectivity for ortho-alkylation reaction molding catalysts of the present invention, based on the type of catalyst used. [Figure 5] This graph shows the conversion rate versus selectivity depending on the type / content of the binder in the ortho-alkylation reaction molding catalyst of the present invention. [Figure 6] This graph shows the pore size to pore volume for different types of molding catalysts in the examples and comparative examples of the present invention. [Modes for carrying out the invention]

[0025] The present invention can be modified in various ways and may take many forms; specific embodiments are described in detail below. However, this is not intended to limit the present invention to any particular disclosure, but rather should be understood to include all modifications, equivalents, or substitutions that fall within the spirit and technical scope of the present invention.

[0026] Furthermore, the terms used herein are used solely to describe exemplary embodiments and are not intended to limit the invention. A singular expression includes plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “includes,” “equip,” or “have” are intended to specify the existence of implemented features, stages, components, or combinations thereof, and should not be understood to preemptively exclude the existence or possibility of adding one or more other features, stages, components, or combinations thereof.

[0027] Furthermore, in the present invention, when it is referred to that each component is formed "on top of" each other, it means that each component is formed directly on top of each other, and that other components may be additionally formed between layers, on the object, or on the substrate.

[0028] I. Ortho-alkylation reaction catalysts (A. Ortho-alkylation reaction catalyst) Magnesium-based catalysts typically used in alkylation reactions are required to have high activity, a long activity lifetime, and high selectivity for the desired reaction product. While most alkylation catalysts used in the past produced large quantities of para-alkylated products, various studies are being conducted to obtain ortho-alkylated products, which are more useful, with high selectivity.

[0029] Specifically, various techniques have recently been developed to combine magnesium-based catalysts with co-catalyst compounds, change the catalyst composition, or alter the reaction conditions. However, these techniques have the problem of making it difficult to obtain ortho-alkylation products with the desired level of selectivity and conversion rate.

[0030] Furthermore, in order to solve these problems, the inventors confirmed that by setting the BET specific surface area and pore structure of the magnesium oxide catalyst to a specific range, remarkably high catalytic activity can be achieved in alkylation reactions. The inventors completed the present invention by finding that the ortho-alkylation reaction catalyst according to the present invention exhibits excellent catalytic activity even as a single catalyst without the use of additional co-catalysts or adjustment of reaction conditions, and that when used to produce ortho-alkylation reaction products, it can exhibit remarkably high selectivity and conversion rate.

[0031] An ortho-alkylation reaction catalyst according to one embodiment of the invention has a bimodal porosity structure and a BET specific surface area of ​​100 m². 2 / g~180m 2 Contains magnesium oxide at / g.

[0032] Generally, the catalytic activity of a catalyst is determined by the reaction conditions and the catalytic acid-base properties. However, in the alkylation reaction of meta-alkyl-substituted phenolic monomers, if the catalyst has basic properties, it will perpendicularly adsorb the reactants and favor ortho-C-alkylation (see chemical formula (a) below). As a result, the ortho-alkylation reaction catalyst according to the present invention contains a magnesium oxide (MgO) component. [ka]

[0033] The magnesium oxide has a bimodal pore structure, specifically a bimodal configuration of mesopores, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. Furthermore, by simultaneously satisfying the aforementioned specific range of BET specific surface area, it exhibits excellent catalytic activity in ortho-alkylation reactions, resulting in high selectivity, conversion rate, and yield.

[0034] Generally, the greater the BET specific surface area, the more active sites the catalyst has. However, in the case of the single-modal form, even if the BET specific surface area increases, the diffusion of reactants is not smooth, making it difficult to carry out the reaction to the desired extent.

[0035] Preferably, in the bi-modal pore structure, the diameter of the first pore is 2 nm to 10 nm, and the diameter of the second pore can be 10 nm to 50 nm. More preferably, the diameter of the first pore is 4 nm to 8 nm, and the diameter of the second pore can be 20 nm to 45 nm or 35 nm to 45 nm. Through the bi-modal pore structure having diameters within the above ranges, excellent catalytic activity, improved selectivity, conversion rate, and yield can be achieved as desired.

[0036] The magnesium oxide has a BET specific surface area of 100 m 2 / g to 180 m 2 / g. Since it has a relatively large specific surface area and many reaction active sites, it has excellent catalytic activity. At the same time, as described above, having a bi-modal pore structure enables smooth diffusion of reactants so that the reaction can be effectively carried out. Thereby, it has excellent catalytic activity in the ortho-alkylation reaction and can exhibit improved selectivity, conversion rate, and yield. When the BET specific surface area is less than 100 m 2 / g, the number of reaction active sites is significantly reduced, resulting in a low reactant conversion rate and difficulty in achieving the desired activity. Also, when the BET specific surface area exceeds 180 m 2 / g, although the number of reaction active sites increases, mainly the first pores are formed, and there is a problem that it is difficult to realize high activity because the diffusion of reactants / products is not smooth.

