Ortho-alkylation reaction catalyst, ortho-alkylation reaction extrusion molding catalyst, and method for producing ortho-alkylation reaction product 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 TO RELATED APPLICATIONS] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0058310 filed on May 12, 2022 and Korean Patent Application No. 10-2023-0055405 filed on April 27, 2023, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] 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 are capable of obtaining an ortho-alkylation product with high selectivity and conversion by minimizing the material diffusion resistance of the catalyst in the ortho-alkylation reaction of a phenolic compound. [Background technology]

[0003] Alkylated hydroxyaromatic compounds are used in a variety of applications and are typically produced by the gas phase reaction of phenol with methanol. Through additional alkylation reactions, compounds with diverse structures can be produced that are amenable to application in high performance thermoplastic products, etc.

[0004] Such further alkylation reactions are usually carried out in the presence of magnesium-based compounds, and extensive research has been carried out to optimize the performance of magnesium-based catalysts.

[0005] In alkylation reactions, magnesium catalysts are required to have high activity, long activity life, and high selectivity to the desired reaction products. Most alkylation catalysts used in the past produced a large amount of para-alkylated products, but various research efforts are being conducted to obtain the more useful ortho-alkylated products in high yields.

[0006] However, the conventional techniques involve the use of a magnesium-based catalyst in combination with an additional promoter compound, the change of catalyst composition, or the change of reaction conditions, and therefore have the problem that it is difficult to obtain ortho-alkylated products with the desired high selectivity and yield.

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

[0008] Meanwhile, for the alkylation reaction, it is possible to use a small amount of powder-form catalyst at the laboratory level, but in order to mass-produce the catalyst and apply it to a commercial fixed-bed reactor, the catalyst must be appropriately shaped to fit the reactor, taking into account the pressure drop during the reaction.

[0009] Generally, the most commonly used methods for forming catalysts are extrusion and tablet forming. Tablet forming can produce precise molded shapes, but the equipment is expensive and the manufacturing cost is high, which significantly reduces the economic efficiency. On the other hand, extrusion forming is a commonly used forming method because the equipment is simple and the manufacturing cost is relatively low. However, forming a catalyst affects the internal / external material diffusion resistance, which can cause a decrease in activity in the formed catalyst, so extensive research is needed to minimize the activity decrease. Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to provide an ortho-alkylation catalyst and an extrusion molding of an ortho-alkylation catalyst that can realize excellent conversion and yield in the production of selective ortho-alkylation products.

[0011] Another object of the present invention is to provide an ortho-alkylation catalyst and an extruded ortho-alkylation catalyst that can realize uniform catalytic activity inside and outside the molded catalyst without activity reduction.

[0012] The present invention also relates to a process for producing an ortho-alkylation reaction product using said catalyst. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention provides It has a bimodal pore structure, BET specific surface area is 100m 2 / g~180m 2 The present invention provides an ortho-alkylation reaction catalyst comprising magnesium oxide having a molecular weight of 1.0 to 1.0 g / g.

[0014] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: Contains magnesium oxide, Contains 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 45m 2 / g~180m 2 / g of an extruded ortho-alkylation catalyst.

[0015] The present invention also provides a method for preparing the extruded ortho-alkylation catalyst.

[0016] Specifically, it has a bimodal pore structure and a BET specific surface area of ​​100 m 2 / g~180m 2 A first step of preparing a mixture of magnesium oxide, an organic binder and a solvent, the mixture having a molecular weight of 0.01 to 0.01 g / g; and A method for preparing an extruded ortho-alkylation catalyst is provided, comprising a second step of extruding the mixture.

[0017] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: An ortho-alkylation reaction composition is provided that includes the ortho-alkylation reaction catalyst or the ortho-alkylation reaction extrusion catalyst and a monomer composition that includes a meta-alkyl substituted phenolic monomer.

[0018] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: A method for producing an ortho-alkylation reaction product is provided, comprising the alkylation of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of the ortho-alkylation catalyst or the ortho-alkylation extrusion catalyst. Effect of the Invention

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

[0020] The ortho-alkylation catalyst according to the present invention exhibits high catalytic activity by itself without the use of a separate cocatalyst or additional additives, and when used to produce an ortho-alkylation product, it exhibits remarkably high selectivity and conversion.

[0021] The extruded ortho-alkylation catalyst of the present invention exhibits high catalytic activity and, when used to produce ortho-alkylation products, exhibits remarkably high selectivity and conversion.

[0022] In addition, the extrusion molded catalyst for ortho-alkylation reaction according to the present invention has appropriately formed macropores and mesopores and an appropriate BET specific surface area, thereby minimizing the material diffusion resistance of the catalyst, thereby providing an extrusion molded catalyst for ortho-alkylation reaction that can realize uniform and excellent catalytic activity inside and outside the molded catalyst without activity reduction.

