Method for manufacturing a catalyst and the catalyst produced thereby

Abstract

The present invention provides a method for manufacturing a catalyst that minimizes the content of impurities by adding a repulping step during the washing stage, and a catalyst manufactured thereby. [Solution] The present invention discloses a method for producing a catalyst, comprising: (a) the step of producing a first slurry by deposition-precipitation of an active metal precursor on a support; (b) the step of filtering the first slurry to obtain a first catalyst cake; (c) the step of primary repulping the first catalyst cake to produce a second slurry; (d) the step of filtering the second slurry to obtain a second catalyst cake; (e) the step of secondary repulping the second catalyst cake to produce a third slurry; (f) the step of filtering the third slurry to obtain a third catalyst cake; and (g) the step of drying and calcining the third catalyst cake. According to the present invention, the content of impurities can be minimized, high activity and a large surface area can be ensured by the deposition-precipitation (DP) method, and the activity of the catalyst for the hydrogenation reaction can be improved.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a catalyst and a catalyst manufactured thereby. More specifically, the present invention can minimize the content of impurities by adding a repulping step, can ensure high activity and a large surface area by the deposition-precipitation (DP) method, and relates to a method for manufacturing a catalyst capable of improving the activity of a catalyst for a hydrogenation reaction and a catalyst manufactured thereby.

Background Art

[0002] Hydrogenation catalysts can be manufactured by the deposition-precipitation (DP) method. When using the DP method, the metal can be uniformly dispersed on the support to ensure high activity and a large surface area. In addition, by using a carrier with adjusted particle size, the catalyst particle size can be maintained small, the catalyst life can be extended, and a uniform reaction is possible even under high temperature and high pressure conditions, so there is an advantage of obtaining a catalyst that acts stably in the hydrogenation reaction.

[0003] Particularly, when manufacturing a catalyst by the DP method, precipitating agents such as Na2CO3, NaOH, and NaHCO3 are required. If Na, which is an impurity in the catalyst, remains, the hydrogenation activity of the catalyst decreases. Therefore, it is necessary to sufficiently remove Na, which is an impurity, in the filtration and washing processes after precipitation.

[0004] In order to solve this problem, it is necessary to develop a method for manufacturing a catalyst with minimized impurity content and improved activity and a catalyst manufactured thereby.

[0005] As a related prior art, there is Korean Patent Publication No. 10-2014-0096279.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] The object of the present invention is to provide a method for producing a catalyst that can minimize the content of impurities by adding a repulping step during the washing stage, and a catalyst produced thereby.

[0008] Another object of the present invention is to provide a method for producing a catalyst that can ensure high activity and a large surface area by deposition-precipitation (DP), and a catalyst produced thereby.

[0009] Another object of the present invention is to provide a method for producing a catalyst that uses a carrier with a uniform particle size distribution, has a uniform catalyst particle size distribution, can extend catalyst life, and can improve the activity of the catalyst for hydrogenation reactions, and a catalyst produced by the same method.

[0010] All of the aforementioned and other objectives of the present invention can be achieved by the present invention as described below. [Means for solving the problem]

[0011] 1. One aspect of the present invention relates to a method for producing a catalyst. The method includes: (a) a step of producing a first slurry by deposition-precipitation of an active metal precursor on a support; (b) a step of filtering the first slurry to obtain a first catalyst cake; (c) a step of producing a second slurry by primary repulping the first catalyst cake; (d) a step of filtering the second slurry to obtain a second catalyst cake; (e) a step of producing a third slurry by secondary repulping the second catalyst cake; (f) a step of filtering the third slurry to obtain a third catalyst cake; and (g) a step of drying and calcining the third catalyst cake.

[0012] 2. In the specific example of 1 above, the active metal precursor can include a nickel compound.

[0013] 3. In the specific examples of 1 - 2 above, the active metal precursor can further include a copper compound.

[0014] 4. In the specific examples of 1 - 3 above, the carrier can include silica powder.

[0015] 5. In the specific examples of 1 - 4 above, the deposition - precipitation in step (a) can include the step of stirring and heating to 60°C - 100°C.

[0016] 6. In the specific examples of 1 - 5 above, the primary repulping in step (c) can be carried out at 60°C - 80°C.

[0017] 7. In the specific examples of 1 - 6 above, the pH of the first slurry can be 7 - 9.

[0018] 8. In the specific examples of 1 - 7 above, the drying in step (g) can be carried out at 100°C - 200°C.

