Hydrogenation catalyst and method for producing same

Abstract

To provide a Ni-based powder catalyst for hydrogenation capable of improving the quality of a petroleum resin and a preparation method for the same, and provide a hydrogenation method capable of giving a transparent water-white petroleum resin which is colorless and odorless and has improved thermal stability.SOLUTION: Provided is a catalyst which includes 40-80 pts.wt. of nickel, 0.01-5 pts.wt. of copper, 1-10 pts.wt. of sulfur, and 10-60 pts.wt. of a silica support based on 100 pts.wt. of the entire dried catalyst including a support.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a catalyst for hydrogenating petroleum resins and a manufacturing method thereof, and more particularly to a nickel-based catalyst for hydrogenating petroleum resins, which is a nickel powder catalyst containing nickel (Ni), copper (Cu) and sulfur (S) and is added to the hydrogenating reaction to improve the color of the petroleum resins. [Background technology]

[0002] Lower olefins (i.e., ethylene, propylene, butylene, and butadiene) and aromatics (i.e., benzene, toluene, and xylene) are basic intermediates that are widely used in the petrochemical and chemical industries. Thermal cracking, or steam pyrolysis, is the primary type of process for forming these materials, typically in the presence of steam and in the absence of oxygen. Feedstocks can include petroleum gases and distillates, such as naphtha, kerosene, and gas oil. Here, naphtha, etc., can be thermally cracked to produce ethylene,

[0003] It can produce substances such as C4 fractions including propylene, butane and butadiene, C5 fractions including dicyclopentadiene (DCPD), cracked gasoline (containing benzene, toluene and xylene), cracked kerosene (C9 and above fractions), cracked heavy oil (ethylene bottom oil) and hydrogen gas, and the fractions can be polymerized to produce petroleum resins.

[0004] However, petroleum resins can contain unsaturated bonds, which can lead to a decline in quality. In this case, if hydrogen is added through a hydrogenation process, the unsaturated bonds are removed, the color becomes brighter, and the odor peculiar to petroleum resins is reduced, improving the quality. In addition, petroleum resins with the unsaturated bonds removed are colorless and transparent, known as water white resins, and are distributed as high-quality resins with excellent heat and UV stability.

[0005] Petroleum resins copolymerized with C5 fraction, C9 fraction, and DCPD have the characteristic that their compatibility with styrene series polymers such as ethylene-vinyl acetate (EVA), styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS), etc. can be adjusted according to the aromatic content. Therefore, during the hydrogenation reaction of petroleum resins, it is necessary to selectively hydrogenate the olefin portion of the resin in order to produce water-white resins while controlling the aromatic content.

[0006] In particular, it is known that precious metal catalysts such as palladium (Pd) and platinum (Pt) are used to selectively hydrogenate olefins from aromatic unsaturated hydrocarbons, and palladium catalysts are mainly used as selective hydrogenation catalysts because they have better activity and selectivity than other metal catalysts. However, when hydrogenation is carried out in liquid form, palladium catalysts have the problem that palladium is lost and Pd complex compounds are formed. On the other hand, when Ni-based catalysts are used, aromatics are hydrogenated together, making them difficult to use in the selective hydrogenation reaction of aromatic compounds.

[0007] German Patent Publication No. 03049414 discloses a catalyst for hydrogenation reaction having a reduction degree of 40 to 77 in the hydrogenation reaction of unsaturated organic compounds such as cyclooctadiene using a catalyst containing nickel and an inorganic support such as silica gel. However, the catalyst composition and reactants are limited to those mentioned above, and there are limitations.

[0008] U.S. Patent Publication No. 4,956,328 discloses a catalyst in which nickel, zirconium, and aluminum are supported on a diatomaceous earth support containing SiO2 to carry out the hydrogenation reaction of nitrobenzene. However, there is a limitation in that the composition of the reactants and catalyst is limited to the above.

[0009] Japanese Patent No. 4958545 discloses a catalyst in which a nickel oxide catalyst supported on alumina is contacted with a sulfur-containing agent, and in particular discloses the use of a nickel-sulfur supported catalyst in carrying out aromatic or hydrocarbon hydrogenation reactions, but this too is limited in the respects mentioned above.