[0023] The extrusion-molded ortho-alkylation catalyst according to the present invention is prepared by combining magnesium oxide having specific physical properties with an organic binder and a solvent, and thus exhibits high catalytic activity without the use of a separate cocatalyst or additional additives. When the catalyst is used to prepare an ortho-alkylation product, it exhibits remarkably high selectivity and conversion. [Brief description of the drawings]

[0024] [Figure 1] 1 is a graph showing the selectivity of reaction products produced using ortho-alkylation catalysts according to examples and comparative examples of the present invention. [Diagram 2] 1 is an XDR graph of ortho-alkylation reaction catalysts of examples of the present invention and comparative examples. [Diagram 3] 1 is a graph showing pore distribution by N2 adsorption-desorption analysis of ortho-alkylation catalysts according to examples and comparative examples of the present invention. [Figure 4] 1 is a graph showing conversion rate versus selectivity depending on the type of catalyst in the ortho-alkylation reaction molded catalysts of the present invention and comparative examples. [Diagram 5] 1 is a graph showing conversion rate versus selectivity depending on the type / content of binder in an ortho-alkylation reaction molded catalyst according to an embodiment of the present invention. [Figure 6] 1 is a graph showing pore size versus pore volume according to the type of molded catalyst in the examples and comparative examples of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The present invention can be modified in various ways and can have various forms, and will be described in detail below by taking specific examples as examples. However, this is not intended to limit the present invention to the specific disclosed forms, and it should be understood that the present invention includes all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0026] In addition, the terms used in this specification are merely used to describe exemplary embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly indicates otherwise. In this specification, the terms "include", "comprise", "have" and the like are intended to specify the presence of an implemented feature, step, component, or combination thereof, and should be understood not to preclude the presence or additional possibility of one or more other features, steps, components, or combinations thereof.

[0027] In addition, in the present invention, when it is said that each component is formed "on" each other, it means that each component is formed directly on each other, and it means that other components may be additionally formed between each layer, on the object, or on the substrate.

[0028] I. Ortho-Alkylation Reaction Catalyst (A. Ortho-Alkylation Reaction Catalyst) Magnesium catalysts used in alkylation reactions are generally required to have high activity, long active life, and high selectivity to the desired reaction product. Most of the alkylation catalysts used in the past produced a large amount of para-alkylated products, but various research efforts are being conducted to obtain the more useful ortho-alkylated products with high selectivity.

[0029] Specifically, various techniques have been developed in recent years, such as using a magnesium catalyst in combination with an additional cocatalyst compound, changing the catalyst composition, or changing the reaction conditions. However, these techniques have the problem that it is difficult to obtain ortho-alkylated products with the desired high selectivity and conversion rate.

[0030] In addition, the present inventors have confirmed that, in order to solve these problems, by setting the BET specific surface area and pore structure of the magnesium oxide catalyst within a specific range, it is possible to realize a significantly high catalytic activity in the alkylation reaction.The ortho-alkylation catalyst according to the present invention shows excellent catalytic activity even as a single catalyst without using an additional cocatalyst or adjusting the reaction conditions, and when an ortho-alkylation product is produced using the same, it shows significantly high selectivity and conversion rate, thereby completing the present invention.

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

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

[0033] The magnesium oxide has a bi-modal pore structure, specifically, a mesopore bi-modal morphology, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. In addition, by simultaneously satisfying the above-mentioned specific range of BET specific surface area, the magnesium oxide has excellent catalytic activity in the ortho-alkylation reaction, and can exhibit high selectivity, conversion rate and yield.

[0034] Generally, the larger the BET specific surface area, the more active sites of the catalyst are. However, in the case of a single-modal catalyst, even if the BET specific surface area is increased, the diffusion of reactants is not smooth, so the reaction is difficult to proceed to the desired extent.

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

[0036] The magnesium oxide has a BET specific surface area of ​​100 m 2 / g~180m 2 / g and has a relatively large specific surface area with many reactive active sites, resulting in excellent catalytic activity. At the same time, as described above, the bimodal pore structure facilitates the diffusion of reactants, allowing the reaction to proceed effectively. As a result, the catalyst has excellent catalytic activity in the ortho-alkylation reaction, and is able to show improved selectivity, conversion rate, and yield. The BET specific surface area is 100 m 2 If the BET specific surface area is less than 180 m / g, the reaction active sites are significantly reduced, the reactant conversion rate is low, and it is difficult to achieve the desired activity. 2 If the content exceeds 1 / g, the reaction active sites increase, but the primary pores are mainly formed, which makes it difficult to achieve high activity because the diffusion of reactants / products is not smooth.

[0037] Preferably, the magnesium oxide has a BET specific surface area of ​​130 m 2 / g~180m 2 / g, more preferably 130m 2 / g~150m 2 / g, and within this range, excellent catalytic activity can be achieved without the above-mentioned problems, which is preferable.

[0038] The ortho-alkylation catalyst may have a granular shape, preferably a particle size of about 212 μm to 425 μm, and is preferred because excellent catalytic activity can be realized within this particle size range.

