Catalyst for producing neopentyl glycol and method for producing same

Abstract

The present invention provides a catalyst for producing neopentyl glycol and a method for producing the catalyst. The catalyst for producing neopentyl glycol according to the present invention is characterized by improved catalyst strength, reactivity, and stability by controlling the Cu / Si weight ratio and the CuO content measured by XRD analysis. The catalyst for producing neopentyl glycol according to the present invention not only improves catalyst strength but also maintains catalytic activity even in high-temperature and high-pressure reactions, thereby improving process stability and achieving a high neopentyl glycol yield.

Description

[Technical Field]

[0001] The present invention relates to a catalyst for producing neopentyl glycol and a method for producing the same.

[0002] This application claims the benefit of the filing dates of Korean Patent Application No. 10-2023-0028645 filed with the Korean Intellectual Property Office on March 3, 2023, and Korean Patent Application No. 10-2024-0020773 filed with the Korean Intellectual Property Office on February 14, 2024, the entire contents of which are incorporated herein by reference. [Background technology]

[0003] Neopentyl glycol (NPG) is a white crystalline substance with a melting point of over 130°C. It is used as an important intermediate for various synthetic resins and is also widely used industrially as a raw material for various plastic powder coatings, synthetic lubricants, plasticizers, surfactants, textile processing agents, etc.

[0004] NPG is generally produced by the aldol condensation of isobutyraldehyde and formaldehyde to form hydroxypivaldehyde (HPA), which is then reacted with hydrogen in the presence of a catalyst. To achieve a high yield, the reaction is carried out under high temperature (above 130°C) and pressure (above 35 bar) in the presence of a copper catalyst.

[0005] Since the reaction is carried out under such high temperature and pressure conditions, the catalyst strength may be reduced, which may cause problems in terms of process stability.

[0006] Furthermore, because the reaction is carried out under high temperature and pressure conditions, catalyst support components may be eluted, physically crushing the catalyst and increasing the pressure difference within the reactor, which may make it impossible to operate the production process.

[0007] Therefore, efforts are being made to develop catalysts that have excellent catalytic strength and stability under high temperature and pressure conditions, and have excellent catalytic activity. In addition, efforts are being made to develop technologies that can prevent the leaching of the catalyst support. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent Publication No. 10-2011-0038324 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a catalyst for producing neopentyl glycol, which has excellent catalytic strength and catalytic activity, and a method for producing the same. [Means for solving the problem]

[0010] One embodiment of the present invention provides a catalyst for producing neopentyl glycol (NPG), comprising: a support; a fibrous binder; and CuO and SiO2, wherein the weight ratio of Cu to Si is 30:70 to 70:30, and the catalyst for producing neopentyl glycol contains 5 to 40 parts by weight of CuO based on 100 parts by weight of the catalyst for producing neopentyl glycol, as determined by XRD analysis.

[0011] One embodiment of the present invention provides a method for producing a catalyst for producing neopentyl glycol, the method comprising the steps of: preparing a coprecipitate containing a copper (Cu) precursor and a silica (SiO) sol; drying the coprecipitate; preparing a coating powder by adding a fiber-based binder to the dried coprecipitate; and coating a support with the coating powder using an alcohol-based aqueous solution, wherein the catalyst for producing neopentyl glycol is the catalyst for producing neopentyl glycol described above. [Effects of the Invention]

[0012] The catalyst for producing neopentyl glycol according to the present invention has excellent catalytic strength, reactivity, and stability, and can maintain catalytic activity even in high-temperature and high-pressure reactions, thereby improving the stability of the process for producing neopentyl glycol. In other words, the process can be carried out for a long period of time, thereby increasing productivity.

[0013] The catalyst for producing neopentyl glycol according to the present invention has excellent catalytic activity, and when used to produce neopentyl glycol, the yield of neopentyl glycol is high. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a photographic image showing the catalyst of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will now be described in detail so that those skilled in the art can easily implement the present invention, but the present invention may be embodied in various different forms and should not be construed as limited to the configurations set forth herein.

[0016] In this specification, when a part is said to "comprise" a certain component, this means that it may further include other components, rather than excluding other components, unless otherwise specified.

[0017] In this specification, "p to q" or "p to q" means "at least p and at most q."