[0037] Preferably, the BET specific surface area of the magnesium oxide is 130 m 2 / g to 180 m 2 / g, more preferably 130 m 2 / g to 150 m 2It can be / g, and is preferable because it can exhibit excellent catalytic activity without the aforementioned problems within the range.

[0038] The orthoalkylation reaction catalyst can have a granular shape, preferably with a particle size of about 212 μm to 425 μm, and is preferred because it can exhibit excellent catalytic activity within this particle size range.

[0039] (B. Ortho-alkylation reaction extrusion catalyst) On the other hand, for alkylation reactions, small amounts of catalyst in powder form can be used at the laboratory level. However, to produce catalysts in large quantities and apply them to commercial fixed-bed reactors, the catalyst must be properly molded to fit the reactor, taking into account the pressure drop during the reaction. The most commonly used methods for molding catalysts are extrusion molding and tablet molding. Tablet molding can produce precisely shaped bodies, but the equipment is expensive and the production cost is high, making it significantly less economical. Conversely, extrusion molding is a widely used molding method because the equipment is simple and the production cost is relatively low. However, when catalysts are extruded, it affects the internal / external material diffusion resistance, which can lead to a decrease in the activity of the extruded catalyst produced.

[0040] Therefore, in order to solve these problems, the inventors identified the main factors that affect the catalytic activity of the molded catalyst during manufacturing by extrusion molding. Specifically, as mentioned above, by using magnesium oxide having a specific pore structure, and simultaneously appropriately forming macro-sized and meso-sized pores in the final catalyst to realize an appropriate BET specific surface area, the influence on the internal / external substance diffusion resistance is minimized, and it was confirmed that uniform catalytic activity can be realized in the manufactured extruded catalyst, thus completing the present invention.

[0041] Furthermore, the inventors have confirmed that extrusion-molded catalysts manufactured containing specific magnesium oxides can exhibit remarkably high catalytic activity in alkylation reactions when the catalyst satisfies the requirements for appropriate pore distribution and BET specific surface area. Therefore, the inventors have found that the ortho-alkylation reaction catalyst according to the present invention exhibits excellent catalytic activity as a single catalyst without the need for additional co-catalysts or adjustments to reaction conditions, and that when used to produce ortho-alkylation reaction products, it exhibits remarkably high selectivity and conversion rates, thus completing the present invention.

[0042] An ortho-alkylation reaction extrusion catalyst according to one embodiment of the invention contains magnesium oxide and includes macropores with a diameter of 50 nm to 10,000 nm and mesopores with a diameter of 2 nm to 50 nm, with a BET specific surface area of ​​45 m². 2 / g~180m 2 Satisfy / g

[0043] As mentioned above, the catalytic activity of a catalyst is generally determined by the reaction conditions and the catalytic acid-base properties. In this way, the ortho-alkylation reaction extruded catalyst according to the present invention contains a magnesium oxide (MgO) component, which gives the catalyst basic properties and favors perpendicular adsorption of reactants for ortho-C-alkylation (see chemical formula (a) above).

[0044] The catalyst is manufactured using magnesium oxide having a bimodal pore structure. Specifically, the magnesium oxide used in the manufacturing step has a bimodal form with mesopores, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. As a result, it exhibits excellent catalytic activity in ortho-alkylation reactions, showing high selectivity, conversion rate, and yield.

[0045] The ortho-alkylation reaction extrusion catalyst includes macropores with a diameter of 50 nm to 10,000 nm and mesopores with a diameter of 2 nm to 50 nm.

[0046] By appropriately forming macropores and mesopores in this way, the material diffusion resistance of the catalyst is minimized, enabling uniform and excellent catalytic activity to be realized both inside and outside the molded catalyst without any reduction in activity.

[0047] The macropores of the ortho-alkylation reaction extruded catalyst may be present in an amount of 1 to 10 vol% relative to the total mixed volume of macropores and mesopores, preferably 1 to 9 vol%, 2 to 10 vol%, 2 to 9 vol%, or 2 to 5 vol%. This range is preferable because it minimizes the material diffusion resistance of the molded catalyst.

[0048] The mesopores of the ortho-alkylation reaction extruded catalyst may be present in an amount of 90-99 vol% relative to the total mixed volume of macropores and mesopores, preferably 90-98 vol%, 91-98 vol%, or 95-98 vol%. When present within these ranges, the molded catalyst is suitable for exhibiting excellent catalytic activity without any reduction in activity.

[0049] The method for measuring the pore size and pore volume distribution of the catalyst will be explained in more detail in the experimental examples described later.

[0050] The ortho-alkylation reaction extrusion catalyst has a BET specific surface area of ​​45 m². 2 / g~180m 2 It is / g.

[0051] The catalyst is designed to have appropriately formed macropores and mesopores, while simultaneously exhibiting a specific range of BET specific surface area values, thereby minimizing the material diffusion resistance of the catalyst and enabling uniform and excellent catalytic activity both inside and outside the formed catalyst without any reduction in activity.

