Catalyst for hydrogenation reaction and preparation method thereof

Abstract

The present invention relates to a catalyst for a hydrogenation reaction and to a preparation method thereof and, more specifically, to a catalyst for a hydrogenation reaction in which a powder catalyst including nickel and copper and a petroleum resin binder are physically mixed, and to a manufacturing method thereof.

Description

Catalyst for hydrogenation reaction and method for producing the same

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0118120, filed September 6, 2023, the entire disclosure of which is incorporated herein by reference.

[0003]

[0004] The present invention relates to a catalyst for hydrogenation reaction and a method for producing the same, and more particularly, to a catalyst for hydrogenation reaction in which a powder catalyst containing nickel and copper and a petroleum resin binder are mixed and combined, and a method for producing the same.

[0005]

[0006] In general, the hydrogenation reaction for organic compounds is a reaction applied to reduce a specific functional group or to convert an unsaturated compound into a saturated compound. It can be applied to various compounds, such as reducing compounds with unsaturated functional groups such as ketones, aldehydes, and imines into compounds such as alcohols and amines, or saturating unsaturated bonds in olefin compounds, and is one of the most important reactions commercially.

[0007] Lower olefins (i.e., ethylene, propylene, butylene, and butadiene) and aromatics (i.e., benzene, toluene, and xylene) are fundamental intermediates widely used in the petrochemical and chemical industries. Thermal cracking, or steam pyrolysis, is the primary type of process for producing 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. By pyrolyzing naphtha and the like, C4 fractions including ethylene, propylene, butane, and butadiene, C5 fractions including dicyclopentadiene (DCPD), cracked gasoline (including benzene, toluene, and xylene), cracked kerosene (C9 or higher fractions), cracked heavy oil (ethylene bottom oil), and hydrogen gas can be produced, and petroleum resins can be manufactured from these fractions by polymerizing them.

[0008] However, petroleum resins may contain unsaturated bonds in some portions. Examples of unsaturated bonds include double bonds in aromatic moieties (hereinafter referred to as "aromatic double bonds") and double bonds in aliphatic moieties (hereinafter referred to as "olefin double bonds"). If the content of these unsaturated bonds in the petroleum resin is high, the quality of the petroleum resin may deteriorate. In this case, if a hydrogenation process is performed to add hydrogen to the unsaturated bonds, the unsaturated double bonds become saturated, thereby improving the quality, such as brightening the color and reducing the characteristic odor of the petroleum resin.

[0009] Hydrogenation of the unsaturated bonds in these petroleum resins is typically accomplished by contacting the hydrogen and the target material with a precious metal catalyst, such as palladium (Pd) or platinum (Pt). However, these precious metal catalysts are very expensive, a major contributor to increased production costs. Therefore, the hydrogenation of petroleum resins is preferred using inexpensive nickel (Ni)-based catalysts.

[0010] Meanwhile, nickel powder catalysts for hydrolysis of petroleum resins generate heat upon contact with air, making it crucial to ensure safety during transport, storage, and use. Therefore, research is needed to develop catalysts that can ensure the safety of hydrogenation catalysts while simultaneously delivering performance comparable to existing catalysts.

[0011]

[0012] The present invention aims to provide a catalyst having excellent reaction activity and a method for producing the same while increasing the safety of a catalyst for a petroleum resin hydrogenation reaction.

[0013]

[0014] To solve the above problem, the present invention provides a catalyst for hydrogenation reaction, comprising a powder catalyst in which nickel and copper are supported on a carrier; and a petroleum resin binder, wherein the powder catalyst and the petroleum resin binder are physically mixed.

[0015]

[0016] In addition, the present invention provides a method for producing a catalyst for hydrogenation reaction, comprising the steps of: preparing a precursor mixture by dissolving or suspending a carrier, a nickel precursor, and a copper precursor in a solvent (step 1); placing the precursor mixture in a precipitation vessel and heating it to 60 to 100° C. while stirring, and then adding a pH adjuster to produce a precipitate (step 2); washing, filtering, and drying the precipitate to produce a dried product (step 3); calcining the dried product in an air atmosphere (step 4); reducing it in a hydrogen atmosphere to produce a reduced product (step 5); passivating the reduced product in an air atmosphere to produce a powder catalyst (step 6); and mixing the powder catalyst with a petroleum resin binder to produce a slurry and solidifying it (step 7).

[0017]

[0018] Furthermore, the present invention provides a method for producing hydrogenated petroleum resin by hydrogenating petroleum resin in the presence of a catalyst for the hydrogenation reaction.

[0019]

[0020] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention.

[0021] Singular expressions include plural expressions unless the context clearly indicates otherwise.

[0022] In this specification, the terms “comprise,” “include,” or “have” are intended to describe a feature, number, step, component, or combination thereof implemented, but do not exclude the possibility of one or more other features, numbers, steps, components, combinations, or additions thereof.

[0023] Additionally, in this specification, when each layer or element is referred to as being formed “on” or “over” each of the layers or elements, it means that each layer or element is formed directly on each of the layers or elements, or that other layers or elements may be additionally formed between each layer, on the object, or on the substrate.

[0024] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this does not limit the invention to a specific disclosed form, but rather encompasses all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0025]

[0026] Hereinafter, the present invention will be described in detail.