[0018] In this specification, "Dn" refers to particle size distribution, and refers to the particle size at the n% point in the cumulative particle number distribution according to particle size. That is, D50 is the particle size (average particle size) at the 50% point in the cumulative particle number distribution according to particle size, D90 is the particle size at the 90% point in the cumulative particle number distribution according to particle size, and D10 is the particle size at the 10% point in the cumulative particle number distribution according to particle size. Meanwhile, particle size distribution can be measured using the laser diffraction method. Specifically, the powder to be measured is dispersed in a dispersion medium and then introduced into a commercially available laser diffraction particle size analyzer (e.g., Microtrac S3500). The particle size distribution is calculated by measuring the difference in diffraction patterns according to particle size when the particles pass through a laser beam.

[0019] In this specification, the term "fiber binder" refers to a binder containing a fiber material, and specific types thereof will be described later.

[0020] In describing the present invention, detailed descriptions of related publicly known technologies that may unnecessarily obscure the gist of the present invention will be omitted.

[0021] One embodiment of the present invention provides a catalyst for producing neopentyl glycol (NPG), comprising: a support; a fibrous binder; and CuO and SiO2, wherein the weight ratio of Cu to Si is 30:70 to 70:30, and the catalyst for producing neopentyl glycol contains 5 to 40 parts by weight of CuO based on 100 parts by weight of the catalyst for producing neopentyl glycol, as determined by XRD analysis.

[0022] That is, the catalyst for producing neopentyl glycol according to the present invention is a copper-based catalyst for producing neopentyl glycol.

[0023] The catalyst for producing neopentyl glycol according to the present invention corresponds to a coated catalyst in which a catalyst component is coated on a support.

[0024] To determine the weight ratio of Cu to Si, the Cu content (wt%) can be measured by ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer). More specifically, it can be measured using an Optima 8300DV device manufactured by Perkin Elmer. After determining the Cu content according to the following Equation 1, the Si content can be determined according to the following Equation 2. [Formula 1] Cu content (wt%) = measured concentration (μg / mL) × (dilution volume (mL) / catalyst weight (μg)) × 100 [Formula 2] Si content (wt%) = 100 wt% - Cu content (wt%)

[0025] The catalyst for producing neopentyl glycol according to the present invention includes a support and a fibrous binder, thereby enhancing the strength, reactivity, and stability of the catalyst. In other words, the catalyst for producing neopentyl glycol according to the present invention has excellent catalytic strength, reactivity, and stability, and can maintain catalytic activity even in high-temperature and high-pressure reactions. Furthermore, the catalyst for producing neopentyl glycol according to the present invention has excellent catalytic activity due to the Cu / Si weight ratio and CuO content within the aforementioned ranges, and when used to produce neopentyl glycol, it has the advantage of achieving a high yield of neopentyl glycol.

[0026] In one embodiment of the present invention, the catalyst for producing neopentyl glycol may contain 5 to 40 parts by weight, preferably 10 to 35 parts by weight, more preferably 10 to 30 parts by weight, and even more preferably 5 to 20 parts by weight of CuO based on 100 parts by weight of the catalyst for producing neopentyl glycol, as determined by XRD analysis.

[0027] As described above, when the weight ratio of Cu to Si and the CuO content of the catalyst for producing neopentyl glycol according to the present invention satisfy the above-mentioned ranges, the catalyst has better catalytic activity, and when neopentyl glycol is produced using the catalyst, the yield of neopentyl glycol can be increased.

[0028] In one embodiment of the present invention, the catalyst for producing neopentyl glycol may include, but is not limited to, CuO / SiO2, CuO / BaO / SiO2, CuO / ZnO / SiO2, CuO / Al2O3 / SiO2, CuO / MnO / SiO2, or CuO / Cr2O3 / SiO2. That is, the catalyst for producing neopentyl glycol according to the present invention is a copper-based catalyst for producing neopentyl glycol.

[0029] In one embodiment of the present invention, the fiber-based binder may be one or more selected from the group consisting of glass fiber, carbon fiber, aramid fiber, alumina fiber, silicon carbide fiber, and boron fiber. When the fiber-based binder is included, it is effective in binding with the support to easily increase the strength of the catalyst and in increasing the dispersion of copper to enhance reactivity.

[0030] In one embodiment of the present invention, the packing density of the support is 600 kg / m 3 ~1500kg / m 3 may be.

[0031] In one embodiment of the present invention, the strength of the support may be 30N to 250N, preferably 40N to 200N.

[0032] In one embodiment of the present invention, the packing density of the support is 600 kg / m 3 ~1,500kg / m 3 , preferably 700 kg / m 3 ~1,400kg / m 3 may be.

[0033] In one embodiment of the present invention, the support may comprise zirconium oxide, aluminum oxide silicate, silicon oxide, or aluminum oxide.