[0039] (B. Ortho-Alkylation Reaction Extrusion Catalyst) Meanwhile, for alkylation reactions, it is possible to use small amounts of powder-type catalysts at the laboratory level, but to mass-produce catalysts 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 accurate molded shapes, but the equipment is expensive and the manufacturing cost is high, which significantly reduces the economic efficiency. On the other hand, extrusion molding is a commonly used molding method because the equipment is simple and the manufacturing cost is relatively cheap. However, when catalysts are extruded, there is a problem that the activity of the extruded catalysts produced decreases due to the effect on the internal / external material diffusion resistance.

[0040] In order to solve these problems, the present inventors have identified the main factors that affect the catalytic activity of the extrusion-molded catalyst during manufacture. Specifically, as described above, by using magnesium oxide with a specific pore structure and simultaneously appropriately forming macro-sized pores and meso-sized pores in the final catalyst to realize an appropriate BET specific surface area, the influence on the internal / external material diffusion resistance is minimized, and it has been confirmed that the extrusion-molded catalyst can realize uniform catalytic activity, thereby completing the present invention.

[0041] In addition, the present inventors have confirmed that an extrusion catalyst prepared containing a specific magnesium oxide can realize a significantly high catalytic activity in an alkylation reaction when the catalyst has an appropriate pore distribution and BET specific surface area. Thus, the present invention has been completed based on the discovery that the ortho-alkylation catalyst according to the present invention exhibits excellent catalytic activity as a single catalyst without the need for an additional cocatalyst or adjustment of reaction conditions, and when an ortho-alkylation product is produced using the catalyst, a significantly high selectivity and conversion rate can be obtained.

[0042] According to one embodiment of the present invention, an extruded ortho-alkylation catalyst includes magnesium oxide, has macropores with a diameter of 50 nm to 10,000 nm and mesopores with a diameter of 2 nm to 50 nm, and has a BET specific surface area of ​​45 m. 2 / g~180m 2 Meets / g.

[0043] As mentioned above, the catalytic activity of a catalyst is generally determined by the reaction conditions and the acid-base properties of the catalyst. Therefore, the extrusion catalyst for ortho-alkylation according to the present invention contains a magnesium oxide (MgO) component, and thus the catalyst has basic properties and adsorbs reactants perpendicularly, favoring ortho-C-alkylation (see formula (a) above).

[0044] The catalyst is prepared using magnesium oxide with a bi-modal pore structure, specifically, the magnesium oxide used in the preparation step has a bi-modal form with mesopores, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. As a result, the catalyst has excellent catalytic activity in the ortho-alkylation reaction, and can exhibit high selectivity, conversion rate, and yield.

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

[0046] In this way, the macropores and mesopores are appropriately formed to minimize the material diffusion resistance of the catalyst, thereby realizing uniform and excellent catalytic activity inside and outside the formed catalyst without activity reduction.

[0047] The ortho-alkylation reaction extrusion molding catalyst may contain macropores in an amount of 1 to 10 vol% based on the total mixed volume of the macropores and mesopores, and preferably contains 1 to 9 vol%, 2 to 10 vol%, 2 to 9 vol%, or 2 to 5 vol%. When contained within the above range, it is preferable because the material diffusion resistance of the molded catalyst can be minimized.

[0048] The mesopores of the ortho-alkylation extrusion catalyst may be present in an amount of 90 to 99 vol%, preferably 90 to 98 vol%, 91 to 98 vol%, or 95 to 98 vol%, based on the total volume of the macropores and mesopores. When present in the above range, the extrusion catalyst is suitable for realizing excellent catalytic activity without activity reduction.

[0049] 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.

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

[0051] The catalyst has the above-mentioned macropores and mesopores appropriately formed and at the same time exhibits a specific range of BET specific surface area value, thereby minimizing the material diffusion resistance of the catalyst and realizing uniform and excellent catalytic activity inside and outside the formed catalyst without activity reduction.

[0052] Preferably, the BET specific surface area is 45 m 2 / g~150m 2 / g, 45m 2 / g~130m 2 / g, or 60m 2 / g~130m 2 / g, and when the specific surface area is in this range, it is preferable because the material diffusion resistance of the molded catalyst can be minimized. The method for measuring the BET specific surface area of ​​the catalyst will be described in more detail in the experimental examples below.

[0053] Meanwhile, the pore distribution and BET specific surface area of ​​the catalyst can be realized by combining magnesium oxide having specific physical properties with an organic binder and a solvent, which will be described in more detail in the preparation method section.

[0054] The ortho-alkylation extrusion catalyst may have a size of 0.5mm to 6.0mm, and may have uniform and excellent catalytic activity within the range. More preferably, the size of the catalyst may be 1.0mm to 3.0mm or 1.2mm to 2.0mm. If the catalyst size is too small outside the above range, a large pressure drop during the alkylation reaction may occur, which may be a problem, and if the catalyst size is too large outside the above range, there may be a problem of reduced catalytic activity.

[0055] 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.

[0056] Generally, the shape of an extruded catalyst is a cylinder formed by an extrusion die, and the extruded catalyst according to the present invention may have a ratio of the diameter of the circular cross section of the cylinder to the length of the cylinder of 1:1 (±0.1).