[0019] 9. In the specific examples of 1 - 8 above, the firing in step (g) can be carried out at 300°C - 400°C.

[0020] 10. In the specific examples of 1 - 9 above, after step (g), it can further include the step of reducing in a hydrogen atmosphere at 200°C - 500°C.

[0021] 11. In the specific examples of 1 - 10 above, after the reduction, it can further include the step of passivating to form a passivation layer.

[0022] 12. In the specific examples of 1 - 11 above, the passivation can be carried out on the reduced product with a nitrogen mixed gas containing 0.1 vol% - 20 vol% oxygen.

[0023] 13. Another aspect of the present invention relates to a catalyst produced by the methods of the above specific examples 1 to 12, wherein the Na content in the catalyst is 200 ppm or less.

[0024] 14. In the specific example of 13 above, the specific surface area of the catalyst can be 150 m / g to 300 m 2 / g.

[0025] 15. In the specific examples of 13 to 14 above, the catalyst can be used in the hydrogenation reaction of petroleum resin.

Effects of the Invention

[0026] The present invention can minimize the content of impurities by adding a repulping step in the washing stage, can ensure high activity and a large surface area by the deposition-precipitation (DP) method, can make the catalyst particle size distribution uniform by using a carrier with a uniform particle size distribution, can extend the catalyst life, and can improve the activity of the catalyst for hydrogenation reaction.

Modes for Carrying Out the Invention

[0027] Hereinafter, the present invention will be described in more detail. When terms such as "comprising", "having", "becoming", etc. mentioned in this specification are used, other parts may be added unless "only" is used. When a component is expressed in the singular, it may include a plurality unless otherwise explicitly stated.

[0028] In interpreting components, it is to be interpreted as including the range of error even without separate explicit description.

[0029] In the present invention, repulping is a process of redispersing the catalyst cake in a solvent and stirring.

[0030] Hereinafter, the method for producing a catalyst according to an embodiment of the present invention and the catalyst produced thereby will be specifically described.

[0031] One aspect of the present invention relates to a method for producing a catalyst.

[0032] The method includes (a) the step of depositing and precipitating an active metal precursor onto a support to produce a first slurry; (b) filtering the first slurry to obtain a first catalyst cake; (c) primary repulping the first catalyst cake to produce a second slurry; (d) filtering the second slurry to obtain a second catalyst cake; (e) secondary repulping the second catalyst cake to produce a third slurry; (f) filtering the third slurry to obtain a third catalyst cake; and (g) drying and calcining the third catalyst cake. The method may further include, after step (g), (h) reduction in a hydrogen atmosphere at 200°C to 500°C; and (i) immobilization after reduction to form an immobilization layer.

[0033] The method for producing the catalyst according to the present invention will be described in detail step by step below.

[0034] The above method employs a deposition-precipitation method using a compound with a uniform particle size distribution as a carrier. The carrier may include silica powder. In this method, a precursor salt solution containing a nickel compound or copper compound, which are active metal precursors, reacts in a carrier dispersion to form a precipitate, which can then be adsorbed and solidified on the carrier surface. When using this method, it is easier to select and optimize a carrier having appropriate particle size, size distribution, surface area, porosity structure, etc.

[0035] The deposition-precipitation step (a) may include stirring and raising the temperature to 60°C to 100°C. The deposition-precipitation (DP) method can ensure high activity and a large surface area. In specific examples, the temperature can be 65°C to 95°C, for example, 70°C to 90°C. Within this range, the activity of the hydrogenation catalyst can be improved.

[0036] When the nickel compound and copper compound are added and the catalyst composition is supported on a silica support by a deposition-precipitation method, a high nickel content can be achieved, resulting in smaller nickel crystals and improved activity of the hydrogenation reaction catalyst.

[0037] The nickel compound precursor includes metal salts such as oxides, nitrates, acetates, sulfates, and chlorides, and preferably, it can be a nickel sulfate precursor containing a sulfate. When the nickel compound is used, the activity of the hydrogenation reaction catalyst can be improved.

[0038] The copper compound precursor includes metal salts such as oxides, nitrates, acetates, sulfates, and chlorides, and preferably, it can be a copper sulfate precursor. When the copper compound is used, its high catalytic activity may be advantageous for the hydrogenation reaction.

