Ortho-alkylation extrusion molding catalyst, preparation method therefor, and method for preparing ortho-alkylation product by using same

Abstract

The present invention relates to an ortho-alkylation extrusion molding catalyst, a preparation method therefor, and a method for preparing an ortho-alkylation product by using same, and, more specifically, provides: an ortho-alkylation extrusion molding catalyst enabling an ortho-alkylation product to be obtained with high selectivity and conversion rate in ortho-alkylation of a phenolic compound; a preparation method therefor; and a method for preparing an ortho-alkylation product by using the catalyst.

Description

Ortho-alkylation reaction extrusion molding catalyst, preparation method thereof, and preparation method of ortho-alkylation reaction product using the same

[0001] The present invention relates to a technology for an ortho-alkylation reaction extrusion molding catalyst, a method for producing the same, and a method for producing an ortho-alkylation reaction product using the same, and more specifically, to an ortho-alkylation reaction extrusion molding catalyst capable of obtaining an ortho-alkylation reaction product with high selectivity and conversion in an ortho-alkylation reaction of a phenolic compound, a method for producing the same, and a method for producing an ortho-alkylation reaction product using the catalyst.

[0002]

[0003] Alkylated hydroxyaromatic compounds have a wide range of applications and are typically prepared by the gas-phase reaction of phenol and methanol. Further alkylation reactions can produce compounds with diverse structures, making them ideal for applications in high-performance thermoplastics.

[0004] These additional alkylation reactions have typically been performed in the presence of magnesium compounds, and various studies have been conducted to optimize the performance of magnesium catalysts.

[0005] In alkylation reactions, magnesium-based catalysts are required to possess high activity, long activity lifetimes, and high selectivity for the desired reaction product. Most alkylation catalysts used in the past produced large quantities of para-alkylated products, but extensive research has been conducted to obtain higher yields of the more useful ortho-alkylated products.

[0006] In the case of magnesium-based catalysts used for conventional alkylation reactions, high ortho selectivity (>95%) could be obtained at very high conversion rates (>93%), but there were problems such as the presence of many over-methylated products due to over-reaction at high reaction temperatures (approximately 450 degrees) and a significant decrease in catalyst activity over time.

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

[0008]

[0009] The present invention provides an ortho-alkylation reaction extrusion molding catalyst capable of achieving excellent conversion and yield in the production of a selective ortho-alkylation reaction product.

[0010] In addition, the present invention provides a method for producing the catalyst.

[0011] In addition, the present invention provides a method for producing an ortho-alkylation reaction product using the above catalyst.

[0012]

[0013] To solve the above problem, the present invention provides an ortho-alkylation reaction extrusion molding catalyst represented by the following chemical formula 1 and including mesopores having a diameter of 50 to 80 nm:

[0014] [Chemical Formula 1]

[0015] Fe 1.0 V 1.0 M a

[0016] M is one or more metals selected from the group consisting of Mg, Mn, Co, Ga, Cu, Ca, Zr, Y and La,

[0017] a is the molar ratio for 1 mole of Fe, and is 0.01 to 0.3.

[0018]

[0019] According to another embodiment of the invention, a method for producing the above-described ortho-alkylation reaction extrusion molding catalyst is provided.

[0020] Specifically, the manufacturing method comprises the steps of: manufacturing a first precursor composition comprising a vanadium precursor and an alcohol amine;

[0021] A step of preparing a second precursor composition comprising an iron precursor and a precursor of metal M;

[0022] A step of preparing a mixed solution by adding a second precursor composition to the first precursor composition;

[0023] A step of adjusting the pH by adding a precipitant to the above mixed solution;

[0024] A step of filtering and washing the pH-adjusted mixed solution to obtain a precipitate;

[0025] A step of producing a composite metal oxide by calcining the above-mentioned precipitate at 250 to 950°C;

[0026] A step of preparing a paste by mixing the above composite metal oxide, binder resin, and solvent;

[0027] A step of manufacturing a molded body by extruding the above paste; and

[0028] It includes a step of manufacturing an extrusion molded catalyst by heat-treating the above molded body at 250 to 950°C.

[0029]

[0030] According to another embodiment of the invention, a method for producing an ortho-alkylation reaction product is provided, comprising an alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of the above-described ortho-alkylation reaction extrusion molding catalyst.