[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 preferred that the circular cross section and the length of the cylinder all simultaneously satisfy the aforementioned ranges.

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

[0059] II. Method for producing extruded ortho-alkylation catalyst According to another embodiment of the present invention, there is provided a method for producing the above-mentioned extruded ortho-alkylation catalyst (B), comprising the steps of:

[0060] Specifically, it has a bimodal pore structure and a BET specific surface area of ​​100 m 2 / g~180m 2 1. preparing a mixture of magnesium oxide having a molecular weight of 0.1 to 0.2 g / g, an organic binder and a solvent; and 2. extruding said mixture.

[0061] Each step will be explained in detail below.

[0062] Phase 1: Preparation of the mixture First, it has a bimodal pore structure and a BET specific surface area of ​​100 m 2 / g~180m 2 A mixture of magnesium oxide having a molecular weight of 1 / g, an organic binder, and a solvent is prepared.

[0063] The same description as for the ortho-alkylation reaction extrusion molding catalyst can be applied to the magnesium oxide.

[0064] Preferably, the magnesium oxide has a bi-modal pore structure, specifically, a bi-modal morphology in the mesopore range, which facilitates the diffusion of reactants to effectively carry out the reaction, and thus has excellent catalytic activity in the ortho-alkylation reaction, and can exhibit high selectivity, conversion rate, and yield.

[0065] Generally, the larger the BET specific surface area, the more active sites of the catalyst are. However, in the case of a single-modal catalyst, even if the BET specific surface area is increased, the diffusion of reactants is not smooth, so the reaction is difficult to proceed to the desired extent.

[0066] Preferably, in the bi-modal pore structure, the diameter of the first pores may be 2 nm to 10 nm, and the diameter of the second pores may be 10 nm to 50 nm, more preferably, the diameter of the first pores may be 4 nm to 8 nm, and the diameter of the second pores may be 20 nm to 45 nm or 35 nm to 45 nm. Through the bi-modal pore structure having diameters in the above ranges, it is 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 m 2 / g~180m 2 / g and has a relatively large specific surface area with many reactive active sites, resulting in excellent catalytic activity. At the same time, as described above, the bimodal pore structure facilitates the diffusion of reactants, allowing the reaction to proceed effectively. As a result, the catalyst has excellent catalytic activity in the ortho-alkylation reaction, and is able to show improved selectivity, conversion rate, and yield. The BET specific surface area is 100 m 2 If the BET specific surface area is less than 180 m / g, the reaction active sites are significantly reduced, resulting in a low conversion rate of reactants, making it difficult to realize the desired activity. 2If the content exceeds 1 / g, the reaction active sites increase, but the primary pores are mainly formed, which makes it difficult to achieve high activity because the diffusion of reactants / products is not smooth.

[0068] Preferably, the magnesium oxide has a BET specific surface area of ​​130 m 2 / g~180m 2 / g, more preferably 130m 2 / g~150m 2 / g, and within this range, excellent catalytic activity can be achieved without the above-mentioned problems, which is preferable.

[0069] The organic binder is a component that has an important effect on realizing uniformity of catalytic activity by uniformly binding magnesium oxide during preparation of a molded catalyst, facilitating catalyst preparation, and in particular, forming appropriate pores inside the catalyst through calcination during preparation of an extrusion molded catalyst. When magnesium oxide having the above-mentioned specific physical properties is used alone, the ease of catalyst preparation may decrease and the formation of the desired pores may be somewhat difficult, but when used in combination, it is preferable because it is possible to realize better catalytic activity uniformly.

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

[0071] The organic binder may be included in an amount of 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. When used in this range, it is suitable for realizing the above-mentioned effects.

[0072] The solvent is used to ensure that the mixture is kneaded uniformly and to facilitate extrusion during the production of extrudates.

[0073] Specific examples of the solvent include water and alcohol, which can be used alone or in combination of two or more. More preferably, water can be used. The water can be high-purity water such as distilled water, ion-exchanged water, or ultrapure water (DIW). When the water contains impurities, the impurities may adhere to the catalyst and reduce the activity of the catalyst, so it is preferable to use ultrapure water or the like. In the case of alcohol, it is preferable to use C 3 The above primary alcohols can be used.

[0074] The solvent may be used in an amount of 50 to 200 parts by weight, preferably 80 to 150 parts by weight or 100 to 120 parts by weight, based on 100 parts by weight of magnesium oxide. The mixture mixed in the above ratio may preferably be in the form of a paste. In this case, it is preferable because the extrusion molding process can be easily performed.

[0075] Meanwhile, according to one embodiment of the present invention, the mixture may optionally contain additional additives, such as a lubricant, so that the final molded catalyst may be produced uniformly and without crushing during the production process. Specific examples of the lubricant include, but are not limited to, magnesium stearate, aluminum stearate, graphite, etc.

[0076] Furthermore, other additives used in the relevant field can be used without any particular restrictions within the scope of not impairing the desired physical properties.

