Copper silicate-based catalyst and manufacturing method thereof

Abstract

A copper silicate-based catalyst according to one embodiment of the present application is a copper silicate-based catalyst comprising copper and silica, wherein the weight ratio of Cu:Si in the copper silicate-based catalyst is 30:70 to 70:30, the Cu content having an oxidation number of 2 according to X-ray photoelectron spectroscopy (XPS) analysis of the copper silicate-based catalyst is 2 at% to 6 at%, and the copper silicate-based catalyst is in the form of cylindrical pellets having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm.

Description

Copper silicate catalyst and method for producing the same

[0001] This application claims the benefit of Korean Patent Application No. 10-2024-0009948, 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 weight ratio of Cu:Si of the above copper silicate catalyst is 30:70 to 70:30,

[0011] The Cu content of oxidation number 2 according to XPS (X-ray Photoelectron Spectroscope) analysis of the above copper silicate catalyst is 2 at% to 6 at%,

[0012] The above copper silicate catalyst is provided in the form of a cylindrical pellet having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm.

[0013] Another embodiment of the present application is:

[0014] A step of preparing a coprecipitate slurry by adding silica sol and an alkaline precipitant to an aqueous solution containing a copper precursor;

[0015] A step of filtering and drying the above-mentioned precipitate slurry to produce a dried product;

[0016] A step of manufacturing a catalyst precursor by mixing a fiber-based binder and an organic compound into the above-mentioned dry material and then molding the mixture into cylindrical pellets having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm; and

[0017] A step of drying and calcining the above catalyst precursor

[0018] A method for producing a copper silicate catalyst including:

[0019] 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,

[0020] The above hydrogenation reactor provides a method for producing neopentyl glycol, which comprises the copper silicate catalyst.

[0021] According to one embodiment of the present application, a copper silicate-based catalyst having improved stability can be produced. In particular, the copper silicate-based catalyst according to one embodiment of the present application can optimize the content of Cu with oxidation number 2 and the specific surface area of ​​the catalyst by producing a molded catalyst that is a cylindrical pellet having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm by mixing a fiber-based binder and an organic compound, thereby preventing a decrease in the strength or reactivity of the catalyst even under high-temperature and high-pressure reaction conditions for a high neopentyl glycol production yield.

[0022] 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.

[0023] FIG. 1 is a diagram showing a nitrogen adsorption-desorption isotherm for measuring the BET surface area of ​​a copper silicate catalyst according to Example 1 of the present application.

[0024] Hereinafter, the present specification will be described in more detail.

[0025] 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.

[0026] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0027] As mentioned above, efforts are continuously being made in the field of technology to produce NPG in a high-yield and economical manner.

[0028] 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.

[0029] 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.

[0030] A copper silicate catalyst according to one embodiment of the present application comprises copper and silica, a weight ratio of Cu:Si of the copper silicate catalyst is 30:70 to 70:30, a content of Cu with an oxidation number of 2 according to XPS (X-ray Photoelectron Spectroscope) analysis of the copper silicate catalyst is 2 at% to 6 at%, and a shape of the copper silicate catalyst is a cylindrical pellet having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm.

[0031] 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.

[0032] In one embodiment of the present application, the content of Cu in oxidation state 2 according to XPS (X-ray Photoelectron Spectroscope) analysis of the copper silicate-based catalyst may be 2 at% to 6 at%, 2.1 at% to 5 at%, or 2.2 at% to 3.0 at%. When the content range of Cu in oxidation state 2 according to XPS (X-ray Photoelectron Spectroscope) analysis of the copper silicate-based catalyst is satisfied, excellent catalytic activity may be exhibited.

[0033] A specific method for measuring the content of Cu in oxidation state 2 according to XPS (X-ray Photoelectron Spectroscope) analysis of the above copper silicate catalyst is described in the examples described below.

[0034] In one embodiment of the present application, the shape of the copper silicate catalyst may be a cylindrical pellet having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm, a cylindrical pellet having a diameter of 3.5 mm to 5 mm and a height of 4 mm to 8 mm, or a cylindrical pellet having a diameter of 5 mm x 5 mm in length. If the diameter of the cylindrical pellet exceeds 6 mm or the height exceeds 9 mm, the catalytic activity may be lowered due to a decrease in surface area, which is not preferable. In addition, if the diameter of the cylindrical pellet is less than 3 mm or the height is less than 3 mm, crushing and resulting drift may occur under the high temperature and high pressure reaction conditions for producing neopentyl glycol, which is not preferable.

[0035] 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.

