Copper silicate-based catalyst and manufacturing method therefor

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, and the Si leaching ratio of the copper silicate-based catalyst after harsh testing according to 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. 10-2024-0009940, 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, separation by simple distillation is impossible. In addition, HPNE is unstable when distilling the reaction mixture, reducing the yield of NPG. Therefore, commercially, sodium hydroxide is added to convert it to NPG through saponification. 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] 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.

[0012] [Method 1]

[0013] 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 2.

[0014] [Equation 2]

[0015] 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

[0016] In addition, another embodiment of the present application is

[0017] A step of preparing a coprecipitate slurry by adding silica sol and an alkaline precipitant to an aqueous solution containing a copper precursor;

[0018] 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;

[0019] A step of drying the filtered precipitate slurry at a temperature of 80°C to 90°C to produce a dried product;

[0020] A step of forming the above-mentioned dried product 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, thereby preventing 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 content of CuO crystal phase and the content of Cu of the catalyst can be optimized by controlling the aging conditions of the coprecipitate slurry, the alkaline precipitant injection conditions, and the drying conditions of the filtered coprecipitate slurry.

[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 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 does not mean that it excludes other components, but rather that it may include 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, the crushing strength of the copper silicate catalyst is 40 N or more, 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 formula 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] 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.

[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 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] In one embodiment of the present application, the content of the CuO crystal phase according to the XRD (X-Ray Diffraction) analysis of the copper silicate-based catalyst may be 1 wt% to 35 wt%, 10 wt% to 34 wt%, or 26 wt% to 34 wt%. When the content of the CuO crystal phase is outside the above-mentioned range during the XRD (X-Ray Diffraction) analysis of the copper silicate-based catalyst, a decrease in catalytic activity may occur due to a change in the catalyst crystal phase, which is not preferable.

[0050] A specific method for measuring the content of CuO crystal phase according to XRD (X-Ray Diffraction) analysis of the above copper silicate catalyst is described in the examples described below.

[0051] In one embodiment of the present application, the Cu content of the copper silicate catalyst according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis may be 26 wt% to 40 wt%, 27 wt% to 35 wt%, or 28 wt% to 34 wt%. If the Cu content range described above is exceeded during ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis of the copper silicate catalyst, the catalytic active component may be insufficient or excessive, which may reduce dispersibility and thus cause a decrease in catalytic activity, which is not preferable.

[0052] A specific method for measuring the Cu content of the above copper silicate catalyst according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis is described in the examples described below.

[0053] In one embodiment of the present application, the bulk density of the copper silicate catalyst may be 500 g / L to 800 g / L, 520 g / L to 750 g / L, or 551 g / L to 595 g / L. If the bulk density of the copper silicate catalyst is less than 500 g / L, the physical stability of the catalyst may be low, making stable process operation difficult, which is not preferable. In addition, if the bulk density of the copper silicate catalyst exceeds 800 g / L, the catalytic activity may be lowered due to a decrease in the dispersibility of the active component, which is not preferable.

[0054] A specific method for measuring the bulk density of the above copper silicate catalyst is described in the examples described below.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] In one embodiment of the present application, the copper silicate catalyst may be used for producing neopentyl glycol.

[0059] 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; molding the dried product 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] A method for producing a copper silicate catalyst according to one embodiment of the present application may further include a step of mixing a fiber-based binder and an organic compound into the dried material after the step of producing the dried material.

[0071] 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.

[0072] 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 3 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 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.

[0073] 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 7 wt% to 25 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.

[0074] 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.

[0075] 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 molding the above-described dried product.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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, thereby preventing a decrease in catalyst strength or reactivity even under high-temperature and high-pressure reaction conditions for a high neopentyl glycol production yield.

[0086] In addition, according to one embodiment of the present application, the ratio of CuO crystal phase and the content of Cu of the catalyst can be optimized by controlling the aging conditions of the coprecipitate slurry, the alkaline precipitant injection conditions, and the drying conditions of the filtered coprecipitate slurry.

[0087] 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.

[0088] 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.

[0089] <Example>

[0090] <Example 1>

[0091] While maintaining the temperature of the double jacket reactor at 15°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 = 35:65. While maintaining the temperature at 15°C, a NaOH aqueous solution was added, and 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.

[0092] 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 a cylindrical shape with a diameter of 3 mm to 5 mm and a height of 3 mm to 9 mm through an extruder.

[0093] The above extruded catalyst intermediate was calcined at 550°C for 8 hours to finally produce a catalyst for producing neopentyl glycol.

[0094] The copper silicate catalyst manufactured in Example 1 is shown in Figure 1 below.

[0095] <Example 2>

[0096] 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 35°C and the temperature at which the NaOH aqueous solution was introduced was adjusted to 35°C.

[0097] <Example 3>

[0098] In the extrusion molding step, a catalyst for producing neopentyl glycol was manufactured in the same manner as in Example 2, except that instead of applying 25 wt% of the organic compound and 5 wt% of the fiber-based binder, 7 wt% of the organic compound (5 wt% of isopropyl alcohol and 2 wt% of glycerin) and 3 wt% of the fiber-based binder were applied.

[0099] <Comparative Example 1>

[0100] 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 10°C and the temperature at which the NaOH aqueous solution was introduced was adjusted to 10°C.

[0101] Comparative Example 2

[0102] 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 40°C and the temperature at which the NaOH aqueous solution was introduced was adjusted to 40°C.

