Copper silicate-based catalyst and method for manufacturing same

Abstract

A copper silicate-based catalyst according to one embodiment of the present application comprises copper and silica, wherein: the crushing strength of the copper silicate-based catalyst is 40 N or more; the Cu surface area according to N(2O pulse chemisorption analysis for the copper silicate-based catalyst is 3 m2 / g to 10 m2 / g; and the Si elution rate after the harshness test for the copper silicate-based catalyst, according to the method 1, is 5 wt % or less.

Description

Copper silicate catalyst and method for producing the same

[0001] This application claims the benefit of Korean Patent Application No. 10-2024-0009938, filed with the Korean Intellectual Property Office on January 23, 2024, the entire contents of which are incorporated herein by reference.

[0002] The present application relates to a copper silicate catalyst and a method for producing the same.

[0003] Neopentyl glycol (NPG) is a white crystalline substance with a melting point of 130°C or higher. 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, and fiber processing agents.

[0004] These NPGs are generally manufactured by aldol condensation of isobutyraldehyde and formaldehyde to form hydroxypivaldehyde (HPA), which is then reacted with hydrogen in the presence of a catalyst.

[0005] Conventionally, HPA was hydrogenated using a slurry-type Ni-based catalyst. In this case, the crude NPG, which is a hydrogenation product, contains 2,2,4-trimethyl-1,3-pentanediol (TMPD) and hydroxypivalic acid NPG ester (HPNE). Since TMPD and HPNE have boiling points very similar to those of NPG, they cannot be separated by simple distillation. In addition, HPNE is unstable when distilling the reaction mixture, which reduces the yield of NPG. Therefore, it is commercially converted to NPG by saponification using sodium hydroxide. However, the sodium salt of HPA or other organic acids produced by the saponification reaction promotes the decomposition reaction of NPG at high temperatures higher than 140°C, which limits the distillation process. In addition, TMPD, which is not converted to a non-volatile sodium salt during the saponification reaction, cannot be removed.

[0006] Therefore, efforts are continuously being made in the field of technology to produce NPG in a high-yield and economical manner.

[0007] The present application provides a copper silicate catalyst and a method for producing the same.

[0008] One embodiment of this application is:

[0009] A copper silicate catalyst containing copper and silica,

[0010] The crushing strength of the above copper silicate catalyst is 40N or more,

[0011] The Cu surface area according to the N2O pulse chemisorption analysis of the above copper silicate catalyst was 3 m 2 / g to 10 m 2 / g and

[0012] A copper silicate catalyst is provided, wherein the Si elution ratio after a harshening test according to the following method 1 of the copper silicate catalyst is 5 wt% or less.

[0013] [Method 1]

[0014] After an experiment in which the copper silicate catalyst is immersed in a hydroxypivaldehyde (HPA) solution and reacted at 180°C in a hydrogen atmosphere for 6 hours, the Si elution ratio is calculated according to the following mathematical formula 1.

[0015] [Mathematical Formula 1]

[0016] Si elution ratio (wt%) = (Si weight contained in the initial catalyst - Si weight contained in the catalyst after the harshness experiment) / Si weight contained in the initial catalyst Х 100

[0017] In addition, another embodiment of the present application is

[0018] A step of preparing a coprecipitate slurry by adding silica sol and an alkaline precipitant to an aqueous solution containing a copper precursor;

[0019] A step of aging the above-mentioned precipitate slurry at a temperature of 80°C to 90°C for 3 hours or more, then filtering and drying to produce a dried product;

[0020] A step of mixing an inorganic binder and an organic compound into the above-mentioned dry material and then molding it to produce a catalyst precursor; and

[0021] Comprising a step of drying and calcining the above catalyst precursor,

[0022] A method for producing a copper silicate catalyst is provided, wherein the alkaline precipitant is added and the temperature is maintained at 15°C to 35°C.

[0023] In addition, another embodiment of the present application includes a step of introducing a hydroxypivaldehyde (HPA) solution and hydrogen into a hydrogenation reactor to perform a hydrogenation reaction,

[0024] The above hydrogenation reactor provides a method for producing neopentyl glycol, which comprises the copper silicate catalyst.

