Catalyst for hydrogenation reaction with improved sulfur tolerance and method for producing the same

Abstract

The present invention relates to a hydrogenation catalyst having improved sulfur resistance and a method for preparing the same. More specifically, the present invention includes cerium and copper, and can improve sulfur resistance, i.e. poisoning resistance, thereby extending catalyst life and improving activity, which is applicable to the hydrogenation reaction of petroleum resins.

Description

[Technical Field]

[0001] The present invention relates to a hydrogenation catalyst having improved sulfur resistance and a method for preparing the same. More specifically, the present invention relates to a catalyst containing cerium and copper that can improve sulfur resistance, i.e., poisoning resistance, thereby extending catalyst life and improving activity, and is intended to apply the catalyst to the hydrogenation of petroleum resins. [Background technology]

[0002] Naphtha cracking is an important process for producing basic intermediates such as lower olefins (i.e., ethylene, propylene, butylene, and butadiene) and aromatic compounds (i.e., benzene, toluene, and xylene), which are widely used in the petrochemical and chemical industries. Thermal cracking, or steam pyrolysis, is a major type of process for forming these compounds, typically in the presence of steam and the absence of oxygen. Feedstocks can include petroleum gases and distillates such as kerosene and gas oil, in addition to naphtha. Thermal cracking of naphtha and other crude oils can produce substances such as C4 oils containing ethylene, propylene, butane, and butadiene; cracked gasoline (containing benzene, toluene, and xylene); C5 oils containing dicyclopentadiene (DCPD); C8 oils; cracked kerosene (C9 or higher oils); cracked heavy oils (ethylene residues, bottom oils); and hydrogen gas. Petroleum resins can also be produced by polymerization of these oils.

[0003] Specifically, the C5 oil refers to petroleum fractions, by-products, and combinations thereof obtained through petroleum pretreatment, distillation, polymerization, etc., and refers to unsaturated hydrocarbons with a carbon number of 5, such as cyclopentadiene, isoprene, and piperylene; the C8 oil refers to petroleum fractions, by-products, and combinations thereof obtained through petroleum pretreatment, distillation, and polymerization, etc., and refers to unsaturated hydrocarbons with a carbon number of 8, such as styrene and octene; and the C9 oil refers to petroleum fractions, by-products, and combinations thereof obtained through petroleum pretreatment, distillation, and polymerization, etc., and refers to unsaturated hydrocarbons with a carbon number of 9, such as vinyltoluene and indene. Polymerized petroleum resins contain double bonds in the aromatic moiety (hereinafter referred to as "aromatic double bonds") and double bonds in the aliphatic moiety (hereinafter referred to as "olefinic double bonds"). A high content of olefinic double bonds can lead to a yellowish color and a foul odor, which can degrade the quality of the petroleum resin. A hydrogenation process, in which hydrogen is added to the olefinic double bonds, can saturate the unsaturated double bonds, brighten the color, and reduce the characteristic odor of petroleum resins, thereby improving the quality. The hydrogenation reaction of petroleum resins is typically carried out by contacting hydrogen and the reactants with a precious metal catalyst such as palladium (Pd) or platinum (Pt) or a nickel (Ni) transition metal catalyst.

[0004] During the hydrogenation of petroleum resins, sulfur poisoning from the petroleum resins can cause deactivation of the petroleum resin hydrogenation catalyst. Petroleum resin polymerization raw materials contain various organosulfur components, and the sulfur content of petroleum resins varies depending on the constituents and composition of the polymerization raw materials. For example, petroleum resins polymerized primarily from C5-based raw materials such as dicyclopentadiene (DCPD) contain sulfur at the 30 ppmw level, while petroleum resins polymerized from C9-based raw materials such as cracked kerosene can contain sulfur components in excess of 300 ppmw. As a result, catalysts with low sulfur resistance quickly lose activity during the hydrogenation reaction, resulting in reduced productivity of hydrogenated petroleum resins.

[0005] Therefore, in order to apply it to the hydrogenation reaction of sulfur-containing petroleum resins, it is necessary to secure a petroleum resin hydrogenation catalyst having excellent sulfur resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-57482 (2012.10.12) [Non-patent literature]

[0007] [Non-Patent Document 1] ACS Omega, 4(2019)P4770 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to solve all of the above problems.