[0027]

[0028] (catalyst for hydrogenation reaction)

[0029] The present invention relates to a hydrogenation catalyst, which comprises a powder catalyst containing nickel and copper supported on a carrier, a petroleum resin as a binder, and a mixture of the powder catalyst and the petroleum resin binder to form a solidified catalyst. Furthermore, the hydrogenation catalyst of the present invention is a physically mixed mixture of the powder catalyst and the petroleum resin binder, which means that the powder catalyst and the petroleum resin binder are mixed in a slurry form and then integrated. In other words, the term "physically mixed" means that the two components are mixed in a solidified state, although the individual components do not form a chemical bond. The specific method for physically mixing the individual components may be specified in the examples described below.

[0030]

[0031] Nickel-based catalysts have high reactivity and potential for use in the hydrogenation reaction of petroleum resins. However, ensuring safety is essential for their practical application. Nickel powder catalysts are composed of evenly dispersed nickel particles smaller than 10 nm in size. Nickel smaller than 10 nm rapidly converts to nickel oxide upon exposure to air (oxidation), generating significant heat of reaction. To minimize this phenomenon, nickel-based catalysts require significant care during storage and use. Therefore, solidifying the nickel-based catalyst with a petroleum resin binder prevents contact with air, inhibiting oxidation and facilitating safe transportation and storage.

[0032] Accordingly, the inventors of the present invention, through continuous research, confirmed that a solidified catalyst in which a nickel-based catalyst in powder form is mixed with a petroleum resin binder can suppress oxidation reactions by blocking contact of nickel active species with air, and thus, even if the solidified catalyst comes into contact with air, there is no heat generation phenomenon, enabling safe transportation and storage, and the reaction activity of the catalyst is at a level equivalent to that of existing powdered catalysts, thereby completing the present invention.

[0033]

[0034] Meanwhile, dicyclopentadiene (DCPD), a type of petroleum resin, has the characteristics of a yellow color, bad smell, and easy oxidation in the air due to the unsaturated bonds (double unsaturated bonds of olefins and aromatics) remaining after polymerization. In order to improve the quality of the petroleum resin, a hydrogenation reaction is performed under high temperature and high pressure conditions (e.g., 250 ℃, 90 bar) to remove the unsaturated bonds, producing a colorless, odorless, and transparent water-white petroleum resin with improved thermal stability. In this way, in order to improve the quality of the petroleum resin manufactured by polymerization using dicyclopentadiene (DCPD) as the main raw material, a hydrogenation reaction of the petroleum resin is required, and at this time, a powder catalyst containing nickel as an active species is mainly used.

[0035]

[0036] Additionally, the powder catalyst of the present invention includes copper along with the nickel. Nickel is known to be highly active in hydrogenation reactions. However, as the nickel content in the catalyst increases, the crystal size increases and dispersibility decreases, resulting in lower catalytic activity. Therefore, in order to control the nickel crystal size, particle size distribution, and dispersion while maintaining an appropriate nickel content, the powder catalyst of the present invention includes copper as well.

[0037]

[0038] The above nickel and copper may be present on the catalyst in the form of nickel metal, copper metal, or in the form of their oxides or a mixture of metals and oxides.

[0039]

[0040] Additionally, the powder catalyst of the present invention is in the form of nickel and copper supported on a carrier. The carrier enhances the structural stability of the catalyst and enables high dispersion of the active species, thereby exhibiting excellent reaction activity. Considering the stability of the nickel and copper support and the specific surface area of ​​the catalyst, the carrier is preferably a porous carrier.

[0041]

[0042] In addition, the hydrogenation catalyst of the present invention includes a petroleum resin binder. The petroleum resin binder is a type of organic binder used to solidify a powdered catalyst. That is, the hydrogenation catalyst of the present invention is a form in which the powdered catalyst is physically mixed with the petroleum resin binder, and becomes a solid catalyst having a certain shape. In this way, the solidified hydrogenation catalyst of the present invention has superior safety compared to existing powdered catalysts.

[0043] Meanwhile, methods using fatty substances have been proposed to prevent oxidation of nickel catalysts and improve their stability. For example, a method is to mix substances such as soybean fat, palm oil fat, and sunflower oil fat with a nickel powder catalyst in a molten state. However, the method of using such fatty substances can lower the quality of hydrogenated petroleum resin due to differences in melting point, boiling point, and polarity compared to petroleum resin components. In addition, fatty substances contain oxygen, which can cause water to be generated during the hydrogenation reaction process, reducing hydrogenation performance and lowering the operational stability of the reactor. Therefore, the application of the petroleum resin binder of the present invention can solve these problems.

[0044]

[0045] Preferably, the carrier may be amorphous silica. More specifically, the silica has a specific surface area of ​​200 to 400 m 2 / g, and may be a porous carrier having a pore size of 10 to 30 nm. When porous silica having the above characteristics is used as a carrier, it is possible to improve catalytic activity and lifespan, and it can optimally provide an effect of improving the efficiency of the process of separating the product and the catalyst. In addition, by providing a silica carrier with a uniform particle size distribution, it is possible to provide an effect of suppressing the crushing of the catalyst even when rotating at high speed in a hydrogenation reaction.