[0025] According to one embodiment of the present application, a copper silicate catalyst having improved stability can be produced. In particular, the copper silicate catalyst according to one embodiment of the present application has a Si elution ratio of 5 wt% or less after a harsh test, and thus, it can prevent a decrease in catalyst strength or reactivity even under high-temperature and high-pressure reaction conditions for a high neopentyl glycol production yield.

[0026] In addition, according to one embodiment of the present application, the surface area of ​​Cu of the catalyst can be optimized by controlling the aging conditions of the co-precipitate slurry, the alkaline precipitant injection conditions, and the drying conditions of the catalyst precursor.

[0027] Therefore, when neopentyl glycol is manufactured using a copper silicate catalyst according to one embodiment of the present application, the manufacturing process can be maintained stably, and thus, an effect of increasing economic efficiency can be obtained.

[0028] FIG. 1 is a diagram showing the results of N2O chemical adsorption analysis for measuring the Cu surface area of ​​a copper silicate catalyst according to Example 1 of the present application.

[0029] Hereinafter, the present specification will be described in more detail.

[0030] In this specification, when it is said that a member is located “on” another member, this includes not only cases where the member is in contact with the other member, but also cases where another member exists between the two members.

[0031] In this specification, when a part is said to "include" a certain component, this means that it may include other components, but not to the exclusion of other components, unless specifically stated otherwise.

[0032] As mentioned above, efforts are continuously being made in the field of technology to produce NPG in a high-yield and economical manner.

[0033] In particular, the neopentyl glycol is manufactured through a hydrogenation process using HPA (Hydroxypivaldehyde) as a raw material under high temperature (160°C or higher) and high pressure (35 bar or higher) conditions in the presence of a catalyst. Under such high temperature and high pressure reaction conditions, the strength of the catalyst may be reduced and the reactivity of the catalyst may be reduced due to the elution of the catalyst components, which may cause problems in the stable operation of the hydrogenation process.

[0034] Accordingly, the present application aims to provide a copper silicate catalyst with excellent stability and a method for producing the same, which can be applied as a catalyst in the process of producing neopentyl glycol.

[0035] A copper silicate catalyst according to one embodiment of the present application comprises copper and silica, and the crushing strength of the copper silicate catalyst is 40 N or more, and the Cu surface area according to N2O pulse chemisorption analysis of the copper silicate catalyst is 3 m 2 / g to 10 m 2 / g, and the Si elution ratio after the harshness test according to the following method 1 of the copper silicate catalyst is 5 wt% or less.

[0036] [Method 1]

[0037] After an experiment in which the copper silicate catalyst is immersed in a hydroxypivaldehyde (HPA) solution and reacted at 180°C in a hydrogen atmosphere for 6 hours, the Si elution ratio is calculated according to the following mathematical formula 1.

[0038] [Mathematical Formula 1]

[0039] Si elution ratio (wt%) = (Si weight contained in the initial catalyst - Si weight contained in the catalyst after the harshness experiment) / Si weight contained in the initial catalyst Х 100

[0040] The Si elution ratio after the harshness test according to the following method 1 of the copper silicate catalyst may be 5 wt% or less, 3 wt% or less, or 0. If the Si elution ratio after the harshness test according to the following method 1 of the copper silicate catalyst exceeds 5 wt%, the strength of the catalyst may be lowered and the reactivity of the catalyst may be lowered due to the elution of Si during the manufacturing process of neopentyl glycol using the hydrogenation process of HPA under high temperature and high pressure reaction conditions, and thus a problem may occur in the stable operation of the hydrogenation process.

[0041] In one embodiment of the present application, the crushing strength of the copper silicate catalyst may be 40 N or more, 42 N to 150 N, or 49 N to 67 N. If the crushing strength of the copper silicate catalyst is less than 40 N, the catalyst is easily broken when introduced into the reactor, and is likely to break within a relatively short period of time, thereby forming a differential pressure within the reactor, which is not preferable.

[0042] A specific method for measuring the crushing strength of the above copper silicate catalyst is described in the examples described below.

[0043] In one embodiment of the present application, the crushing strength reduction rate after the harshness test according to the following method 2 of the copper silicate catalyst may be 10% or less, 5% or less, 3% or less, or 0.

