Catalyst for ortho-alkylarion reaction and preparation method of ortho-alkylarion reaction product using the same

Abstract

The present invention relates to a catalyst composition for producing an ortho-alkylation reaction product and a method for producing an ortho-alkylation reaction product using the same, and more specifically, to a catalyst composition for producing an ortho-alkylation reaction product capable of achieving high selectivity and conversion rate in the selective ortho-alkylation reaction of phenolic compounds and a method for producing an ortho-alkylation reaction product using the same.

Description

Technology Field

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

[0003] Alkylated hydroxyaromatic compounds are used for various purposes and are typically produced by the gas-phase reaction of phenol and methanol. Additionally, through further alkylation reactions, compounds of various structures can be produced, which are easy to apply to high-performance thermoplastic products.

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

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

[0006] However, conventional technologies involve using a co-catalyst compound in addition to a magnesium-based catalyst, changing the composition of the catalyst, or changing the reaction conditions. With these conventional technologies, there was a problem in that it was difficult to obtain ortho-alkylation products with high selectivity and yield to the desired degree.

[0007] Accordingly, in ortho-alkylation reactions, there is a need to develop catalysts that are improved in terms of catalyst selectivity, catalytic activity, production yield, cost reduction, and total productivity. The problem to be solved

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

[0010] In addition, the present invention provides a method for producing an ortho-alkylation reaction product using the catalyst. means of solving the problem

[0012] In order to solve the above problem, the present invention,

[0013] It has a bimodal pore structure and a BET specific surface area of ​​100 m² 2 / g to 180 m 2 Containing magnesium oxide in g / g,

[0014] Provides an ortho-alkylation reaction catalyst.

[0016] In addition, the present invention,

[0017] A monomer composition comprising the above-described ortho-alkylation reaction catalyst and a meta-alkyl substituted phenolic monomer,

[0018] An ortho-alkylation reaction composition is provided.

[0020] In addition, the present invention,

[0021] alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of the aforementioned ortho-alkylation reaction catalyst,

[0022] A method for preparing an ortho-alkylation reaction product is provided. Effects of the invention

[0024] The ortho-alkylation reaction catalyst according to the present invention exhibits high catalytic activity by using magnesium oxide having specific physical properties and a pore structure, and when an ortho-alkylation reaction product is prepared using the same, it exhibits significantly high selectivity and conversion rate.

[0025] The ortho-alkylation reaction catalyst according to the present invention exhibits high catalytic activity alone without the use of a separate co-catalyst or additional additives, and when an ortho-alkylation reaction product is prepared using the same, it exhibits significantly high selectivity and conversion rate. Brief explanation of the drawing

[0027] Figure 1 is a graph showing the selectivity of reaction products prepared using the ortho-alkylation reaction catalysts of the examples and comparative examples of the present invention. Figure 2 is an XDR graph of the ortho-alkylation reaction catalysts of the examples and comparative examples of the present invention. Figure 3 is a graph showing the pore distribution according to N2 adsorption-desorption analysis of the ortho-alkylation reaction catalysts of the examples and comparative examples of the present invention. Specific details for implementing the invention

[0028] The present invention is capable of various modifications and may take various forms, and specific embodiments are illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0029] Furthermore, the terms used herein are used merely to describe exemplary embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “comprising,” or “having” are intended to indicate the existence of the implemented features, steps, components, or combinations thereof, and should be understood as not precluding the existence or addition of one or more other features, steps, components, or combinations thereof.

[0030] Furthermore, in the present invention, when each component is described as being formed "on" or "above" 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 an object, or on a substrate.

[0032] Magnesium-based catalysts typically used in alkylation reactions are required to have high activity, a long active life, and high selectivity for the desired reaction product. Most alkylation catalysts used in the past produced large quantities of para-alkylated products, and various studies have been conducted to obtain more useful ortho-alkylated products with high selectivity.

[0033] However, conventional technologies involve using a co-catalyst compound in combination with a magnesium-based catalyst, changing the composition of the catalyst, or changing the reaction conditions, and there was a problem in that it was difficult to obtain ortho-alkylation products with high selectivity and conversion rates to the desired degree using such technologies.