[0010] Finally, the non-patent publication RUSS. CHEM. BULL., INTERNATIONAL EDITION, VOL. 65, NO. 12, pp. 2841-2844 discloses the selective hydrogenation of 1,3-pentadiene using a nickel-sulfur / silica catalyst, the main purpose of which is to improve the hydrogenation selectivity of 1,3-pentadiene by adding sulfur.

[0011] Therefore, there is a pressing need for the development of a catalyst which overcomes the above problems, is easy to select a carrier suitable for the reaction, and is easy to optimize the hydrogenation reaction of petroleum resins, and has good activity as a hydrogenation catalyst. [Prior art documents] [Patent documents]

[0012] (Patent Document 1) German Patent Publication No. 03049414 (September 17, 1981) (Patent Document 2) U.S. Patent Publication No. 4,956,328 (April 11, 1990) (Patent Document 3) Japanese Patent Registration No. 4958545 (March 30, 2012) (Patent document 4) (Non-patent document 4) RUSS.CHEM.BULL., INTERNATIONAL EDITION, VOL.65, NO.12, PP.2841-2844 (2016.11) Summary of the Invention [Problem to be solved by the invention]

[0013] An object of the present invention is to solve all of the above problems.

[0014] Another object of the present invention is to provide a nickel-based powder catalyst for hydrogenation reaction to improve the quality of petroleum resins.

[0015] The nickel-based powder catalyst for hydrogenation according to the present invention provides a hydrogenation catalyst having a high degree of reduction and high activity in the hydrogenation reaction of petroleum resins.

[0016] Another object of the present invention is to provide a transparent, water-white petroleum resin that is colorless, odorless, and has improved thermal stability by removing unsaturated bonds from petroleum resin produced by polymerization using a catalyst with a nickel (Ni) reduction degree of 90% or more and fractions such as C5, C9, and DCPD as main raw materials.

[0017] In particular, the hydrogenation reaction is characterized by a higher selectivity for aromatics versus olefins in the unsaturated bonds.

[0018] Also, the petroleum resin hydrogenated with the catalyst produced according to the present invention is intended to have an APHA (American Public Health Association) value of 30 or less. [Means for solving the problem]

[0019] In order to achieve the object of the present invention as described above and to realize the characteristic effects of the present invention, which will be described later, the present invention has the following characteristic configurations.

[0020] According to one embodiment of the present invention, a hydrogenation catalyst is provided that contains 40-80 parts by weight of nickel, 0.01-5 parts by weight of copper, 1-10 parts by weight of sulfur, and 10-60 parts by weight of a silica carrier, based on 100 parts by weight of the total dried catalyst including the carrier. In this case, the reduction degree of the hydrogenation catalyst is preferably 90% or more.

[0021] According to another embodiment of the present invention, the nickel crystals may have an average size of 3 to 10 nm, and the catalyst particle size distribution may be such that the average particle size is 3 to 10 μm, and the ratio of particles with a size of 1 μm or less is 10% or less. Also, the specific surface area of ​​the catalyst may be 150 to 300 m. 2 It can be provided that the amount is / g.

[0022] According to one embodiment of the present invention, the silica carrier has a specific surface area of ​​200 to 400 m 2 / g and can be a porous support with pore sizes of 10-30 nm.

[0023] According to one embodiment of the present invention, the nickel reduction degree can be measured by H2-TPR (Hydrogen-Temperature Program Reduction), and in this case, the hydrogen adsorption amount per sample weight of 0.01 to 0.3 (mmol-H2 / g-Ni) can be provided by H2-chemisorption measurement.

[0024] According to one embodiment of the present invention, a hydrogenation catalyst is provided that has an electronic absorption peak due to Ni-S bond in the bonding energy range of 159 to 166 eV through X-ray photoelectron spectroscopy (XPS) analysis of the catalyst.

[0025] According to one embodiment of the present invention, there is provided a hydrogenation catalyst, characterized in that the nickel forms a precipitate with the copper and sulfur, and is supported on a support, preferably a silica support, by deposition-precipitation.

[0026] In particular, it is provided that the hydrogenation reaction is characterized by a higher selectivity for olefins relative to aromatics.

[0027] Also, the reactant of the hydrogenation reaction can be a petrocarbon resin, preferably a petrocarbon resin containing dicyclopentadiene (DCPD). In addition, the reactant can be a petrocarbon resin containing a C9 fraction, or a petrocarbon resin containing a C5 fraction. In this case, the petrocarbon resin provides a catalyst for hydrogenation reaction, characterized in that it has an APHA value of 30 or less after the hydrogenation reaction is completed.