[0036] In one embodiment of the present application, the specific surface area of ​​the copper silicate catalyst is 1 m 2 / g to 200 m 2 / g can be 20 m 2 / g to 180 m 2 / g can be 64 m 2 / g to 128 m 2 / g. If the specific surface area of ​​the copper silicate catalyst exceeds the above-mentioned range, the catalytic activity is reduced, which is not desirable.

[0037] In one embodiment of the present application, 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.

[0038] [Method 1]

[0039] 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.

[0040] [Equation 2]

[0041] 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

[0042] 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 problems may arise in the stable operation of the hydrogenation process.

[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 formula 3.

[0046] [Equation 3]

[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] A specific method for measuring the specific surface area of ​​the above copper silicate catalyst is described in the examples described below.

[0050] 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 52 N to 89 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.

[0051] A specific method for measuring the crushing strength of the above copper silicate catalyst is described in the examples described below.

[0052] In one embodiment of the present application, the copper silicate catalyst may be used for producing neopentyl glycol.

[0053] 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 and drying the coprecipitate slurry to produce a dried product; mixing a fiber-based binder and an organic compound with the dried product and then molding the mixture into cylindrical pellets having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm to produce a catalyst precursor; and drying and calcining the catalyst precursor.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] When the above alkaline precipitant is added, the temperature increase due to the heat of neutralization can be maintained at room temperature using cooling water, etc.

[0058] 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.

[0059] 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.

[0060] A method for producing a copper silicate catalyst according to one embodiment of the present application includes a step of filtering and drying the coprecipitate slurry to produce a dried product.

[0061] The method for filtering the above-mentioned precipitate slurry is not particularly limited and any method known in the art can be used.

[0062] 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.

[0063] A method for producing a copper silicate catalyst according to one embodiment of the present application includes a step of producing a catalyst precursor by mixing a fiber-based binder and an organic compound into the dried material and then molding the mixture into cylindrical pellets having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm.

[0064] 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.

[0065] 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%, 1 wt% to 10 wt%, or 5 wt% to 10 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 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.

[0066] 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 20 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.

[0067] 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.

[0068] In one embodiment of the present application, a catalyst precursor may be manufactured by mixing a fiber-based binder and an organic compound into the dried material and then molding the mixture into cylindrical pellets having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm, and a catalyst precursor may be manufactured by molding the mixture into cylindrical pellets having a diameter of 3.5 mm to 5 mm and a height of 4 mm to 8 mm. If the diameter of the cylindrical pellet exceeds 6 mm or the height exceeds 9 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 pellet is less than 3 mm or the diameter is less than 3 mm, crushing and resulting drift may occur under high temperature and high pressure reaction conditions for manufacturing neopentyl glycol, which is not preferred.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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 can optimize the content of Cu with oxidation number 2 and the specific surface area of ​​the catalyst by producing a molded catalyst by mixing a fiber-based binder and an organic compound, thereby preventing a decrease in the strength or reactivity of the catalyst even under high-temperature and high-pressure reaction conditions for a high neopentyl glycol production yield.

[0079] 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.

[0080] 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.

[0081] <Example>

[0082] <Example 1>

[0083] A copper precursor (Cu(NO3)2·3H2O) aqueous solution was prepared in a double-jacket reactor, and silica sol was added so that the weight ratio of Cu and Si was Cu:Si = 30:70. After adding a NaOH aqueous solution, aging was performed to prepare a coprecipitate. The coprecipitate was filtered and washed with distilled water, and the wet cake obtained thereby was dried. The dried material was pulverized to prepare a catalyst intermediate powder.

[0084] Based on the total weight of the above catalyst intermediate powder, 25 wt% of an organic compound (20 wt% of isopropyl alcohol and 5 wt% of glycerin), 5 wt% of a fiber-based binder (ceramic wool, aluminum silicate component) and distilled water were mixed and extruded into cylindrical pellets having a diameter of 5 mm and a length of 5 mm through an extruder.

[0085] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to finally produce a catalyst for producing neopentyl glycol.

[0086] <Example 2>

[0087] A catalyst for producing neopentyl glycol was prepared in the same manner as in Example 1, except that a coprecipitate was prepared so that the weight ratio of Cu and Si was Cu:Si = 50:50.

[0088] <Example 3>

[0089] In the extrusion molding step, a catalyst for producing neopentyl glycol was manufactured in the same manner as in Example 1, except that 10 wt% of the fiber-based binder was applied instead of 5 wt% of the fiber-based binder.

[0090] <Comparative Example 1>

[0091] A catalyst for producing neopentyl glycol was manufactured in the same manner as in Example 1, except that in the extrusion molding step, the catalyst was extruded into cylindrical pellets having a diameter of 2.5 mm and a length of 10 mm instead of a diameter of 5 mm and a length of 5 mm.

[0092] <Comparative Example 2>

[0093] 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.