[0044] [Method 2]

[0045] After an experiment in which the copper silicate catalyst is immersed in a hydroxypivaldehyde (HPA) solution and reacted at 180°C in a hydrogen atmosphere for 6 hours, the crushing strength reduction rate is calculated according to the following mathematical equation 2.

[0046] [Equation 2]

[0047] Crushing strength reduction rate (%) = (Crushing strength of initial catalyst - Crushing strength of catalyst after harshness test) / Crushing strength of initial catalyst Х 100

[0048] If the crushing strength reduction rate of the copper silicate catalyst exceeds 10% after the harshness test according to the above method 2, the strength of the catalyst may be reduced and the reactivity of the catalyst may be reduced during the manufacturing process of neopentyl glycol using the hydrogenation process of HPA under high temperature and high pressure reaction conditions, and thus problems may arise in the stable operation of the hydrogenation process.

[0049] In one embodiment of the present application, the Cu surface area according to the N2O chemisorption analysis of the copper silicate catalyst is 3 m 2 / g to 10 m 2 / g can be 4 m 2 / g to 9 m 2 / g can be 5 m 2 / g to 9 m 2 / g. If the Cu surface area according to the N2O chemical adsorption analysis of the copper silicate catalyst is outside the above-mentioned range, the catalytic activity is reduced, which is not desirable.

[0050] The specific measurement method of Cu surface area according to N2O chemisorption analysis of the above copper silicate catalyst is described in the examples described below.

[0051] In one embodiment of the present application, the weight ratio of Cu:Si of the copper silicate catalyst may be 30:70 to 70:30, 30:70 to 50:50, or 35:65 to 50:50. The weight ratio of Cu:Si of the copper silicate catalyst is an indicator of the content of Cu, which is an active component of the catalyst. If the weight ratio of Cu:Si is outside the above-mentioned range, the catalytic activity may be lowered, which is not preferable.

[0052] In one embodiment of the present application, the copper silicate catalyst may be a catalyst extruded into a cylindrical shape having a diameter of 2 mm to 6 mm and a height of 2 mm to 10 mm, or a catalyst extruded into a cylindrical shape having a diameter of 3 mm to 5 mm and a height of 3 mm to 9 mm. If the diameter of the cylindrical catalyst exceeds 6 mm or the height exceeds 10 mm, the catalytic activity may be reduced due to a decrease in surface area, which is not preferred. In addition, if the diameter of the cylindrical catalyst is less than 2 mm or the height is less than 2 mm, crushing and resulting drift may occur under the high temperature and high pressure reaction conditions for producing neopentyl glycol, which is not preferred.

[0053] Catalyst shaping is crucial for physical durability and reactant flow in the reactor. Powder catalysts, due to their large surface area per small particle size, can be advantageous for catalytic activity. However, in commercial-scale fixed-bed reactors, they restrict reactant flow and can cause drift and pressure differentials. For this reason, it is preferable to use catalysts formed through extrusion, tableting, or coating. The pores formed by the formed catalyst in a fixed-bed reactor have the effect of reducing the pressure differential caused by the high flow rate of reactants supplied for commercial productivity. In particular, catalysts formed by extrusion offer the advantage of high durability due to high strength, which reduces the possibility of drift and pressure differentials caused by wear and fracture during long-term use.

[0054] In one embodiment of the present application, the copper silicate catalyst may be used for producing neopentyl glycol.

[0055] In addition, a method for producing a copper silicate catalyst according to an embodiment of the present application comprises the steps of: adding a silica sol and an alkaline precipitant to an aqueous solution containing a copper precursor to produce a coprecipitate slurry; aging the coprecipitate slurry at a temperature of 80°C to 90°C for 3 hours or more, and then filtering it; drying the filtered coprecipitate slurry at a temperature of 80°C to 90°C to produce a dried product; mixing an inorganic binder including a fiber-based binder and graphite; and an organic compound with the dried product, and then molding the mixture to produce a catalyst precursor; and drying and calcining the catalyst precursor, and is characterized in that the temperature is maintained at 15°C to 35°C when the alkaline precipitant is added.

[0056] A method for producing a copper silicate catalyst according to one embodiment of the present application includes a step of producing a coprecipitate slurry by adding a silica sol and an alkaline precipitant to an aqueous solution containing a copper precursor.

