Copper silicate-based catalyst and method for producing same

Abstract

A method for producing a copper silicate-based catalyst according to an embodiment of the present application provides a copper silicate-based catalyst comprising copper and silica. The crush strength of the copper silicate-based catalyst is 40 N or higher, and the content of impurities in the copper silicate-based catalyst is 2 wt% or less according to the inductively coupled plasma optical emission spectrometer (ICP-OES) analysis, wherein the impurities include at least one of K, Zr, Fe, Mo, Na, and Al. The Si elution ratio in the copper silicate-based catalyst is 5 wt% or less after the harshness test according to method 1.

Description

Copper silicate catalyst and method for producing the same

[0001] This application claims the benefit of Korean Patent Application No. 10-2024-0009951, 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 the 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 content of impurities according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis of the above copper silicate catalyst is 2 wt% or less,

[0012] The above impurities include at least one of K, Zr, Fe, Mo, Na and Al,

[0013] 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.

[0014] [Method 1]

[0015] 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 equation 2.

[0016] [Equation 2]

[0017] 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

[0018] In addition, another embodiment of the present application is

[0019] A step of preparing a coprecipitate slurry by adding silica sol and an alkaline precipitant to an aqueous solution containing a copper precursor;

[0020] A step of filtering the above-mentioned precipitate slurry, washing it with water, and drying it to produce a dried product;

[0021] A step of mixing a fiber-based binder and an organic compound into the above-mentioned dry material and then molding it to produce a catalyst precursor; and

[0022] Comprising a step of drying and calcining the above catalyst precursor,

[0023] 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.

[0024] 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,

[0025] The above hydrogenation reactor provides a method for producing neopentyl glycol, which comprises the copper silicate catalyst.

[0026] 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.

[0027] In addition, according to one embodiment of the present application, by controlling the alkaline precipitant injection conditions and the washing conditions of the coprecipitate slurry, the Si elution ratio of the catalyst after the harshness test can be characterized as 5 wt% or less, while the residual impurity concentration of the catalyst can be minimized.

[0028] 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.

[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, the content of impurities according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis of the copper silicate catalyst is 2 wt% or less, and the impurities include at least one of K, Zr, Fe, Mo, Na, and Al, and the Si elution ratio of the copper silicate catalyst after a harshness test according to the following method 1 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 equation 2.

[0038] [Equation 2]

[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] In one embodiment of the present application, the content of impurities according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis of the copper silicate catalyst may be 2 wt% or less, 1.7 wt% or less, 1.4 wt% or less, or 0.3 wt% to 1.4 wt%. When the content of the impurities exceeds 2 wt%, the content of copper, which is a catalytically active metal, may decrease, resulting in a decrease in reactivity, and the content of silicate, which is a support, may decrease, resulting in a decrease in catalyst stability, which is not preferable.

[0041] The above impurities may include one or more of K, Zr, Fe, Mo, Na, and Al.

[0042] A specific method for measuring the content of impurities in the above copper silicate catalyst according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis is described in the examples described below.

[0043] The Si elution ratio after the harshness test according to the above 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 above 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.

[0044] In one embodiment of the present application, the crushing strength of the copper silicate catalyst may be 40 N or more, 42 N to 170 N, or 69 N to 151 N. If the crushing strength of the copper silicate catalyst is less than 40 N, the catalyst may easily break within the reactor, which is not preferable because the catalyst layer within the reactor may become clogged.

[0045] A specific method for measuring the crushing strength of the above copper silicate catalyst is described in the examples described below.

[0046] 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, 7% or less, 5% or less, or 3% or less.

[0047] [Method 2]

[0048] 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 formula 3.

[0049] [Equation 3]

[0050] Crushing strength reduction rate (%) = (Crushing strength of initial catalyst - Crushing strength of catalyst after harshness test) / Crushing strength of initial catalyst Х 100

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] In one embodiment of the present application, the copper silicate catalyst may be used for producing neopentyl glycol.

[0056] 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; filtering the coprecipitate slurry, washing it with water, and drying it to produce a dried product; mixing a fiber-based binder and an organic compound with the dried product, and then molding it 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.

[0057] 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.

[0058] In one embodiment of the present application, the copper precursor may be one or more of Cu(NO3)2·3H2O, CuCl2·2H2O, CuSO4, Cu(CO3)2·Cu(OH)2, Cu(CH3COO)2, etc., but is not limited thereto.

[0059] 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. By applying the alkaline precipitant, the sizes of Cu particles and SiO2 can be controlled.