[0052] Preferably, the BET specific surface area is 45 m². 2 / g~150m 2 / g, 45m 2 / g~130m 2 / g, or 60m 2 / g~130m 2 It is preferable that the specific surface area be within the range of / g, as this minimizes the material diffusion resistance of the molded catalyst. The method for measuring the BET specific surface area of ​​the catalyst will be explained in more detail in the experimental examples described later.

[0053] On the other hand, the pore distribution and BET specific surface area of ​​the catalyst can preferably be realized by combining magnesium oxide with specific properties with an organic binder and a solvent. This will be explained in more detail in the section on the manufacturing method.

[0054] The ortho-alkylation reaction extruded catalyst can satisfy a size range of 0.5 mm to 6.0 mm, and can exhibit uniform and excellent catalytic activity within this range. More preferably, the size of the catalyst may be 1.0 mm to 3.0 mm or 1.2 mm to 2.0 mm. If the catalyst size is excessively small outside the aforementioned range, a large pressure drop may occur during the alkylation reaction, which can be problematic. Conversely, if the size is excessively large outside the aforementioned range, there is a risk of a decrease in catalytic activity.

[0055] The size of the catalyst can be controlled by the diameter of the extrusion die used in the final extrusion stage of the manufacturing process.

[0056] While conventional extruded catalysts are formed into a cylindrical shape by an extrusion die, the extruded catalyst according to the present invention can have a ratio of 1:1 (±0.1) between the diameter of the circular cross-section of the cylinder and the length of the cylinder.

[0057] 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, and it is preferable that both the circular cross-section and the length of the cylinder simultaneously satisfy the aforementioned ranges.

[0058] The specific method for measuring the size of the catalyst will be explained in more detail in the experimental examples described later.

[0059] II. Method for Producing Ortho-Alkylation Reaction Extrusion Catalysts Furthermore, according to another embodiment of the invention, a method for producing the ortho-alkylation reaction extrusion catalyst (B) described above is provided, comprising the following steps.

[0060] Specifically, it has a bimodal porosity structure and a BET specific surface area of ​​100 m². 2 / g~180m 2 The process includes a first step of producing a mixture of magnesium oxide, an organic binder, and a solvent in a quantity of / g; and a second step of extruding the mixture.

[0061] The following provides a detailed explanation of each stage.

[0062] Stage 1: Mixture manufacturing stage First, it has a bimodal porosity structure and a BET specific surface area of ​​100 m². 2 / g~180m 2 A mixture is prepared by combining magnesium oxide (at a concentration of / g), an organic binder, and a solvent.

[0063] The magnesium oxide described above can be the same as the one described for ortho-alkylation reaction extrusion catalysts.

[0064] Preferably, the magnesium oxide has a bimodal porosity structure, specifically a bimodal morphology in the mesopore range, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. This results in excellent catalytic activity in ortho-alkylation reactions, exhibiting high selectivity, conversion rate, and yield.

[0065] Normally, a larger BET specific surface area increases the number of active sites of the catalyst. However, in the single-modal configuration, even if the BET specific surface area increases, the diffusion of reactants is not smooth, making it difficult for the reaction to proceed to the desired extent.

[0066] Preferably, in the bimodal pore structure, the diameter of the first pore may be 2 nm to 10 nm and the diameter of the second pore may be 10 nm to 50 nm, more preferably the diameter of the first pore may be 4 nm to 8 nm and the diameter of the second pore may be 20 nm to 45 nm or 35 nm to 45 nm. Through a bimodal pore structure having diameters in the above range, it becomes possible to exhibit the desired excellent catalytic activity, improved selectivity, conversion rate, and yield.

[0067] The magnesium oxide has a BET specific surface area of ​​100 m². 2 / g~180m 2 It satisfies the requirement of / g and has a relatively large specific surface area with many reactive sites, resulting in excellent catalytic activity. At the same time, as mentioned above, it has a bimodal pore structure that facilitates the diffusion of reactants, allowing the reaction to proceed effectively. As a result, it exhibits excellent catalytic activity in ortho-alkylation reactions, showing improved selectivity, conversion rate, and yield. The BET specific surface area is 100m². 2 If the amount is less than / g, the number of reactive sites decreases significantly, the reaction conversion rate becomes low, and it becomes difficult to realize the desired activity. Also, if the BET specific surface area is 180m² 2When the amount exceeds [amount] / g, the number of reaction active sites increases, but the primary pores are mainly formed, and the diffusion of reactants / products is not smooth, which presents a problem in that it is difficult to achieve high activity.

[0068] Preferably, the BET specific surface area of ​​the magnesium oxide is 130 m². 2 / g~180m 2 / g, comfortably, 130m 2 / g~150m 2 It can be / g, and is preferable because it can exhibit excellent catalytic activity without the aforementioned problems within the range.

[0069] The aforementioned organic binder is a component that plays a crucial role in achieving uniform catalytic activity by uniformly binding magnesium oxide during the production of molded catalysts, thereby facilitating catalyst manufacturing, and particularly by forming appropriate pores within the catalyst through calcination during the production of extruded catalysts. Using magnesium oxide with the aforementioned specific physical properties alone may reduce the ease of catalyst manufacturing and make it somewhat difficult to form the desired pores, but using it in combination is preferable because it allows for the uniform achievement of superior catalytic activity.