[0046]

[0047] Preferably, nickel may be included in an amount of 40 to 80 parts by weight, based on 100 parts by weight of the powder catalyst. If the nickel content is less than 40 parts by weight, the hydrogenated petroleum resin reaction activity may be reduced, and as a result, the APHA value of the hydrogenated petroleum resin may not reach the desired level. If the nickel content exceeds 80 parts by weight, the production may not be easy, and there may be a problem of reduced catalytic activity due to reduced dispersibility. More preferably, nickel may be included in an amount of 45 parts by weight or more, 50 parts by weight or more, or 55 parts by weight or more, and 77 parts by weight or less, 75 parts by weight or less, or 70 parts by weight or less, based on 100 parts by weight of the powder catalyst.

[0048]

[0049] Preferably, the petroleum resin binder may be included in an amount of 45 to 95 parts by weight, based on 100 parts by weight of the catalyst for hydrogenation reaction. When the petroleum resin binder is less than 45 parts by weight, the amount of the powder catalyst becomes relatively high, so that the solidification of the powder catalyst may not occur properly, and an exothermic phenomenon may occur when it comes into contact with air. When the petroleum resin binder exceeds 95 parts by weight, the amount of the powder catalyst becomes relatively low, so that it is difficult to achieve the desired degree of reaction activity, and thus a problem may arise that the degree of hydrogenation of the petroleum resin is somewhat low. More preferably, the petroleum resin binder may be included in an amount of 46 parts by weight or more, 47 parts by weight or more, 48 parts by weight or more, or 49 parts by weight or more, but 94 parts by weight or less, 93 parts by weight or less, 92 parts by weight or less, or 90 parts by weight or less, based on 100 parts by weight of the catalyst for hydrogenation reaction.

[0050]

[0051] In addition, preferably, the Cu / Ni (weight / weight)% of the catalyst for the hydrogenation reaction may be 1.0% to 1.4%. If the Cu / Ni (weight / weight)% in the catalyst is less than 1.0%, the reaction activity may be lowered during the hydrocarbon resin hydrogenation reaction, and if it exceeds 1.4%, the dispersibility of nickel and copper, which are active species, may be reduced, thereby lowering the reaction stability. More preferably, the Cu / Ni (weight / weight)% of the catalyst for the hydrogenation reaction may be 1.12% or more, 1.13% or more, 1.14% or more, or 1.15% or more, and 1.35% or less, 1.30% or less, or 1.25% or less.

[0052]

[0053] Meanwhile, the powder catalyst may contain a carrier in an amount of 10 to 55 wt%. When the carrier content is less than 10 wt%, the improvement effect due to the inclusion of the carrier is not sufficient, and when it exceeds 55 wt%, there is a concern that the catalytic activity may be reduced due to the relative decrease in the content of the active metal and the cocatalyst. Preferably, the carrier may be contained in an amount of 10 wt% or more, or 20 wt% or more, or 30 wt% or more, and 55 wt% or less, or 50 wt% or less, or 45 wt% or less, based on the total weight of the powder catalyst.

[0054]

[0055] The petroleum resin binder can be appropriately selected by considering the degree of solidification of the powder catalyst, the degree of heat generation upon contact with air, and the activity of the petroleum resin hydrogenation reaction. The petroleum resin binder is C 3-10 It may include a hydrocarbon polymer, and at this time, the hydrocarbon polymer may be a single substance or a mixture. The polymer may be a polymer of a single monomer, or a copolymer of two or more monomers. In addition, when an unsaturated bond is included in the hydrocarbon polymer, it may be in a form in which all or part of the unsaturated bond is hydrogenated. Specifically, the petroleum resin may include at least one selected from the group consisting of an aliphatic (C5) petroleum resin, an aromatic (C9) petroleum resin, a copolymer petroleum resin, a dicyclopentadiene (DCPD) petroleum resin, a copolymer petroleum resin thereof, and a hydrogenated product thereof. Preferably, the petroleum resin binder may include a dicyclopentadiene-based hydrogenated petroleum resin.

[0056]

[0057] The above petroleum resin binder may have a softening point of 70° C. to 150° C. Preferably, the petroleum resin binder may have a softening point of 75° C. or more, 80° C. or more, 85° C. or more, 90° C. or more, or 95° C. or more, and may be 145° C. or less, 140° C. or less, 135° C. or less, 130° C. or less, 125° C. or less, 120° C. or less, 115° C. or less, 110° C. or less, or 105° C. The petroleum resin binder having a softening point within the above range has a lower softening point than the mixing temperature with the powdered catalyst described below, and is suitable for uniformly mixing the powdered catalyst and the petroleum resin binder.

[0058]

[0059] In addition, the petroleum resin binder may have a weight average molecular weight (Mw) of 300 g / mol to 1000 g / mol. Preferably, the weight average molecular weight (Mw) of the petroleum resin binder may be 320 g / mol or more, 350 g / mol or more, 370 g / mol or more, 400 g / mol or more, or 430 g / mol or more, and 950 g / mol or less, 900 g / mol or less, 800 g / mol or less, 750 g / mol or less, 700 g / mol or less, 650 g / mol or less, or 600 g / mol or less.