[0060] In one embodiment of the present application, it is characterized in that the alkaline precipitant is maintained at 15°C to 35°C when 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. By maintaining the alkaline precipitant at 15°C to 35°C when added, the size and oxidation degree of the Cu particles can be made uniform, thereby improving the uniformity of the catalyst.

[0061] In addition, 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, which may cause a decrease in catalytic activity due to a change in the crystal phase of the coprecipitate slurry, which is not preferable.

[0062] The method for producing a copper silicate catalyst according to one embodiment of the present application may further include a step of aging the coprecipitate slurry at a temperature of 80°C to 90°C for 3 hours or more. The aging may be performed at a temperature of 80°C to 90°C for 3 hours or more, or may 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] In one embodiment of the present application, the pH of the coprecipitate slurry may be 10 to 14, 10 to 13, or 10 to 11. In addition, the average particle size of the coprecipitate slurry may be 10 µm to 150 µm, 15 µm to 50 µm, or 24 µm to 36 µm. In this case, the coprecipitate slurry refers to a solution immediately after being taken out of the reactor before filtration and washing.

[0065] A method for producing a copper silicate catalyst according to one embodiment of the present application includes a step of filtering the coprecipitate slurry, washing it with water, and drying it to produce a dried product.

[0066] The method for filtering the above-mentioned precipitate slurry is not particularly limited and any method known in the art can be used.

[0067] In one embodiment of the present application, the water washing step following the filtration step of the coprecipitate slurry is a step for removing alkaline precipitates and copper precursor residues. If the alkaline precipitates and copper precursor residues are not removed, the catalytic reaction may be inhibited and the pH of the reactant may be altered, thereby affecting catalyst durability. Furthermore, molding workability and molding strength may also be reduced.

[0068] In one embodiment of the present application, the step of drying the filtered co-precipitate slurry can be performed at 60°C to 120°C for 5 to 72 hours, and can be performed at 70°C to 110°C for 7 to 48 hours.

[0069] A method for producing a copper silicate catalyst according to one embodiment of the present application includes a step of mixing a fiber-based binder and an organic compound into the above-described dry material and then molding the mixture to produce a catalyst precursor.

[0070] 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.

[0071] In one embodiment of the present application, the content of the fiber-based binder may be 0.1 wt% or more and less than 15 wt%, 0.5 wt% to 10 wt%, or 0.7 wt% to 5 wt%, based on the total weight of the dry material. When the content of the fiber-based 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 fiber-based binder is 15 wt% or more, the flowability of the catalyst may deteriorate 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.

[0072] 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 5 wt% to 20 wt%, based on the total weight of the dried material. 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 material, 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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 the characteristic that the Si elution ratio of the catalyst is 5 wt% or less after a harsh test, and thus, it can prevent a decrease in the strength or reactivity of the catalyst even under high-temperature and high-pressure reaction conditions for a high production yield of neopentyl glycol.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] <Example>

[0087] <Example 1>

[0088] 85.0 g of Cu(NO3)2·3H2O was dissolved in 75 ml of distilled water and maintained at 30°C. While maintaining the temperature at 30°C, 382.8 g of a 4 wt% NaOH solution was added to the solution and stirred for an additional 10 minutes. Thereafter, 52.5 g of a 40 wt% silica sol was added to the solution. The solution was recovered, filtered, washed three times with distilled water, and the obtained solid was dried. After drying, the obtained solid was pulverized with a mortar to prepare a catalyst intermediate powder.

[0089] Based on the total weight of the above catalyst intermediate powder, 11 wt% of organic compound (8 wt% of isopropyl alcohol and 3 wt% of glycerin), 1 wt% of fiber binder (ceramic wool, aluminum silicate component) and distilled water 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.

[0090] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to obtain a catalyst.

[0091] <Example 2>

[0092] 83.9 g of Cu(NO3)2·3H2O was dissolved in 75 ml of distilled water and maintained at 30°C. While maintaining the temperature at 30°C, 382.8 g of a 4 wt% NaOH solution was added to the solution and stirred for an additional 10 minutes. Thereafter, 52.5 g of a 40 wt% silica sol was added to the solution. The solution was recovered, filtered, washed three times with distilled water, and the obtained solid was dried. After drying, the obtained solid was pulverized in a mortar to prepare a catalyst intermediate powder.

[0093] Based on the total weight of the above catalyst intermediate powder, 11 wt% of organic compound (8 wt% of isopropyl alcohol and 3 wt% of glycerin), 1 wt% of fiber binder (ceramic wool, aluminum silicate component) and distilled water 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.