[0034] In addition, to solve these problems, the inventors confirmed that significantly high catalytic activity can be achieved in alkylation reactions by setting the BET specific surface area and pore structure of the magnesium oxide catalyst to a specific range. The ortho-alkylation reaction catalyst according to the present invention exhibits excellent catalytic activity as a single catalyst without additionally using a co-catalyst or adjusting reaction conditions, and the inventors completed the present invention by discovering that significantly high selectivity and conversion rate can be achieved when an ortho-alkylation reaction product is prepared using this catalyst.

[0036] (Ortho-alkylation reaction catalyst)

[0037] An ortho-alkylation reaction catalyst according to one embodiment of the invention has a bimodal pore structure and a BET specific surface area of ​​100 m² 2 / g to 180 m 2It contains magnesium oxide in / g.

[0038] Generally, the catalytic activity of a catalyst is determined by reaction conditions or the acid-base properties of the catalyst. In the alkylation reaction of meta-alkyl substituted phenolic monomers, if the catalyst has basic properties, it perpendicularly adsorbs the reactants and favors ortho-C-alkylation (see Figure (a) below). Accordingly, the ortho-alkylation reaction catalyst according to the present invention contains a magnesium oxide (MgO) component.

[0039]

[0041] The magnesium oxide described above has a bimodal pore structure, specifically a mesopore bimodal form, which facilitates the diffusion of reactants and enables the reaction to be carried out effectively. In addition, by simultaneously satisfying the aforementioned specific range of BET specific surface area, it can exhibit excellent catalytic activity in ortho-alkylation reactions and demonstrate high selectivity, conversion rate, and yield.

[0042] Generally, as the BET specific surface area increases, the number of active sites of the catalyst increases; however, in the case of a single-modal form, even if the BET specific surface area increases, the diffusion of reactants is not smooth, making it difficult to carry out the reaction to the desired extent.

[0043] Preferably, in the bi-modal pore structure, the diameter of the first pore may be 2 nm to 10 nm and the diameter of the second pore may be 10 nm to 50 nm, and more preferably, the diameter of the first pore may be 4 nm to 8 nm and the diameter of the second pore may be 20 nm to 45 nm or 35 nm to 45 nm. Through 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.

[0044] The above magnesium oxide has a BET specific surface area of ​​100 m² 2 / g to 180 m 2 It satisfies / g and exhibits excellent catalytic activity due to a large number of reaction active sites resulting from a relatively large specific surface area. At the same time, as previously mentioned, it possesses a bimodal pore structure that facilitates the diffusion of reactants, enabling the reaction to proceed effectively. Accordingly, it possesses excellent catalytic activity in ortho-alkylation reactions and can demonstrate improved selectivity, conversion rate, and yield. The above BET specific surface area is 100 m² 2 If the value is less than / g, the number of reaction active sites decreases significantly, resulting in a low reactant conversion rate and making it difficult to achieve the desired activity. Additionally, the BET specific surface area is 180 m². 2 When the value exceeds / g, the reaction active sites increase, but primary pores are predominantly formed, hindering the smooth diffusion of reactants and products, which makes it difficult to achieve high activity.

[0045] Preferably, the BET specific surface area of ​​the magnesium oxide is 130 m² 2 / g to 180 m 2 / g, more preferably, 130 m 2 / g to 150 m 2 It can be / g, and it is desirable to be able to achieve excellent catalytic activity without the aforementioned problems within the above range.

[0047] (Ortho-alkylation reaction composition)

[0048] According to one embodiment of the invention, the ortho-alkylation reaction composition comprises the aforementioned ortho-alkylation reaction catalyst and a monomer composition comprising a meta-alkyl substituted phenolic monomer.

[0049] The above ortho-alkylation reaction catalyst has a bimodal pore structure and a BET specific surface area of ​​100 m² 2 / g to 180 m 2 It contains magnesium oxide in g, and all of the above-mentioned contents can be applied equally.

[0050] Specifically, magnesium oxide has a bimodal pore structure, specifically a mesopore bimodal form, which facilitates the diffusion of reactants and enables the reaction to be carried out effectively. In addition, by simultaneously satisfying the aforementioned specific range of BET specific surface area, it is possible to have excellent catalytic activity in the ortho-alkylation reaction and exhibit high selectivity and conversion rate.