[0060]

[0061] In addition, the color of the petroleum resin binder may be APHA 30 or less. Preferably, the color of the petroleum resin binder may be APHA 25 or less, 20 or less, 15 or less, or 10 or less. Using a petroleum resin binder having a weight average molecular weight and color within the above range is preferred in terms of easy mixing with a powdered catalyst and catalyst color after mixing.

[0062]

[0063] (Method for producing a catalyst for hydrogenation reaction)

[0064] Hereinafter, a method for manufacturing a catalyst for hydrogenation reaction will be described. The method for manufacturing a catalyst for hydrogenation reaction of the present invention largely includes a step of manufacturing a powder catalyst (steps 1 to 6), and a step of solidifying the powder catalyst using a petroleum resin binder (step 7).

[0065]

[0066] For a description of the powder catalyst and petroleum resin binder used in the preparation of the above hydrogenation reaction catalyst, refer to the above description. Each step is described in detail below.

[0067]

[0068] (Step 1)

[0069] Step 1 of the present invention is a step of preparing a precursor mixture by dissolving or suspending a carrier, a nickel precursor, and a copper precursor in a solvent.

[0070]

[0071] The nickel catalyst used in the present invention can be prepared using various nickel precursors. Examples of nickel precursors include nickel, nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, etc., and preferably, nickel sulfate containing sulfate can be used, but is not limited thereto.

[0072]

[0073] The type of the above carrier is not particularly limited, and for example, at least one selected from the group consisting of SiO2, Al2O3, MgO, MgCl2, CaCl2, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, SiO2-Al2O3, SiO2-MgO, SiO2-TiO2, SiO2-V2O5, SiO2-CrO2O3, SiO2-TiO2-MgO, and zeolite may be used. Among these, a silica (SiO2)-containing carrier may be representatively used, and among these, the amorphous silica described above may be used.

[0074]

[0075] In addition, the type of the copper precursor is not particularly limited, and may be, for example, copper, copper nitrate, copper acetate, copper sulfate, copper chloride, or a combination thereof, and preferably, copper sulfate may be used, but is not limited thereto.

[0076]

[0077] Meanwhile, the type of the solvent is not particularly limited, but water, methanol, ethanol, etc. can be used, and water is preferably used. In addition, the mixing method of the catalyst precursor mixture is not particularly limited. For example, it can be prepared by dissolving nickel and copper precursors in a solvent and then adding a carrier, or it can be prepared by adding a carrier to a solvent to prepare a suspension and then adding nickel and copper precursors, or the carrier, nickel precursor, and copper precursor can be mixed in the solvent simultaneously.

[0078]

[0079] Preferably, the contents of the carrier, nickel precursor, and copper precursor of step 1 may be such that the carrier is comprised in an amount of 10 to 55 parts by weight, nickel in an amount of 40 to 80 parts by weight, and copper in an amount of 0.1 to 15 parts by weight, based on 100 parts by weight of the powder catalyst. When each material is used within the above range, nickel and copper can be smoothly supported on the carrier, and nickel and copper can be highly dispersed in the carrier.

[0080]

[0081] (Step 2)

[0082] Step 2 of the present invention is a step of preparing a precipitate using a pH regulator from the precursor mixture prepared in step 1. More specifically, it is a step of preparing a precipitate by placing the precursor mixture in a precipitation vessel, stirring it, heating it to 60 to 100°C, and then adding a pH regulator.

[0083]

[0084] In the above step 1, a nickel precursor, a promoter precursor, and a carrier are introduced into a solvent to prepare a catalyst precursor, and then a pH adjuster is introduced into the catalyst precursor mixture so that nickel and copper components can be deposited on a solid carrier suspended in the solvent.

[0085]

[0086] Preferably, the pH may be 7 to 9 during the preparation of the precipitate in step 2. The precipitation of the precursor mixture may be carried out in an environment having a pH of 7 or higher. The pH adjuster is a precipitant and may be selected in consideration of the nickel loading amount of the prepared catalyst, the size of the nickel crystals, and the dispersibility of nickel. The pH adjuster may be any one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate, and hydrates thereof. Preferably, it may be sodium carbonate and / or hydrates thereof.

[0087]

[0088] (Step 3)

[0089] Step 3 of the present invention is a step of washing, filtering, and drying the catalyst precursor manufactured in step 2 to manufacture a dried product.

[0090]

[0091] Preferably, the drying in step 3 is performed at 100°C to 200°C for 5 to 30 hours. Moisture in the sediment can be effectively removed within the above temperature and time range.

[0092]

[0093] (Step 4)

[0094] Step 4 of the present invention is a step of firing the above-mentioned dry product in an air atmosphere.

[0095]

[0096] After the above-mentioned dried product is prepared, the catalyst precursor is calcined. Preferably, the calcination in step 4 can be performed at 200°C to 500°C, 230°C to 400°C, or 250°C to 350°C. If the calcination temperature is below the above range, there may be a problem with the stability of the catalyst during the reaction, and if it exceeds the above range, sintering of nickel, which is the active species, may occur, resulting in a decrease in the reaction activity.

[0097]

[0098] (Step 5)

[0099] Step 5 of the present invention is a step of performing reduction after the calcination. Since the calcination is generally performed in air, most of the nickel contained in the catalyst precursor exists in the form of nickel oxide. Nickel oxide generally has lower hydrogenation reaction activity than nickel, so it is generally used after being reduced again.