[0094] <Comparative Example 3>

[0095] 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.

[0096] <Experimental Example>

[0097] 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.

[0098] In addition, the crushing strength of the catalysts of the examples and comparative examples and the BET surface area according to nitrogen adsorption / desorption experiments were evaluated and are shown in Table 1 below.

[0099] In addition, the Cu(II) content according to XPS (X-ray Photoelectron Spectroscope) 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.

[0100] Additionally, the nitrogen adsorption / desorption isotherm for measuring the BET surface area of ​​the copper silicate catalyst according to Example 1 is shown in Figure 1 below.

[0101] The measurement method for the evaluation results described in Tables 1 and 2 below is as follows.

[0102] <Crushing strength>

[0103] 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.

[0104] 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.

[0105] <BET 표면적>

[0106] The above BET surface area was derived by measuring the amount of nitrogen adsorbed / desorbed according to the nitrogen partial pressure using the BET (Brunauer-Emmett-Teller) equation.

[0107] <Cu(II) 함량>

[0108] The above Cu(II) content was measured according to XPS (X-ray Photoelectron Spectroscope) analysis.

[0109] More specifically, the catalyst was pulverized to prepare a sample of a circular pellet having a diameter of 2 mm and a thickness of 1 mm, and the sample was measured using a monochromatic Al k-alpha X-ray α (1486.6 eV) having a size of 400 μm Х 800 μm. After deriving the first XPS spectrum (XPS spectrum before correction) by XPS (X-ray photoelectron spectroscopy) under the pass energy condition of 50 eV in the measurement range of 925 eV to 970 eV in a vacuum atmosphere, the second XPS spectrum (XPS spectrum after correction) was derived by correcting the peak of the XPS spectrum. The Cu (II) content refers to the relative ratio of the content of Cu atoms with an oxidation number of 2 derived from the second XPS spectrum described above.

[0110] <Experiment with Harshness>

[0111] 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 dissolution rate was calculated according to the following mathematical equation 1, and the strength reduction rate of the catalyst was calculated according to the following mathematical equation 2.

[0112] [Mathematical Formula 1]

[0113] 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

[0114] [Equation 2]

[0115] Strength reduction rate (%) = (Initial catalyst crushing strength - Catalyst crushing strength after harshness test) / Initial catalyst crushing strength Х 100

[0116] [Table 1]

[0117]

[0118] [Table 2]

[0119]

[0120] 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 content of oxidation number 2 in the range of 2 at% to 6 at% according to XPS (X-ray Photoelectron Spectroscope) analysis, and thus were confirmed to have excellent catalytic activity compared to the catalysts of Comparative Examples 1 and 2.

[0121] The catalyst for producing neopentyl glycol of Comparative Example 1 was manufactured as cylindrical pellets of a smaller size than the examples, and it was confirmed that the catalyst strength was weak and that Si was easily eluted, resulting in low physical stability. In addition, in Comparative Example 2, it was confirmed that the catalyst strength and catalytic activity decreased when a fiber-based binder was not used.

[0122] 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.

[0123] 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 weight ratio of Cu:Si of the above copper silicate catalyst is 30:70 to 70:30, The Cu content of oxidation number 2 according to XPS (X-ray Photoelectron Spectroscope) analysis of the above copper silicate catalyst is 2 at% to 6 at%, A copper silicate catalyst having a shape of a cylindrical pellet having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm.

2. In claim 1, the specific surface area of the copper silicate catalyst is 1 m 2 / g to 200 m 2 A copper silicate catalyst having a / g content.

3. A copper silicate catalyst according to claim 1, wherein the crushing strength of the copper silicate catalyst is 40 N or more.

4. In claim 1, 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 5. 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 6. In claim 1, the copper silicate catalyst is a copper silicate catalyst for producing neopentyl glycol.

7. 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 and drying the above-mentioned precipitate slurry to produce a dried product; A step of manufacturing a catalyst precursor by mixing a fiber-based binder and an organic compound into the above-mentioned dry material and then molding the mixture into cylindrical pellets having a diameter of 3 mm to 6 mm and a height of 3 mm to 9 mm; and 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 6.

8. A method for producing a copper silicate catalyst according to claim 7, wherein the alkaline precipitant comprises at least one of NH4OH, (NH4)2CO3, NH4HCO3, CH4N2O, NaOH, and Na2CO3.

9. A method for producing a copper silicate catalyst according to claim 7, 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 7, 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.

11. A method for producing a copper silicate catalyst according to claim 7, 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 method for producing a copper silicate catalyst according to claim 7, wherein the content of the organic compound is 0.1 wt% to 50 wt% based on the total weight of the dried product.

13. 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 catalyst according to any one of claims 1 to 6.

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