[0031]

[0032] The ortho-alkylation reaction extrusion molding catalyst according to the present invention is an extrusion molding catalyst having a specific metal composition and BET specific surface area, exhibits high catalytic activity, and when using the same to produce an ortho-alkylation reaction product, exhibits high selectivity and conversion even at a relatively low reaction temperature.

[0033]

[0034] Figure 1 shows data measuring the pore size and pore volume of catalysts according to manufacturing examples and comparative manufacturing examples.

[0035] Figure 2 shows the conversion rate and selectivity in the ortho-alkylation reaction according to examples and comparative examples.

[0036] Figure 3 shows the conversion rate and selectivity according to the control of the alkylation reaction temperature in the ortho-alkylation reaction according to the embodiment.

[0037]

[0038] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0039] Furthermore, the terminology used herein is merely for the purpose of describing exemplary embodiments and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, it should be understood that terms such as "comprise," "include," or "have" indicate the presence of implemented features, steps, components, or combinations thereof, but do not preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

[0040] Additionally, in the present invention, when each component is referred to as being formed “on” or “over” each component, it means that each component is formed directly on each component, or that other components may be additionally formed between each layer, on the object, or on the substrate.

[0041]

[0042] Magnesium-based catalysts typically used in alkylation reactions require high activity, long lifespan, and high selectivity for the desired reaction product. Most alkylation catalysts used in the past produced large quantities of para-alkylated products, but extensive research has been conducted to obtain the more useful ortho-alkylated products with high selectivity.

[0043] However, conventional technologies have had the problem of making it difficult to obtain ortho-alkylation products with the desired degree of selectivity and conversion by using technologies that combine a cocatalyst compound with a magnesium catalyst, change the composition of the catalyst, or change the reaction conditions.

[0044] In particular, in the case of magnesium-based catalysts, high ortho selectivity (>95%) could be obtained at a very high conversion rate (>93%), but there was a problem that many over-methylated products existed due to over-reaction at high reaction temperatures (about 450 degrees or more), and the catalyst activity decreased significantly over time.

[0045] In order to solve these problems, the inventors of the present invention have confirmed that when an extruded catalyst having a specific metal composition and mesopores is produced, it exhibits high catalytic activity, and in particular, when producing an ortho-alkylation reaction product, it exhibits high selectivity and conversion even under relatively low temperature reaction conditions, thereby completing the present invention.

[0046]

[0047] (Ortho-alkylation reaction extrusion molding catalyst)

[0048] An ortho-alkylation reaction extrusion molding catalyst according to one embodiment of the invention is represented by the following chemical formula 1 and includes mesopores having a diameter of 50 to 80 nm:

[0049] [Chemical Formula 1]

[0050] Fe 1.0 V 1.0 M a

[0051] M is one or more metals selected from the group consisting of Mg, Mn, Co, Ga, Cu, Ca, Zr, Y and La, and a is a molar ratio to 1 mol of Fe, and may be 0.01 to 0.3, preferably 0.05 to 0.2.

[0052] The above ortho-alkylation reaction extrusion molding catalyst is a catalyst containing Fe (iron) and V (vanadium) as essential components, and can perform high catalytic activity and advantageous selective alkylation reaction even under lower reaction temperature conditions compared to conventional Mg (magnesium)-based catalysts.

[0053] In particular, the combined metal M can be used in combination with iron-vanadium as a cocatalyst component to improve the activity enhancing effect. Preferably, the metal M may be one or more metals selected from the group consisting of Mg, Mn, Co, Ga, Cu, Y, and La, and more preferably, one or more metals selected from the group consisting of Mg, Mn, Co, and Ga.

[0054] The above ortho-alkylation reaction extrusion molding catalyst comprises a composite metal oxide composed of iron, vanadium, and metal M, and includes mesopores having a diameter of 50 to 80 nm. The mesopores having the above size minimize the diffusion resistance of the reactants / products, thereby enabling high catalytic activity to be realized. The diameter of the mesopores may preferably be 61 to 77 nm. This is preferable because excellent catalytic activity can be realized within this range.

[0055] Preferably, the volume of the mesopores of the ortho-alkylation reaction extrusion molding catalyst is 0.500 to 0.690 cm 3 / g, preferably 0.557 to 0.667 cm 3 / g can be achieved. It is desirable because it can achieve excellent catalytic activity in that range.

[0056] Preferably, the BET specific surface area of ​​the mesopores of the ortho-alkylation reaction extrusion molding catalyst is 30 to 50 m 2 / g, more preferably 35 to 45 m 2 / g can be achieved. It is desirable because it can achieve excellent catalytic activity in that range.