[0070] Specific examples of the organic binder include methylcellulose, carboxymethylcellulose, ethylene glycol, polyethylene glycol, polyphenylene oxide, glycerin, and propylene glycol, which can be used individually or in combination of two or more. More preferably, methylcellulose, carboxymethylcellulose, and polyethylene glycol (PEG20000 or PEG400) can be used.

[0071] The organic binder may be present in an amount of 0.1 to 20 parts by weight per 100 parts by weight of magnesium oxide, and is preferably used in amounts of 0.1 to 15 parts by weight, 0.1 to 10 parts by weight, or 1 to 5 parts by weight. It is suitable to be used within the above range to embody the effects described above.

[0072] The solvent is used to ensure that the mixture is uniformly kneaded, thereby facilitating extrusion during the manufacturing of the extruded product.

[0073] Specific examples of the solvent include water and alcohol, which can be used alone or in combination of two or more. Water is more preferably used. The water can be distilled water, deionized water, or highly purified water such as ultrapure water (DIW). If the water contains impurities, these impurities may adhere to the catalyst and reduce its activity; therefore, it is preferable to use ultrapure water or the like. In the case of alcohol, primary alcohols of C3 or higher are preferably used.

[0074] The solvent may be present in an amount of 50 to 200 parts by weight per 100 parts by weight of magnesium oxide, preferably 80 to 150 parts by weight or 100 to 120 parts by weight. The mixture obtained in the above ratio may preferably be in paste form. This is preferable because it allows for easy extrusion molding.

[0075] On the other hand, according to one embodiment of the invention, additional additives can be selectively used in the mixture, such as a lubricant, so that the final molding catalyst can be produced uniformly in the manufacturing process without crushing. Specific examples of the lubricant include, but are not limited to, magnesium stearate, aluminum stearate, and graphite.

[0076] Furthermore, other additives used in the field can be used without special restrictions, as long as they do not impair the desired physical properties.

[0077] Stage 2: Extrusion molding stage Next, the process includes a second step of extruding the mixture.

[0078] Tablet molding, a commonly used catalyst molding method, can produce precisely shaped molded bodies, but the equipment is expensive and the unit cost of production is high, resulting in significantly reduced economic efficiency. On the other hand, extrusion molding is a widely used molding method because the equipment is simple and the unit cost of production is relatively low. However, when a catalyst is molded, it affects the diffusion resistance of the material inside and outside, which can lead to a decrease in activity in the manufactured molded catalyst. In the present invention, however, by using magnesium oxide with specific physical properties in combination with an organic binder and solvent as described above, it is possible to manufacture an extruded catalyst that has high activity and uniformity inside and outside the catalyst without such problems.

[0079] The extrusion process can generally be carried out using a screw extruder or a piston extruder, but preferably using a single-piston extruder, in which case it is possible to produce an extruded catalyst with high pressure, low moisture content, and high compressibility. In this case, the extrusion process may be carried out through a die of a specific diameter, but is not limited thereto.

[0080] The average diameter of the extrusion die used can be appropriately adjusted according to the desired diameter range of the final molding catalyst.

[0081] Additional steps: Drying and firing steps In one embodiment of the invention, the steps of drying and firing may be further included after the extrusion molding.

[0082] The process conditions for the drying and firing stages can be those commonly applied in the art without any special restrictions.

[0083] Specifically, the temperature at which the drying step is performed is not particularly limited, but can be, for example, 80°C to 120°C, and preferably 90°C to 110°C.

[0084] The duration of the drying step is not particularly limited, but can be, for example, 1 to 13 hours, preferably 3 to 8 hours, or 4 to 6 hours.

[0085] The temperature at which the firing step is performed is not particularly limited, but can be, for example, 300°C to 600°C, and preferably 400°C to 550°C.

[0086] The duration of the calcination step is not particularly limited, but it should be carried out for a sufficient amount of time to remove the organic binder and solvent from the mixture and form the desired pores in the catalyst, preferably 1 to 9 hours or 3 to 6 hours.

[0087] The catalyst produced by the ortho-alkylation reaction extrusion catalyst manufacturing method described above can exhibit uniform and excellent catalytic activity both inside and outside the molded catalyst without any reduction in activity by using a combination of magnesium oxide, organic binder, and solvent with specific physical properties.

[0088] III. Ortho-alkylation reaction compositions According to one embodiment of the invention, the ortho-alkylation reaction composition comprises a monomer composition containing the aforementioned ortho-alkylation reaction catalyst (A) or ortho-alkylation reaction extrusion catalyst (B) and a meta-alkyl-substituted phenolic monomer.

[0089] The ortho-alkylation reaction catalyst (A) has a bimodal porosity structure and a BET specific surface area of ​​100 m². 2 / g~180m 2It contains magnesium oxide at a concentration of / g, to which all of the above-mentioned provisions can be applied equally. Specifically, the magnesium oxide has a bimodal pore structure, specifically a bimodal form of mesopores, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. Furthermore, by simultaneously satisfying the aforementioned specific range of BET specific surface area, it can exhibit excellent catalytic activity in ortho-alkylation reactions, showing high selectivity and conversion rates.