[0028] According to an embodiment of the present invention, the hydrogenation catalyst may be in any one or more forms selected from powder, particle and granule, and preferably in powder form.

[0029] According to one embodiment of the present invention, there is provided a method for preparing a catalyst for hydrogenation reaction, the method including the steps of: (a) dissolving 40-80 parts by weight of a nickel precursor, 0.01-5 parts by weight of a copper precursor, and 10-60 parts by weight of a silica carrier in a solvent, based on 100 parts by weight of a total dried catalyst including a carrier, to prepare a first solution; (b) putting the first solution into a precipitation vessel and heating the solution to 60-100°C while stirring; (c) after the heating, adding a pH adjuster and a sulfur precursor to the precipitation vessel to prepare a second solution, and adding the second solution dropwise to the first solution to prepare a precipitate; (d) washing and rinsing the precipitate, and then drying the precipitate to prepare a dried product; and (e) reducing the dried product in a hydrogen atmosphere to prepare a reduced product.

[0030] Also, after the step (d), the method may further include a step of calcining the prepared dried product in an air atmosphere. That is, the step of calcining in an air atmosphere may be provided selectively according to need.

[0031] The temperature of the hydrogen atmosphere can be provided to be 200 to 500° C. The temperature of the air atmosphere can also be provided to be 200 to 500° C.

[0032] Also, the method may further include a step of passivating the reduced material with a nitrogen mixed gas containing 0.1 to 20% oxygen, and a step of passivating the reduced material by directly depositing the reduced material in an organic solvent. The organic solvent may be D40 Exxsol, or any organic solvent that can be sealed off from air may be used.

[0033] According to one embodiment of the present invention, the pH during preparation of the precipitate in step (c) may be 7 to 9, and the heating and drying in step (d) may be performed at 100 to 200° C. for 5 to 24 hours.

[0034] According to one embodiment of the present invention, there is provided a method for hydrogenating a petroleum resin by contacting the petroleum resin with hydrogen in the presence of the hydrogenation catalyst prepared according to the above-mentioned method, wherein the petroleum resin as the reactant may contain dicyclopentadiene (DCPD).

[0035] In accordance with one embodiment of the present invention, there is provided a hydrogenation method, wherein the petroleum resin has an APHA (American Public Health Association) value of 30 or less after contacting with hydrogen and completing the hydrogenation reaction. Effect of the Invention

[0036] The nickel-based catalyst for hydrogenation according to the present invention has the effect of improving the quality of petroleum resins, particularly, the effect of providing a catalyst having a reduction degree of 90% or more.

[0037] The catalyst according to the present invention has the effect of improving the quality of petroleum resins, and has the effect of removing unsaturated bonds in petroleum resins to provide transparent water-white petroleum resins that are colorless, odorless, and have improved thermal stability.

[0038] The present invention has an effect of providing a catalyst characterized by a higher selectivity for olefins relative to aromatics among the unsaturated bonds.

[0039] In addition, hydrogenated petroleum resin has the effect of providing an APHA (American Public Health Association) value of 30 or less.

[0040] The catalyst according to the present invention is easily effective in optimizing the production of a hydrogenation catalyst having a nickel (Ni) reduction degree of 90% or more and a particle size, size distribution, surface area, pore structure, etc. suitable for the reaction by supporting the catalyst composition on the carrier using a deposition-precipitation (DP) method. [Brief description of the drawings]

[0041] [Figure 1] FIG. 1 shows the results of X-ray photoelectron spectroscopy (XPS) analysis of a catalyst according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] The following detailed description of the present invention will refer to specific embodiments in which the present invention may be practiced. These embodiments are described in sufficient detail to enable one skilled in the art to practice the present invention. It should be understood that the various embodiments of the present invention are different from one another but are not necessarily mutually exclusive. For example, specific features, structures and characteristics described herein with respect to one embodiment 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. Accordingly, the following detailed description is not intended to be taken in a limiting sense, and the scope of the present invention is limited only by the appended claims together with the full scope of equivalents to which such claims are entitled, if properly interpreted.

[0043] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to preferred embodiments in order to enable those skilled in the art to easily practice the present invention.