[0057] More preferably, the ortho-alkylation reaction extrusion molding catalyst can simultaneously satisfy the above-described pore diameter, pore volume, and BET surface area ranges, thereby minimizing the diffusion resistance of the reactants / products and thereby realizing improved catalytic activity.

[0058] The pore size, pore volume and BET specific surface area of ​​the above catalyst can be measured according to BET (Brunauer-Emmett-Teller) through N2 adsorption-desorption analysis, and the specific measurement method thereof will be specifically described in the experimental examples described below.

[0059]

[0060] (Method for producing an ortho-alkylation reaction extrusion molding catalyst)

[0061] According to one embodiment of the invention, a method for producing an ortho-alkylation reaction extrusion molding catalyst is provided, comprising the following steps.

[0062] First, a step of preparing a first precursor composition including a vanadium precursor and an alcohol amine; a step of preparing a second precursor composition including an iron precursor and a precursor of metal M; a step of adding the second precursor composition dropwise to the first precursor composition to prepare a mixed solution; a step of adjusting pH by adding a precipitant to the mixed solution; a step of filtering and washing the mixed solution, the pH of which has been adjusted, to obtain a precipitate; a step of calcining the precipitate at 250 to 950°C to prepare a composite metal oxide; a step of mixing the composite metal oxide, a solid binder, and a solvent to prepare a paste; a step of extruding the paste to prepare a molded body; and a step of heat-treating the molded body at 250 to 950°C to prepare an extrusion-molded catalyst.

[0063] Below, each step will be explained in detail.

[0064] (Stage 1)

[0065] First, a first precursor composition including a vanadium precursor and an alcohol amine is prepared.

[0066] Any commonly used vanadium precursor can be used as the precursor without limitation. For example, ammonium metavanadate is preferably used, but is not limited thereto, and other commonly used vanadium precursors may be further included depending on the purpose. However, when ammonium metavanadate is used as the vanadium precursor, the ammonium ion is removed through a heat treatment process after impregnation and drying, so that the influence of the ion can be minimized, making it preferable as an iron-vanadium-metal catalyst.

[0067] The above alcohol amine is a component that can increase the solubility of the vanadium precursor, and by including the same, the vanadium precursor can be stably manufactured as a first precursor composition.

[0068] The type of the above alcohol amine is not particularly limited, but may include monoethanol amine, diethanol amine, triethanolamine, monoisopropylamine, N,N-methylethanolamine, and aminoethyl ethanolamine, and these may be used alone or in combination of two or more. More preferably, ethanolamine may be used.

[0069] In addition, a solvent is used in the first precursor composition to dissolve the components. The type of the solvent is not particularly limited, but may include water, alcohol, etc., and these may be used alone or in combination of two or more. More preferably, water may be used. The water may be high-purity water such as distilled water, ion-exchanged water, or ultrapure water (DIW). If the water contains impurities, the impurities may be adsorbed to the catalyst, thereby reducing the activity of the catalyst. Therefore, it is preferable to use ultrapure water, etc.

[0070] (Stage 2)

[0071] A second precursor composition comprising an iron precursor and a metal M precursor is prepared.

[0072] Any precursor commonly used for the iron precursor and metal M precursor used in the above step can be used.

[0073] For example, as the iron precursor, one or more selected from iron chloride precursors and iron nitrate precursors can be used. As the metal M precursor, one or more selected from metal chloride precursors and nitrate precursors can be used. Specifically, in the case of zirconium among the metal M, it is preferable to use one or more selected from zirconium chloride precursors, oxynitrate precursors, and oxychloride precursors as the precursor.

[0074] In addition, a solvent is used in the second precursor composition to dissolve the components. The type of the solvent is not particularly limited, but may include water, alcohol, etc., and these may be used alone or in combination of two or more. More preferably, water may be used. The water may be high-purity water such as distilled water, ion-exchanged water, or ultrapure water (DIW). If the water contains impurities, the impurities may be adsorbed to the catalyst, thereby reducing the activity of the catalyst. Therefore, it is preferable to use ultrapure water, etc.

[0075] (Stage 3)

[0076] A mixed solution is prepared by adding a second precursor composition dropwise to the first precursor composition.

[0077] The step of preparing the above mixed solution is performed slowly for co-precipitation, and specifically, can be performed by evenly adding the second precursor composition to the first precursor composition over a period of 1 to 2 hours.