[0039] The nickel compound and copper compound may be included as active substances in amounts of 50 parts by weight or more, specifically 60 parts by weight or more, for example, 65 to 80 parts by weight, per 100 parts by weight of the total catalyst.

[0040] The silica support is used as a support, and the catalyst produced using silica with a uniform particle size distribution has a uniform particle size distribution, which can extend the life of the catalyst and may have excellent activation effects on nickel compounds and copper compounds. The silica support may be present in amounts of 10 to 50 parts by weight, specifically 15 to 45 parts by weight, or for example, 20 to 40 parts by weight, per 100 parts by weight of the total catalyst.

[0041] The pH of the first slurry in step (a) above may be 7 to 9. The precipitate can be formed at a pH of 7 to 9 by adding a basic compound or by electrochemical means. The basic compound may include, but is not limited to, Na2CO3, NaOH, NaHCO3, NH3, their hydrates, or combinations thereof.

[0042] Before filtering the first slurry, aging can be performed for 0.5 to 2 hours. In specific examples, aging can be performed for 0.8 to 1.8 hours, or for example, 1 to 1.5 hours. Within this range, the formation of uniform particles becomes possible.

[0043] Step (b) above removes the solvent and impurities used in the reaction through filtration and uniformly adjusts the particle size of the catalyst, thereby increasing the activity and reactivity of the catalyst. Furthermore, after filtration, the resulting catalyst cake can be easily reused after post-treatment such as drying, calcination, and reduction, or adjusted to a form with the desired properties.

[0044] In step (b) above, the first slurry can be filtered to obtain the first catalyst cake. The first slurry is a mixture in which particles are dispersed and can be filtered using a pressure filter, gravity filter, membrane filter, vacuum filter, etc., preferably a vacuum filter.

[0045] Step (c) involves dispersing the first catalyst cake in a solvent and then stirring it to dissolve impurities present inside the catalyst cake into the solvent, thereby separating the impurities and residual reaction by-products. In specific examples, the solvent may include distilled water, ethanol, or an organic solvent.

[0046] More specifically, the primary repulping involves adding the first catalyst cake to a stirrer containing the solvent, dispersing it uniformly, and then stirring. During stirring, impurities dissolve into the solvent, and the solvent containing the impurities can then be removed by filtration. The primary repulping effectively separates and removes impurities and residual reaction by-products remaining on the catalyst surface, maximizing the cleaning effect.

[0047] The primary repulping can be carried out by stirring at a speed of 300 rpm to 1000 rpm for 0.5 to 2 hours at a temperature of 60°C to 80°C. In a specific example, it can be carried out by stirring at a speed of 400 rpm to 900 rpm, for example, 500 rpm to 800 rpm, for 0.5 to 1.2 hours, for example, 0.7 to 1.0 hours at a temperature of 62°C to 78°C, for example, 65°C to 75°C. Within this range, the catalyst particles can be uniformly dispersed in the solvent, improving the activity of the catalyst for the hydrogenation reaction. Furthermore, within this range, the Na content in the catalyst can be reduced to 160 ppm or less, for example, 100 ppm or less, preferably 50 ppm or less.

[0048] If sodium (Na), an impurity in the catalyst, remains, the hydrogenation activity of the catalyst decreases. Therefore, it is necessary to thoroughly remove the sodium impurity during the filtration and washing process after precipitation. The present invention is characterized by thoroughly washing the catalyst cake by repeating the filtration and repulping process three or more times. That is, the second slurry produced after the primary repulping is filtered to obtain a second catalyst cake, the third slurry produced by secondary repulping of the second catalyst cake is filtered to obtain a third catalyst cake, and the third catalyst cake is dried and calcined. The filtration and repulping process has been described in detail and will be omitted below. In other words, by adding a repulping step at the washing stage, the content of sodium-containing impurities can be minimized. In a specific example, the sodium content in the catalyst can be 200 ppm or less, for example, 100 ppm or less, preferably 50 ppm or less.

[0049] The drying in step (g) can be carried out using a drying oven at 100°C to 200°C for 5 to 24 hours. In specific examples, it can be carried out at 120°C to 180°C, for example, 140°C to 160°C. In other specific examples, it can be carried out for 8 to 20 hours, for example, 10 to 18 hours. Within this range, the activity of the hydrogenation reaction catalyst can be improved.