[0090] Furthermore, the ortho-alkylation reaction extrusion catalyst (B) contains magnesium oxide and includes macropores with a diameter of 50 nm to 10,000 nm and mesopores with a diameter of 2 nm to 50 nm, and 45 m 2 / g~180m 2 It has a BET specific surface area of ​​ / g. All of the above-mentioned provisions can be applied equally to this. Specifically, the extruded catalyst is designed so that the macropores and mesopores described above are appropriately formed to minimize the material diffusion resistance of the catalyst, thereby enabling uniform and excellent catalytic activity to be realized inside and outside the molded catalyst without any reduction in activity.

[0091] Furthermore, the magnesium oxide contained in the ortho-alkylation reaction extrusion catalyst has a bimodal pore structure, specifically a bimodal configuration of mesopores, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. In addition, by simultaneously satisfying the aforementioned specific range of BET specific surface area, it is possible to achieve excellent catalytic activity in the ortho-alkylation reaction and exhibit high selectivity and conversion rate.

[0092] In the monomer composition, the meta-alkyl-substituted phenol monomer may be m-cresol.

[0093] The monomer composition is preferable because, in addition to the meta-alkyl-substituted phenol monomer, it further comprises an alkanol and distilled water (DI Water), and the alkyl group can be introduced through a reaction with the alkanol, and the use of distilled water together can suppress the decomposition reaction of the alkanol. The alkanol is preferably methanol.

[0094] The monomer composition may preferably contain phenolic monomer:alkanol:distilled water in a ratio of 1:3 to 10:1 to 5 parts by weight, and more preferably in a ratio of 1:4 to 6:1 to 3 parts by weight. In this case, if the alkanol content is outside the range and is too low, there will be fewer alkylation mediators (agents) and the conversion rate will be low. If the distilled water content is outside the range and is too low, the effect of suppressing the decomposition reaction of the alkanol will decrease. If the alkanol or distilled water is outside the range and in excess, it may become competitively adsorbed to the catalytic active site with the phenolic monomer, leading to a decrease in reactivity.

[0095] When the content is within the aforementioned range, it is preferable because it allows for the production of ortho-alkylation reaction products with the desired selectivity and conversion rate.

[0096] IV. Method for producing ortho-alkylation reaction products According to one embodiment of the invention, a method for producing an ortho-alkylation reaction product comprises an alkylation reaction of a monomer composition containing a meta-alkyl-substituted phenolic monomer in the presence of the aforementioned ortho-alkylation reaction catalyst (A) or ortho-alkylation reaction extrusion catalyst (B). Specifically, the method for producing an ortho-alkylation reaction product can be carried out using an ortho-alkylation reaction composition containing the aforementioned ortho-alkylation reaction catalyst or ortho-alkylation reaction extrusion catalyst. The contents described above can all be applied identically to the catalyst and reaction composition.

[0097] Specifically, by including the aforementioned ortho-alkylation reaction catalyst (A) or ortho-alkylation reaction extrusion catalyst (B), it is possible to realize uniform and excellent catalytic activity both inside and outside the molded catalyst without any reduction in activity.

[0098] In the method for producing the ortho-alkylation reaction product, the monomer composition may be the same as described above. Specifically, the meta-alkyl-substituted phenol monomer in the monomer composition may be meta-cresol (m-cresol). By using the reaction composition containing the extrusion catalyst described above, the method for producing the ortho-alkylation reaction product can exhibit high selectivity and conversion rate for the desired ortho-alkylation reaction product.

[0099] The ortho-alkylation reaction product may be one or more selected from the group consisting of, for example, 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 3,4-dimethylphenol, and tetramethylphenol, and can be produced, for example, by selectively substituting an alkyl group at the ortho position with metacresol (m-cresol) through a multi-step reaction as described below. [ka]

[0100] The alkylation reaction can preferably be carried out at 350°C to 550°C, and more preferably at 350°C to 550°C. In this case, if the temperature is below 350°C, the alkylation reaction may not be sufficiently activated, and if it exceeds 550°C, a large amount of by-products will be produced due to overreaction.

[0101] The alkylation reaction can be carried out under inert conditions, for example, in the presence of an inert carrier gas. Examples of inert carrier gases include nitrogen, helium, neon, and argon, with nitrogen being preferred.

[0102] The nitrogen flow rate is not particularly limited, but is preferably 5-70 cc / min, 10-50 cc / min, or 15-40 cc / min. This is preferable because it allows for the production of ortho-alkylation reaction products with the desired selectivity and conversion rate under these conditions.

[0103] On the other hand, in the alkylation reaction, before adding the monomer composition, a step can be performed to raise and maintain the temperature inside the reactor to the activation temperature for catalyst activation, and this temperature range may be the same as the reaction temperature. The time required for catalyst activation is not particularly limited, but it may be about 30 minutes to 1 hour.