[0078] The amount of each metal precursor used in the step of preparing the above mixed solution is not particularly limited, but in order to prepare a catalyst for effectively obtaining an ortho-product with a high conversion rate, it is preferable to adjust the amount of the iron precursor, the vanadium precursor, and the metal M precursor so as to satisfy a molar ratio of 1:1:0.01 to 0.3, and preferably, so as to satisfy a molar ratio of 1:1:0.05 to 0.2.

[0079] (Stage 4)

[0080] The pH is adjusted by adding a precipitant to the above mixed solution.

[0081] The step of introducing the above precipitant is a step performed to increase the yield of a precipitate having a stable iron-vanadium-metal bond, and can preferably be performed so that the pH can be adjusted to 7 to 8.

[0082] Any precipitant commonly used can be used as the precipitant used in the above step, but ammonia water is preferred.

[0083] (Step 5)

[0084] The above pH-adjusted mixed solution is filtered and washed to obtain a precipitate.

[0085] The above filtration and washing steps are not particularly limited, and may be performed by filtering using a paper filter and washing using distilled water.

[0086] The above filtration and washing steps are steps for removing harmful substances that cannot be decomposed and removed during the firing process, and each may be performed at least once, and each may be performed 1 to 3 times.

[0087] (Step 6)

[0088] The above precipitate is calcined at 250 to 950°C to produce a composite metal oxide.

[0089] The step of preparing the composite metal oxide by calcination can be performed at 250 to 950°C, preferably 350 to 650°C, and is preferably performed at the temperature range for 1 to 12 hours, preferably 3 to 7 hours. If the heat treatment temperature is less than 250°C or the heat treatment time is less than 1 hour, the formation of the iron vanadate phase in the catalyst is not sufficient, which is undesirable. If the heat treatment temperature exceeds 950°C or the heat treatment time exceeds 12 hours, there is a concern that the iron vanadate phase may be transformed, which is undesirable.

[0090] (Step 7)

[0091] A paste is prepared by mixing the above composite metal oxide, binder resin, and solvent.

[0092] The step of preparing the paste includes 0.1 to 20 parts by weight of binder resin and 50 to 200 parts by weight of solvent, based on 100 parts by weight of the composite metal oxide, and preferably 0.1 to 10 parts by weight of binder resin and 100 to 150 parts by weight of solvent can be used.

[0093] The above binder resin is a component that has an important influence on implementing catalytic activity by facilitating the manufacture of a molded catalyst during extrusion and forming appropriate mesopores inside the catalyst through sintering.

[0094] In addition, the solvent is used to enable the paste to be kneaded uniformly, and to facilitate the manufacture of a molded catalyst during extrusion.

[0095] The binder used to make the above paste can be any solid or liquid form to improve the properties and stability of the molded body. YB-152A of the methyl cellulose series, which is a solid binder, is preferred, and water is preferred as the solvent.

[0096] (Step 8)

[0097] The above paste is extruded to produce a molded body.

[0098] The above extrusion step is manufactured using appropriate equipment so that the final extruded catalyst can be in the shape of a cylinder with a diameter of 1.0 to 1.2 mm and a height of 1 to 2 mm. For example, a screw extruder and a piston extruder can be used, but preferably, a single piston extruder can be used, and in this case, it is possible to manufacture an extruded catalyst with a low moisture content and a high extrusion rate at high pressure.

[0099] (Step 9)

[0100] The above molded body is heat-treated at 250 to 950°C to produce an extrusion molded catalyst.

[0101] Finally, a final heat treatment step is performed to remove the binder and solvent introduced into the molded body, form pores, and impart strength. The heat treatment is preferably performed at a temperature range of 250 to 950°C, preferably 350 to 650°C, for 1 to 12 hours, preferably 3 to 7 hours. If the heat treatment temperature is less than 250°C or the heat treatment time is less than 1 hour, the binder is not removed, and thus pores are not properly formed, which is undesirable. On the other hand, if the heat treatment temperature exceeds 950°C or the heat treatment time exceeds 12 hours, there is a risk of catalytically active phase being denatured, which is undesirable.

[0102]

[0103] (Ortho-alkylation reaction composition)

[0104] According to one embodiment of the invention, the ortho-alkylation reaction composition comprises the above-described ortho-alkylation reaction extrusion molding catalyst and a monomer composition comprising a meta-alkyl substituted phenolic monomer.

[0105] The above ortho-alkylation reaction extrusion molding catalyst can be applied equally to all of the above-mentioned contents.