[0034] When the support satisfies the above-mentioned strength and packing density, or when the support contains the above-mentioned oxide type, it has the effect of satisfying both the above-mentioned reactivity and stability of the catalyst.

[0035] In this specification, "strength" refers to the measurement of the desorption strength of a single catalyst, specifically, calculated from the average value of 20 maximum desorption strengths at the initial collapse point using an FGN-50B manufactured by Shimpo Co., Ltd. In other words, the strength in the present invention may refer to the strength measured by the above measurement method.

[0036] In this specification, the term "packing density" refers to a measured apparent density, and specifically, is calculated by measuring the weight of an empty measuring cylinder, filling it with 100 cc of a shaped catalyst, measuring the weight, and dividing the difference in weight by the volume of the shaped catalyst. That is, the packing density in the present invention may refer to the apparent density measured by the above-mentioned measurement method.

[0037] In one embodiment of the present invention, the shape of the support may be, but is not limited to, a sphere type, a cylinder type, a flat type, or the like.

[0038] In one embodiment of the present invention, the support may be a spherical support, and the average particle size of the spherical support may be 3 mm to 7 mm.

[0039] In one embodiment of the present invention, the spherical support may have an average particle size of 3 mm to 7 mm, preferably 3 mm to 5 mm. The average particle size means the particle size at the 50% point (D50) of the cumulative particle number distribution according to particle size, as described above.

[0040] When the spherical support satisfies the above-mentioned average particle size range, it has the effect of further improving the reactivity and stability of the catalyst.

[0041] One embodiment of the present invention provides a method for producing a catalyst for producing neopentyl glycol, comprising the steps of preparing a coprecipitate containing a copper (Cu) precursor and a silica (SiO) sol, drying the coprecipitate, adding a fibrous binder to the dried coprecipitate to prepare a coating powder, and coating the coating powder on a support using an alcohol-based aqueous solution, wherein the catalyst for producing neopentyl glycol is the catalyst for producing neopentyl glycol described above. For reference, silica is another term for silicon dioxide.

[0042] In one embodiment of the present invention, the copper precursor may be, but is not limited to, Cu(NO3)2·3H2O.

[0043] In one embodiment of the present invention, the coprecipitate may further contain sodium hydroxide, which functions as a precipitant to produce the coprecipitate.

[0044] The method for preparing a catalyst for producing neopentyl glycol according to an embodiment of the present invention may further include preparing an aqueous alcohol solution. The type and content of the aqueous alcohol solution may be as described below.

[0045] The method for preparing a catalyst for producing neopentyl glycol according to an embodiment of the present invention may further include filtering and washing the coprecipitate before drying it. The washing may be performed with distilled water.

[0046] In one embodiment of the present invention, the fibrous binder may be included in an amount of 5 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the coprecipitate. The types of the fibrous binder may be as described above, and when the amount of the fibrous binder in the coprecipitate satisfies the above-described range, it can be easily bonded to the support, thereby enhancing the activity of the catalyst.

[0047] In one embodiment of the present invention, the step of drying the coprecipitate may be performed at a temperature of 80°C to 120°C for 12 to 48 hours, but is not limited thereto, and the temperature and time conditions may be changed depending on the total amount of the coprecipitate. The drying may be performed using a drying oven.

[0048] In one embodiment of the present invention, the step of preparing a coating powder by adding a fiber-based binder to the dried coprecipitate may include the steps of: pulverizing the dried coprecipitate and the fiber-based binder; and classifying the pulverized material to prepare a powder.

[0049] In one embodiment of the present invention, the classification range of the powder may be 5 μm to 100 μm, preferably 5 μm to 85 μm. In this specification, classification means dividing powder particles of the same density into two or more particle groups according to the particle diameter. That is, the classification range of the powder is 5 μm to 100 μm, preferably 5 μm to 85 μm, meaning that the powder can be classified according to the diameter. When the classification range is satisfied, it is easier to enhance the activity of the catalyst.

[0050] In one embodiment of the present invention, the step of coating the support with the coating powder using an alcoholic aqueous solution may include, but is not limited to, the steps of: putting the support into a sugar coater; and spraying the coating powder and the alcoholic aqueous solution onto the support while rotating the sugar coater. Any method that can coat the support with the coating powder and the alcoholic aqueous solution may be used.

[0051] In one embodiment of the present invention, the aqueous alcohol solution may be an aqueous solution containing one or more selected from the group consisting of methanol, ethanol, and isopropyl alcohol.

[0052] In one embodiment of the present invention, the concentration of the aqueous alcohol solution may be 0.1 to 80 parts by weight of alcohol based on 100 parts by weight of the aqueous alcohol solution.