[0077] Second stage: Extrusion stage A second step then involves extruding the mixture.

[0078] Tablet molding, which is commonly used as a catalyst molding method, can produce accurate molded shapes, but the equipment is expensive and the manufacturing cost is high, which significantly reduces the economic efficiency. On the other hand, extrusion molding is a molding method that is widely used because the equipment is simple and the manufacturing cost is relatively low. However, molding a catalyst can affect the internal / external material diffusion resistance, which can cause a decrease in activity of the molded catalyst. In the present invention, however, by using a combination of magnesium oxide with specific physical properties, an organic binder, and a solvent as described above, it is possible to manufacture an extrusion molded catalyst that has high activity without such problems and has uniformity both inside and outside the catalyst.

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

[0080] The average diameter of the extrusion die used can be appropriately adjusted depending on the desired diameter range of the final shaped catalyst.

[0081] Additional steps: drying and baking In one embodiment of the invention, the extrusion process may further include a drying and calcination step.

[0082] The process conditions for the drying and calcination steps may be any process commonly used in the art without any particular limitations.

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

[0084] The time for which the drying step is performed is not particularly limited, but may be, for example, 1 hour to 13 hours, preferably 3 hours to 8 hours, or 4 hours to 6 hours.

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

[0086] The time for performing the calcination step is not particularly limited, but may be an appropriate time or more to remove the organic binder and the solvent in the mixture and form the desired pores in the catalyst, and preferably, the calcination step may be performed for 1 hour to 9 hours, or 3 hours to 6 hours.

[0087] The catalyst prepared by the above-mentioned method for preparing an extrusion-molded ortho-alkylation catalyst can realize uniform and excellent catalytic activity inside and outside the molded catalyst without activity reduction 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 the above-described ortho-alkylation reaction catalyst (A) or the extrusion ortho-alkylation reaction catalyst (B) and a monomer composition comprising a meta-alkyl substituted phenolic monomer.

[0089] The ortho-alkylation catalyst (A) has a bimodal pore structure and a BET specific surface area of ​​100 m 2 / g~180m 2 / g, to which all the above-mentioned contents can be applied equally. Specifically, magnesium oxide has a bi-modal pore structure, specifically a bi-modal form of mesopores, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. In addition, by simultaneously satisfying the above-mentioned specific range of BET specific surface area, it is possible to have excellent catalytic activity in the ortho-alkylation reaction and to show high selectivity and conversion rate.

[0090] The ortho-alkylation reaction extrusion molding catalyst (B) contains magnesium oxide, has macropores with a diameter of 50 nm to 10,000 nm and mesopores with a diameter of 2 nm to 50 nm, and has a diameter of 45 mm. 2 / g~180m 2 / g BET specific surface area. The above contents can be applied equally to this. Specifically, the extrusion molded catalyst has the above-mentioned macropores and mesopores appropriately formed to minimize the material diffusion resistance of the catalyst, thereby realizing uniform and excellent catalytic activity inside and outside the molded catalyst without activity reduction.

[0091] In addition, the magnesium oxide contained in the ortho-alkylation reaction extrusion catalyst has a bi-modal pore structure, specifically, a bi-modal form with mesopores, which facilitates the diffusion of reactants and allows the reaction to proceed effectively. In addition, by simultaneously satisfying the above-mentioned specific range of BET specific surface area, the catalyst has excellent catalytic activity in the ortho-alkylation reaction and shows high selectivity and conversion rate.

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

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

[0094] The monomer composition may preferably contain phenol-based monomer: alkanol: distilled water in a ratio of 1: 3-10: 1-5 parts by weight, more preferably 1: 4-6: 1-3 parts by weight. At this time, if the alkanol content is low outside the above range, the alkylation agent is low, resulting in a low conversion rate, if the distilled water content is low outside the above range, the effect of suppressing the decomposition reaction of the alkanol is reduced, and if the alkanol or distilled water is excessive outside the above range, it may competitively adsorb with the phenol-based monomer at the catalytic active site, resulting in a problem of reduced reactivity.

[0095] When the content is within the above range, an ortho-alkylation reaction product can be produced with the desired selectivity and conversion rate, which is preferable.

[0096] IV. Methods for Producing Ortho-Alkylated Reaction Products According to one embodiment of the invention, the method for producing an ortho-alkylation reaction product includes an alkylation reaction of a monomer composition containing a meta-alkyl-substituted phenolic monomer in the presence of the above-mentioned ortho-alkylation catalyst (A) or the ortho-alkylation 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 above-mentioned ortho-alkylation catalyst or the ortho-alkylation extrusion catalyst. The above-mentioned contents can be equally applied to the catalyst and the reaction composition.

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

[0098] In the method for producing the ortho-alkylation reaction product, the monomer composition may be the same as described above, and specifically, the monomer composition may be a meta-alkyl substituted phenol monomer m-cresol. The method for producing the ortho-alkylation reaction product can exhibit high selectivity and conversion of the desired ortho-alkylation reaction product by using a reaction composition including the extrusion catalyst described above.