[0009] An object of the present invention is to provide a hydrogenation catalyst having improved sulfur tolerance, i.e., improved resistance to sulfur poisoning by residual sulfur in the hydrogenation of petroleum resins, thereby improving catalyst activity and life.

[0010] Another object of the present invention is to provide a catalyst that has a high nickel content, a small crystal size, a uniform particle size distribution, and a high degree of dispersion, thereby providing excellent activity in a hydrogenation reaction. [Means for solving the problem]

[0011] The characteristic features of the present invention for achieving the above-mentioned object of the present invention and realizing the characteristic effects of the present invention, which will be described later, are as follows.

[0012] According to an embodiment of the present invention, there is provided a hydrogenation catalyst comprising, as catalytically active components, 40 to 80 parts by weight of nickel, 0.01 to 5 parts by weight of copper, and 0.05 to 5 parts by weight of cerium, and, as a support, 10 to 30 parts by weight of silica.

[0013] According to an embodiment of the present invention, there is provided a method for preparing a hydrogenation catalyst, the method including: preparing a first solution by dissolving a nickel precursor in a solvent to give a nickel weight concentration (g / L) of 25 to 100 in the solution; preparing a second solution by adding a copper precursor and a cerium precursor to the first solution to give a copper weight concentration (g / L) of 0.01 to 5 in the solution and a cerium weight concentration (g / L) of 0.05 to 5 in the solution; preparing a third solution by dispersing a silica carrier in the second solution to give a silica weight concentration (g / L) of 5 to 30 in the solution; adding the third solution to a precipitation vessel while stirring and heating the vessel to 50°C to 120°C; adding a pH adjuster to the heated third solution to precipitate the precursors on the silica carrier, thereby preparing a catalyst; washing, filtering, and drying the catalyst; and reducing and activating the dried catalyst.

[0014] According to an embodiment of the present invention, there is provided a method for hydrogenating a petroleum resin, comprising contacting the petroleum resin with hydrogen in the presence of the hydrogenation catalyst.

[0015] According to an embodiment of the present invention, there is provided a hydrogenated petroleum resin by the method for hydrogenating a petroleum resin. [Effects of the Invention]

[0016] According to the present invention, the resistance to sulfur poisoning caused by sulfur remaining in petroleum resin during the hydrogenation reaction of petroleum resin can be improved, and the activity and life of the catalyst can be improved.

[0017] According to the present invention, a catalyst having a high nickel content, a small crystal size, a uniform particle size distribution, and a high degree of dispersion can be provided for the hydrogenation reaction of petroleum resins. DETAILED DESCRIPTION OF THE INVENTION

[0018] (Best Mode for Carrying Out the Invention) The structure and operation of the present invention will be described in more detail below with reference to preferred embodiments of the present invention, which are presented as preferred examples of the present invention and should not be construed as limiting the present invention in any way.

[0019] The contents not described here can be easily understood by those skilled in the art, and therefore, the explanation thereof will be omitted.

[0020] Example 1 300m 237.5 g of porous silica powder with a surface area of ​​1 / g and an average particle size of 7 μm and 1875 mL of a solution of nickel nitrate (60 g / L nickel), copper nitrate (0.8 g / L copper), and cerium nitrate (1.5 g / L cerium) dissolved in distilled water were placed in a precipitation vessel and stirred. The vessel was heated to 80°C. After the temperature reached 80°C, 1500 mL of a sodium carbonate (175 g / L) solution was added using a burette within 1 hour. After precipitation was complete, the slurry had a pH of 8. It was washed with approximately 2 L of distilled water, filtered, and then dried in a drying oven at 105°C for at least 8 hours. The slurry was divided into small portions and activated by reduction in a hydrogen atmosphere at 400°C. The activated catalyst was passivated using a nitrogen gas mixture containing 1% oxygen by volume to produce a hydrogenation catalyst. The specific composition ratios of nickel, copper, and cerium are listed in Table 1.

[0021] Example 2 The same procedure as in Example 1 was carried out except that the specific composition ratios of nickel, copper, and cerium were changed. The specific composition ratios of nickel, copper, and cerium are shown in Table 1.