[0053] The method for preparing a catalyst for producing neopentyl glycol according to one embodiment of the present invention may further include the steps of drying the support coated with the coating powder; and calcining the dried support coated with the coating powder.

[0054] In one embodiment of the present invention, the step of drying the substrate coated with the coating powder may be performed at a temperature of 80°C to 120°C for 6 to 24 hours, but is not limited thereto. The temperature and time conditions may be changed depending on the total amount of the coating powder and the alcohol aqueous solution and the size of the substrate. However, the drying time may be shorter than that of the step of drying the coprecipitate. In this case, the drying may also be performed using a drying oven.

[0055] In one embodiment of the present invention, the step of calcining the substrate coated with the dried coating powder may be performed at a temperature of 250° C. to 650° C. for 2 hours to 8 hours. The calcination may be performed using a calcination furnace.

[0056] In one embodiment of the present invention, the step of firing the substrate coated with the dried coating powder may be performed at a temperature of 250°C to 650°C, preferably 250°C to 450°C.

[0057] In one embodiment of the present invention, the step of calcining the support coated with the dried coating powder may be performed for 2 to 8 hours, preferably 3 to 5 hours.

[0058] In one embodiment of the present invention, the step of firing the substrate coated with the dried coating powder may be performed in an air atmosphere.

[0059] One embodiment of the present invention provides a method for producing neopentyl glycol, comprising: introducing a hydroxypivaldehyde (HPA) solution and hydrogen into a hydrogenation reactor to perform a hydrogenation reaction, wherein the hydrogenation reactor comprises the catalyst for producing neopentyl glycol according to the present invention.

[0060] In one embodiment of the present invention, the method for producing neopentyl glycol may be a method well known in the art, except that it includes the catalyst for producing neopentyl glycol according to the present invention.

[0061] For example, the hydrogenation reactor may be a fixed bed reactor (FBR) filled with the catalyst for producing neopentyl glycol. In this case, separation of the catalyst and the reaction product is not required, and the reaction temperature and reaction pressure can be lowered compared to conventional methods, resulting in stable and economical operation. In addition, catalyst replacement is easy, and the reactor size can be reduced, resulting in significant savings in investment costs.

[0062] In one embodiment of the present invention, the hydroxypivaldehyde solution may contain 50 wt % to 80 wt % of hydroxypivaldehyde, 1 wt % to 5 wt % of neopentyl glycol, 15 wt % to 35 wt % of alcohol, 1 wt % to 10 wt % of water, and 1 wt % to 10 wt % of hydroxypivalic hydroxypivalate (hereinafter, referred to as HPNE). In this case, the reaction heat can be minimized without reducing the reactivity, which has the effect of suppressing the generation of by-products.

[0063] In one embodiment of the present invention, the hydrogenation reaction may be carried out at a reaction temperature of 100°C to 250°C, preferably 100°C to 200°C, and more preferably 100°C to 180°C.

[0064] In one embodiment of the present invention, the hydrogenation reaction may be carried out at a reaction pressure of 35 bar or more. The reaction pressure refers to a measurement pressure.

[0065] When the catalyst for producing neopentyl glycol according to one embodiment of the present invention is used during the production of neopentyl glycol, it is possible to prevent the problem of elution of catalyst components (e.g., copper components) in the produced neopentyl glycol solution.

[0066] Therefore, when the catalyst for producing neopentyl glycol according to one embodiment of the present invention is applied to the production of neopentyl glycol, a purification step involving elution of catalyst components (e.g., copper components) is not required, the catalyst life is extended, and the production costs can be reduced.

[0067] [Example] Hereinafter, the present invention will be described in detail with reference to examples. However, the examples of the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided to more completely explain the present invention to those skilled in the art.

[0068] Example 1 Silica sol and NaOH were added to an aqueous solution of Cu(NO3)2·3H2O so that the weight ratio of Cu to Si was 40:60, and co-precipitation was carried out to produce a slurry-like coprecipitate. The slurry-like coprecipitate was filtered and washed with distilled water to obtain a cake-like coprecipitate. The coprecipitate cake was dried in an oven at 80°C for 15 hours.

[0069] Next, ceramic wool, which corresponds to a fiber-based binder, was added to the dried coprecipitate cake in an amount of 7 wt % based on the total weight of the dried coprecipitate cake. After adding the ceramic wool, the coprecipitate cake to which the ceramic wool had been added was pulverized and classified to 45 μm or less to prepare a mixed powder (coating powder). Then, in order to coat the mixed powder on a support, which will be described later, the mixed powder, isopropyl alcohol (IPA), and water were mixed to prepare a mixed solution. Here, ceramic wool refers to a type of fiber-based binder formed by stacking ceramic fibers and then sewing and punching them into a roll shape.