[0050] The calcination in step (g) above can be performed by filtering the powder with a standard to a constant particle size after drying to ensure uniform particles for optimal reactivity. The sieved powder can then be divided into smaller portions. This division allows for uniform distribution of the powder, improving the heat treatment efficiency during calcination. Subsequently, the reaction during calcination fills the interior with hydrogen, creating a reducing atmosphere. This hydrogen atmosphere promotes reduction and activates the metal surface. After that, calcination can be performed at 300°C to 400°C for 1 to 5 hours. In specific examples, it can be performed at 320°C to 380°C, for example, 340°C to 360°C. Also, in specific examples, it can be performed for 1.5 to 4 hours, for example, 2 to 4 hours. Within this range, the structure and performance of the catalyst surface can be optimized to improve the activity of the catalyst for the hydrogenation reaction.

[0051] In step (h) above, after the firing is complete, hydrogen is filled into the interior by the reaction to create a reducing atmosphere, and reduction can be carried out at 200°C to 500°C for 1 to 4 hours. In specific examples, it can be carried out at 300°C to 400°C, for example, 350°C to 450°C. Also in specific examples, it can be carried out for 1.5 to 3.5 hours, for example, 2 to 3 hours. Within the above range, the activity of the hydrogenation reaction catalyst can be improved.

[0052] In step (i) above, after reduction, the temperature is gradually lowered by the reaction, and immobilization can be carried out for 1 to 3 hours by slowly injecting an immobilizing gas at approximately 25°C to 50°C. The immobilizing gas can contain a mixture of nitrogen and oxygen, and by adjusting the oxygen concentration using this mixture, a thin, uniform oxide layer can be formed. In specific examples, this can be carried out for 1.5 to 2.5 hours, for example, 1.8 to 2.3 hours. Within this range, the activity of the hydrogenation catalyst can be improved.

[0053] The immobilization in step (i) above can be carried out with a nitrogen gas mixture containing 0.1% to 20% by volume of oxygen. In specific examples, the oxygen may be 0.5% to 15% by volume, for example, 1% to 10% by volume, preferably 1% to 5% by volume. Within this range, a catalyst that acts stably in the hydrogenation reaction can be produced.

[0054] Another aspect of the present invention relates to a catalyst produced by the method described above, wherein the Na content in the catalyst is 200 ppm or less.

[0055] In a specific example, the Na content in the catalyst can be 160 ppm or less, for example, 100 ppm or less, preferably 50 ppm or less, and more preferably 0.5 ppm to 20 ppm or less.

[0056] The catalyst has a specific surface area of ​​150 m². 2 / g~300m 2 It can be / g. In a specific example, the specific surface area is 170m². 2 / g~280m 2 / g, for example 190m 2 / g~260m 2 It can be as low as / g. Within the aforementioned range, the activity of the catalyst can be improved.

[0057] The catalyst can be used in the hydrogenation reaction of petroleum resins. In specific examples, the petroleum resin may include, but is not limited to, petroleum resins containing C5 oil, petroleum resins containing C9 oil, by-products, and combinations thereof obtained by distillation, pretreatment, and polymerization.

[0058] The present invention will be described in more detail below with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples. [Examples]

[0059] Example 1 12 g of amorphous silica powder, 168 g of nickel sulfate, 2 g of copper sulfate, and 600 ml of distilled water were placed in a precipitation vessel, stirred, and heated to 80°C. After reaching 80°C, 500 ml of a precipitant solution containing 87 g of sodium carbonate was injected entirely into the raw material solution reactor using a syringe pump over a period of 1 hour. After precipitation was complete, the slurry pH was 8.5, and it was aged for 1 hour to ensure uniform particle formation. Subsequently, the slurry containing the catalyst cake was filtered using a vacuum filter. The filtered catalyst cake was redispersed in 2 L of distilled water, stirred for 30 minutes, and repulped at 70°C. The slurry containing the repulped catalyst cake was then filtered using a vacuum filter. The filtration and repulping process was repeated three times to thoroughly wash the catalyst cake. The catalyst cake was then dried in a drying oven at 105°C for at least 12 hours. After drying, the sample was filtered to a constant particle size using a standard, then divided into smaller portions and calcined at 350°C in an air atmosphere. These portions were then divided again and reduced at 400°C in a hydrogen atmosphere. Following reduction, the nickel-based catalyst was produced by immobilization using a nitrogen gas mixture containing 1% by volume of oxygen.

[0060] Examples 2-3 After precipitation was complete, the catalyst cake was thoroughly washed by repeating the filtration and repulping process, as in Example 1, and then dried and calcined before being reduced and immobilized to produce a nickel-based catalyst.