[0057] In one embodiment of the present application, the copper precursor may be Cu(NO3)2·3H2O, Cu(CO3)2·Cu(OH)2, CuCl2·2H2O, etc., but is not limited thereto.

[0058] In one embodiment of the present application, the alkaline precipitant may be an alkali metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, a mixture thereof, or the like. More specifically, the alkaline precipitant may include at least one of NH4OH, (NH4)2CO3, NH4HCO3, CH4N2O, NaOH, and Na2CO3, but is not limited thereto.

[0059] In one embodiment of the present application, the alkaline precipitant is characterized in that the temperature is maintained at 15°C to 35°C when the alkaline precipitant is added. When the alkaline precipitant is added, the temperature increase due to the heat of neutralization can be maintained at 15°C to 35°C using cooling water or the like.

[0060] The temperature condition maintained when adding the alkaline precipitant is to control the heat of neutralization. Depending on the degree of control of the heat of neutralization, the initial particle size of the coprecipitate slurry may vary, which may affect the activity and physical stability of the catalyst. If the temperature maintained when adding the alkaline precipitant is less than 15°C, Si elution may be facilitated, which may weaken the physical stability of the catalyst, and thus is not preferable. In addition, if the temperature maintained when adding the alkaline precipitant exceeds 35°C, a change in the crystal phase of the coprecipitate slurry may cause a decrease in catalytic activity, which is not preferable.

[0061] A method for producing a copper silicate catalyst according to one embodiment of the present application includes a step of filtering after aging the coprecipitate slurry at a temperature of 80°C to 90°C for 3 hours or more.

[0062] The above aging can be performed at a temperature of 80°C to 90°C for 3 hours or more, and can be performed at a temperature of 80°C to 90°C for 3 hours to 8 hours.

[0063] A bond is formed between the copper precursor and silica through the above aging process, and when the above aging temperature and time are met simultaneously, unreaction of the copper precursor does not occur. If unreaction of the copper precursor occurs, it is undesirable as it may cause a decrease in catalyst activity.

[0064] After the above aging, the method of filtering the above-mentioned precipitate slurry is not particularly limited and any method known in the art can be used.

[0065] A method for producing a copper silicate catalyst according to one embodiment of the present application includes a step of drying the filtered coprecipitate slurry at a temperature of 80°C to 90°C to produce a dried product. If the drying conditions for the filtered coprecipitate slurry are exceeded, a decrease in catalytic activity may occur due to a change in catalyst crystallinity, which is undesirable.

[0066] A method for producing a copper silicate catalyst according to one embodiment of the present application comprises the steps of mixing a fiber-based binder and an inorganic binder including graphite and an organic compound into the dried material, and then molding the mixture to produce a catalyst precursor.

[0067] In one embodiment of the present application, the fiber-based binder may include at least one of glass fiber, carbon fiber, aramid fiber, alumina fiber, aluminum silicate fiber, silicon carbide fiber, and boron fiber.

[0068] In one embodiment of the present application, the content of the inorganic binder may be 0.1 wt% or more and less than 15 wt%, 1 wt% to 10 wt%, or 7 wt% to 10 wt%, based on the total weight of the dry material. When the content of the inorganic binder is less than 0.1 wt% based on the total weight of the dry material, the strength of the catalyst may be significantly lowered, which may weaken the physical stability under high temperature and high pressure reaction conditions, and thus is not preferable. In addition, when the content of the inorganic binder is 15 wt% or more, the flowability of the catalyst deteriorates during extrusion molding, which may lower the productivity of catalyst production and the compressibility may not be good, which may also lower the strength of the catalyst.

[0069] In one embodiment of the present application, the content of the organic compound may be 0.1 wt% to 50 wt%, 1 wt% to 40 wt%, or 10 wt% to 30 wt%, based on the total weight of the dried product. The organic compound serves as a lubricant during the catalyst forming process. If the content of the organic compound is less than 0.1 wt%, based on the total weight of the dried product, forming may be impossible, and if it exceeds 50 wt%, the catalyst strength may be weakened or the activity may be reduced, which is not preferable.