[0070] Then, alumina balls with a size of 3.2 mm (strength of about 150 N) corresponding to the support were placed in the chamber, and the mixed solution was sprayed onto the alumina balls to coat them with the mixed solution. At this time, the coating thickness was 2 mm to 4 mm. For reference, the coating thickness refers to the calculated value obtained by subtracting the size of the alumina balls from the size of the catalyst for producing neopentyl glycol and dividing the result by 2.

[0071] After completing the coating on the alumina balls, the alumina balls coated with the mixed solution were dried in an oven at a temperature of 80°C for 7 hours, and the dried alumina balls coated with the mixed solution were calcined in a calcination furnace at a temperature of 250°C to 550°C for 8 hours to produce the catalyst for producing neopentyl glycol of Example 1.

[0072] FIG. 1 is a photographic image showing the catalyst of Example 1 produced by the above method.

[0073] <Examples 2 to 9, Comparative Examples 1 to 4, 7, and 8> Catalysts for producing neopentyl glycol in Examples 2 to 9 and Comparative Examples 1 to 4, 7, and 8 were prepared in the same manner as in Example 1, except that coprecipitates were prepared, mixed powders were used, and alumina ball coating was performed so that the weight ratio of Cu to Si, the type of fiber-based binder, the amount of powder used, and the coating thickness satisfied the values ​​in Table 1 below.

[0074] <Comparative Example 5> Powder was prepared in the same manner as in Example 1, except that only Cu(NO3)2·3H2O was used, and no fiber-based binder (Silicaul) was used. Then, in order to coat the powder onto a support, a mixture was prepared by mixing the powder, isopropyl alcohol (IPA), and water. Since no fiber-based binder was used, the powder was referred to as "powder" rather than "mixed powder."

[0075] Next, a 3.2 mm alumina ball (strength approximately 150 N) corresponding to the support was placed in the chamber, and the mixed solution containing only Cu(NO3)2·3H2O was sprayed onto the alumina ball, coating it with the mixed solution containing only Cu(NO3)2·3H2O to a thickness of 0.3 mm to 1 mm.

[0076] Thereafter, the alumina balls coated with the mixture containing only Cu(NO3)2·3H2O were dried in an oven at a temperature of 80°C for 7 hours, and the dried alumina balls coated with the mixture were calcined in a calcination furnace at a temperature of 250°C to 550°C for 8 hours to produce the catalyst for producing neopentyl glycol of Comparative Example 1.

[0077] <Comparative Example 6> The catalysts for producing neopentyl glycol in Comparative Example 6 were prepared in the same manner as in Example 1, except that hydroxypropyl methylcellulose (HPMC) was used instead of the ceramic wool in Example 1. The hydroxypropyl methylcellulose (HPMC) is an organic binder, not a fibrous binder.

[0078] The catalysts for producing neopentyl glycol of Examples 1 to 9 and Comparative Examples 1 to 8 were each subjected to XRD analysis to measure the CuO content, and the results are shown in Table 1. In order to measure the CuO content by XRD analysis, the diffraction angle (2θ) at the CuK-α characteristic X-ray wavelength was measured by XRD (X-ray Diffracion) analysis.

[0079] More specifically, MgO heat-treated at 800°C for 5 hours was introduced at arbitrary contents (5, 10, 20 wt%) as a spike for quantification during CuO content measurement, and the relative contents of crystalline CuO and amorphous Cu-silicate were calculated.

[0080] In addition, the types of substances used in the catalysts for producing neopentyl glycol in Examples 1 to 9 and Comparative Examples 1 to 8, the weight ratio of Cu to Si (Cu:Si), the coating thickness, and the amount of powder used are also shown in Table 1 below.

[0081] <Reference example 1> A conventional extruded catalyst (CuO / SiO2 with a CuO content of 40 wt%) was prepared to evaluate the performance of the catalysts for producing neopentyl glycol in Examples 1 to 9 and Comparative Examples 1 to 8. The catalyst of Reference Example 1 was prepared in the same manner as in Example 1, up to the process of preparing a coprecipitate cake using a coprecipitate with a Cu:Si weight ratio of 40:60 and a fibrous binder. Finally, without coating the support, the catalyst was extruded to a size of 5 mm x 5 mm.