[0106] In the above monomer composition, the meta-alkyl substituted phenolic monomer may be meta-cresol (m-cresol).

[0107] The above monomer composition further comprises, in addition to the meta-alkyl substituted phenolic monomer, an alkanol and distilled water (DI water), and an alkyl group can be introduced through a reaction with the alkanol. By using the distilled water together, the decomposition reaction of the alkanol can be suppressed, which is preferable. The alkanol can preferably be methanol.

[0108] The monomer composition may preferably contain phenolic monomer: alkanol: distilled water in an amount of 1:3 to 10:1 to 5 parts by weight, and more preferably, 1:4 to 6:1 to 3 parts by weight. At this time, if the content of alkanol is included in a small amount outside the above range, the alkylation mediator (agent) is reduced, resulting in a lower conversion rate. If the content of distilled water is included in a small amount outside the above range, the effect of suppressing the decomposition reaction of the alkanol is reduced. If the alkanol or distilled water is included in an excessive amount outside the above range, the reactivity may be reduced due to competitive adsorption with the phenolic monomer at the catalyst active site.

[0109] When included in the above content range, it is preferable to produce an ortho-alkylation reaction product with the desired selectivity and conversion rate.

[0110]

[0111] (Method for producing ortho-alkylation reaction product)

[0112] According to one embodiment of the invention, a method for producing an ortho-alkylation reaction product comprises an alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of the above-described ortho-alkylation reaction extrusion molding catalyst. Specifically, the method for producing an ortho-alkylation reaction product can be performed using an ortho-alkylation reaction composition comprising the above-described ortho-alkylation reaction extrusion molding catalyst. The above-described contents can be equally applied to both the catalyst and the reaction composition.

[0113] The above ortho-alkylation reaction product may be, for example, at least one selected from the group consisting of 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylphenol, and tetramethylphenol, and may be produced by selectively substituting an alkyl group at the ortho position in m-cresol through a multi-step reaction as follows.

[0114]

[0115]

[0116] The above alkylation reaction can be performed at 300°C to 400°C, and can achieve excellent selectivity and conversion even at relatively low temperatures. This is achieved using the extruded catalyst having the iron-vanadium composition of the present disclosure described above, and is preferable because it can achieve excellent effects even at lower temperatures compared to conventional magnesium-based catalysts.

[0117] The above alkylation reaction can be carried out under inert conditions, for example, in the presence of an inert carrier gas. Nitrogen, helium, neon, argon, etc. can be used as the inert carrier gas, and nitrogen is preferably used. By carrying out under the above conditions, the ortho-alkylation reaction product can be produced with the desired selectivity and conversion, which is preferable.

[0118] The above alkylation reaction can be preferably carried out using a continuous flow gas phase reactor, in which case the monomer composition is introduced into the continuous flow gas phase reactor at a rate of 0.5 hr. -1 2.0 hr -1 It can be performed by injecting at the LHSV (liquid hourly space velocity). At this time, if the space velocity range is exceeded, the reactants may not be sufficiently activated at the catalytic active site, making it difficult to obtain the product smoothly, and also the activity or selectivity of the catalyst may decrease, reducing the amount of the product.

[0119] By performing the process under the above conditions, it is preferable to produce an ortho-alkylation reaction product with the desired selectivity and conversion.

[0120]

[0121] Hereinafter, the functions and effects of the invention will be described in more detail through specific examples. However, these examples are provided merely as examples of the invention and do not define the scope of the invention.

[0122]

[0123] [Examples and Comparative Examples]

[0124] Manufacturing example: Manufacturing of catalyst

[0125] Manufacturing Example 1: Manufacturing of Fe-V-Mg extrusion molded catalyst

[0126] After adding 11.698 g of ammonium metavanadate and 6.415 g of ethanolamine to 150 g of distilled water (DIwater), the mixture was heated to approximately 120°C and stirred sufficiently, then cooled to room temperature (approximately 25°C) to prepare a transparent solution A.

[0127] Solution B was prepared by dissolving 40.4 g of iron nitrate and 2.564 g of magnesium nitrate in 100 g of distilled water (DIwater) at room temperature (approximately 25°C).

[0128] Solution A was slowly injected dropwise into the stirred solution B using a syringe to prepare a mixed solution C containing a precipitate.

[0129] Ammonia solution was added to the mixed solution C to adjust the pH to 7, and the mixture was aged by stirring for an additional 3 hours at 80°C.