[0099] The ortho-alkylation reaction product may be 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 substituting an alkyl group at the ortho position of m-cresol through the following multi-step reaction: [ka]

[0100] The alkylation reaction can be carried out preferably at 350° C. to 550° C., and more preferably at 350° C. to 550° C. At this time, if the temperature is less than 350° C., the alkylation reaction may not be sufficiently activated, whereas if the temperature exceeds 550° C., a large amount of by-products due to over-reaction is generated.

[0101] The alkylation reaction can be carried out under inert conditions, for example, in the presence of an inert carrier gas, such as nitrogen, helium, neon, argon, etc., and preferably nitrogen.

[0102] The nitrogen flow rate is not particularly limited, but can be preferably 5 to 70 cc / min, 10 to 50 cc / min, or 15 to 40 cc / min. By carrying out the reaction under the above conditions, an ortho-alkylation reaction product can be produced with the desired selectivity and conversion rate, which is preferable.

[0103] Meanwhile, in the alkylation reaction, before the monomer composition is added, a process 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.

[0104] The alkylation reaction can be preferably carried out using a continuous flow gas phase reactor, in which case the monomer composition is kept in the continuous flow gas phase reactor for 0.5 hours. -1 ~2.0hr -1 If the space velocity is outside the above range, the reactants may not be sufficiently activated at the catalytic active sites, making it difficult to obtain products smoothly, and the activity and selectivity of the catalyst may be reduced, resulting in a reduced amount of products.

[0105] By carrying out the reaction under the above conditions, it is possible to produce an ortho-alkylated reaction product with the desired selectivity and conversion rate, which is preferable.

[0106] The functions and effects of the present invention will be described in more detail below through specific examples of the present invention, however, these examples are presented only as examples of the present invention and do not define the scope of the invention.

[0107] [Example 1 and Comparative Example 1: Ortho-alkylation reaction using ortho-alkylation catalyst (A)] Example 1-1 The alkylation reaction of m-cresol was carried out using a continuous flow gas phase reactor. First, magnesium oxide (MgO-1, crystalline structure: MgO) having the physical properties shown in Table 1 was produced in granule form (212-425um), and 1g of catalyst was filled into a 1 / 2 inch diameter x 50 cm long stainless steel tube type reactor, which was then installed in the main furnace.

[0108] Then, a mass flow controller (MFC) was used to supply N 2 was flowed out (37.5cc / min), and the inside of the reactor was heated to the activation temperature (450℃) for catalyst activation and maintained for 1 hour. Then, the monomer composition (12.5mg / min, m-cresol:methanol:DIwater=1:5:1, LHSV 0.75 / h) was vaporized through a pre-heater (250℃) and then introduced. The reaction composition including the catalyst and monomer composition was introduced into the reactor, and then the alkylation reaction (450℃, normal pressure) was carried out for 5 hours to obtain the reaction product.

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

[0110] Example 1-2 and Comparative Examples 1-1 to 1-9 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.

[0111] [Experimental Example 1-1: Analysis of physical properties of ortho-alkylation catalyst (A)] (1)XRD analysis The catalysts used in the examples and comparative examples were analyzed by XRD to confirm their crystallite structure, and the crystallite size was calculated using the Scherrer equation based on the maximum peak value of the XRD patterns. The results are shown in Table 1 and FIG. 2.

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

[0113] (2)N 2 Adsorption-desorption analysis The catalysts used in the examples and comparative examples were 2 The BET (Brunauer-Emmett-Teller) surface area, pore volume and size distribution were determined through adsorption-desorption analysis.

[0114] 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.

[0115] [Table 1]

[0116] [Experimental Example 1-2: Analysis of ortho-alkylation reaction products] The liquid in which the reaction products prepared in Example 1 and Comparative Example 1 were collected was analyzed using a gas chromatograph (GC) equipped with a flame ionization detector (FID). From the GC results, the m-cresol conversion rate and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated according to the following Equations 1 and 2, and the results are shown in Table 2.

[0117] The target products were defined as the final product, 2,3,6-TMP, and intermediate substances, 2,5-DMP and 2,3-DMP, which can be used to obtain the final products 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 specific physical properties and pore structure of the present invention exhibits high catalytic activity even as a single catalyst, and when used to produce an ortho-alkylation reaction product, it was confirmed that it can exhibit remarkably high selectivity and conversion rate.

[0122] [Example 2 and Comparative Example 2: Ortho-alkylation reaction extrusion molding catalyst (B)] Example 2-1. Production of extrudate catalyst (production of extrusion-molded catalyst) Magnesium oxide (MgO powder, Crystallite size 9nm, BET surface area 144.4m 2 / g, Total pore volume 0.72cm 3 50g of cellulose acetate (1.0g / g, pore size 6, 40nm), 1g of organic binder (methyl cellulose), and 60g of distilled water were mixed uniformly in a mixing bowl to produce a paste. When the paste was complete, it was extruded through a 2mm diameter die using a single piston extruder catalyst molding equipment. The noodle shape extruded with the single piston extruder was spread evenly on a tray.