[0082] <Reference example 2> A conventional tablet catalyst (CuO / SiO2 with a CuO content of 40 wt%) was prepared to evaluate the performance of the catalysts for producing neopentyl glycol in Examples 1 to 9 and Comparative Examples 1 to 8. The catalyst of Reference Example 2 was prepared in the same manner as in Example 1, up to the process of preparing a coprecipitate cake using a coprecipitate with a Cu:Si weight ratio of 40:60 and a fibrous binder. Finally, without coating the support, the catalyst was pressed into a tablet machine to a size of 5 mm x 5 mm.

[0083] Information about the catalysts for producing neopentyl glycol in Reference Examples 1 and 2 is also shown in Table 1 below. For reference, the alumina balls are not listed in Table 1 below because they are the same type.

[0084] To determine the weight ratio of Cu to Si (Cu:Si in Table 1 below), the Cu content can be measured by ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer). The Cu content was measured using an Optima 8300DV instrument manufactured by Perkin Elmer. Specifically, the measured catalyst and nitric acid were placed in a platinum crucible and then diluted with ultrapure water to a concentration of 10M. The Cu content was then calculated according to the following Equation 1. The Si content was then calculated according to the following Equation 2. [Formula 1] Cu content (wt%) = measured concentration (μg / mL) × (dilution volume (mL) / catalyst weight (μg)) × 100 [Formula 2] Si content (wt%) = 100 wt% - Cu content (wt%)

[0085] [Table 1] JPEG2026508452000003.jpg96140

[0086] In Table 1, the material written in parentheses next to the catalyst type indicates the type of binder used, and Cu:Si indicates the weight ratio of Cu to Si in the coprecipitate or catalyst.

[0087] In this case, it is separately stated that Reference Example 1 corresponds to an extruded catalyst and Reference Example 2 corresponds to a tableted catalyst.

[0088] In addition, the CuO content indicates the content of CuO in the catalyst, the coating thickness, as described above, means the calculated value obtained by subtracting the size of the alumina ball from the size of the catalyst for producing neopentyl glycol and dividing the result by 2, and the powder usage amount means the relative usage amount (%) when the usage amount (by mass) in Example 1 is defined as 1 (100%).

[0089] In the case of Comparative Example 5, only a copper precursor was used, and in Reference Examples 1 and 2, the amounts of powder used are not shown because they correspond to conventional extrusion catalysts and tableting catalysts.

[0090] <Experimental Example 1> Neopentyl glycol was produced using a fixed-bed reactor (FBR) packed with the neopentyl glycol production catalysts of Reference Examples 1 and 2, Examples 1 to 9, and Comparative Examples 1 to 8. Specifically, using reaction raw materials consisting of 65 wt% hydroxypivaldehyde (HPA), 2 wt% neopentyl glycol (NPG), 25 wt% 2-isopropylethanol (2-EH), 5 wt% water (HO), and 3 wt% HPNE, a hydrogenation reaction was carried out in an air atmosphere at a temperature of 160°C and a pressure of 35 bar for 1 hour.

[0091] During this process, the amount of hydrogen consumed was measured, and the catalytic activity of the catalysts for producing neopentyl glycol in Reference Examples 1 and 2, Examples 1 to 9, and Comparative Examples 1 to 8 was measured.

[0092] The results are shown in Table 2 below.

[0093] <Experimental Example 2> The strength and Si content of each of the catalysts for producing neopentyl glycol in Reference Examples 1 and 2, Examples 1 to 9, and Comparative Examples 1 to 8 were measured by ICP-OES analysis.

[0094] In the stability test, the catalysts for producing neopentyl glycol of Reference Examples 1 and 2, Examples 1 to 9, and Comparative Examples 1 to 8 were immersed in the liquid reaction raw material of Experimental Example 1 in a hydrogen atmosphere at a temperature of 180°C for 6 hours to cause a reaction.

[0095] In another form of the stability test, the catalysts for producing neopentyl glycol of Reference Examples 1 and 2, Examples 1 to 9, and Comparative Examples 1 to 8 were immersed in a liquid neopentyl glycol solution in a hydrogen atmosphere at a temperature of 180°C for 18 hours to cause a reaction.

[0096] Thereafter, the strengths of the catalysts for producing neopentyl glycol in Reference Examples 1 and 2, Examples 1 to 9, and Comparative Examples 1 to 8 after the reaction were measured, and the differences were confirmed by comparing the strengths of the catalysts measured before the reaction.

[0097] Thereafter, the Si content of the catalysts for producing neopentyl glycol of Reference Examples 1 and 2, Examples 1 to 9, and Comparative Examples 1 to 8 after the stability test reaction under the reaction raw material conditions of Experimental Example 1 was measured by ICP-OES analysis, and the difference was calculated by comparing the Si content of the catalyst measured before the reaction.