[0104] The alkylation reaction can preferably be carried out using a continuous flow gas-phase reactor, in which case the monomer composition is exposed inside the continuous flow gas-phase reactor for 0.5 hours. -1 ~2.0hr -1 This can be carried out by injection at the LHSV (liquid hourly space velocity). However, if the space velocity falls outside the aforementioned range, the reactants may not be sufficiently activated at the catalytic active site, making it difficult to obtain the product smoothly, and the catalytic activity and selectivity may decrease, resulting in a reduction in the amount of product.

[0105] It is preferable to carry out the reaction under the above conditions because it is possible to produce the ortho-alkylation reaction product with the desired selectivity and conversion rate.

[0106] The operation and effects of the invention will be described in more detail below through specific embodiments of the invention. However, these embodiments are presented merely as examples of the invention and do not determine the scope of the invention's rights.

[0107] [Example 1 and Comparative Example 1: Orthoalkylation reaction using orthoalkylation catalyst (A)] Example 1-1 The alkylation reaction of metacresol (m-cresol) was carried out using a continuous flow gas-phase reactor. First, a magnesium oxide component (MgO-1, crystalline structure: MgO) having the physical properties shown in Table 1 was prepared in granular form (212-425 μm). 1 g of catalyst was then packed into a stainless steel tube-type reactor with a diameter of 1 / 2 inch and a length of 50 cm, and the reactor was placed in the main furnace.

[0108] Subsequently, a mass flow controller (MFC) was used to release the carrier gas N2 (37.5 cc / min), and the reactor temperature was raised to the activation temperature (450°C) and maintained for 1 hour to activate the catalyst. Then, the monomer composition (12.5 mg / min, m-cresol:Methanol:DIwater = 1:5:1, LHSV 0.75 / h) was added after vaporization via a preheater (250°C). The reactor contained the catalyst and the monomer composition, and the alkylation reaction was then carried out for 5 hours at 450°C under atmospheric pressure to obtain the reaction product.

[0109] The reaction products were collected in liquid form (using IPA (isopropyl alcohol) as the solvent) for analysis.

[0110] Examples 1-2 and Comparative Examples 1-1 to 1-9 The 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 the reaction product.

[0111] [Experimental Example 1-1: Physical property analysis of ortho-alkylation reaction catalyst (A)] (1)XRD analysis The crystallite structure of the catalysts used in the examples and comparative examples was confirmed by XRD analysis, and the crystallite size was calculated using Scherrer's equation, which utilizes the maximum peak value of the XRD patterns. The results are shown in Table 1 and Figure 2.

[0112] At this time, K = 0.89 (the shape factor of the average crystallite), L = 1.5418 Å (the wavelength for CuKα), FWHM represents the full width at half maximum of the peak, and θ = the maximum peak position.

[0113] (2) Analysis of N2 adsorption-desorption The catalysts used in the examples and comparative examples were analyzed by N2 adsorption-desorption to determine their BET (Brunauer-Emmett-Teller) surface area, pore volume, and size distribution.

[0114] The BET surface area was calculated using the adsorption P / P0 = 0.05-0.3 value, and the pore volume and size distribution were calculated using the desorption value. The results are shown in Table 1 and Figure 3.

[0115] [Table 1]

[0116] [Experimental Example 1-2: Analysis of Ortho-alkylation Reaction Products] The liquids from which the reaction products produced in Example 1 and Comparative Example 1 were collected were analyzed using a gas chromatography (GC) apparatus equipped with a Flame Ionization detector (FID). The m-cresol conversion rate and the selectivity of the target product (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated from the GC results using the following equations 1 and 2, and the results are shown in Table 2.

[0117] The target product was defined as 2,3,6-TMP, the final target product, and 2,5-DMP and 2,3-DMP, which act as intermediate substances to obtain the final product through additional reactions.

[0118]

number

[0119]

number

[0120] [Table 2]

[0121] As can be seen from the experimental data in Table 2, the catalyst containing magnesium oxide having the specific physical properties and porosity structure of the present invention exhibits high catalytic activity even as a single catalyst, and it was confirmed that it can produce ortho-alkylation reaction products with remarkably high selectivity and conversion rates when used to produce ortho-alkylation reaction products.

[0122] [Example 2 and Comparative Example 2: Orthoalkylation reaction extrusion catalyst (B)] Example 2-1. Production of Extrudate Catalyst (Production of Extrusion Molding Catalyst) Magnesium oxide (MgO powder, Crystallite size 9nm, BET surface area 144.4m²) 2 / g, Total pore volume 0.72cm³ 3 50g of (pure size 6, 40nm), 1g of organic binder (methyl cellulose), and 60g of distilled water were placed in a mixing bowl and mixed uniformly to produce a paste. Once the paste was complete, it was extruded through a 2mm diameter die using a single-piston extruder catalytic molding equipment. The noodle-shaped extruded by the single-piston extruder was spread uniformly on a tray.

[0123] Next, the extruded catalyst was dried at 100°C for 4 hours using a convection oven. The dried extruded catalyst was then cut into 2 mm intervals and fired at 450°C for 6 hours using a muffle furnace to produce a magnesium-based extruded catalyst (A-1).