[0103] <Comparative Example 3>

[0104] A catalyst for producing neopentyl glycol was prepared in the same manner as in Example 1, except that instead of aging at 80°C for 3 hours, aging was performed at 55°C for 3 hours.

[0105] Comparative Example 4

[0106] 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.

[0107] Comparative Example 5

[0108] 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.

[0109] Comparative Example 6

[0110] 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.

[0111] <Comparative Example 7>

[0112] 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.

[0113] Comparative Example 8

[0114] 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.

[0115] <Experimental Example>

[0116] 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.

[0117] In addition, the crushing strength and bulk density of the catalysts of the examples and comparative examples were evaluated and are shown in Table 1 below.

[0118] In addition, the content of CuO crystal phase according to XRD (X-Ray Diffraction) analysis of the catalysts of the examples and comparative examples, the content of Cu according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis, and the Si elution rate and strength reduction rate according to the harshness test were evaluated and shown in Table 2 below.

[0119] The measurement method for the evaluation results described in Tables 1 and 2 below is as follows.

[0120] <Crushing strength>

[0121] 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 section was lowered from above to press against the catalyst. The maximum pressure value corresponding to the peak pressure value generated at this moment was used. Twenty catalysts were individually measured using the same method and the average value was calculated.

[0122] 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.

[0123] Bulk density

[0124] The bulk density was measured using the apparent density. More specifically, the weight of an empty graduated cylinder was measured, then 100 cc of catalyst was added, and the weight was measured. The difference in weight was then divided by the volume of the catalyst, resulting in the calculated value.

[0125] <CuO 결정상 함량>

[0126] The above CuO crystal phase content was measured by XRD (X-Ray Diffraction) analysis. More specifically, it was measured using a D8 Endeavor equipment from Bruker. 10 wt% of heat-treated MgO was added to the catalyst as a spike for quantitative determination, ground into fine powder, placed in an XRD measurement holder, and the sample was prepared by adjusting the height to the edge of the holder to ensure an even surface. The 2theta 10 to 90 degree region was measured every 0.03 for 1.5 seconds. The crystal phases present in the sample were identified by comparison with the database, and the relative content of the CuO crystal phase was measured by performing Rietveld refinement using the complete structure model.

[0127] <Cu 함량>

[0128] The above Cu content was measured according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis. More specifically, it was measured using Optima 8300DV equipment from Perkin Elmer. Accurately weighed catalyst and 2 mL of nitric acid were placed in a platinum crucible and completely dissolved. Then, 1,000 ppm of internal standard substance Sc, 0.1 mL was added, and the mixture was diluted to 10 mL with ultrapure water. The concentration of the sample prepared in this way was measured, and the Cu content was calculated according to the following mathematical equation 1.

[0129] [Mathematical Formula 1]

[0130] Cu content (wt%) = measured concentration (μg / mL) Х dilution volume (mL) / weight of catalyst (μg) Х 100

[0131] <Experiment with Harshness>

[0132] 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).

[0133] [Equation 2]

[0134] 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

[0135] [Equation 3]

[0136] Crushing strength reduction rate (%) = (Crushing strength of initial catalyst - Crushing strength of catalyst after harshness test) / Crushing strength of initial catalyst Х 100

[0137] [Table 1]

[0138]

[0139] [Table 2]

[0140]

[0141] 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 7, as the Si elution ratio after the harshness test was in the range of 5 wt% or less.

[0142] In the neopentyl glycol production catalyst of Comparative Example 1, it can be confirmed that the particle size of the coprecipitate is unsuitable due to the low alkaline precipitant injection and maintenance temperature, which weakens the strength of the catalyst and causes a decrease in physical stability due to Si elution. In addition, in the neopentyl glycol production catalyst of Comparative Example 2, it can be confirmed that the neutralization heat is not controlled due to the high alkaline precipitant injection and maintenance temperature, which reduces the catalytic activity. In addition, in the neopentyl glycol production catalysts of Comparative Examples 3 and 4, it can be confirmed that the unreacted copper precursor occurs due to the aging temperature conditions, which reduces the catalytic activity and weakens the physical stability. In addition, in the neopentyl glycol production catalyst of Comparative Example 5, it can be confirmed that the catalytic activity and physical stability are reduced due to a change in the crystal phase of the catalyst precursor due to the high drying temperature. In addition, in Comparative Examples 6 and 7, it can be confirmed that the catalyst strength and catalytic activity are reduced when a fiber-based binder is not used.

[0143] 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.

[0144] 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, 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. A copper silicate catalyst according to claim 1, wherein the content of the CuO crystal phase according to XRD (X-Ray Diffraction) analysis of the copper silicate catalyst is 1 wt% to 35 wt%.

4. A copper silicate catalyst according to claim 1, wherein the copper silicate catalyst has a Cu content of 26 wt% to 40 wt% according to ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer) analysis.

5. A copper silicate catalyst according to claim 1, wherein the bulk density of the copper silicate catalyst is 500 g / L to 800 g / L.

6. 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.

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

8. 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 forming the above-mentioned dried product 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 7, wherein the temperature is maintained at 15°C to 35°C when the alkaline precipitant is added.

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

10. A method for producing a copper silicate catalyst according to claim 8, further comprising a step of mixing a fiber-based binder and an organic compound into the dried material after the step of producing the dried material.

11. A method for producing a copper silicate catalyst according to claim 10, 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.

12. A method for producing a copper silicate catalyst according to claim 10, 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.

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

14. A method for producing a copper silicate catalyst according to claim 10, 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.

15. 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 7.

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