[0098] The results are shown in Table 2 below.

[0099] [Table 2]

[0100] In Table 2, the Si elution (%) is a value calculated by [{Si content (weight) of the initial catalyst (before the reaction) - Si content (weight) of the catalyst after the stability test (after the reaction)} / Si content (weight) of the initial catalyst (before the reaction)] × 100.

[0101] The catalytic activity is a value indicating the relative catalytic activity when the catalytic activity (unit: mL / min Cat mL) of Example 1 is set as 1 (100%). That is, for example, if the catalytic activity of Example 1 is 100 mL / min Cat mL, the catalytic activity of Example 2 is 119 mL / min Cat mL. The above examples are arbitrary values ​​and do not represent the actual activity values ​​of the catalyst.

[0102] From the results in Table 2, it was confirmed that the catalysts for producing neopentyl glycol in Examples 1 to 9 are coated catalysts and have superior catalytic activity compared to the extruded catalyst in Reference Example 1 and the tableted catalyst in Reference Example 2.

[0103] Furthermore, the catalysts for producing neopentyl glycol in Examples 1 to 9 were coated catalysts and had similar fresh strength to the extruded catalyst in Reference Example 1 and the tableted catalyst in Reference Example 2. It was also confirmed that the change in strength and the amount of Si elution were small after stability tests. The small change in strength and the small amount of Si elution indicate excellent physical stability of the catalyst. In other words, this means that the catalyst durability was improved, which has the advantage of improving the stability of catalytic process operation and catalyst life.

[0104] Furthermore, the catalysts for producing neopentyl glycol in Examples 6 and 7 were coated catalysts using carbon fiber and alumina fiber as fiber binders, respectively, and were confirmed to have similar fresh strength and low Si elution amounts to the coated catalyst in Example 1 using ceramic wool as a fiber binder, confirming their excellent physical stability. In other words, this means that as long as they fall within the scope of usable fiber binders, they are not limited to ceramic wool and can exhibit the intended effects.

[0105] It was also confirmed that Comparative Examples 1 to 3 and 5 to 8 were less physically stable than the Examples.

[0106] Specifically, in Comparative Example 1, the weight of Cu in the coprecipitate was less than the weight of Si, as in the Examples. However, the specific weight ratio of Cu to Si in the coprecipitate did not satisfy the weight ratio of the catalyst for producing neopentyl glycol according to the present invention. Therefore, it was confirmed that the coating thickness had to be excessively thick to support the same copper content as in Example 1 in order to ensure catalyst performance. If the coating thickness is excessively thick, the physical stability of the catalyst will be reduced. That is, the catalyst of Comparative Example 1 had poor catalyst durability, which reduced the stability of catalytic process operation and catalyst life.

[0107] Comparative Examples 2 and 3 satisfied the Cu to Si weight ratio of the catalyst for producing neopentyl glycol according to the present invention, but the CuO content was outside the range of the catalyst for producing neopentyl glycol. As a result, it was confirmed that the catalytic activity was poor and that there was a large change in strength and a large amount of Si elution even after the stability test.

[0108] In Comparative Example 4, the weight of Cu in the coprecipitate was greater than the weight of Si, and it was confirmed that the catalytic activity was also poor in this case. This is believed to be due to the fact that the particle size of Cu, which is known to be an active substance in hydrogenation reactions, was larger than in the Examples, resulting in a decrease in activity.

[0109] Unlike the catalysts for producing neopentyl glycol in Examples 1 to 9, which used coprecipitates containing Cu and Si, Comparative Example 5 is a catalyst for producing neopentyl glycol that was produced by coating with a substance containing only Cu. In other words, Comparative Example 5 also falls under the category of a coated catalyst.

[0110] However, when compared under the same conditions as in Experimental Example 1, it was confirmed that Comparative Example 5 did not exhibit catalytic activity. This is believed to be due to the effect of Si controlling the particle size growth of Cu, which is known to be an active substance in hydrogenation reactions, in the neopentyl glycol production catalyst (coated catalyst) of the Examples. That is, it is believed that in Comparative Example 5, the Cu particle size has increased to a size that does not have catalytic activity, similar to Comparative Example 4.