[0044] According to one embodiment of the present invention, a hydrogenation catalyst is provided that contains 40-80 parts by weight of nickel, 0.01-5 parts by weight of copper, and 1-10 parts by weight of sulfur, and 10-60 parts by weight of a silica carrier, based on 100 parts by weight of a total dried catalyst including a carrier, and the catalyst is characterized in that the nickel reduction degree is 90% or more.

[0045] According to one embodiment of the present invention, a nickel hydride catalyst is provided for hydrogenation reaction to improve the quality of petroleum resin produced by polymerization using dicyclopentadiene (DCPD) as the main raw material. DCPD petroleum resin is characterized by yellow color, foul odor, and easy oxidation in air due to unsaturated bonds (olefin and aromatic unsaturated bonds) remaining after polymerization. In order to improve the quality of the petroleum resin, hydrogenation reaction is performed using a nickel (Ni) catalyst, preferably a nickel powder catalyst, under high temperature and pressure conditions (e.g., 250°C 90 bar), which removes unsaturated bonds, producing a transparent water-white petroleum resin that is colorless, odorless, and has improved thermal stability.

[0046] In particular, according to one embodiment of the present invention, when a copper (Cu) and sulfur (S)-containing Ni powder catalyst is used in the hydrogenation of DCPD petroleum resin, it has an advantage of high selectivity for aromatics versus olefins.

[0047] According to one embodiment of the present invention, the nickel crystal has an average size of 3 to 10 nm. The catalyst particle size distribution may be an average particle size of 3 to 10 μm, and the ratio of particles with a size of 1 μm or less may be 0 to 10%. The specific surface area of ​​the catalyst may be 150 to 300 m. 2 / g. A hydrogenation catalyst with a nickel (Ni) reduction degree of 90% or more has such properties, which makes it possible to improve activity and catalyst life, and to optimally provide an improved efficiency in the process of separating the product and catalyst.

[0048] According to one embodiment of the present invention, the hydrogenation catalyst can be prepared by mixing the precursor forms of nickel, copper and sulfur in a solvent, or by using a precipitate, the nickel, copper and sulfur components can be deposited on a solid support suspended in a solvent.

[0049] In this case, the carrier is preferably a silica carrier, and the silica carrier has a specific surface area of ​​200 to 400 m 2 / g and is characterized in that it is a porous carrier having a pore size of 10 to 30 nm. In this case, it provides the effect of making nickel, copper and sulfur exhibit excellent activity.

[0050] According to one embodiment of the present invention, the catalyst is characterized in that nickel forms a precipitate with the copper and sulfur and is supported on a silica carrier by deposition-precipitation, and the nickel reduction degree is 90% or more.

[0051] In addition, in comparison with catalysts prepared by the coprecipitation method, when a catalyst is prepared by the DP method using silica with a uniform particle size distribution as a carrier, it has the advantage that it is easy to prepare a catalyst with particle size, size distribution, surface area, pore structure, etc. suitable for the reaction by supporting the catalyst composition on a carrier with a controlled particle size.

[0052] Nickel catalysts are characterized by their excellent catalytic activity in hydrogenation reactions, but in the DP method, where nickel is supported on a silica carrier and precipitated, there is a problem that if a high content of nickel is supported, the crystal size of the nickel becomes large, which reduces dispersibility and activity.In addition, if the nickel content is low, there is a problem that the activity of the catalyst decreases.

[0053] The hydrogenation catalyst according to an embodiment of the present invention uses nickel catalyst, but by adding copper (Cu) and sulfur (S), it has a high nickel content, high nickel dispersion, and excellent catalytic activity, and a high Ni reduction degree. Even if it is supported by the deposition-precipitation method (DP method), the nickel dispersion after reduction is high and the crystal size is small, so that it can provide excellent activity in the hydrogenation reaction.

[0054] According to one embodiment of the present invention, when nickel forms a precipitate with the sulfur and is supported on a silica carrier, the sulfur is 1 to 10 parts by weight. When it is within this range, the unsaturated bonds of the petroleum resin are removed in the hydrogenation reaction, contributing to the provision of a colorless, odorless, and thermally stable petroleum resin, and helping to improve the selectivity of aromatics to olefins in the unsaturated bonds.