[0022] Example 3 The same procedure as in Example 1 was carried out except that the specific composition ratios of nickel, copper, and cerium were changed. The specific composition ratios of nickel, copper, and cerium are shown in Table 1.

[0023] Example 4 250m 2 The same procedure as in Example 1 was carried out, except that a porous silica powder having a surface area of ​​1 / g and an average particle size of 20 μm was used. The specific composition ratios of nickel, copper, and cerium are shown in Table 1.

[0024] Comparative Example 1 300m 237.5 g of porous silica powder with a surface area of ​​1 / g and an average particle size of 7 μm and 1875 mL of a solution of nickel nitrate (60 g / L nickel) dissolved in distilled water were placed in a precipitation vessel and stirred. The vessel was heated to 80°C. After the temperature reached 80°C, 1500 mL of a sodium carbonate (175 g / L) solution was added using a burette within 1 hour. After precipitation was complete, the slurry had a pH of 8. It was washed with approximately 2 L of distilled water, filtered, and then dried in a drying oven at 105°C for at least 8 hours. The mixture was divided into small portions and activated by reduction in a hydrogen atmosphere at 400°C. The activated catalyst was passivated using a nitrogen gas mixture containing 1% oxygen by volume to produce a hydrogenation catalyst. The specific composition of the catalyst is listed in Table 1.

[0025] Comparative Example 2 The same procedure as in Example 1 was carried out except that cerium nitrate (1.5 g / L of cerium) was not included. The specific composition ratio of nickel and copper is shown in Table 1.

[0026] Comparative Example 3 Aldrich provided the Pd / C commercial catalyst.

[0027] [Table 1]

[0028] In this case, nickel (Ni), copper (Cu), and cerium (Ce) may exist in the form of oxides, and therefore, in each of the examples and comparative examples, the remainder excluding the constituent components contains oxygen (O).

[0029] Experimental Example 1: Measurement of catalyst properties To measure the physical properties of the catalysts of the Examples and Comparative Examples having the compositions shown in Table 1, the crystal size of nickel, the specific surface area of ​​the catalyst, the total pore volume, the average pore diameter, and the average particle diameter were measured. The results are shown in Table 2.

[0030] The crystal size of nickel was measured using X-ray diffraction (XRD) analysis and the Scherrer equation, and the specific surface area of ​​the catalyst was measured by the BET method. The total pore volume was measured by single-point adsorption at P / P = 0.99 during nitrogen adsorption / desorption analysis, and the average pore diameter was measured based on the Barrett-Joyner-Halenda (BJH) adsorption average size. The average particle diameter (d 50 ) was measured using the laser diffraction method.

[0031] [Table 2]

[0032] Experimental Example 2: Catalyst Activity Test To evaluate the sulfur tolerance of the catalyst, a hydrogenation reaction experiment was conducted by adding 1 wt% of the catalyst (based on the mass of the petroleum resin) to a CSTR reactor, where the reactants and products were fed and discharged. The reactant to be hydrogenated was a petroleum resin (manufactured by Hanwha Solutions) containing C9 oil feedstock containing 60 ppmw of sulfur. This was dissolved in Exxsol D40 solvent at a concentration of 30 wt% and used as the reactant. The reaction temperature and pressure were 250°C and 285 bar of H2O, respectively. After 1 hour of reaction, the hydrogenated petroleum resin solution was discharged and recovered, and the unreacted petroleum resin solution was re-fed to evaluate the catalyst's lifespan. The used catalyst was reused without replacement. The catalyst's hydrogenation conversion rate and the APHA value of the hydrogenated resin were measured according to the amount of petroleum resin hydrogenated, and are shown in Table 3 below.

[0033] The hydrogenation conversion rate was measured from the change in the olefin and aromatic content in the resin measured by 1H-NMR before and after the hydrogenation reaction, and is specifically as follows:

[0034] The petroleum resin before and after the hydrogenation reaction was dissolved in a solvent CDCl3 at a concentration of 2.5 wt %, and then subjected to 1H-NMR analysis (300 MHz), and the hydrogenation conversion rate was calculated using the following mathematical formula 1.