[0070] In one embodiment of the present application, the organic compound may include at least one of polyvinyl alcohol, isopropyl alcohol, ethanol, polyacrylate, polyethylene glycol, glycerin, starch, dextrin, wax, methylcellulose, carboxymethylcellulose, hydroxypropyl methylcellulose, paraffin, lignosulfonate, steric acid, and palmitic acid.

[0071] A method for manufacturing a copper silicate catalyst according to one embodiment of the present application includes a step of drying and calcining the catalyst precursor.

[0072] In one embodiment of the present application, the step of drying the catalyst precursor may be performed at 60°C to 120°C for 5 to 24 hours, or at 70°C to 110°C for 7 to 20 hours.

[0073] In one embodiment of the present application, the step of calcining the dried catalyst precursor may be performed at 350°C to 600°C for 5 to 24 hours, or may be performed at 400°C to 550°C for 7 to 20 hours.

[0074] If the above drying and calcination conditions are exceeded, the catalyst activity may decrease due to changes in the catalyst crystallinity, which is not desirable.

[0075] In addition, another embodiment of the present application provides a method for producing neopentyl glycol, which comprises a step of introducing a hydroxypivaldehyde (HPA) solution and hydrogen into a hydrogenation reactor to perform a hydrogenation reaction, wherein the hydrogenation reactor includes the copper silicate-based catalyst.

[0076] In one embodiment of the present application, the method for producing neopentyl glycol may utilize a method known in the art, except that it includes the copper silicate catalyst.

[0077] For example, the hydrogenation reactor may be a fixed bed reactor (FBR) filled with the copper silicate catalyst, in which case there is no need for separation of the catalyst and the reaction product, the reaction temperature and reaction pressure can be lowered compared to the conventional ones, so operation is stable and economical, and catalyst replacement work is easy, and the reactor size can be reduced, so there is the effect of greatly reducing investment costs.

[0078] In addition, the hydroxypivaldehyde solution may contain 65 wt% or less of hydroxypivaldehyde, 10 wt% or less of neopentyl glycol, 15 to 35 wt% of alcohol, and 15 wt% or less of water, in which case the heat of reaction can be minimized without lowering the reactivity, thereby having the effect of suppressing the production of by-products.

[0079] The above hydrogenation reaction may be carried out at a reaction temperature of 100°C to 250°C, 100°C to 200°C, or 100°C to 180°C.

[0080] According to one embodiment of the present application, a copper silicate catalyst having improved stability can be produced. In particular, the copper silicate catalyst according to one embodiment of the present application has a Si elution ratio of 5 wt% or less after a harsh test, and thus, it can prevent a decrease in catalyst strength or reactivity even under high-temperature and high-pressure reaction conditions for a high neopentyl glycol production yield.

[0081] In addition, according to one embodiment of the present application, the surface area of ​​Cu of the catalyst can be optimized by controlling the aging conditions of the coprecipitate slurry, the alkaline precipitant injection conditions, the drying conditions of the filtered coprecipitate slurry, and the type of inorganic binder.

[0082] Therefore, when neopentyl glycol is manufactured using a copper silicate catalyst according to one embodiment of the present application, the manufacturing process can be maintained stably, and thus, an effect of increasing economic efficiency can be obtained.

[0083] Hereinafter, examples will be provided to specifically explain the present application. However, the embodiments according to the present application may be modified in various ways, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to more fully explain the present application to those of average skill in the art.

[0084] <Example>

[0085] <Example 1>

[0086] While maintaining the temperature of the double jacket reactor at 30°C, a copper precursor (Cu(NO3)2·3H2O) aqueous solution was prepared, and silica sol was added so that the weight ratio of Cu and Si was Cu:Si = 45:55. After adding a NaOH aqueous solution while maintaining the temperature at 30°C, the temperature of the reactor was increased and aged at 80°C for 3 hours to prepare a coprecipitate. The coprecipitate was filtered and washed with distilled water, and the wet cake obtained thereby was dried in an oven at 80°C for 24 hours. The dried product was pulverized to prepare a catalyst intermediate powder.

[0087] Based on the total weight of the above catalyst intermediate powder, 10 wt% of an organic compound (8 wt% of isopropyl alcohol and 2 wt% of glycerin), 0.1 wt% of a fiber-based binder (ceramic wool, aluminum silicate component), and 6.9 wt% of graphite were mixed, and extruded into a cylindrical shape with a diameter of 3 mm to 5 mm and a height of 3 mm to 9 mm through an extruder.