[0100]

[0101] Preferably, the reduction in step 5 may be performed at a temperature of 300°C to 600°C. If the reduction temperature is below the above range, the catalyst may not be properly reduced, and if the reduction temperature exceeds the above range, sintering of the active metal may occur. More preferably, the reduction may be performed at a temperature of 350°C to 550°C, or 400°C to 500°C.

[0102]

[0103] (Step 6)

[0104] Step 6 of the present invention is a step of preparing a powder catalyst by passivating the reduced product obtained through step 5 in an air atmosphere. Through the passivation step, the highly reactive nickel component reacts with air to convert into less reactive nickel oxide (NiO), thereby ensuring the usability of the nickel catalyst.

[0105]

[0106] Specifically, the above step 6 is preferably performed in an air atmosphere, and a mixed gas containing air and an inert gas can be used to create the air atmosphere. More specifically, the present invention can utilize a mixed gas containing 0.5 vol% to 2.0 vol%, 0.7 to 1 vol%, or 1.0 vol% air.

[0107]

[0108] Additionally, the above step 6 can be performed at 20°C to 80°C, 30°C to 70°C, or 35°C to 60°C, for 5 to 20 hours, or 10 to 15 hours. The catalyst can be stably immobilized within the above temperature and time ranges.

[0109]

[0110] Meanwhile, after the passivation step, it is preferable from the viewpoint of catalyst stability to gradually increase the air concentration in the mixed gas and then recover the powder catalyst. Specifically, after the passivation step, it is preferable to gradually stabilize the mixed gas containing 5 vol%, 10 vol%, 15 vol%, 50 vol%, and 100 vol% air.

[0111]

[0112] (Step 7)

[0113] Step 7 of the present invention is a step of mixing the powder catalyst manufactured through steps 1 to 6 with a petroleum resin binder to manufacture a slurry and solidifying the mixture.

[0114]

[0115] As described above, by solidifying the powder catalyst using a petroleum resin binder to ensure safety during transportation, storage, and use of the powder catalyst, the problems of the powder catalyst can be solved, while achieving a reaction activity level equivalent to that of the powder catalyst.

[0116]

[0117] The method for mixing the powder catalyst and the petroleum resin binder may include, for example, a method of mixing the powder catalyst and the petroleum resin binder by placing them in a reaction tank, a method of spraying the petroleum resin binder onto the powder catalyst, a method of continuously supplying the powder catalyst and the petroleum resin binder to a continuously operated mixer, and a method of mixing them.

[0118]

[0119] Preferably, the slurry preparation in step 7 can be performed at 100°C to 200°C. More preferably, it can be performed at 110°C to 190°C, 120°C to 180°C, or 130°C to 170°C. When a mixed slurry of a powder catalyst and a petroleum resin binder is prepared at a temperature within the above range, it is possible to prepare a uniform slurry by appropriately securing the fluidity of the petroleum resin while preventing physical and chemical modification of the powder catalyst.

[0120] In addition, the slurry preparation time can be selected within an appropriate range considering the amount of powder catalyst and petroleum resin used, and can be performed for, for example, 15 minutes to 2 hours, 20 minutes to 1 hour, or 25 minutes to 40 minutes.

[0121]

[0122] The powder catalyst and petroleum resin binder mixed slurry manufactured through the above process can be solidified through a pastillation process, and at this time, can be formed into an appropriate catalyst shape, for example, a pellet shape, a ring shape, a cylinder shape, a star shape, a wheel shape, or a sphere shape.

[0123]

[0124] (Method for producing hydrogenated petroleum resin)

[0125] Meanwhile, the present invention provides a method for producing hydrogenated petroleum resin by hydrogenating petroleum resin in the presence of the above-described catalyst for hydrogenation reaction.

[0126]

[0127] Specifically, the method for producing hydrogenated petroleum resin comprises introducing petroleum resin, hydrogen gas, a hydrogenation catalyst, and optionally a solvent into a reactor to perform a hydrogenation reaction. The hydrogenation reaction of the petroleum resin may be performed in various reactors, including a batch reactor, a continuous stirred tank reactor (CSTR), a fixed-bed reactor, or a loop reactor.

[0128]

[0129] The above petroleum resin is a target for which selective hydrogenation is requested, and may include, for example, dicyclopentadiene (DCPD), C5 fraction, C8 fraction, C9 fraction, or a polymer thereof. The above C5 fraction refers to unsaturated hydrocarbons having 5 carbon atoms, such as cyclopentadiene, isoprene, and piperylene, which are obtained through petroleum pretreatment, distillation, and polymerization, etc., petroleum fractions, by-products, and combinations thereof; the C8 fraction refers to unsaturated hydrocarbons having 8 carbon atoms, such as styrene and octene, which are obtained through petroleum pretreatment, distillation, and polymerization, etc., petroleum fractions, by-products, and combinations thereof; and the C9 fraction refers to unsaturated hydrocarbons having 9 carbon atoms, such as vinyltoluene and indene, which are obtained through petroleum pretreatment, distillation, and polymerization, etc., petroleum fractions, by-products, and combinations thereof.