[0035] [Formula 1] Hydrogenation conversion rate (%) = (1 - (sum of the amount of hydrogen contained in the aromatic and olefinic groups in the petroleum resin after hydrogenation / sum of the amount of hydrogen contained in the aromatic and olefinic groups in the petroleum resin before hydrogenation)) x 100

[0036] In the above formula 1, The amount of hydrogen contained in the aromatic group in the petroleum resin is measured as the number of protons calculated from the area ratio of the hydrogen peak bonded to aromatic hydrocarbons in the aromatic region, specifically, in the region of 6.0 ppm to 9.0 ppm relative to the internal standard (0 ppm) of tetramethylsilane (TMS) in 1H-NMR analysis. The amount of hydrogen contained in the olefin group in the petroleum resin was measured as the number of protons calculated from the area ratio of the hydrogen peak appearing in the olefin region, specifically, in the region of 4.0 ppm to 6.0 ppm relative to the internal standard (TMS, 0 ppm).

[0037] APHA values ​​were determined by applying the ASTM D1209 method after hydrogenation.

[0038] [Table 3]

[0039] The results of Experimental Example 2 (Table 3) demonstrate that the hydrogenation catalyst containing cerium and copper according to the present invention exhibits excellent conversion even in the hydrogenation of petroleum resin containing 60 ppmw of sulfur. Furthermore, it was confirmed that the activity decrease was small even when the amount of petroleum resin hydrogenated increased, demonstrating superior sulfur resistance compared to the comparative example. Furthermore, it was confirmed that the APHA value of the hydrogenated resin was 30 or less, enabling the production of high-quality, water-white petroleum resin.

[0040] (Mode for Carrying Out the Invention) The following detailed description of the present invention refers to the accompanying drawings, which show, by way of example, specific embodiments in which the present invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the present invention. It should be understood that various embodiments of the present invention, although different from one another, are not necessarily mutually exclusive. For example, specific shapes, structures, and characteristics described herein may be embodied in other embodiments without departing from the spirit and scope of the present invention. It should also be understood that the location or arrangement of individual components within each disclosed embodiment may be modified without departing from the spirit and scope of the present invention. Therefore, the following detailed description is not to be taken in a limiting sense, and the scope of the present invention is limited only by the appended claims, if appropriate, along with the full scope of equivalents to which those claims are entitled. In the drawings, like reference numerals designate the same or similar functionality throughout the many aspects.

[0041] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

[0042] The deposition-precipitation (DP) method involves the reaction of a metal precursor salt solution and a pH adjuster in a support dispersion to form precipitates, which are then adsorbed and solidified on the support surface. This method provides catalyst uniformity that is incomparable to existing catalyst preparation methods, such as co-precipitation and impregnation, where individual metal catalysts are prepared. Another advantage is that it is easy to select and optimize a support with particle size, size distribution, surface area, pore structure, etc., suitable for the reaction. Therefore, the hydrogenation catalyst referred to in the present invention can be prepared by the deposition-precipitation (DP) method.

[0043] According to one embodiment of the present invention, there is provided a hydrogenation catalyst comprising 40 to 80 parts by weight of nickel, 0.01 to 5 parts by weight of copper, and 0.05 to 5 parts by weight of cerium as catalytically active components, and 10 to 30 parts by weight of silica as a support.

[0044] The hydrogenation catalyst may be produced by mixing nickel or nickel oxide as a nickel source (precursor) in a solvent, and may provide a nickel nitrate precursor containing metal salts such as nitrate, acetate, sulfate, chloride, etc., most preferably a nitrate.

[0045] The copper source (precursor) may be prepared by mixing copper and copper oxide in a solvent, or may be provided in a state bound to each metal salt, such as nitrate, acetate, sulfate, chloride, or a combination thereof.

[0046] The cerium source (precursor) may be prepared by mixing cerium and cerium oxide together in a solvent, or may be provided in a state bound to a metal salt such as a nitrate, acetate, sulfate, chloride, or a combination thereof.

[0047] The above-mentioned sources (precursors) may be used in the form of powder and mixed in a solvent, or a solid support may be suspended in the solvent, and the nickel compound and promoter may form a precipitate and be deposited on the solid support, followed by washing, filtering, drying, calcination, reduction, etc. to finally obtain the catalyst.