[0088] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to finally produce a catalyst for producing neopentyl glycol.

[0089] <Example 2>

[0090] In the extrusion molding step, instead of applying 10 wt% of the organic compound, 0.1 wt% of the fiber-based binder, and 6.9 wt% of the graphite, 20 wt% of the organic compound (20 wt% of isopropyl alcohol and 5 wt% of glycerin), 1 wt% of the fiber-based binder, and 9 wt% of the graphite were applied, and the same procedure as in Example 1 was followed to produce a catalyst for producing neopentyl glycol.

[0091] <Example 3>

[0092] In the extrusion molding step, instead of applying 10 wt% of the organic compound, 0.1 wt% of the fiber-based binder, and 6.9 wt% of the graphite, 20 wt% of the organic compound (20 wt% of isopropyl alcohol and 5 wt% of glycerin), 3 wt% of the fiber-based binder, and 7 wt% of the graphite were applied, and the same procedure as in Example 1 was followed to produce a catalyst for producing neopentyl glycol.

[0093] <Comparative Example 1>

[0094] A catalyst for producing neopentyl glycol was manufactured in the same manner as in Example 1, except that the temperature of the double jacket reactor was maintained at 45°C and the temperature at which the NaOH aqueous solution was introduced was adjusted to 45°C.

[0095] <Comparative Example 2>

[0096] A catalyst for producing neopentyl glycol was prepared in the same manner as in Example 1, except that aging was performed at 95°C for 3 hours instead of aging at 80°C for 3 hours.

[0097] <Comparative Example 3>

[0098] A catalyst for producing neopentyl glycol was prepared in the same manner as in Example 1, except that the wet cake was dried in an oven at 95°C instead of drying in an oven at 80°C.

[0099] <Comparative Example 4>

[0100] In the extrusion molding step, a catalyst for producing neopentyl glycol was manufactured in the same manner as in Example 1, without using the fiber-based binder and graphite.

[0101] Comparative Example 5

[0102] In the extrusion molding step, a catalyst for producing neopentyl glycol was manufactured in the same manner as in Example 1, without using the organic compound.

[0103] <Comparative Example 6>

[0104] In the extrusion molding step, the same process as in Example 1 was performed without using the fiber-based binder, graphite, and organic compound. However, in the extrusion molding step, lubrication was not performed properly in the extruder, making extrusion impossible, and as a result, making the production of the catalyst impossible.

[0105] <Experimental Example>

[0106] In the presence of the catalyst prepared in the examples or comparative examples, a hydrogenation reaction was performed for 1 hour under the conditions of 160°C and 35 bar using an HPA solution composed of 65 wt% HPA, 2 wt% NPG, 25 wt% 2-ethylhexanol, 5 wt% H2O, and 3 wt% high-boiling-point substances. The hydrogen consumption was measured to determine each catalyst activity, which is shown in Table 1 below. The catalyst activity was expressed based on the results of Example 1 as 100.

[0107] In addition, the crushing strength of the catalysts of the examples and comparative examples and the average particle size of the co-precipitate slurry were evaluated and shown in Table 1 below.

[0108] In addition, the Cu surface area according to the N2O chemisorption analysis of the catalysts of the examples and comparative examples and the Si elution rate and strength reduction rate according to the harshness test were evaluated and are shown in Table 2 below.

[0109] In addition, the results of N2O chemical adsorption analysis for measuring the Cu surface area of ​​the copper silicate catalyst according to Example 1 are shown in Fig. 1 below.

[0110] The measurement method for the evaluation results described in Tables 1 and 2 below is as follows.

[0111] <Crushing strength>

[0112] The above crushing strength was measured using SHIMPO's FGN-50B. More specifically, a cylindrically extruded catalyst was placed in the strength measuring device holder with its side facing the floor, and the measuring part was lowered from above to press against the catalyst. The maximum pressure corresponding to the peak pressure value among the pressure values ​​generated at this moment was used. In the same manner, 20 catalysts were individually measured and the average value was calculated.