[0130]

[0131] In the method for producing a hydrogenated petroleum resin according to the present invention, the catalyst for hydrogenation reaction may be used in an amount of 0.5 to 10 wt% based on the weight of the petroleum resin. If the concentration of the catalyst is low, less than 0.5 wt%, the efficiency of the hydrogenation reaction may decrease, and if the concentration of the catalyst is too high, exceeding 10 wt%, the fluidity of the reactant petroleum resin may decrease, resulting in lower productivity.

[0132]

[0133] Preferably, the catalyst for the hydrogenation reaction can be used in an amount of 0.5 wt% or more, or 1 wt% or more, or 2 wt% or more, or 3 wt% or more, and 10 wt% or less, or 8 wt% or less, or 7 wt% or less, based on the weight of the petroleum resin.

[0134]

[0135] In addition, saturated hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, undecane, dodecane, cyclohexane, and methylcyclohexane can be used as the solvent, but the present invention is not limited thereto.

[0136]

[0137] The petroleum resin hydrogenation reaction is carried out by introducing the reactants petroleum resin, hydrogen gas, and a catalyst into a reactor. The temperature of the hydrogenation reaction may be 100 to 400°C, preferably 200 to 300°C, and the pressure may be 1 to 200 bar, preferably 30 to 100 bar. If the hydrogenation reaction temperature is lower than 100°C or the pressure is lower than 1 bar, sufficient reaction may not occur, and if the reaction temperature exceeds 400°C or the pressure exceeds 100 bar, there is a risk of overreaction and side reactions occurring. Meanwhile, the hydrogenation reaction time may vary mainly depending on the temperature, amount of catalyst, and degree of hydrogenation.

[0138]

[0139] In addition, a step of purging the inside of the reactor containing the mixture of the hydrogenation catalyst and the petroleum resin before the introduction of the hydrogen gas may be further included with an inert gas such as nitrogen or argon, or a reducing gas such as hydrogen. Preferably, a process of purging with hydrogen after purging with an inert gas such as nitrogen may be performed. At this time, the purging process may be performed according to a conventional method, and may be repeated once or twice or more.

[0140]

[0141] The hydrogenated petroleum resin manufactured according to the method for manufacturing a hydrogenated petroleum resin of the present invention may have an APHA value measured according to ASTM D1209 of 10 or less, or 9 or less, or 8 or less, or 7 or less, or 6 or less, or 5 or less, or 4 or less. Since a lower APHA value is preferable, there is no particular limitation on the lower limit thereof, but may be, for example, 0.3 or more, or 0.5 or more, 0.7 or more, or 1 or more.

[0142]

[0143] In addition, it was confirmed that the hydrogenation degree of the hydrogenated petroleum resin manufactured according to the present invention was 99% or more.

[0144]

[0145] As described above, the catalyst for hydrogenation reaction according to the present invention has excellent catalyst safety and reaction activity through solidification of the powder catalyst, and the hydrogenated petroleum resin manufactured using the catalyst for hydrogenation reaction of the present invention has excellent color.

[0146]

[0147] Hereinafter, preferred embodiments are presented to aid understanding of the invention. However, the following examples are intended only to illustrate the invention and are not intended to limit the invention to these embodiments.

[0148]

[0149] <Example>

[0150] Example 1

[0151] Amorphous silica powder (1.5 kg), nickel sulfate (20 kg), copper sulfate (222 g), and distilled water (60 L) were placed in a precipitation vessel, stirred, and heated to 75°C. 75 L of a precipitant solution containing 12.5 kg of sodium carbonate was injected entirely into the raw material solution reactor using a diaphragm pump over 2 hours to adjust the pH to 8. After completion, the solution was filtered using a filter press and washed with 600 L of distilled water. After washing, it was dried in a drying oven at 120°C for 24 hours. After being divided into small pieces, it was calcined at 300°C in an air atmosphere. After being divided again, it was reduced to 440°C in a hydrogen atmosphere. After reduction, it was treated at 35°C to 60°C for 12 hours using a nitrogen mixture containing 1 vol% air.

[0152] Next, under a nitrogen atmosphere, 100 g of a powder catalyst and 900 g of a DCPD (dicyclopentadiene) hydrogenated petroleum resin (HC-100, manufactured by Hanwha Solutions, softening point 100°C, weight average molecular weight (Mw) 450 g / mol, color APHA 3) were mixed in an autoclave reactor, heated to 150°C, and stirred for 30 minutes. After stirring, the slurry was made into pellets of a uniform size of 1 cm or less in diameter through a pastelization process to produce a catalyst for hydrogenation reaction.

[0153]

[0154] Example 2

[0155] A catalyst for hydrogenation reaction was prepared in the same manner as in Example 1, except that 300 g of powder catalyst and 700 g of DCPD hydrogenated petroleum resin (HC-100, manufactured by Hanwha Solutions Co., Ltd.) were used when preparing pellets.

[0156]

[0157] Example 3

[0158] A catalyst for hydrogenation reaction was prepared in the same manner as in Example 1, except that 500 g of powder catalyst and 500 g of DCPD hydrogenated petroleum resin (HC-100, manufactured by Hanwha Solutions Co., Ltd.) were used when preparing pellets.