[0051] In the above monomer composition, the meta-alkyl substituted phenolic monomer may be metacresol (m-cresol).

[0052] The monomer composition further comprises an alkanol and distilled water (DI Water) in addition to the meta-alkyl substituted phenolic monomer, and an alkyl group can be introduced through a reaction with the alkanol. It is preferable that the distilled water is used together to suppress the decomposition reaction of the alkanol. The alkanol may preferably be methanol.

[0053] The monomer composition may preferably be composed of a phenolic monomer, an alkanol, and distilled water in a ratio of 1:3 to 10:1 to 5 parts by weight, and more preferably in a ratio of 1:4 to 6:1 to 3 parts by weight. At this time, if the content of alkanol is included in a low amount outside the above range, the alkylation agent is low and the conversion rate is reduced; if distilled water is included in a low amount outside the above range, the effect of inhibiting the decomposition reaction of alkanol is reduced; and if alkanol or distilled water is included in an excessive amount outside the above range, it may compete with the phenolic monomer for adsorption at the catalytic active site, resulting in a problem of reduced reactivity.

[0054] It is desirable that the ortho-alkylation reaction product can be produced with the desired selectivity and conversion rate when included within the above content range.

[0056] (Method for preparing ortho-alkylation reaction products)

[0057] According to one embodiment of the invention, a method for preparing 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 aforementioned ortho-alkylation reaction catalyst. Specifically, the method for preparing an ortho-alkylation reaction product may be carried out using an ortho-alkylation reaction composition comprising the aforementioned ortho-alkylation reaction catalyst. The details regarding the catalyst and the reaction composition may all be applied identically to the details described above.

[0058] The above ortho-alkylation reaction catalyst has a bimodal pore structure and a BET specific surface area of ​​100 m² 2 / g to 180 m 2 It contains magnesium oxide in g, and all of the above-mentioned contents can be applied equally.

[0059] Specifically, magnesium oxide has a bimodal pore structure, specifically a mesopore bimodal form, which facilitates the diffusion of reactants and enables the reaction to be carried out effectively. In addition, by simultaneously satisfying the aforementioned specific range of BET specific surface area, it is possible to have excellent catalytic activity in the ortho-alkylation reaction and exhibit high selectivity and conversion rate.

[0060] In the method for preparing the above ortho-alkylation reaction product, the meta-alkyl substituted phenolic monomer of the monomer composition may be meta-cresol (m-cresol).

[0061] The above method for preparing the ortho-alkylation reaction product enables high selectivity and conversion rate of the desired ortho-alkylation reaction product by using a reaction composition containing the aforementioned catalyst.

[0062] The above ortho-alkylation reaction product may be, for example, 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, and may be prepared by selectively substituting an alkyl group at the ortho position in metacresol (m-cresol) through a multi-step reaction as described below.

[0063]

[0065] The above alkylation reaction can preferably be carried out at 350°C to 550°C, and more preferably at 350°C to 550°C. At this time, if the temperature is below 350°C, the alkylation reaction may not be sufficiently activated, and if it exceeds 550°C, a large amount of by-products are generated due to overreaction.

[0066] The above alkylation reaction can be carried out under inert conditions, for example, in the presence of an inert carrier gas. As the inert carrier gas, nitrogen, helium, neon, argon, etc., may be used, and preferably, nitrogen may be used. It is desirable to carry out the reaction under these conditions so that the ortho-alkylation reaction product can be prepared with the desired selectivity and conversion rate.

[0067] The above alkylation reaction can preferably be carried out using a continuous flow gas-phase reactor, in which case the monomer composition is introduced into the continuous flow gas-phase reactor 0.5 hr -1 Up to 2.0 hr -1 This can be carried out by injecting at the liquid hourly space velocity (LHSV). At this time, if the space velocity is outside the above range, the reactants may not be sufficiently activated at the catalyst active site, making it difficult to obtain the product smoothly, and the activity or selectivity of the catalyst may be reduced, which may result in a decrease in the amount of product.