[0113] In the above Example 1, the crushing strength of the catalyst intermediate powder itself without performing the extrusion molding step was attempted to be measured, but the powder catalyst had a particle size of approximately 100 μm, making measurement impossible due to the different method for measuring the maximum pressure value when using the FGN-50B from SHIMPO mentioned above. Accordingly, the crushing strength of the powder catalyst was evaluated to be 0.

[0114] <Average particle size of the co-precipitate slurry>

[0115] The average particle size of the above-mentioned co-precipitate slurry was measured using a wet particle size analysis method.

[0116] More specifically, the back ground was measured using Microtrac's S3500, and the particle size distribution was measured by adding about 3 drops of the co-precipitate slurry under ultrasonic vibration conditions to calculate the average particle size.

[0117] <Cu 표면적>

[0118] The above Cu surface area was measured according to N2O chemisorption analysis.

[0119] More specifically, using AutoChem± from Micromeritics, approximately 0.2 g of a catalyst sample was filled into a U-shaped tube and pretreated at 250°C in a hydrogen atmosphere for 2 hours. Then, N2O was pulse-injected using a loop of a certain volume at 60°C, and the surface area of ​​Cu was calculated from the cumulative amount of N2O used and the Cu weight% of the catalyst.

[0120] <Experiment with Harshness>

[0121] A harshening experiment was conducted in which the catalysts of the examples or comparative examples were immersed in the above liquid HPA solution and reacted at 180°C in a hydrogen atmosphere for 6 hours. Thereafter, the solution remaining on the catalyst was removed by washing with acetone and water and then drying at room temperature. The Si elution rate was calculated according to the following mathematical equation 1, and the crushing strength reduction rate of the catalyst was calculated according to the following mathematical equation 2.

[0122] [Mathematical Formula 1]

[0123] Si elution ratio (wt%) = (Si weight contained in the initial catalyst - Si weight contained in the catalyst after the harshness experiment) / Si weight contained in the initial catalyst Х 100

[0124] [Equation 2]

[0125] Crushing strength reduction rate (%) = (Crushing strength of initial catalyst - Crushing strength of catalyst after harshness test) / Crushing strength of initial catalyst Х 100

[0126] [Table 1]

[0127]

[0128] [Table 2]

[0129]

[0130] As shown in the results in Tables 1 and 2 above, the catalysts for producing neopentyl glycol of Examples 1 to 3 had a Cu surface area of ​​3 m according to N2O pulse chemisorption analysis. 2 / g to 10 m 2 / g, and the Si elution ratio after the above harshness test was in the range of 5 wt% or less, so it was confirmed that it had excellent catalytic activity compared to the catalysts of Comparative Examples 1 to 7.

[0131] It can be confirmed that the catalyst for producing neopentyl glycol of Comparative Example 1 did not control the heat of neutralization due to the high alkaline precipitant injection maintenance temperature, and thus the catalytic activity was reduced. In addition, it can be confirmed that the catalyst for producing neopentyl glycol of Comparative Example 2 showed a change in the coprecipitate slurry due to the high aging temperature condition, resulting in a decrease in catalytic activity and a weakening of physical stability. In addition, it can be confirmed that the catalyst for producing neopentyl glycol of Comparative Example 3 showed a change in the crystal phase of the catalyst precursor due to the high drying temperature, resulting in a decrease in catalytic activity and physical stability. In addition, it can be confirmed that the catalysts for producing neopentyl glycol of Comparative Examples 4 and 5 did not apply an inorganic binder or an organic compound, so that Si elution could not be effectively controlled, resulting in low physical stability and low catalytic activity.

[0132] In addition, the catalyst for producing neopentyl glycol according to one embodiment of the present application is a catalyst extruded into a cylindrical shape, and can be applied to a commercial-scale fixed-bed reactor where a powder catalyst that has not undergone a molding process is difficult to apply, and has excellent strength and durability, so that the possibility of drift or differential pressure due to wear or crushing, etc., can be reduced during long-term use of the catalyst.

[0133] Therefore, the catalyst for producing neopentyl glycol according to one embodiment of the present application has excellent catalyst strength, reactivity, and stability, and can maintain catalytic activity even in high-temperature and high-pressure reactions, thereby increasing the stability of the process for producing neopentyl glycol, and confirming that the catalytic activity is excellent.