[0111] Comparative Example 6 is a coated catalyst produced using a coprecipitate containing Cu and Si, similar to the catalysts for neopentyl glycol production in Examples 1 to 9. Although the catalytic activity was similar to that of the Examples, the coating strength was very weak and it was determined that it was impossible to use in the catalytic process. In the case of Comparative Example 6, a fibrous binder was not used, and it was confirmed that the use of a fibrous binder, similar to the catalyst for neopentyl glycol production according to the present invention, is effective in increasing the strength (durability) of the catalyst.

[0112] Furthermore, the neopentyl glycol production catalysts of Comparative Examples 7 and 8 were coated catalysts using carbon fiber and alumina fiber as fibrous binders, respectively, and were produced by the same method as the ceramic wool-based coated catalyst of Comparative Example 1. Despite the change in fibrous binder, the fresh strength was low and Si elution occurred at a high rate, just like in Comparative Example 1. This means that even if the type of fibrous binder used is changed, if the Cu:Si ratio of the coprecipitate is outside the appropriate range, the fibrous binder will not have the effect of improving physical stability.

[0113] That is, the catalyst for producing neopentyl glycol according to the present invention has excellent catalytic strength, reactivity, and stability, and can maintain catalytic activity even in high-temperature and high-pressure reactions, thereby improving the stability of the process for producing neopentyl glycol and demonstrating excellent catalytic activity.

[0114] As a result, it was confirmed that when the catalyst for producing neopentyl glycol according to the present invention is used, the process can be carried out for a long period of time, and the yield of neopentyl glycol can be increased, thereby providing the advantage of increasing productivity.

Claims

1. Support; a fiber-based binder; and CuO and SiO ２ A catalyst for producing neopentyl glycol, comprising: The weight ratio of Cu to Si is 30:70 to 70:30, The catalyst for producing neopentyl glycol is A catalyst for producing neopentyl glycol (NPG), which contains 5 to 40 parts by weight of CuO based on 100 parts by weight of the catalyst for producing neopentyl glycol according to XRD analysis.

2. The catalyst for producing neopentyl glycol is CuO / SiO ２ , CuO / BaO / SiO ２ , CuO / ZnO / SiO ２ , CuO / Al ２ O ３ / SiO ２ , CuO / MnO / SiO ２ , or CuO / CrO ３ / SiO ２ The catalyst for producing neopentyl glycol according to claim 1, comprising:

3. 2. The catalyst for producing neopentyl glycol according to claim 1, wherein the fibrous binder is at least one selected from the group consisting of glass fiber, carbon fiber, aramid fiber, alumina fiber, silicon carbide fiber, and boron fiber.

4. The packing density of the support is 600 kg / m ３ ~1500 kg / m ３ 2. The catalyst for producing neopentyl glycol according to claim 1, wherein

5. 2. The catalyst for producing neopentyl glycol according to claim 1, wherein the support comprises zirconium oxide, aluminum oxide silicate, silicon oxide, or aluminum oxide.

6. Copper (Cu) precursor and silica (SiO ２ ) preparing a coprecipitate containing a sol; drying the coprecipitate; adding a fiber-based binder to the dried coprecipitate to prepare a coating powder; and A method for preparing a catalyst for producing neopentyl glycol, comprising: coating the coating powder on a support using an alcohol aqueous solution, The method for producing a catalyst for producing neopentyl glycol, wherein the catalyst for producing neopentyl glycol is the catalyst for producing neopentyl glycol according to any one of claims 1 to 5.

7. 7. The method for producing a catalyst for producing neopentyl glycol according to claim 6, wherein the fiber binder is contained in an amount of 5 to 20 parts by weight based on 100 parts by weight of the coprecipitate.

8. The step of preparing a coating powder by adding a fiber-based binder to the dried coprecipitate includes: grinding the dried coprecipitate to which the fiber-based binder has been added; and 7. The method for producing a catalyst for producing neopentyl glycol according to claim 6, further comprising the step of classifying the pulverized material to produce a powder.

9. 9. The method for producing a catalyst for producing neopentyl glycol according to claim 8, wherein the powder has a classification range of 5 μm to 100 μm.

10. 7. The method for producing a catalyst for producing neopentyl glycol according to claim 6, wherein the weight ratio of copper (Cu) to silicon (Si) in the coprecipitate is 20:80 to 50:

50.

11. 7. The method for producing a catalyst for producing neopentyl glycol according to claim 6, wherein the aqueous alcohol solution is an aqueous solution containing one or more selected from the group consisting of methanol, ethanol, and isopropyl alcohol.

12. 12. The method for producing a catalyst for producing neopentyl glycol according to claim 11, wherein the concentration of the aqueous alcohol solution is 0.1 to 80 parts by weight of alcohol based on 100 parts by weight of the aqueous alcohol solution.

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