[0068] It is desirable that the ortho-alkylation reaction product can be produced with the desired selectivity and conversion rate by performing the process under the above conditions.

[0070] The operation and effects of the invention will be described in more detail below through specific embodiments. However, these embodiments are merely examples of the invention and do not define the scope of the invention.

[0072] [Examples and Comparative Examples]

[0073] Example 1

[0074] The alkylation reaction of m-cresol was carried out using a continuous flow gas phase reactor. First, a magnesium oxide component (MgO-1, crystalline structure: MgO)) having the properties of Table 1 was prepared in granule form (212 - 425 μm), and 1 g of catalyst was packed into a stainless steel tube-type reactor with a diameter of 1 / 2 inch x a length of 50 cm, and then installed inside the main furnace.

[0075] Subsequently, N2 as a carrier gas was flowed using a mass flow controller (MFC) (37.5 cc / min), and the inside of the reactor was raised to the activation temperature (450 ℃) and maintained for 1 hour for catalyst activation. Afterwards, a monomer composition (12.5 mg / min, m-cresol : Methanol : DIwater = 1:5:1, LHSV 0.75 / h) was passed through a preheater (250 ℃), vaporized, and then introduced. A reaction composition containing the catalyst and monomer composition was introduced into the reactor, and subsequently, an alkylation reaction (450 ℃, maintained at atmospheric pressure) was carried out for 5 hours to obtain the reaction product.

[0076] The product during the reaction was collected in liquid form (using IPA (isopropyl alcohol) as a solvent) for analysis.

[0078] Example 2 and Comparative Examples 1 to 9

[0079] The alkylation reaction was carried out in the same manner as in Example 1, except that the magnesium oxide component was changed as shown in Table 1 below, and the reaction product was obtained.

[0081] Experimental Example 1: Analysis of Catalyst Properties

[0082] (1) XRD analysis

[0083] The crystallite structure of the catalysts used in the examples and comparative examples was confirmed through XRD analysis, and the crystallite size was calculated using the Scherrer equation with the maximum peak value of the XRD patterns, and the results are shown in Table 1 and Figure 2.

[0084] At this time, K = 0.89 (the shape factor of the average crystallite), L = 1.5418 (the wavelength for Cu Kα), FWHM is the full width half maximum of the peak, and θ represents the maximum peak position.

[0086] (2) N2 adsorption-desorption analysis

[0087] The BET (Brunauer-Emmett-Teller) surface area, pore volume, and size distribution of the catalysts used in the examples and comparative examples were confirmed through N2 adsorption-desorption analysis.

[0088] The BET surface area was calculated using the adsorption P / P0 = 0.05-0.3 value, and the pore volume and size distribution were calculated using the desorption value, and the results are shown in Table 1 and Figure 3.

[0090] division type crystallite size, nm BET surface area, m 2 / g Total Pore Volume, cm 3 / g Pore ​​Size, nm Example 1 Mg0-1 9 144.4 0.72 6, 40 Example 2 Mg0-9 10 134.2 0.7 6, 40 Comparative Example 1 Mg0-2 17 44.3 0.4 50 Comparative Example 2 Mg0-3 37 32.6 0.39 60 Comparative Example 3 Mg0-4 10 125.9 0.46 10 Comparative Example 4 Mg0-5 12 107.7 0.29 7 Comparative Example 5 Mg0-6 40 25.7 0.2 25 Comparative Example 6 Mg0-7 5.4 195.4 0.77 4, 6 Comparative Example 7 Mg0-8 5.4 188.3 0.82 4, 6 Comparative Example 8 Mg0-10 13 102.7 0.72 8, 40 Comparative Example 9 Mg0-11 20 34.1 0.41 60

[0092] Experimental Example 2: Analysis of Ortho-Alkylation Reaction Products

[0093] The liquid containing the reaction products prepared in the examples and comparative examples was analyzed using a gas chromatography (GC) device equipped with a flame ionization detector (FID), and the m-cresol conversion rate and selectivity of the target product (2,3,6-TMP, 2,5-DMP, 2,3-DMP) were calculated from the GC results using the following Equations 1 and 2, and the results are shown in Table 2.