[0055] In addition, when nickel forms a precipitate with copper and is supported on a silica carrier, the amount of copper is 0.01 to 5 parts by weight. When the amount is within the above range, nickel reduction can be easily performed and a high degree of metal reduction can be obtained at a relatively low temperature.

[0056] According to one embodiment of the present invention, there is provided a hydrogenation catalyst having a nickel reduction degree of 90% or more as measured by H2-TPR (Hydrogen-Temperature Program Reduction). H2-TPR is used to evaluate the reduction ability of catalyst particles. The nickel reduction degree of the present invention is 90% or more according to the above analysis method, whereas the nickel reduction degree of a conventional powder-type nickel-based catalyst for petroleum resin hydrogenation does not exceed 90%. The reduction degree analysis method through the analysis method is as follows.

[0057] JPEG0007614251000001.jpg187161

[0058] According to one embodiment of the present invention, a nickel-based catalyst containing 40-80 parts by weight of nickel, 0.01-5 parts by weight of copper, and 1-10 parts by weight of sulfur, and 10-60 parts by weight of silica carrier, based on 100 parts by weight of the total dry weight including the carrier, is used to provide a silica carrier having a particle size, size distribution, surface area, pore structure, etc. suitable for the reaction, and a catalyst in the above-mentioned optimized combination range. The catalyst according to the present invention can provide a nickel (Ni) reduction degree of 90% or more in the hydrogenation reaction. In particular, by supporting sulfur (S) together with nickel, the hydrogenation reaction has an effect of providing a higher selectivity for olefins compared to aromatics. After hydrogenation of olefin-based unsaturated hydrocarbons, petroleum resins containing aromatic parts also have higher compatibility with base polymers such as ethylene vinyl acetate (EVA), styrene-isoprene-styrene (SIS), etc., compared to petroleum resins that do not contain aromatic parts.

[0059] The reactants of the hydrogenation reaction according to one embodiment of the present invention may be petroleum resins consisting of C5 or C9 fractions obtained from naphtha, DCPD fraction by-products, and combinations thereof, and may be composed of cyclic diene and benzene functional groups, but are not limited thereto.

[0060] In addition, the hydrogenation catalyst according to the present invention is characterized by having an APHA value of 30 or less after the hydrogenation of the petroleum resin is completed. When the color of the petroleum resin is 30 or less, the color and odor of the petroleum resin are almost completely eliminated, and the residual olefin content (NMR % area) is less than 0.1%. Therefore, when the hydrogenation catalyst according to the present invention is used, it is useful for improving the selectivity of olefins to aromatics.

[0061] The catalyst according to the invention may be in the form of a powder, particles or granules, preferably in the form of a powder.

[0062] The catalyst according to the present invention has a hydrogen adsorption amount per catalyst weight in the range of 0.01~0.3 (mmol-H2 / g-catalyst) through hydrogen-chemisorption analysis. H2-chemisorption was analyzed using ASAP2020 equipment from Micromeritics. The sample used was 0.25g, and was heated to 90℃ for 30 minutes before analysis and degassed at 200℃ for 4 hours. The analysis temperature was 50℃, and the sample was pretreated at 300℃ in H2 atmosphere.

[0063] The catalyst according to the present invention is characterized by having an electronic absorption peak due to Ni-S bond in the range of 159 to 166 eV (bonding energy) through X-ray photoelectron spectroscopy (XPS).

[0064] XPS is a device that can analyze the oxidation state of atoms, and the oxidation state has different binding energy values ​​depending on the type of atoms bonded. The binding energy on atoms can be measured by measuring the kinetic energy of the photoelectrons emitted when characteristic X-rays are incident on the surface of the sample. XPS was measured at room temperature in a vacuum atmosphere using Multilab 2000 equipment.

[0065] According to one embodiment of the present invention, there is provided a method for producing a catalyst for hydrogenation reaction, the method including the steps of: (a) dissolving 40-80 parts by weight of nickel, 0.01-5 parts by weight of copper, and 10-60 parts by weight of silica support in a solvent, based on 100 parts by weight of a total dried catalyst including a support, to prepare a first solution; (b) putting the first solution into a precipitation vessel and heating the solution to 60-100°C while stirring; (c) after the heating, adding a pH adjuster and a sulfur precursor to the precipitation vessel to prepare a second solution, and adding the second solution dropwise to the first solution to prepare a precipitate; (d) washing and filtering the precipitate, and then drying the precipitate to prepare a dried product; and (e) reducing the dried product in a hydrogen atmosphere to prepare a reduced product. In the case of a catalyst produced according to the method, a nickel reduction degree of 90% or more is provided.