[0094] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to obtain a catalyst.

[0095] <Example 3>

[0096] 42.5 g of Cu(NO3)2·3H2O was dissolved in 75 ml of distilled water and maintained at 30°C. While maintaining the temperature at 30°C, 382.8 g of a 4 wt% NaOH solution was added to the solution and stirred for an additional 10 minutes. Subsequently, 52.5 g of a 40 wt% silica sol was added to the solution. Subsequently, the solution was recovered, filtered, washed three times with distilled water, and the obtained solid was dried. After drying, the obtained solid was pulverized with a mortar to prepare a catalyst intermediate powder.

[0097] Based on the total weight of the above catalyst intermediate powder, 11 wt% of organic compound (8 wt% of isopropyl alcohol and 3 wt% of glycerin), 1 wt% of fiber binder (ceramic wool, aluminum silicate component) and distilled water 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.

[0098] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to obtain a catalyst.

[0099] <Comparative Example 1>

[0100] 85.0 g of Cu(NO3)2·3H2O was dissolved in 75 ml of distilled water and maintained at 40°C. While maintaining the temperature at 40°C, 382.8 g of a 4 wt% NaOH solution was added to the solution and stirred for an additional 10 minutes. Thereafter, 52.5 g of a 40 wt% silica sol was added to the solution. The solution was recovered, filtered, washed three times with distilled water, and the obtained solid was dried. After drying, the obtained solid was pulverized with a mortar to prepare a catalyst intermediate powder.

[0101] Based on the total weight of the above catalyst intermediate powder, 11 wt% of organic compound (8 wt% of isopropyl alcohol and 3 wt% of glycerin), 1 wt% of fiber binder (ceramic wool, aluminum silicate component) and distilled water 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.

[0102] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to obtain a catalyst.

[0103] <Comparative Example 2>

[0104] 83.9 g of Cu(NO3)2·3H2O was dissolved in 75 ml of distilled water and maintained at 40°C. While maintaining the temperature at 40°C, 382.8 g of a 4 wt% NaOH solution was added to the solution and stirred for an additional 10 minutes. Thereafter, 52.5 g of a 40 wt% silica sol was added to the solution. The solution was recovered, filtered, washed three times with distilled water, and the obtained solid was dried. After drying, the obtained solid was ground in a mortar to prepare a catalyst intermediate powder.

[0105] Based on the total weight of the above catalyst intermediate powder, 11 wt% of organic compound (8 wt% of isopropyl alcohol and 3 wt% of glycerin), 1 wt% of fiber binder (ceramic wool, aluminum silicate component) and distilled water 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.

[0106] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to obtain a catalyst.

[0107] <Comparative Example 3>

[0108] 42.9 g of Cu(NO3)2·3H2O was dissolved in 75 ml of distilled water and maintained at 40°C. While maintaining the temperature at 40°C, 382.8 g of a 4 wt% NaOH solution was added to the solution and stirred for an additional 10 minutes. Thereafter, 52.5 g of a 40 wt% silica sol was added to the solution. The solution was recovered, filtered, washed three times with distilled water, and the obtained solid was dried. After drying, the obtained solid was pulverized with a mortar to prepare a catalyst intermediate powder.

[0109] Based on the total weight of the above catalyst intermediate powder, 11 wt% of organic compound (8 wt% of isopropyl alcohol and 3 wt% of glycerin), 1 wt% of fiber binder (ceramic wool, aluminum silicate component) and distilled water 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.

[0110] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to obtain a catalyst.

[0111] <Comparative Example 4>

[0112] 42.9 g of Cu(NO3)2·3H2O was dissolved in 75 ml of distilled water and maintained at 30°C. While maintaining the temperature at 30°C, 382.8 g of a 4 wt% NaOH solution was added to the solution and stirred for an additional 10 minutes. Subsequently, 52.5 g of a 40 wt% silica sol was added to the solution. The solution was recovered, filtered, and the obtained solid was dried. After drying, the obtained solid was pulverized in a mortar to prepare a catalyst intermediate powder.

[0113] Based on the total weight of the above catalyst intermediate powder, 11 wt% of organic compound (8 wt% of isopropyl alcohol and 3 wt% of glycerin), 1 wt% of fiber binder (ceramic wool, aluminum silicate component) and distilled water 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.

[0114] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to obtain a catalyst.

[0115] Comparative Example 5

[0116] In the extrusion molding step, a catalyst for producing neopentyl glycol was manufactured in the same manner as in Example 1, without using either the organic compound or the fiber-based binder.