[0048] Generally, nickel-containing catalysts have the advantage of being more active in hydrogenation reactions than catalysts containing other metals. However, when a nickel precursor is supported on a support using the DP method, the higher the nickel content, the larger the crystal size, which reduces dispersibility and reduces catalytic activity. Reducing the nickel content to prevent this results in relatively good dispersibility, but also reduces activity, making it difficult to produce commercially viable nickel-supported catalysts using the DP method. To address this issue, the present invention provides a catalyst that has a small crystal size, a uniform particle size distribution, and high dispersibility despite a high nickel content by adding copper.

[0049] Furthermore, the present invention contains cerium, which improves resistance to sulfur poisoning caused by sulfur remaining in petroleum resin during the hydrogenation reaction of petroleum resin, thereby extending the catalyst life.

[0050] According to an embodiment of the present invention, a catalyst having a nickel crystal size of 3 to 8 nm is provided. Compared to catalysts produced by existing manufacturing methods such as coprecipitation, the catalyst according to the present invention can maintain high dispersibility while controlling the nickel crystal size to 3 to 8 nm.

[0051] That is, the catalyst according to the present invention may have improved sulfur poisoning resistance due to the addition of cerium and copper during the hydrogenation reaction of sulfur-containing petroleum resin, thereby improving catalyst activity and lifespan, as can be confirmed by the results of the examples described below.

[0052] According to one embodiment of the present invention, the specific surface area, total pore volume, and average pore diameter of a catalyst may be measured using nitrogen adsorption / desorption analysis. The specific surface area is measured using the Brunauer, Emmett, and Teller (BET) method, which is an analytical method for measuring the specific surface area of ​​a powder by measuring the amount of nitrogen gas adsorbed on the catalyst surface. The total pore volume may be measured by single-point adsorption at P / P = 0.99 during nitrogen adsorption / desorption analysis. The average pore diameter may also be measured based on the Barrett-Joyner-Halenda (BJH) adsorption average size.

[0053] The specific surface area of ​​the catalyst provided in this invention is 150 m 2 / g~300m 2 / g, total pore volume is 0.2 c m 3 / g~0.4 c m 3 / g, and the average pore size of the catalyst is in the range of 5 nm to 10 nm, which increases the dispersion of nickel and improves the activity of the catalyst in the hydrogenation reaction.

[0054] The catalyst also has an average particle diameter (d 50 ) is provided in the range of 3 μm to 100 μm. Therefore, the catalyst has a uniform particle size distribution, which can provide excellent dispersibility and filterability.

[0055] In the present invention, the average particle diameter (d 50 ) refers to the particle size at the 50% point of the cumulative particle volume distribution by particle size when analyzing particle size distribution, and can be measured using the laser diffraction method. Specifically, the catalyst powder to be measured is dispersed in distilled water as a dispersion medium, and then introduced into a laser diffraction particle size analyzer (model: Malvern, Mastersizer 2000). When each particle passes through a laser beam, the difference in diffraction pattern due to particle size is measured, and the particle size distribution can be calculated.

[0056] The catalyst according to the present invention may be in the form of a powder, particles or granules, and is preferably in the form of a powder.

[0057] Meanwhile, a method for producing a hydrogenation catalyst according to the present invention will be provided below. The same content as that of the above-mentioned hydrogenation catalyst may be applied, and therefore, a description thereof will be omitted to the extent that it overlaps.

[0058] A method for preparing a hydrogenation catalyst according to an embodiment of the present invention includes the steps of: preparing a first solution by dissolving a nickel precursor in a solvent so that the weight concentration of nickel in the solution is 25 to 100 g / L; preparing a second solution by adding a copper precursor and a cerium precursor to the first solution so that the weight concentration of copper in the solution is 0.01 to 5 g / L and the weight concentration of cerium in the solution is 0.05 to 5 g / L; preparing a third solution by adding and dispersing a silica carrier in the second solution so that the weight concentration of silica in the solution is 5 to 30 g / L; adding the third solution to a precipitation vessel while stirring and heating the vessel to 50°C to 120°C; adding a pH adjuster to the heated third solution to precipitate the precursors on the silica carrier, thereby preparing a catalyst; washing, filtering, and drying the catalyst; and reducing and activating the dried catalyst.

[0059] Here, the precursors used to prepare the first to third solutions may be provided as nickel, copper, and cerium themselves, or may be provided in a state bound to their respective metal salts, such as oxides, nitrates, acetates, sulfates, chlorides, or combinations thereof.