[0130] After leaving it at room temperature (approximately 25°C) for about a day, the upper solution was discarded and filtered and washed using distilled water (DIwater) using a filter device to obtain a solid sample.

[0131] The obtained sample was sufficiently dried at 80°C in a drying oven. The dried sample was heat-treated in a furnace at 450°C for 5 hours under air conditions to obtain the active ingredient.

[0132] Next, 10 g of heat-treated iron-vanadium-based active ingredient, 0.2 g of organic binder (YB-152A, YUKEN), and 12 g of distilled water were placed in a mixing bowl and mixed well to prepare a paste. Once the dough was kneaded, it was extruded through a 1.2 mm diameter die using a single piston extruder catalyst molding equipment. The noodle shape extruded from the single piston extruder was evenly spread on a tray, and then dried in a convection oven at 80℃ for 4 hours. The dried molded catalyst was cut into 1-2 mm intervals and calcined in a muffle furnace at 450℃ for 3 hours to complete the iron-vanadium-based extruded molded catalyst.

[0133]

[0134] Manufacturing Example 2: Manufacturing of Fe-V-Mn extrusion molded catalyst

[0135] It was manufactured in the same manner as in Manufacturing Example 1, except that 1.790 g of manganese nitrate was used instead of 2.564 g of magnesium nitrate.

[0136]

[0137] Manufacturing Example 3: Manufacturing of Fe-V-Co extrusion molded catalyst

[0138] It was manufactured in the same manner as in Manufacturing Example 1, except that 2.910 g of cobalt nitrate was used instead of 2.564 g of magnesium nitrate.

[0139]

[0140] Manufacturing Example 4: Manufacturing of Fe-V-Ga extrusion molded catalyst

[0141] It was manufactured in the same manner as in Manufacturing Example 1, except that 2.557 g of gallium nitrate was used instead of 2.564 g of magnesium nitrate.

[0142]

[0143] Comparative Manufacturing Example 1: Manufacturing of Fe Catalyst

[0144] A metal precursor solution was prepared by dissolving 40.4 g of iron nitrate in 150 g of distilled water (DI water) and stirring thoroughly. Ammonia water was slowly added dropwise to the metal precursor solution to adjust the pH to 7, and the solution was further stirred and aged for 3 hours. After standing at room temperature (approximately 25°C) for about a day, the upper solution was discarded, and a solid sample was obtained by filtering and washing with distilled water (DI water) using a filter. The obtained sample was thoroughly dried at 80°C in a drying oven. The dried sample was heat-treated in a furnace at 450°C under air conditions for 5 hours. The heat-treated sample was pulverized and sieved to produce granules with a size of 212 to 425 μm containing the final iron-based active ingredient.

[0145]

[0146] Comparative Manufacturing Example 2: Manufacturing of Mg Catalyst

[0147] Magnesium oxide (MgO powder, Crystallite size 9 nm, BET surface area 144.4 m 2 / g, Total pore volume 0.72 cm 3 / g, pore size 6, 40 nm) was pressed into a disc shape using a plate-type press machine and an aluminum dish, and then crushed to produce granules with a size of 212 to 425 μm.

[0148]

[0149] Comparative Manufacturing Example 3: Manufacturing of Mg Extrusion Molded Catalyst

[0150] Magnesium oxide (MgO powder, Crystallite size 9 nm, BET surface area 144.4 m 2 / g, Total pore volume 0.72 cm 3 / g, Pore size 6, 40 nm), 50 g of organic binder (YB-152A, YUKEN), and 60 g of distilled water were added to a mixing bowl and mixed evenly to prepare a paste. Once the dough was completed, it was extruded through a 1.2 mm diameter die using a single piston extruder catalyst molding equipment. The noodle shape extruded from the single piston extruder was evenly spread on a tray and dried using a convection oven at 100℃ for 4 hours. The dried molded catalyst was cut into 1-2 mm intervals and calcined using a muffle furnace at 450℃ for 6 hours to prepare a magnesium-based molded catalyst.

[0151]

[0152] Experimental Example 1: Analysis of catalyst properties

[0153] In the manufacturing examples and comparative manufacturing examples, the BET (Brunauer-Emmett-Teller) surface area, volume, and size distribution of the mesopores of the catalyst were confirmed through N2 adsorption-desorption analysis.

[0154] 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, and the results are shown in Table 1 and Figure 1 below.