[0117] <Comparative Example 6>

[0118] 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.

[0119] Comparative Example 7

[0120] In the extrusion molding step, the same procedure as in Example 1 was followed without using the 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.

[0121] <Experimental Example>

[0122] 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.

[0123] In addition, the crushing strength of the catalysts of the examples and comparative examples was evaluated and shown in Table 1 below.

[0124] In addition, the average particle size of the co-precipitate slurry of the catalysts of the examples and comparative examples was evaluated and shown in Table 1 below.

[0125] In addition, the impurity content of the catalysts of the examples and comparative examples was evaluated by ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis and is shown in Table 2 below.

[0126] In addition, the Si elution ratio after the harshness test of the catalysts of the examples and comparative examples was calculated and shown in Table 2 below.

[0127] The measurement method for the evaluation results described in Tables 1 and 2 below is as follows.

[0128] <Crushing strength>

[0129] 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.

[0130] 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 about 100 μm, which was small, and therefore, the method for measuring the maximum pressure value was different from that used in the aforementioned SHIMPO FGN-50B, making measurement impossible. Accordingly, the crushing strength of the powder catalyst was evaluated to be 0.

[0131] <Average particle size of the co-precipitate slurry>

[0132] The average particle size of the above-mentioned co-precipitate slurry was measured using a wet particle size analysis method.

[0133] 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.

[0134] <Impurity content>

[0135] The content of the above impurities was measured according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis. More specifically, the measurement was performed using the Optima 8300DV equipment of Perkin Elmer. The accurately weighed catalyst, 1 mL of ultrapure water, 1 mL of nitric acid, and 0.1 mL of hydrofluoric acid were placed in a platinum crucible and completely dissolved. Then, 0.5 mL of 1,000 ppm of the internal standard substance Sc was added, and the mixture was diluted to 50 mL with ultrapure water. The concentration of the sample thus prepared was measured, and the content of the impurities was calculated according to the following mathematical equation 1.

[0136] At this time, the impurities include one or more of K, Zr, Fe, Mo, Na, Al, etc.

[0137] [Mathematical Formula 1]

[0138] Impurity content (wt%) = measured concentration (μg / mL) Х dilution volume (mL) / weight of catalyst (μg) Х 100

[0139] <Experiment with Harshness>

[0140] 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 (2). In addition, the crushing strength reduction rate of the catalyst was calculated according to the following mathematical equation (3).

[0141] [Equation 2]

[0142] 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

[0143] [Equation 3]

[0144] Crushing strength reduction rate (%) = (Crushing strength of initial catalyst - Crushing strength of catalyst after harshness test) / Crushing strength of initial catalyst Х 100

[0145] [Table 1]

[0146]

[0147] [Table 2]

[0148]

[0149] As shown in the results in Tables 1 and 2 above, it was confirmed that the catalysts for producing neopentyl glycol of Examples 1 to 3 had excellent catalytic activity compared to the catalysts of Comparative Examples 1 to 6, as the Si elution ratio after the harshness test was in the range of 5 wt% or less.

[0150] It can be confirmed that the catalysts for producing neopentyl glycol of Comparative Examples 1 to 3 showed a phenomenon of reduced physical stability in which the particle size of the coprecipitate was unsuitable due to the high alkaline precipitant injection and maintenance temperature, which resulted in a weakening of the catalyst strength and the occurrence of Si elution. In addition, the catalyst for producing neopentyl glycol of Comparative Example 4 did not perform a water washing process after the filtration process of the coprecipitate slurry, so the alkaline precipitate and the residue of the copper precursor were not removed, and thus the content of impurities in the catalyst was high and the crushing strength of the catalyst was low. In addition, it can be confirmed that the catalyst strength and catalytic activity decreased when a fiber-based binder was not used in Comparative Examples 5 and 6.

[0151] 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.

[0152] 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 content of impurities according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis of the above copper silicate catalyst is 2 wt% or less, The above impurities include at least one of K, Zr, Fe, Mo, Na and Al, 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 equation 2. [Equation 2] 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 formula 3. [Equation 3] 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 copper silicate catalyst that is 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 filtering the above-mentioned precipitate slurry, washing it with water, and drying it to produce a dried product; A step of mixing a fiber-based binder and an organic compound into the above-mentioned dry material and then molding it 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 content of the fiber-based binder is 0.1 wt% or more and less than 15 wt% based on the total weight of the dried product.

8. 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.

9. 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.

10. 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.

11. A step of introducing a hydroxypivaldehyde (HPA) solution and hydrogen into a hydrogenation reactor to perform 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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