[0124] Comparative Example 2-1. Production of Tablet Catalyst Magnesium oxide (MgO powder, Crystallite size 9nm, BET surface area 144.4m²) 2 / g, Total pore volume 0.72cm³ 3 A tablet (6 / g, 40nm pore size) was subjected to primary tableting into a disc shape through a plate-type press and an aluminum dish. This was then crushed to produce granules with an appropriate particle size, which provided flowability. 10 wt% of an organic binder (PPO, polyphenylene oxide) and 1 wt% of a lubricant (magnesium stearate) were mixed with the produced granules, and tablets with a diameter of 2.4 mm were manufactured using a single rotary tablet press catalytic molding equipment.

[0125] Next, the magnesium-based tablet-molded catalyst (B-1) was completed by drying it in a convection oven at 100°C for 4 hours, followed by firing the dried tablet-molded catalyst in a muffle furnace at 450°C for 1 hour.

[0126] Examples 2-2 to 2-8 The same procedure was followed, except that the components and content of the binder resin and solvent used in Example 1-1 were changed as shown in Table 3 below.

[0127] [Table 3]

[0128] [Experimental Example 2-1: Analysis of Ortho-alkylation reaction extrusion catalyst (B)] (1) Analysis of BET specific surface area The catalysts of Example 1 and Comparative Example 1 were subjected to nitrogen-adsorption-desorption analysis experiments to obtain isothermal adsorption curves and the amount of adsorbed nitrogen at standard temperature and pressure. The BET (Brunauer Emmett Teller) specific surface area value was measured using the BET formula, and the results are shown in Table 4.

[0129] The average diameter of an extrudate catalyst refers to the diameter of the circular cross-section of a cylindrical catalyst manufactured by a die mounted on a single-piston extruder, while the average diameter of a tablet catalyst refers to the diameter of the circular cross-section of a cylindrical catalyst manufactured by a punch mounted on a rotary tablet press.

[0130] [Table 4]

[0131] (2) Analysis of Hg porosity The pore structures of the catalysts in Example 2-1 and Comparative Example 2-1 were examined in the macro and meso regions via Hg porosity, and the results are shown in Table 5 and Figure 6.

[0132] [Table 5]

[0133] As can be seen from Tables 4 and 5 and Figure 4, in order to minimize the reduction in activity due to the resistance of internal / external substance diffusion, it is preferable to produce the extruded catalyst through Extrudate using the appropriate organic binder and solvent specified in this application. This confirmed that it forms appropriate pores in the meso to micro regions and simultaneously has an appropriate BET specific surface area.

[0134] By realizing the aforementioned pore distribution and BET specific surface area value, the resistance to mass diffusion during alkylation reactions can be minimized, resulting in high conversion rates and selectivity. This will be explained in more detail in Experimental Example 2-2.

[0135] [Example 3 and Comparative Example 3: Orthoalkylation reaction using extrusion catalyst (B)] Example 3-1: Preparation of alkylation reaction product of metacresol (m-cresol) The alkylation reaction of m-cresol was carried out using a continuous flow gas-phase reactor. First, 1 g of the molded catalyst of Example 1-1, having the physical properties shown in Table 1, was packed into a stainless steel tube-type reactor with a diameter of 1 / 2 inch and a length of 50 cm, and then placed in the main furnace.

[0136] Subsequently, a mass flow controller (MFC) was used to release the carrier gas N2 (37.5 cc / min), and the reactor temperature was raised to the activation temperature (450°C) and maintained for 1 hour to activate the catalyst. Then, the monomer composition (12.5 mg / min, m-cresol:Methanol:DIwater = 1:5:1, LHSV 0.75 / h) was added after vaporization via a preheater (250°C). The reactor now contained the catalyst and the monomer composition, and the alkylation reaction was then carried out for 5 hours at 450°C under atmospheric pressure to obtain the reaction product.

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

[0138] Examples 3-2 to 3-8, Comparative Example 3-1 The alkylation reaction was carried out in the same manner as in Example 3-1, except that the catalyst was changed from the catalyst in Example 2-1 to the catalysts in Examples 2-2 to 2-8 and Comparative Example 2-1 in Table 3, and the reaction product was obtained.

[0139] [Experimental Example 3-2: Analysis of Ortho-alkylation Reaction Products] (3-2-1) Analysis of reaction products by catalyst type The liquids from which the reaction products produced in Example 3 and Comparative Example 3 were collected were analyzed using a gas chromatography (GC) apparatus equipped with a Flame Ionization detector (FID). The m-cresol conversion rate and the selectivity of the target product (2,3,6-TMP, 2,5-DMP, 2,3-DMP, Tetra-methylphenol) were calculated from the GC results using the following equations 1 and 2. The results are shown in Table 6, Figure 4 (Type of catalyst (size / shape)), and Figure 5 (Type / content of binder used in catalyst production).

[0140] The target products were defined as 2,3,6-TMP, the final target product, and 2,5-DMP and 2,3-DMP, which act as intermediate substances to obtain the final product through additional reactions.