[0155] Average pore size (nm)Pore volume (cm) 3 / g)BET specific surface area (m 2 / g) Manufacturing Example 177.700.62536.67 Manufacturing Example 261.060.55739.44 Manufacturing Example 366.860.64742.25 Manufacturing Example 464.430.66744.67 Comparative Manufacturing Example 118.970.0466.48 Comparative Manufacturing Example 214.640.590119.16 Comparative Manufacturing Example 314.490.660140.20

[0156]

[0157] Example 1: Preparation of alkylation reaction product

[0158] The alkylation reaction of m-cresol was performed using a continuous flow gas phase reactor. 1 g of the catalyst of the above Preparation Example 1 was charged into a stainless steel tube type reactor with a diameter of 1 / 2 inch x a length of 50 cm, and then installed in the main furnace.

[0159] Afterwards, N2 as a carrier gas was flowed (40 cc / min) using a mass flow controller (MFC), and the inside of the reactor was raised to the activation temperature (350 ℃) for catalyst activation and maintained for 1 hour. Afterwards, a liquid mixture containing the reactant (12.5 mg / min, m-cresol: Methanol: DI water = 1:5:1, LHSV 0.75 / h) was passed through a pre-heater (350 ℃), vaporized, and then introduced to perform the methylation reaction (350 ℃) for 5 hours.

[0160] During the methylation reaction, the reaction pressure was maintained at atmospheric pressure, and the reaction product was collected in liquid form (IPA (isopropyl alcohol) as a solvent) for analysis. The collected liquid was analyzed using a gas chromatography (GC) equipped with a flame ionization detector (FID), and the m-cresol conversion and the selectivity of the target products (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated from the GC results using the following equations.

[0161] The target product was defined as 2,3,6-TMP, the final product, and 2,5-DMP and 2,3-DMP, which can be obtained as the final product through further reaction as intermediate materials.

[0162]

[0163] Examples 2 to 4 and Comparative Examples 1 to 3

[0164] An alkylation reaction product was prepared in the same manner as in Example 1, except that Preparation Examples 2 to 4 and Comparative Preparation Examples 1 to 3 were used instead of the active ingredient of Preparation Example 1.

[0165]

[0166] Experimental Example 2: Analysis of ortho-alkylation reaction products

[0167] The liquids in which the reaction products manufactured in the examples and comparative examples were collected were analyzed using a gas chromatography device (GC) equipped with a flame ionization detector (FID), 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 from the GC results using the following mathematical equations 1 and 2, and the results are shown in Table 2 and Fig. 2.

[0168] The target product was defined as 2,3,6-TMP, the final product, and 2,5-DMP and 2,3-DMP, which can be obtained as the final product through further reaction as intermediate materials.

[0169] [Mathematical Formula 1]

[0170]

[0171] [Equation 2]

[0172]

[0173]

[0174] Conversion rate selectivity m-cresolTargetproduct a 2,5-DMP2,3-DMP2,3,6-TMPAnisole b Isomer c Over- dExample 198.9495.0126.773.3264.920.172.111.77 Example 298.6795.8535.715.5554.590.111.711.53 Example 399.1596.6432.523.9860.140.211.451.24 Example 498.0096.7434.924.9556.870.331.241.20 Comparative Example 111.1095.2966.8225.562.9100.720 Comparative Example 25.5881.1262.0819.0408.122.790 Comparative Example 36.6888.8667.9020.9607.753.390 a Target product: 2,5-DMP, 2,3-DMP, and 2,3,6-TMP b Anisole: 3-MA (methylanisole), DMA (dimethylanisole), TMA (trimethylanisole) c Isomer: DMP and TMP isomer d Over: Tetra- / penta-MP (methylphenol)

[0175]

[0176] Experimental Example 3: Analysis of ortho-alkylation reaction products (analysis of the effect of reaction temperature)

[0177] The alkylation reaction was performed in the same manner as in Example 1, except that the methylation reaction temperature was changed to 300°C, 310°C, 320°C, 330°C, and 340°C, respectively. Next, the m-cresol conversion and the selectivity of the target product (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated in the same manner as in Experimental Example 2, and the results are shown in Table 3 and Fig. 3.