[0123] Next, the catalyst was dried at 100°C for 4 hours in a convection oven, and the dried extrusion catalyst was cut into 2 mm intervals and calcined at 450°C for 6 hours in a muffle furnace to prepare a magnesium-based extrusion catalyst (A-1).

[0124] Comparative Example 2-1. Preparation of Tablet Catalyst Magnesium oxide (MgO powder, Crystallite size 9nm, BET surface area 144.4m 2 / g, Total pore volume 0.72cm 3 The granules were mixed with 10wt% organic binder (PPO, polyphenylene oxide) and 1wt% lubricant (magnesium stearate) and then made into tablets with a diameter of 2.4mm using a single rotary tablet press catalytic molding equipment.

[0125] Next, the catalyst was dried at 100° C. for 4 hours using a convection oven, and the dried tablet-formed catalyst was calcined at 450° C. for 1 hour using a muffle furnace to complete a magnesium-based tablet-formed catalyst (B-1).

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

[0127] [Table 3]

[0128] [Experimental Example 2-1: Analysis of ortho-alkylation reaction extrusion molding catalyst (B)] (1) BET specific surface area analysis The catalysts of Example 1 and Comparative Example 1 were subjected to a nitrogen adsorption / desorption analysis experiment to measure the isothermal adsorption curve, the amount of adsorbed nitrogen at standard temperature and pressure, and the BET specific surface area value according to the BET (Brunauer Emmett Teller) equation. The results are shown in Table 4.

[0129] The average diameter of an extrudate-type catalyst means the diameter of a circular cross section of a cylindrical catalyst produced by a die attached to a single piston extruder, and the average diameter of a tablet-type catalyst means the diameter of a circular cross section of a cylindrical catalyst produced by a punch attached to a rotary tablet press.

[0130] [Table 4]

[0131] (2)Hg porosity analysis The pore structures of the macro and meso regions of the catalysts of Example 2-1 and Comparative Example 2-1 were confirmed through Hg porosity, and the results are shown in Table 5 and FIG.

[0132] [Table 5]

[0133] As can be seen from Tables 4, 5 and FIG. 4, in order to minimize activity reduction due to internal / external material diffusion resistance, it is preferable to prepare an extrusion molded catalyst through extruding using the appropriate organic binder and solvent defined in the present application, and it has been confirmed that this forms appropriate pores in the meso to micro regions and at the same time has an appropriate range of BET specific surface area.

[0134] By realizing the above pore distribution and BET specific surface area, material diffusion resistance during alkylation reaction can be minimized, and high conversion rate and selectivity can be achieved, which will be described in more detail in Experimental Example 2-2.

[0135] [Example 3 and Comparative Example 3: Ortho-alkylation reaction using extrusion molding catalyst (B)] Example 3-1: Preparation of alkylation reaction product of m-cresol The alkylation reaction of m-cresol was carried out in 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 in a stainless steel tube type reactor having a diameter of 1 / 2 inch and a length of 50 cm, and then the catalyst was placed in the main furnace.

[0136] Then, a mass flow controller (MFC) was used to supply N 2was flowed out (37.5cc / min), and the inside of the reactor was heated to the activation temperature (450℃) for catalyst activation and maintained for 1 hour. Then, the monomer composition (12.5mg / min, m-cresol:methanol:DIwater=1:5:1, LHSV0.75 / h) was vaporized through a pre-heater (250℃) and then introduced. The reaction composition including the catalyst and monomer composition was introduced into the reactor, and then an alkylation reaction (450℃, normal pressure) was carried out for 5 hours to obtain a reaction product.

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

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

[0139] [Experimental Example 3-2: Analysis of ortho-alkylation reaction products] (3-2-1) Analysis of reaction products by catalyst type The liquid in which the reaction products produced in Example 3 and Comparative Example 3 were collected was analyzed using a gas chromatograph (GC) equipped with a flame ionization detector (FID). From the GC results, the m-cresol conversion rate and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP, tetra-methyl phenol) were calculated using the following Equation 1 and Equation 2. The results are shown in Table 6, FIG. 4 (type (size / shape) of catalyst) and FIG. 5 (type / content of binder used in the preparation of catalyst).

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

[0141]

number

[0142]

number

[0143] [Table 6]

[0144] As can be seen from the experimental data in Table 6, when the extruded catalyst according to the present invention is used, even a single catalyst exhibits high catalytic activity, and when the extruded catalyst is used to produce an ortho-alkylation reaction product, it is possible to exhibit remarkably high selectivity and conversion rate.

[0145] In the case of Comparative Example 3-1, it was confirmed that it was difficult to realize the desired catalytic activity due to the use of a tablet-shaped molded catalyst, and therefore the conversion rate was lower than that of the Examples.