[0141]

number

[0142]

number

[0143] [Table 6]

[0144] As can be seen from the experimental data in Table 6, when using the extrusion catalyst according to the present invention, even a single catalyst exhibits high catalytic activity, and when used to produce ortho-alkylation reaction products, it was confirmed that remarkably high selectivity and conversion rates can be achieved.

[0145] In the case of Comparative Example 3-1, it was found that using a tablet-shaped molded catalyst made it difficult to achieve the desired level of catalytic activity, resulting in a decrease in conversion rate and other parameters compared to the examples.

[0146] (3-2-2) Analysis of products under reaction conditions Example 4: Changing the reaction temperature Except for the fact that the methylation reaction temperature in Example 3-1 was changed from 400°C to 450°C by increasing it by 10°C every 3 hours, the alkylation reaction was carried out in the same manner, and the m-cresol conversion rate and the selectivity of the target product (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated using the method described in Experimental Example 3-2, and the resulting values ​​are shown in Table 7 below.

[0147] Example 5: Changing the carrier gas flow rate The alkylation reaction was carried out in the same manner as in Example 3-1, except that the carrier gas flow rate was set to 18.7 cc / min. The m-cresol conversion rate and the selectivity of the target product (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated using the method described in Experimental Example 3-2, and the resulting values ​​are shown in Table 7 below.

[0148] Example 6: Changing the amount of methanol injected Except for the injection of m-cresol:Methanol:DIwater=1:4:1 (11.1 mg / min, LHSV 0.666 / h) and m-cresol:Methanol:DIwater=1:3:1 (9.7 mg / min, LHSV 0.582 / h) into the liquid mixture containing the reactants in Example 3-1, the alkylation reaction was carried out in the same manner. The conversion rate of m-cresol and the selectivity of the target product (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated using the method described in Experimental Example 3-2, and the resulting values ​​are shown in Table 7 below.

[0149] [Table 7]

[0150] As can be seen from the experimental data in Table 7, in Example 4, the methylation reaction temperature was changed from 400°C to 450°C by increasing it by 10°C every 3 hours, and it was confirmed that the catalytic performance increased with the reaction temperature.

[0151] In Example 5, the nitrogen flow rate was changed, which allowed us to confirm the effect on the contact time between the catalyst and the reactants (GHSV, Gas hourly space velocity).

[0152] In Example 6, the ratio of the feed added was changed, which allowed us to confirm that the ratio of the reactant, metha-cresol, and the alkylation mediator, methanol, had an effect.

Claims

1. It has a bimodal porosity structure and a BET specific surface area of ​​130 m². ２ / g to 150m ２ It contains magnesium oxide at a concentration of / g, In the aforementioned bimodal pore structure, The diameter of the first pore is 4 nm to 8 nm. The diameter of the second pore is 35 nm to 45 nm. Ortho-alkylation reaction catalyst.

2. Contains magnesium oxide, It includes macropores with a diameter of 50 nm to 10,000 nm and mesopores with a diameter of 2 nm to 50 nm. BET specific surface area is 45 m² ２ / g to 180m ２ / g, The ortho-alkylation reaction catalyst described in claim 1 is produced by extrusion molding, Ortho-alkylation reaction extrusion catalyst.

3. For the total mixed volume of macropores and mesopores The aforementioned macropores are present in an amount of 1 to 10 vol%, The aforementioned mesopores are present at 90-99 vol%. The ortho-alkylation reaction extrusion catalyst according to claim 2.

4. The size of the extruded catalyst is 0.5 mm to 6.0 mm. The ortho-alkylation reaction extrusion catalyst according to claim 2.

5. A method for producing a catalyst according to claim 2, It has a bimodal porosity structure and a BET specific surface area of ​​130 m². ２ / g to 150m ２ The first step is to produce a mixture of magnesium oxide, an organic binder, and a solvent in a quantity of / g; and The second step includes extruding the mixture, In the aforementioned bimodal pore structure, The diameter of the first pore is 4 nm to 8 nm. The diameter of the second pore is 35 nm to 45 nm. A method for producing an ortho-alkylation reaction extrusion catalyst.

6. With respect to 100 parts by weight of the magnesium oxide, 0.1 to 20 parts by weight of organic binder resin, and Containing 50 to 200 parts by weight of solvent, A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 5.

7. The organic binder comprises one or more selected from the group consisting of methylcellulose, carboxymethylcellulose, ethylene glycol, polyethylene glycol, polyphenylene oxide, glycerin, and propylene glycol. A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 5.

8. The solvent is an alcohol, water, or a mixture thereof. A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 5.

9. The solvent is water. A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 5.

10. The second stage of extrusion is carried out using a single-piston extruder. A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 5.

11. The second step of extrusion molding is further comprising drying and firing, A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 5.

12. The drying is carried out at 80°C to 120°C. A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 11.

13. The aforementioned firing is carried out at 300°C to 600°C. A method for producing an ortho-alkylation reaction extrusion catalyst according to claim 11.

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