[0066] Also, after step (d), the method may further include a step of calcining the dried product in an air atmosphere. The calcination step is not necessarily provided, and those skilled in the art may appropriately select the step according to need. In this case, the temperature may be provided to be 200 to 500°C. The temperature of the hydrogen atmosphere may also be provided to be 200 to 500°C. Calcination and reduction effects are provided accordingly.

[0067] The method may further include passivating the reduced material with a nitrogen mixed gas containing 0.1 to 20% oxygen or immersing the reduced material in a solution containing an organic solvent and a petroleum resin.

[0068] According to one embodiment of the present invention, the nickel feedstock precursor in step (a) is a nickel sulfate precursor including nickel and metal salts such as nitrates, acetates, sulfates, chlorides, etc., most preferably sulfates.

[0069] Alternatively, copper and sulfur feedstock precursors may be used in combination with metal salts such as nitrates, acetates, sulfates, chlorides, or combinations thereof, preferably sodium sulfide or copper sulfate, and furthermore, a precipitating agent such as sodium carbonate or sodium bicarbonate may be used.

[0070] According to one embodiment of the present invention, the preparation of the precipitate in step (c) may be performed at a pH of 7 to 10. Precipitation of the catalyst precursor may be achieved by adding a base or by electrochemical means in an environment of pH 7 or higher, preferably pH 7 to 9. In this case, a basic compound may be added to add the base, and the basic additive may include, but is not limited to, sodium carbonate, sodium hydroxide, sodium bicarbonate, ammonia, or a hydrate thereof, and preferably includes sodium carbonate or a hydrate thereof.

[0071] According to one embodiment of the present invention, the drying in step (d) is performed at 100 to 200° C. for 5 to 24 hours. The above range provides an effect of removing moisture contained in the precipitate.

[0072] According to one embodiment of the present invention, the hydrogenation reaction is characterized by a higher selectivity for olefins relative to aromatics.

[0073] According to one embodiment of the present invention, there is provided a hydrogenation method comprising contacting a hydrocarbon resin with hydrogen in the presence of a hydrogenation catalyst produced by the method.

[0074] When hydrogenating the petroleum resin, the temperature may be 100-400°C, preferably 200-300°C, and the pressure may be 1-200 bar, preferably 30-100 bar. The hydrogenation time may vary mainly depending on the temperature, the amount of catalyst, and the degree of hydrogenation.

[0075] The hydrogenation reaction can be carried out in various reactors, preferably in a continuous stirred tank reactor (CSTR) or a loop reactor, and the reduction temperature is 200 to 500°C, preferably 350 to 450°C, as described above, to show optimal activity.

[0076] According to one embodiment of the present invention, the petroleum resin, which is a reactant in the hydrogenation reaction, may be characterized by including dicyclopentadiene (DCPD). Also, a petroleum resin including a C5 fraction may be provided, and further, a petroleum resin including a C9 fraction may be provided.

[0077] In addition, the petroleum resin has an APHA value of 30 or less after contact with hydrogen and completion of hydrogenation reaction. APHA color is called Hazen scale or Cobalt (Pt / Co) scale, and the color of hydrogenated petroleum resin is analyzed by APHA value according to the color standard analysis method (ASTM D1209) named by the American Public Health Association. When the color of petroleum resin is 30 or less, the color and odor of petroleum resin are almost completely disappeared and it becomes a water-white resin, and the residual olefin content (NMR % area) is less than 0.1%.

[0078] The configuration and operation of the present invention will be described in more detail with reference to the preferred embodiments of the present invention below, however, these are presented as preferred examples of the present invention and should not be construed as limiting the present invention in any way.