[0060] The catalyst precursor may be precipitated in an environment of pH 7 or higher by adding a base or by electrochemical means, preferably in an environment of pH 7 to 9. In this case, a basic compound may be added as a pH adjuster, and the basic additive may include, but is not limited to, sodium carbonate, sodium hydroxide, sodium bicarbonate, or a hydrate thereof, preferably sodium carbonate or a hydrate thereof.

[0061] Furthermore, in the case of drying after washing and filtering the catalyst, it can be carried out at a temperature of 100°C to 200°C for 5 to 24 hours.

[0062] In the step of reducing and activating the dried catalyst, the reduction is carried out in a hydrogen atmosphere at a temperature of 200 to 500°C.

[0063] Furthermore, the method for preparing a hydrogenation catalyst according to the present invention may further include a step of passivating the activated catalyst. In this case, the passivation step may be provided by two methods, i.e., passivation with a gas or passivation by immersion in an organic solvent or a solution containing a petroleum resin in an organic solvent.

[0064] For example, when passivating with a gas, it may be performed with a nitrogen gas mixture containing 0.1% to 20% by volume of oxygen.

[0065] When passivating with an organic solvent, any organic solvent that can block air can be used, such as Exxsol D40. Also, a solution containing petroleum resin in an organic solvent can be used.

[0066] Meanwhile, the following provides a method for hydrogenating a petroleum resin, which comprises contacting the petroleum resin with hydrogen in the presence of the hydrogenation catalyst according to the present invention.

[0067] According to the present invention, a petroleum resin may be provided as a reactant for the hydrogenation reaction. The petroleum resin may be polymerized from raw materials including C5, C8, and C9 petroleum fractions, by-products, and combinations thereof through distillation, pretreatment, and polymerization, and then hydrogenated.

[0068] For example, petroleum resins containing C5 oil or petroleum resins containing C9 oil may be provided, or petroleum resins made from DCPD oil by-products and combinations thereof may be provided.

[0069] Furthermore, the petroleum resin, which is a reactant of the hydrogenation reaction, may contain an olefin group and an aromatic group. After polymerization of the petroleum resin, the unsaturated bonds (olefin and aromatic unsaturated bonds) remaining in the resin cause the resin to have a yellowish color, a foul odor, and be easily oxidized in the air. Therefore, in order to improve the quality of the petroleum resin, hydrogenation is performed using the hydrogenation catalyst according to the present invention under high temperature and pressure conditions. This removes the unsaturated bonds, resulting in a colorless, odorless, and water-white petroleum resin with improved thermal stability.

[0070] In addition, the petroleum resin used as a reactant in the hydrogenation reaction can contain 1 ppmw to 300 ppmw of sulfur components. For example, petroleum resins polymerized from C5 feedstocks such as dicyclopentadiene (DCPD) can contain 30 ppmw or less, while petroleum resins polymerized from C9 feedstocks such as cracked kerosene can contain 300 ppmw or less. When the hydrogenation reaction of petroleum resins is carried out using the hydrogenation catalyst having excellent resistance to sulfur poisoning according to the present invention, the catalyst can provide excellent activity and life even under conditions of high sulfur content, and a hydrogenated petroleum resin of satisfactory quality can be obtained.

[0071] For the hydrogenation of petroleum resins, the temperature may be 100°C to 400°C, preferably 200°C to 300°C, and the hydrogen pressure may be 1 bar to 200 bar, preferably 50 bar to 100 bar. The hydrogenation reaction time may vary depending on the temperature, the amount of catalyst, and the degree of hydrogenation. The hydrogenation reaction may be carried out in various reactors, preferably a continuous stirred tank reactor (CSTR) or a loop reactor.

[0072] The petroleum resin according to the present invention is characterized in that it has an APHA value of 30 or less after the hydrogenation reaction is completed by contact with hydrogen.

[0073] APHA color, also known as the Hazen scale or Cobalt (Pt / Co) scale, is a standard color analysis method (ASTM D1209) named after the American Public Health Association, and the color of hydrogenated petroleum resins is analyzed based on the APHA value. When the color of a petroleum resin is 30 or less, the color and odor of the petroleum resin have almost disappeared, resulting in a water-white resin, and the olefin content (NMR% area) measured by 1H-NMR is less than 0.1% by weight.