[0159]

[0160] Example 4

[0161] A catalyst for hydrogenation reaction was prepared in the same manner as in Example 1, except that 300 g of powder catalyst and 700 g of DCPD hydrogenated petroleum resin (HS-100, manufactured by Hanwha Solutions, softening point 100°C, weight average molecular weight (Mw) 540 g / mol, color APHA 2) were used when preparing pellets.

[0162]

[0163] Example 5

[0164] A catalyst for hydrogenation reaction was prepared in the same manner as in Example 1, except that 300 g of powder catalyst and 700 g of DCPD hydrogenated petroleum resin (HP-100, manufactured by Hanwha Solutions Co., Ltd., softening point 100°C, weight average molecular weight (Mw) 730 g / mol, color APHA 5) were used when preparing pellets.

[0165]

[0166] Example 6

[0167] A catalyst for hydrogenation reaction was prepared in the same manner as in Example 1, except that 300 g of powder catalyst and 700 g of DCPD hydrogenated petroleum resin (HC-90, manufactured by Hanwha Solutions Co., Ltd., softening point 90°C, weight average molecular weight (Mw) 440 g / mol, color APHA 5) were used when preparing pellets.

[0168]

[0169] Example 7

[0170] A catalyst for hydrogenation reaction was prepared in the same manner as in Example 1, except that 300 g of powder catalyst and 700 g of DCPD hydrogenated petroleum resin (HS-130, manufactured by Hanwha Solutions Co., Ltd., softening point 130°C, weight average molecular weight (Mw) 710 g / mol, color APHA 1) were used when preparing pellets.

[0171]

[0172] Comparative Example 1

[0173] A powder catalyst was prepared in the same manner as in Example 1, except that it was not mixed with hydrogenated petroleum resin.

[0174]

[0175] Comparative Example 2

[0176] A powder catalyst was prepared in the same manner as in Example 1, except that 900 g of hydrogenated soybean fat (soy bean, Alfa Aesar, melting point 70°C, weight average molecular weight 800 g / mol, color APHA 10) was used instead of hydrogenated petroleum resin.

[0177]

[0178] Comparative Example 3

[0179] A powder catalyst was prepared in the same manner as in Example 1, except that 900 g of hydrogenated sunflower oil fat (sun flower oil fat, Alfa Aesar, melting point 85°C, weight average molecular weight 700 g / mol, color APHA 7) was used instead of hydrogenated petroleum resin.

[0180]

[0181] XRF (X-ray fluorescence) analysis was performed on the catalysts manufactured in the examples and comparative examples, and the composition of the main components is shown in Table 1 below.

[0182]

[0183] ClassificationNi(wt%)Petroleum Resin Binder(wt%)Cu / Ni((wt / wt)%)Example 16.2891.20Example 219.5711.21Example 333.2491.19Example 420.2691.23Example 518.3721.18Example 619.3731.21Example 720.5711.20Comparative Example 163.201.21Comparative Example 26.190.41.28Comparative Example 35.891.21.25

[0184] Hydrogenation reaction

[0185] A hydrogenation reaction was performed as follows using the catalysts manufactured in the above examples and comparative examples.

[0186]

[0187] Catalyst Activity Test

[0188] A 500 ml reactor with a stirring speed of 1,200 rpm was used. 100 g of a solution of 50 wt% unhydrogenated petroleum resin dissolved in cyclohexane (Daejung Chemicals) was hydrogenated for 2 hours at 260°C and H260 bar with the catalyst of the above example or comparative example added at 4% of the mass of the petroleum resin. The APHA value of the petroleum resin before hydrogenation was 750.

[0189]

[0190] <Experimental Example>

[0191] After the above hydrogenation reaction, the degree of hydrogenation and APHA value of the petroleum resin were measured and the results are shown in Table 2 below.

[0192]

[0193] (1) Measurement of hydrogenation rate

[0194] The petroleum resin before and after the hydrogenation reaction was dissolved in the solvent CDCl3 at a concentration of 2.5 wt%, and then 1H-NMR analysis (600 MHz) was performed, and the degree of hydrogenation (%) was calculated as in the following mathematical equation 1.

[0195] [Mathematical Formula 1]

[0196] Degree of hydrogenation (%) = (1-(sum of hydrogen contained in olefin groups in petroleum resin after hydrogenation) / (sum of hydrogen contained in olefin groups in petroleum resin before hydrogenation)) × 100

[0197] In the above mathematical formula 1,

[0198] The amount of hydrogen contained in the olefin group in the petroleum resin was measured by the number of protons obtained from the area ratio of the hydrogen peak appearing in the olefin region, specifically, in the 4.0 to 10.0 ppm region compared to the internal standard reference (TMS: 0 ppm) of tetramethylsilane (TMS) in 1H NMR analysis.

[0199]

[0200] (2) APHA measurement

[0201] The APHA value was measured according to ASTM D1209 for hydrogenated petroleum resin, which is a reaction product of the above hydrogenation reaction.