[0061] Comparative Example 1 The catalyst cake was manufactured in the same manner as in Example 1, except that the process of washing the catalyst cake by filtration and repulping after precipitation was omitted.

[0062] Comparative Examples 2-3 The catalyst cake was prepared in the same manner as in Example 1, except that the filtration and precipitation process was performed once to adequately wash it.

[0063] The physical properties of the examples and comparative examples were evaluated using the following method, and the results are shown in Table 1:

[0064] Methods for evaluating physical properties (1)ICP-AES analysis For ICP-AES analysis, the catalyst was completely dissolved using nitric acid and hydrofluoric acid, and the resulting solution was diluted 500-fold. The content of Na, an impurity in the catalyst, was then measured by ICP-AES analysis.

[0065] (2) Experiments on catalyst activity A 75g solution was prepared by dissolving a non-hydrogenated petroleum resin in Esol D15 at a concentration of 30% by weight. Subsequently, a hydrogenation reaction was carried out at 230°C and 80 bar with the addition of a catalyst prepared at a concentration of 0.5% relative to the mass of the petroleum resin for 1 hour. After the reaction, the petroleum resin underwent a degassing process, and the content of aromatics, olefins, and alphatic components was analyzed by 1H-NMR. The catalyst activity (%) was calculated according to the degree of saturation of the unsaturated bonds of the aromatics and olefins.

[0066] The hydrogenation reaction was carried out using a 300 mL autoclave equipped with a hollow shaft stirrer and having a stirring speed of 1,200 rpm.

[0067] [Table 1]

[0068] As shown in Table 1 above, Examples 1 to 3 have a Na content of less than 200 ppm in the finished catalyst and demonstrate high catalytic activity. On the other hand, Comparative Examples 1 to 3 have a very high Na content in the finished catalyst and demonstrate low catalytic activity.

[0069] Simple modifications and alterations of the present invention can be readily carried out by a person with ordinary skill in the art, and all such modifications and alterations can be considered to fall within the scope of the present invention.

Claims

1. (a) A step of preparing a first slurry by depositing and precipitating an active metal precursor on a support; (b) The step of filtering the first slurry to obtain the first catalyst cake; (c) The step of producing a second slurry by primary repulping the first catalyst cake; (d) The step of filtering the second slurry to obtain a second catalyst cake; (e) The step of producing a third slurry by secondary repulping of the second catalyst cake; (f) The step of filtering the third slurry to obtain a third catalyst cake; and (g) A method for producing a catalyst, comprising the step of drying and baking the third catalyst cake.

2. The method for producing a catalyst according to claim 1, wherein the activated metal precursor contains a nickel compound.

3. The method for producing a catalyst according to claim 1, wherein the activated metal precursor further comprises a copper compound.

4. The method for producing a catalyst according to claim 1, wherein the carrier contains silica powder.

5. The method for producing a catalyst according to claim 1, wherein the deposition-precipitation in step (a) includes a step of stirring and raising the temperature to 60°C to 100°C.

6. The method for producing a catalyst according to claim 1, wherein the primary repulping in step (c) is carried out at 60°C to 80°C.

7. The method for producing a catalyst according to claim 1, wherein the pH of the first slurry is 7 to 9.

8. The method for producing a catalyst according to claim 1, wherein the drying in step (g) is carried out at 100°C to 200°C.

9. The method for producing a catalyst according to claim 1, wherein the calcination in step (g) is carried out at 300°C to 400°C.

10. A method for producing a catalyst according to claim 1, further comprising the step of reducing the catalyst in a hydrogen atmosphere at 200°C to 500°C after step (g).

11. A method for producing a catalyst according to claim 10, further comprising the step of immobilizing the catalyst after reduction to form an immobilized layer.

12. The method for producing a catalyst according to claim 11, wherein the immobilization is carried out with a nitrogen mixed gas containing 0.1% to 20% by volume of oxygen as the reducing agent.

13. A catalyst manufactured by the method described in any one of claims 1 to 12, A catalyst having a Na content of 200 ppm or less.

14. The specific surface area of ​​the catalyst is 150 m². ２ / g to 300m ２ The catalyst according to claim 13, wherein the amount is / g.

15. The catalyst according to claim 13, wherein the catalyst is used in the hydrogenation reaction of petroleum resin.

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