[0079] The contents not described here can be sufficiently inferred by those skilled in the art, so the explanation thereof will be omitted. EXAMPLES

[0080] Example 1 300m 2 40g of porous silica powder with a surface area of ​​1 / g and a pore size of 28nm, 491g of nickel sulfate, 6g of copper sulfate, and 2000mL of distilled water were placed in a precipitation vessel and heated to 80℃ while stirring. After reaching 80℃, 1500mL of a solution containing 262g of sodium carbonate and 19.1g of sodium sulfide was injected using a syringe pump within 1 hour. After precipitation was completed, the pH of the slurry was 7.6, and it was washed with about 15L of distilled water, filtered, and then dried at 100℃ in a drying oven for more than 12 hours. It was divided into small portions and calcined at 400℃ in an air atmosphere. It was also divided into small portions and reduced at 400℃ in a hydrogen atmosphere. After reduction, the powder was passivated using a nitrogen mixed gas containing 1% oxygen to produce a hydrogenation catalyst.

[0081] The nickel content of the passivated catalyst was 65.7%, the sulfur content was 3.1%, and the copper content was 0.79% based on the weight of the catalyst. The average nickel crystallite size was measured to be 5.8 nm. The BET specific surface area was 220 m 2 / g, total pore volume 0.28m 3 / g, and average pore size of 5.1nm. Hydrogen adsorption is 0.021mmol H2 / g-catalyst. Ni reduction rate is 96.6% as analyzed by H2-TPR. XPS analysis shows an absorption peak at 163.1 eV. The results are shown in Figure 1.

[0082] The hydrogenation reaction for the activity test of the catalyst was carried out at a temperature of 230°C.

[0083] Example 2 A solution containing 262g of sodium carbonate and 17g of sodium sulfide as precipitants was injected into the hydrogenation catalyst within 1 hour using a syringe pump so that the sulfur / nickel weight ratio of the hydrogenation catalyst became 4.3%. After the precipitation was completed, the pH of the slurry was 7.7. The remaining methods such as washing, filtration, and drying were the same as those in Example 1.

[0084] The nickel content of the passivated catalyst was 63.3%, sulfur content 2.7%, copper content 0.87% based on the weight of the catalyst, and the average nickel crystallite size was measured to be 4.8 nm. The BET specific surface area was 220 m 2 / g, total pore volume 0.28m 3 / g, with an average pore size of 5.1nm. Hydrogen adsorption is 0.039mmol H2 / g-catalyst. Ni reduction rate is 92.9% as analyzed by H2-TPR. XPS analysis shows an absorption peak centered at 162.9 eV. The results are shown in Figure 1.

[0085] The hydrogenation reaction for the activity test of the catalyst was carried out at a temperature of 230°C.

[0086] Example 3 A solution containing 262g of sodium carbonate and 15g of sodium sulfide as precipitants was injected into the hydrogenation catalyst within 1 hour using a syringe pump so that the sulfur / nickel weight ratio of the hydrogenation catalyst was 3.8%. After the precipitation was completed, the pH of the slurry was 7.5. The remaining methods such as washing, filtration, and drying were the same as those in Example 1.

[0087] The nickel content of the passivated catalyst was 60.8%, copper 0.8%, and sulfur 2.3% by weight based on the weight of the catalyst. The average nickel crystallite size was measured to be 4.7 nm. The BET specific surface area was 230 m 2 / g, total pore volume 0.29m 3 / g, and average pore size is 4.9nm. Hydrogen adsorption is 0.053mmol H2 / g-catalyst. Ni reduction degree is 94.3% as analyzed by H2-TPR. XPS analysis shows an absorption peak centered at 163.2 eV. The results are shown in Figure 1.

[0088] The hydrogenation reaction for the activity test was carried out at a temperature of 230°C.

[0089] Comparative Example 1 A typical hydrogenation catalyst that does not contain sulfur was prepared in the same manner as in Example 1, but sodium sulfide was not used.

[0090] The nickel content of the passivated catalyst was 62.3%, sulfur by weight 0.3%, copper by weight 0.76% based on the weight of the catalyst, and the average nickel crystallite size was measured to be 4.9 nm. The BET specific surface area was 220 m 2 / g, total pore volume 0.31m 3 / g, and the average pore size is 5.6 nm. The Ni reduction degree analyzed by H2-TPR is 83.4%. The hydrogen adsorption capacity is 0.56 mmol H2 / g-catalyst.

[0091] The hydrogenation reaction for the activity test of the catalyst was carried out at a temperature of 230°C.

[0092] Table 1 below shows the components of the catalyst compositions of Examples 1 to 3 and Comparative Example 1.