[0202]

[0203] Catalyst used Hydrogenation degree (%) APHA Olefin content (%) Example 199.3 2.10.08 Example 299.5 1.8 0.02 Example 396.6 1.30.05 Example 499.4 2.8 0.06 Example 599.6 2.5 0.05 Example 699.5 3.5 0.04 Example 799.8 3.10.05 Comparative example 199.7 1.9 0.02 Comparative example 298.5 5.2 0.11 Comparative example 398.3 7.3 0.12

[0204] As shown in Table 2 above, when the catalysts of Examples 1 to 7 according to the present invention were used to carry out the hydrogenation reaction of the petroleum resin, the degree of hydrogenation of the petroleum resin was 99% or more, and it was confirmed that the degree of hydrogenation was at the same level as that of the powder catalyst of the comparative example even when solidification was performed to improve the safety of use. In addition, when the color of the petroleum resin is 30 or less, it becomes a water-white resin, and in light of the fact that the residual olefin content (NMR % area) at this time is less than 0.1%, it was confirmed that the catalysts of Examples 1 to 7 can provide a water-white petroleum resin through the hydrogenation reaction of the petroleum resin. In the case of Comparative Examples 2 and 3 using fatty acids as a solidification binder, the degree of hydrogenation was 98% or less and the olefin content exceeded 0.1%, which was confirmed to be disadvantageous for the hydrogenation of the petroleum resin compared to the petroleum resin binder.

Claims

1. Powder catalyst containing nickel and copper supported on a carrier; and Contains a petroleum resin binder, The above powder catalyst and petroleum resin binder are physically mixed, Catalyst for hydrogenation reaction.

2. In paragraph 1, The above carrier is amorphous silica, Catalyst for hydrogenation reaction.

3. In paragraph 1, With respect to 100 parts by weight of the above powder catalyst, nickel is included in an amount of 40 to 80 parts by weight. Catalyst for hydrogenation reaction.

4. In paragraph 1, For 100 parts by weight of the catalyst for the hydrogenation reaction, a petroleum resin binder is included in an amount of 45 to 95 parts by weight. Catalyst for hydrogenation reaction.

5. In paragraph 1, The Cu / Ni (weight / weight)% of the above hydrogenation reaction catalyst is 1.0% to 1.4%. Catalyst for hydrogenation reaction.

6. In paragraph 1, The above petroleum resin binder comprises at least one selected from the group consisting of aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized petroleum resins, dicyclopentadiene (DCPD) petroleum resins, copolymerized petroleum resins thereof, and hydrogenated products thereof. Catalyst for hydrogenation reaction.

7. In paragraph 1, The above petroleum resin binder has a softening point of 70 to 150°C, a weight average molecular weight (Mw) of 300 g / mol to 1000 g / mol, and a color of APHA 30 or less. Catalyst for hydrogenation reaction.

8. A step of preparing a precursor mixture by dissolving or suspending a carrier, a nickel precursor, and a copper precursor in a solvent (step 1); Step 2: placing the precursor mixture into a precipitation vessel, stirring, heating to 60 to 100°C, and then adding a pH adjuster to prepare a precipitate; A step of washing, filtering and drying the above sediment to produce a dried product (step 3); A step of firing the above-mentioned dried product in an air atmosphere (step 4); Step of producing a reduced product by reduction in a hydrogen atmosphere (step 5); Step 6 of preparing a powder catalyst by passivating the above-mentioned reduced material in an air atmosphere, and A step (step 7) comprising mixing the above powder catalyst with a petroleum resin binder to prepare a slurry and solidifying it. Method for producing a catalyst for hydrogenation reaction.

9. In paragraph 8, The contents of the carrier, nickel precursor, and copper precursor of the above step 1 are such that the carrier is included in an amount of 10 to 55 parts by weight, nickel in an amount of 40 to 80 parts by weight, and copper in an amount of 0.1 to 15 parts by weight, based on 100 parts by weight of the powder catalyst. Method for producing a catalyst for hydrogenation reaction.

10. In paragraph 8, When preparing the precipitate in step 2 above, the pH is 7 to 9. Method for producing a catalyst for hydrogenation reaction.

11. In paragraph 8, The drying in step 3 above is performed at 100°C to 200°C for 5 to 30 hours. Method for producing a catalyst for hydrogenation reaction.

12. In paragraph 8, The firing of the above step 4 is performed at 200 ℃ to 500 ℃. Method for producing a catalyst for hydrogenation reaction.

13. In paragraph 8, The reduction in step 5 above is performed at 300°C to 600°C. Method for producing a catalyst for hydrogenation reaction.

14. In paragraph 8, The above step 6 is a process in which a nitrogen mixture containing 0.5 vol% to 2.0 vol% air is used, and the process is performed at 20°C to 80°C for 5 to 20 hours. Method for producing a catalyst for hydrogenation reaction.

15. In paragraph 8, The slurry preparation in step 7 above is performed at 100°C to 200°C. Method for producing a catalyst for hydrogenation reaction.

16. A method for producing hydrogenated petroleum resin by hydrogenating petroleum resin in the presence of a catalyst for hydrogenation reaction according to any one of claims 1 to 7.

17. In paragraph 16, The above petroleum resin comprises dicyclopentadiene (DCPD), C5 fraction, C8 fraction, C9 fraction, or a polymer thereof. Method for producing hydrogenated petroleum resin.

18. In paragraph 16, The above catalyst for hydrogenation reaction is used in an amount of 0.5 to 10 wt% based on the weight of the petroleum resin. Method for producing hydrogenated petroleum resin.

19. In paragraph 16, An APHA value of 10 or less as measured according to ASTM D1209, Method for producing hydrogenated petroleum resin.