[0178] Reaction Conditions Conversion Selectivity m-cresol Target Product 2,5-DMP 2,3-DMP 2,3,6-TMPA Nisole Isopropyl Alcohol Over-300 ℃ 50.20 96.046 2.37 21.23 12.44 0.37 0.60 44 310 ℃ 65.62 97.096 1.78 19.29 16.02 0.47 0.34 0.47 320 ℃ 86.85 97.045 5.42 13.96 27.66 0.21 06 0.64 330 ℃ 88.09 96.21 53.72 14.65 27.84 0.21 610.83 340 ℃98.9795.4432.454.1858.810.2121.66350 ℃98.9495.0126.773.3264.920.172.111.77

Claims

1. It is represented by the following chemical formula 1, Containing mesopores with a diameter of 50 to 80 nm, Ortho-alkylation reaction extrusion molding catalyst: [Chemical Formula 1] Fe 1.0 V 1.0 M a M is one or more metals selected from the group consisting of Mg, Mn, Co, Ga, Cu, Ca, Zr, Y and La, a is the molar ratio for 1 mole of Fe, and is 0.01 to 0.

3.

2. In paragraph 1, In the above chemical formula 1, M is one or more metals selected from the group consisting of Mg, Mn, Co, and Ga. Ortho-alkylation reaction extrusion molding catalyst.

3. In paragraph 1, The volume of the above mesopores is 0.500 to 0.690 cm 3 / g person, Ortho-alkylation reaction extrusion molding catalyst.

4. In paragraph 1, The BET surface area of ​​the above mesopores is 30 to 80 m 2 / g person, Ortho-alkylation reaction extrusion molding catalyst.

5. A method for producing an ortho-alkylation reaction extrusion molding catalyst according to Article 1, A step of preparing a first precursor composition comprising a vanadium precursor and an alcohol amine; A step of preparing a second precursor composition comprising an iron precursor and a precursor of metal M; A step of preparing a mixed solution by adding a second precursor composition to the first precursor composition; A step of adjusting the pH by adding a precipitant to the above mixed solution; A step of filtering and washing the pH-adjusted mixed solution to obtain a precipitate; A step of producing a composite metal oxide by calcining the above-mentioned precipitate at 250 to 950°C; A step of preparing a paste by mixing the above composite metal oxide, binder resin, and solvent; A step of manufacturing a molded body by extruding the above paste; and A step of manufacturing an extrusion molding catalyst by heat-treating the above molded body at 250 to 950°C; including; Method for producing an ortho-alkylation reaction extrusion molding catalyst.

6. In paragraph 5, The above alcohol amine is at least one selected from the group consisting of monoethanol amine, diethanol amine, triethanolamine, monoisopropylamine, N,N-methylethanolamine and aminoethyl ethanolamine. Method for producing an ortho-alkylation reaction extrusion molding catalyst.

7. In paragraph 5, In the step of preparing the above mixed solution, Iron precursor, vanadium precursor and metal M precursor, Satisfying the molar ratio of 1:1:0.01 to 0.3, Method for producing an ortho-alkylation reaction extrusion molding catalyst.

8. In paragraph 5, In the step of manufacturing the above paste, With respect to 100 parts by weight of the above composite metal oxide, 0.1 to 20 parts by weight of binder resin and 50 to 200 parts by weight of solvent are included. Method for producing an ortho-alkylation reaction extrusion molding catalyst.

9. Comprising an alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of an ortho-alkylation reaction extrusion molding catalyst according to paragraph 1. A method for producing an ortho-alkylation reaction product.

10. In paragraph 9, The above meta-alkyl substituted phenolic monomer is meta-cresol, A method for producing an ortho-alkylation reaction product.

11. In paragraph 9, The above monomer composition further comprises an alkanol and distilled water, A method for producing an ortho-alkylation reaction product.

12. In paragraph 11, The above monomer composition comprises phenolic monomer: alkanol: distilled water in a ratio of 1:3 to 10:1 to 5 parts by weight. A method for producing an ortho-alkylation reaction product.

13. In paragraph 9, The above alkylation reaction is carried out at 300 to 400°C. A method for producing an ortho-alkylation reaction product.

14. In paragraph 9, The above alkylation reaction is performed using a continuous flow gas phase reactor. A method for producing an ortho-alkylation reaction product.

15. In paragraph 14, 0.5 hr into the above continuous flow gas phase reactor -1 2.0 hr -1 The monomer composition is injected at a liquid hourly space velocity (LHSV). A method for producing an ortho-alkylation reaction product.

16. In paragraph 9, The above ortho-alkylation reaction product is at least one selected from the group consisting of 2,5-dimethylphenol, 2,3-dimethylphenol, 2,3,6-trimethylphenol, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylphenol and tetramethylphenol. A method for producing an ortho-alkylation reaction product.

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