[0074] Therefore, when the hydrogenation reaction of petroleum resins is carried out using the hydrogenation catalyst having excellent sulfur resistance according to the present invention, sulfur poisoning can be effectively suppressed, and the activity and life of the catalyst can be improved.

[0075] Although the present invention has been described above using specific details such as specific components, limited examples, and drawings, these are provided merely to facilitate a more general understanding of the present invention, and the present invention is not limited to the above examples. Those skilled in the art will be able to make various modifications and variations from such descriptions.

[0076] Therefore, the concept of the present invention should not be limited to the embodiments described above, and it can be said that not only the scope of the claims described below, but also all modifications equivalent to or similar to the scope of the claims fall within the scope of the concept of the present invention.

[0077] (Addendum) (Appendix 1) as catalytically active components, comprising 40 to 80 parts by weight of nickel, 0.01 to 5 parts by weight of copper, and 0.05 to 5 parts by weight of cerium; A hydrogenation catalyst comprising 10 to 30 parts by weight of silica as a carrier.

[0078] (Appendix 2) 2. The hydrogenation catalyst according to claim 1, wherein the nickel, copper, and cerium are in a metallic or oxide state.

[0079] (Appendix 3) 2. The hydrogenation catalyst according to claim 1, wherein the nickel has a crystal size of 3 nm to 8 nm.

[0080] (Appendix 4) The catalyst has a BET specific surface area of ​​150 m 2 / g~300m 2 / g of the hydrogenation catalyst according to Appendix 1.

[0081] (Appendix 5) The catalyst has a total pore volume of 0.2 c m 3 / g~0.4 c m 3 / g of the hydrogenation catalyst according to Appendix 1.

[0082] (Appendix 6) 2. The hydrogenation catalyst according to claim 1, wherein the catalyst has an average pore diameter of 5 nm to 10 nm.

[0083] (Appendix 7) The average particle diameter (d 50 2. The hydrogenation catalyst according to claim 1, wherein the average particle diameter is 3 μm to 100 μm.

[0084] (Appendix 8) preparing a first solution by dissolving a nickel precursor in a solvent so that the weight concentration (g / L) of nickel in the solution is 25 to 100; preparing a second solution by adding a copper precursor and a cerium precursor to the first solution so that the weight concentration of copper in the solution (g / L) is 0.01 to 5 and the weight concentration of cerium in the solution (g / L) is 0.05 to 5; preparing a third solution by dispersing a silica carrier in the second solution so that the weight concentration (g / L) of silica in the solution is 5 to 30; adding the third solution to a precipitation vessel, stirring the solution, and heating the vessel to a temperature of 50°C to 120°C; adding a pH adjuster to the heated third solution, and precipitating the precursors onto the silica support to prepare a catalyst; washing and filtering the catalyst, followed by drying; and reducing and activating the dried catalyst; A method for producing a catalyst for hydrogenation reaction, comprising:

[0085] (Appendix 9) 9. The method for producing a catalyst for a hydrogenation reaction according to claim 8, further comprising: passivating the activated catalyst.

[0086] (Appendix 10) 10. The method for producing a hydrogenation catalyst according to claim 9, wherein the passivation is carried out with a nitrogen mixed gas containing 0.1% by volume to 20% by volume of oxygen.

[0087] (Appendix 11) 10. The method for producing a hydrogenation catalyst according to claim 9, wherein the passivation is carried out by depositing the activated catalyst in an organic solvent or a solution containing a petroleum resin in an organic solvent.

[0088] (Appendix 12) A method for hydrogenating a petroleum resin, comprising contacting the petroleum resin with hydrogen in the presence of the hydrogenation catalyst according to Appendix 1.

[0089] (Appendix 13) 13. The method for hydrogenating a petroleum resin according to claim 12, wherein the petroleum resin is polymerized from a raw material containing at least one selected from C5, C8, and C9 petroleum fractions, by-products, and combinations thereof.

[0090] (Appendix 14) 13. The method for hydrogenating a petroleum resin according to claim 12, wherein the petroleum resin comprises a material selected from the group consisting of an olefin group, an aromatic group, and combinations thereof.