[0146] (3-2-2) Analysis of products depending on reaction conditions Example 4: Varying the reaction temperature The alkylation reaction was carried out in the same manner as in Example 3-1, except that the methylation reaction temperature was changed from 400°C to 450°C by increasing the temperature by 10°C every 3 hours. The m-cresol conversion rate and the selectivity to the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated using the method of Experimental Example 3-2 described above, and the results 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 to the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated using the method of Experimental Example 3-2 described above, and the results are shown in Table 7 below.

[0148] Example 6: Changing the amount of methanol injected The alkylation reaction was carried out in the same manner as in Example 3-1, except that the liquid mixture containing the reactants was injected in the following amounts: 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). The m-cresol conversion rate and the selectivity to the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated using the method of Experimental Example 3-2 described above, and the results 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 the temperature by 10°C every 3 hours. It was confirmed that the catalytic performance increased depending on the reaction temperature.

[0151] In the case of Example 5, the flow rate of the nitrogen introduced was changed, and the effect on the contact time between the catalyst and the reactant (GHSV, Gas Hourly Space Velocity) was confirmed.

[0152] In the case of Example 6, the ratio of the input feed was changed, and it was confirmed that there was an effect of the ratio of meta-cresol as a reactant and methanol as an alkylation medium.

Claims

1. It has a bimodal pore structure and a BET specific surface area of ​​100 m ２ / g~180m ２ / g magnesium oxide, Ortho-alkylation reaction catalyst.

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

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

4. Contains magnesium oxide, Contains 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 45m ２ / g~180m ２ / g, Ortho-alkylation reaction extrusion catalyst.

5. With respect to the total mixed volume of the macropores and mesopores The macropores are contained in an amount of 1 to 10 vol %; The mesopores are contained in an amount of 90 to 99 vol %. The extruded ortho-alkylation catalyst according to claim 4.

6. The size of the extruded catalyst is 0.5 mm to 6.0 mm; The extruded ortho-alkylation catalyst according to claim 4.

7. A method for producing the catalyst according to claim 4, comprising the steps of: It has a bimodal pore structure and a BET specific surface area of ​​100 m ２ / g~180m ２ a first step of preparing a mixture of magnesium oxide, an organic binder and a solvent, the mixture having a molecular weight of 1.0 to 1.0 g / g; and A second step of extruding the mixture. A method for producing an extruded ortho-alkylation catalyst.

8. The bimodal pore structure of the magnesium oxide is First pores having a diameter of 2 nm to 10 nm; and The second pores have a diameter of 10 nm to 50 nm. The method for producing the extruded ortho-alkylation catalyst according to claim 7.

9. For 100 parts by weight of the magnesium oxide, 0.1 to 20 parts by weight of an organic binder resin, and Contains 50 to 200 parts by weight of a solvent; The method for producing the extruded ortho-alkylation catalyst according to claim 7.

10. The organic binder includes one or more selected from the group consisting of methyl cellulose, carboxymethyl cellulose, ethylene glycol, polyethylene glycol, polyphenylene oxide, glycerin, and propylene glycol. The method for producing the extruded ortho-alkylation catalyst according to claim 7.

11. The solvent is an alcohol, water or a mixture thereof; The method for producing the extruded ortho-alkylation catalyst according to claim 7.

12. The solvent is water. The method for producing the extruded ortho-alkylation catalyst according to claim 7.

13. The second stage extrusion is carried out using a single piston extruder. The method for producing the extruded ortho-alkylation catalyst according to claim 7.

14. The method further comprises drying and calcining the second extrusion step. The method for producing the extruded ortho-alkylation catalyst according to claim 7.

15. The drying is carried out at 80°C to 120°C. The method for producing the extruded ortho-alkylation catalyst according to claim 14.

16. The firing is carried out at 300°C to 600°C. The method for producing the extruded ortho-alkylation catalyst according to claim 14.

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

18. The meta-alkyl substituted phenolic monomer is meta-cresol.

18. The ortho-alkylation reaction composition of claim 17.

19. The monomer composition further comprises an alkanol and distilled water.

18. The ortho-alkylation reaction composition of claim 17.

20. The monomer composition contains phenolic monomer: alkanol: distilled water in a ratio of 1: 3 to 10: 1 to 5 parts by weight.

20. The ortho-alkylation reaction composition of claim 19.

21. The method includes the alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of the ortho-alkylation catalyst of claim 1 or the ortho-alkylation extrusion catalyst of claim 4. A process for producing an ortho-alkylated reaction product.

22. The alkylation reaction is carried out at 350 to 550° C. A method for producing the ortho-alkylated reaction product of claim 21.

23. The alkylation reaction is carried out using a continuous flow gas phase reactor. A method for producing the ortho-alkylated reaction product of claim 21.

24. The monomer composition was stirred in a continuous flow gas phase reactor for 0.5 hours. －１ ~2.0hr －１ is injected at a liquid hourly space velocity (LHSV) of A method for producing the ortho-alkylated reaction product of claim 23.

25. The ortho-alkylation reaction product is one or more selected from the group consisting of 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 3,4-dimethylphenol, and tetramethylphenol; A method for producing the ortho-alkylated reaction product of claim 21.

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