[0093] [Table 1]

[0094] Experimental Example 1 Catalyst Activity Test A 300 ml autoclave with a hollow shaft stirrer and an agitation speed of 1600 rpm was used. TM75g of a 30wt% solution of D40 was hydrogenated at 230℃ and H290 bar for 1 hour with 1~2% catalyst (Catal / DCPD resin) based on the mass of the petroleum resin. The color of the petroleum resin solution after hydrogenation was measured according to ASTM D1209.

[0095] The color of petroleum resin (APHA value, a standard for expressing the color of a solution), which is largely proportional to the olefin content in the petroleum resin, is 750 before hydrogenation, and the aromatic content is 18%.

[0096] Aromaticity 1 Analysis was performed by 1 H NMR.

[0097] [Table 2]

[0098] The hydrogenation reaction was carried out under the conditions shown in Table 2 according to Experimental Example 1, and the results are shown in Table 2.

[0099] The hydrogenation reaction result of Comparative Example 1 shows that the aromaticity content of the hydrogenated petroleum resin cannot be adjusted by hydrogenating not only olefin but also aromaticity.

[0100] On the other hand, when Examples 1 to 3 are used, the APHA value is the same, but since olefins are preferentially hydrogenated, it is possible to selectively adjust the aromaticity content.In addition, when the color of petroleum resin is 30 or less, it becomes a water-white resin, and in this case, the residual olefin content (NMR % area) is less than 0.1%, so it is also confirmed that when Examples 1 to 3 are used, it is possible to obtain an excellent catalyst that can provide water-white petroleum resin through hydrogenation reaction.

[0101] Although the present invention has been described above using specific details such as concrete components and limited examples, this is provided only to assist in 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.

[0102] Therefore, the concept of the present invention should not be limited to the above-described embodiments, and all modifications equivalent to or equivalent to the scope of the claims, as well as the scope of the claims described below, should be considered to fall within the scope of the concept of the present invention.

Claims

1. (a) preparing a first solution by dissolving 40 to 80 parts by weight of a nickel precursor, 0.01 to 5 parts by weight of a copper precursor, and 10 to 60 parts by weight of a silica carrier in a solvent; (b) putting the first solution into a precipitation vessel and heating it to 60 to 100° C. while stirring; (c) after heating, adding a pH adjuster and 1 to 10 parts by weight of a sulfur precursor to the precipitation vessel to prepare a second solution, and adding the second solution dropwise to the first solution to prepare a precipitate; (d) washing and filtering the precipitate, and then drying the precipitate to produce a dried product; and (e) reducing the dried material in a hydrogen atmosphere to produce a reduced material. A method for producing a hydrogenation catalyst comprising the steps of: The hydrogenation catalyst comprises 40 to 80 parts by weight of nickel, 0.01 to 5 parts by weight of copper, 1 to 10 parts by weight of sulfur, and 10 to 60 parts by weight of a silica carrier, based on 100 parts by weight of a total dry weight including the carrier.

2. 2. The method for producing a hydrogenation catalyst according to claim 1, wherein the temperature of the hydrogen atmosphere is 200 to 500° C.

3. 2. The method of claim 1, further comprising the step of calcining the dried product prepared after step (d) in an air atmosphere.

4. The method for producing a hydrogenation catalyst according to claim 3, wherein the temperature of the air atmosphere is 200 to 500° C.

5. 2. The method of claim 1, further comprising passivating the reduced product with a nitrogen mixed gas containing 0.1 to 20% oxygen.

6. 2. The method for producing a hydrogenation catalyst according to claim 1, further comprising the step of passivating the reduced product by precipitating it in an organic solvent.

7. 2. The method of claim 1, wherein the pH of the precipitate is 7 to 9 during the preparation of the precipitate in step (c).

8. 2. The method for preparing a hydrogenation catalyst according to claim 1, wherein the heating and drying in step (d) is performed at 100 to 200° C. for 5 to 24 hours.

9. A hydrogenation method comprising contacting a petroleum resin with hydrogen in the presence of the hydrogenation catalyst produced by the method according to any one of claims 1 to 8.

10. The hydrogenation method according to claim 9, wherein the petroleum resin contains dicyclopentadiene (DCPD).

11. The method of claim 9, wherein the petroleum resin has an APHA value of 30 or less after contacting with hydrogen and completing the hydrogenation reaction.

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