[0091] (Appendix 15) 13. The method for hydrogenating a petroleum resin according to claim 12, wherein the petroleum resin contains 1 ppmw to 300 ppmw of a sulfur component.

[0092] (Appendix 16) 13. The method for hydrogenating a petroleum resin according to claim 12, wherein the APHA value of the petroleum resin after the hydrogenation method is 30 or less.

[0093] (Appendix 17) A petroleum resin hydrogenated by the hydrogenation method described in Appendix 12. [Industrial Applicability]

[0094] According to the present invention, the resistance to sulfur poisoning caused by sulfur remaining in petroleum resin during the hydrogenation reaction of petroleum resin can be improved, and the activity and life of the catalyst can be improved.

[0095] According to the present invention, a catalyst having a high nickel content, a small crystal size, a uniform particle size distribution, and a high degree of dispersion can be provided for the hydrogenation reaction of petroleum resins.

Claims

1. as catalytically active components, comprising 40 to 80 parts by weight of nickel, 0.01 to 5 parts by weight of copper, and 0.05 to 5 parts by weight of cerium; The carrier contains 10 to 30 parts by weight of silica, the nickel crystal size is 3 nm to 8 nm; A sulfur-containing catalyst for hydrogenation of petroleum resins, having a BET specific surface area of ​​150 m 2 / g to 300 m 2 / g, a total pore volume of 0.2 cm 3 / g to 0.4 cm 3 / g, and an average pore diameter of 5 nm to 10 nm.

2. 2. The hydrogenation catalyst according to claim 1, wherein the nickel, copper and cerium are in a metallic or oxide state.

3. The average particle diameter (d ５０ 2. The hydrogenation catalyst according to claim 1, wherein the average particle diameter is 3 μm to 100 μm.

4. preparing a first solution by dissolving a nickel precursor in a solvent so that the weight concentration (g / L) of nickel in the solution is 25 to 100; preparing a second solution by adding a copper precursor and a cerium precursor to the first solution such that the weight concentration of copper in the solution (g / L) is 0.01 to 5 and the weight concentration of cerium in the solution (g / L) is 0.05 to 5; preparing a third solution by dispersing a silica carrier in the second solution so that the weight concentration (g / L) of silica in the solution is 5 to 30; adding the third solution to a precipitation vessel, stirring the solution, and heating the vessel to a temperature of 50°C to 120°C; adding a pH adjuster to the heated third solution, and precipitating the precursors onto the silica support to prepare a catalyst; washing and filtering the catalyst, followed by drying; and reducing and activating the dried catalyst; Including, The catalyst has a nickel crystal size of 3 nm to 8 nm, a BET specific surface area of ​​150 m 2 / g to 300 m 2 / g, a total pore volume of 0.2 cm 3 / g to 0.4 cm 3 / g, and an average pore diameter of 5 nm to 10 nm.

5. 5. The method for producing a catalyst for a hydrogenation reaction according to claim 4, further comprising the step of passivating the activated catalyst.

6. 6. The method for preparing a hydrogenation catalyst according to claim 5, wherein the passivation is carried out with a nitrogen mixed gas containing 0.1 to 20% by volume of oxygen.

7. 6. The method for preparing a hydrogenation catalyst according to claim 5, wherein the passivation is carried out by immersing the activated catalyst in an organic solvent or a solution containing a petroleum resin in an organic solvent.

8. A method for hydrogenating a petroleum resin, comprising contacting a sulfur-containing petroleum resin with hydrogen in the presence of the hydrogenation catalyst according to claim 1.

9. The method for hydrogenating a petroleum resin according to claim 8, wherein the petroleum resin is polymerized from a raw material containing at least one selected from C5, C8, and C9 petroleum fractions, by-products, and combinations thereof.

10. 9. The method for hydrogenating a petroleum resin according to claim 8, wherein the petroleum resin comprises a material selected from the group consisting of an olefin group, an aromatic group, and combinations thereof.

11. The method for hydrogenating a petroleum resin according to claim 8, wherein the petroleum resin contains 1 ppmw to 300 ppmw of a sulfur component.

12. 9. The method for hydrogenating a petroleum resin according to claim 8, wherein the APHA value of the petroleum resin after the hydrogenation method is 30 or less.

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