Claims

1. A copper silicate catalyst containing copper and silica, The crushing strength of the above copper silicate catalyst is 40N or more, The Cu surface area according to the N2O pulse chemisorption analysis of the above copper silicate catalyst was 3 m 2 / g to 10 m 2 / g and A copper silicate catalyst having a Si elution ratio of 5 wt% or less after a harshness test according to the following method 1 of the copper silicate catalyst: [Method 1] After an experiment in which the copper silicate catalyst is immersed in a hydroxypivaldehyde (HPA) solution and reacted at 180°C in a hydrogen atmosphere for 6 hours, the Si elution ratio is calculated according to the following mathematical formula 1. [Mathematical Formula 1] Si elution ratio (wt%) = (Si weight contained in the initial catalyst - Si weight contained in the catalyst after the harshness experiment) / Si weight contained in the initial catalyst Х 100 2. In claim 1, a copper silicate catalyst having a crushing strength reduction rate of 10% or less after a harshness test according to the following method 2 of the copper silicate catalyst: [Method 2] After an experiment in which the copper silicate catalyst is immersed in a hydroxypivaldehyde (HPA) solution and reacted at 180°C in a hydrogen atmosphere for 6 hours, the crushing strength reduction rate is calculated according to the following mathematical equation 2. [Equation 2] Crushing strength reduction rate (%) = (Crushing strength of initial catalyst - Crushing strength of catalyst after harshness test) / Crushing strength of initial catalyst Х 100 3. In claim 1, the copper silicate catalyst is a catalyst extruded into a cylindrical shape with a diameter of 2 mm to 6 mm and a height of 2 mm to 10 mm.

4. In claim 1, the copper silicate catalyst is a copper silicate catalyst for producing neopentyl glycol.

5. A step of preparing a coprecipitate slurry by adding silica sol and an alkaline precipitant to an aqueous solution containing a copper precursor; A step of aging the above-mentioned precipitate slurry at a temperature of 80°C to 90°C for 3 hours or more, and then filtering; A step of drying the filtered precipitate slurry at a temperature of 80°C to 90°C to produce a dried product; A step of mixing a fiber-based binder and an inorganic binder including graphite in the above-mentioned dry material; and an organic compound, and then molding the mixture to produce a catalyst precursor; and Comprising a step of drying and calcining the above catalyst precursor, A method for producing a copper silicate catalyst according to any one of claims 1 to 4, wherein the temperature is maintained at 15°C to 35°C when the alkaline precipitant is added.

6. A method for producing a copper silicate catalyst according to claim 5, wherein the alkaline precipitant comprises at least one of NH4OH, (NH4)2CO3, NH4HCO3, CH4N2O, NaOH, and Na2CO3.

7. A method for producing a copper silicate catalyst according to claim 5, wherein the average particle size of the coprecipitate slurry is 10 µm to 150 µm.

8. A method for producing a copper silicate catalyst according to claim 5, wherein the fiber-based binder comprises at least one of glass fiber, carbon fiber, aramid fiber, alumina fiber, aluminum silicate fiber, silicon carbide fiber, and boron fiber.

9. A method for producing a copper silicate catalyst according to claim 5, wherein the content of the inorganic binder is 0.1 wt% or more and less than 15 wt% based on the total weight of the dried product.

10. A method for producing a copper silicate catalyst according to claim 5, wherein the content of the organic compound is 0.1 wt% to 50 wt% based on the total weight of the dried product.

11. A method for producing a copper silicate catalyst according to claim 5, wherein the organic compound comprises at least one of polyvinyl alcohol, isopropyl alcohol, ethanol, polyacrylate, polyethylene glycol, glycerin, starch, dextrin, wax, methylcellulose, carboxymethylcellulose, hydroxypropyl methylcellulose, paraffin, lignosulfonate, steric acid, and palmitic acid.

12. A step of introducing a hydroxypivaldehyde (HPA) solution and hydrogen into a hydrogenation reactor to carry out a hydrogenation reaction, A method for producing neopentyl glycol, wherein the hydrogenation reactor comprises a copper silicate-based catalyst according to any one of claims 1 to 4.

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