[0094] The target product was defined as 2,3,6-TMP, the final target product, and 2,5-DMP and 2,3-DMP as intermediate substances that can be used to obtain the final product through additional reactions.

[0095] [Mathematical Formula 1]

[0096]

[0097] [Mathematical Formula 2]

[0098]

[0100] division catalyst m-cresol conversion rate Selectivity (mol%) Target product A B C D E F G Example 1 Mg0-1 88.1 95.3 49.7 12.7 32.9 0.6 0.4 0.2 1.3 Example 2 Mg0-9 79.8 95.6 50.3 13.6 31.7 0.6 0.6 0.1 1.4 Comparative Example 1 Mg0-2 46.1 92.6 62.8 18.7 11.0 1.8 2.3 1.2 - Comparative Example 2 Mg0-3 24.2 97.7 68.7 24.7 4.4 0.2 0.7 1.0 - Comparative Example 3 Mg0-4 43.4 95.0 65.4 20.6 8.9 0.8 2.2 0.5 0.1 Comparative Example 4 Mg0-5 35.5 91.5 63.5 20.5 7.4 0.6 4.5 2.9 0.5 Comparative Example 5 Mg0-6 44.5 96.1 66.8 20.1 9.2 0.7 1.4 0.8 - Comparative Example 6 Mg0-7 32.9 95.2 66.7 22.3 6.1 1.6 2.5 - - Comparative Example 7 Mg0-8 32.5 94.6 66.4 21.8 6.4 1.5 2.7 0.3 0.1 Comparative Example 8 Mg0-10 52.7 94.0 63.9 19.4 10.7 1.3 1.9 0.4 0.4 Comparative Example 9 Mg0-11 31.7 92.3 65.0 20.7 6.6 1.6 3.4 0.8 0.4

[0102] As can be seen from the experimental data in Table 2 above, the catalyst containing magnesium oxide having specific physical properties and a pore structure of the present invention exhibits high catalytic activity with only a single catalyst, and it was confirmed that when using this to produce ortho-alkylation reaction products, significantly high selectivity and conversion rates can be exhibited.

Claims

Claim 1 It has a bimodal pore structure and a BET specific surface area of ​​130 m² 2 / g to 150 m 2 An ortho-alkylation reaction catalyst comprising magnesium oxide in g / g, wherein in the bi-modal pore structure, the diameter of the first pore is 4 nm to 8 nm and the diameter of the second pore is 35 nm to 45 nm. Claim 2 delete Claim 3 delete Claim 4 An ortho-alkylation reaction composition comprising an ortho-alkylation reaction catalyst according to claim 1 and a monomer composition comprising a meta-alkyl substituted phenolic monomer. Claim 5 In paragraph 4, the meta-alkyl substituted phenolic monomer is metacresol, an ortho-alkylation reaction composition. Claim 6 In paragraph 4, the monomer composition further comprises an alkanol and distilled water, an ortho-alkylation reaction composition. Claim 7 In claim 6, the monomer composition is an ortho-alkylation reaction composition comprising a phenolic monomer : alkanol : distilled water in a ratio of 1 : 3 to 10 : 1 to 5 parts by weight. Claim 8 In claim 6, the monomer composition is an ortho-alkylation reaction composition comprising a phenolic monomer : alkanol : distilled water in a ratio of 1 : 4 to 6 : 1 to 3 parts by weight. Claim 9 A method for preparing an ortho-alkylation reaction product, comprising an alkylation reaction of a monomer composition comprising a meta-alkyl substituted phenolic monomer in the presence of an ortho-alkylation reaction catalyst according to claim 1. Claim 10 A method for preparing an ortho-alkylation reaction product according to claim 9, wherein the alkylation reaction is performed at 350 to 550 ℃. Claim 11 A method for producing an ortho-alkylation reaction product, wherein the alkylation reaction is performed using a continuous flow gas phase reaction apparatus in claim 9. Claim 12 In claim 11, the monomer composition is introduced into a continuous flow gas phase reaction apparatus for 0.5 hr -1 Up to 2.0 hr -1 A method for preparing an ortho-alkylation reaction product injected at the liquid hourly space velocity (LHSV). Claim 13 A method for preparing an ortho-alkylation reaction product according to claim 9, wherein 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.

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