TW202231676A - Continuous preparation method of hydrogenated petroleum resin - Google Patents

Abstract

Provided is a method of continuously preparing a hydrogenated petroleum resin. More particularly, provided is a method of continuously preparing a hydrogenated petroleum resin, the method capable of easily controlling an APHA value and aromaticity according to application of the hydrogenated petroleum resin through a continuous hydrogenation reaction.

Description

Method for continuous preparation of hydrogenated petroleum resin

[Cross-reference between related applications]

This application claims priority based on Korean Patent Application No. 10-2020-0172597 filed on December 10, 2020, and all the contents disclosed in this Korean Patent Application Document are incorporated in and made a part of this specification.

The present invention relates to a method for continuous preparation of hydrogenated petroleum resin, in particular to a method for easily controlling APHA value and aromaticity through continuous hydrogenation reaction according to the application of hydrogenated petroleum resin. Process for the continuous preparation of hydrogenated petroleum resins.

In general, the hydrogenation reaction of organic compounds is a reaction for reducing a specific functional group, or converting an unsaturated compound into a saturated compound, and it can be applied to various compounds to convert compounds with, for example, ketones. ), aldehyde (aldehyde), imine (imine) and other unsaturated functional group compounds are reduced to alcohol (alcohol), amine (amine) and other compounds, or the unsaturated bond of the olefin compound is saturated, and the hydrogenation reaction is a commercial One of the very important responses.

Lower olefins (ie, ethylene, propylene, butylene, and butadiene) and aromatic compounds (ie, benzene, toluene, di- Toluene (xylene) is a basic intermediate material widely used in petrochemical and chemical industries. Thermal cracking or steam thermal decomposition is the main type of process used to form these materials in the presence of steam and in the absence of oxygen. Feedstocks may include petroleum gas and distillates such as naphtha, kerosene, and gas oil. In this regard, through thermal decomposition of naphtha, etc., C4 petroleum fractions including ethylene, propylene, butane and butadiene, pyrolysis gasoline (including benzene, toluene and xylene) can be produced ), C5 petroleum fractions including dicyclopentadiene (DCPD), cracked kerosene (petroleum fractions above C9), cracked heavy oils (ethylene bottoms), and hydrogen, and can be prepared by polymerization from petroleum fractions Out of petroleum resin (petroleum resin).

However, the petroleum resin moiety includes a double bond of an aromatic moiety (hereinafter referred to as "aromatic double bond") and a double bond of an aliphatic moiety (hereinafter referred to as "olefin double bond") olefinic double bond”), and when the content of olefinic double bonds is high, the quality of the petroleum resin will decrease. Therefore, when the hydrogenation process of adding hydrogen to the olefin double bond is performed, the unsaturated double bond can be saturated, the color can be brighter, and the peculiar smell of petroleum resin can be reduced, thereby improving the quality.

In the hydrogenation reaction of this kind of petroleum resin, in order to control the content of aromatic double bonds, it is necessary to selectively hydrogenate the olefin bonds of the resin. The selective hydrogenation of olefinic double bonds can generally be carried out by contacting the hydrogen gas and the hydrogenation reaction host with a noble metal catalyst such as palladium (Pd), platinum (Pt), or the like. Precious metal catalysts are very expensive and cause increased costs. However, when metals other than noble metal catalysts are used, such as nickel (Ni)-based catalysts, aromatic double bonds are hydrogenated together with olefinic double bonds, so it is difficult to control the aromatic double bond content, APHA value, aromatic degree, etc.

[technical problem]

In order to solve the above problems, there is provided a method for continuously preparing a hydrogenated petroleum resin, which can easily control the APHA value and the aromaticity according to the application of the hydrogenated petroleum resin.

[Technical solutions]

According to a specific example of the present invention, there is provided a method for continuously preparing hydrogenated petroleum resin, the method comprising the following steps:

introducing the petroleum resin, solvent, first hydrogenation catalyst, second hydrogenation catalyst and hydrogen into a continuous slurry reactor for continuous hydrogenation;

The catalyst mixture in which the first hydrogenation catalyst and the second hydrogenation catalyst are contained is periodically or aperiodically introduced and discharged during the hydrogenation reaction such that, based on the total weight of the reaction solution including the petroleum resin and the solvent, there is a continuous slurry reaction The concentration of the total hydrogenation catalyst in the vessel comprising the first hydrogenation catalyst and the second hydrogenation catalyst is maintained at 0.5 wt % to 20 wt %;

the first hydrogenation catalyst is a non-selective hydrogenation catalyst, and the second hydrogenation catalyst is a selective hydrogenation catalyst; and

The hydrogenated petroleum resin obtained by the continuous hydrogenation reaction has an APHA value of 25 or less as measured by ASTM D1209, and an aromaticity of 3% to 20% as measured by 1H-NMR.

[Beneficial effect]

According to the preparation method of the present invention, hydrogenated petroleum resins with excellent color and aromaticity can be prepared by highly selective hydrogenation of olefinic double bonds in petroleum resins having aromatic double bonds and olefinic double bonds.

In addition, by periodically or aperiodically introducing a catalyst mixture comprising the first hydrogenation catalyst and the second hydrogenation catalyst into the continuous slurry reactor during the hydrogenation reaction, the color and aromaticity of the hydrogenated petroleum resin can be constantly maintained .

The present invention is capable of various modifications and forms, and specific embodiments will be described and explained in detail hereinafter. However, it is not intended herein to limit the present invention to these specific embodiments, and it must be understood that the present invention includes all modifications, equivalents or substitutions included within the spirit and technical scope of the present invention.

The terminology used herein is used to describe illustrative specific examples only and is not intended to limit the scope of the invention. The singular forms are also intended to include the plural forms unless the context clearly dictates otherwise. The terms "comprising", "comprising" and "containing" are used in this disclosure to indicate the presence of certain features, steps, ingredients, or combinations thereof, but do not preclude the presence of one or more different features, steps, ingredients, or combinations thereof. Possibility to exist or add.

Also, in the present invention, when an element is referred to as being formed "on" or "over" another element, it means that each element is formed directly on the other element, or may be additionally between layers, bodies or substrates form other elements.

The method for continuously producing hydrogenated petroleum resin of the present invention will be described in detail below.

The method for continuously preparing hydrogenated petroleum resin according to an embodiment of the present invention is characterized in that the method comprises introducing petroleum resin, a solvent, a first hydrogenation catalyst, a second hydrogenation catalyst and hydrogen into a continuous slurry reactor to conduct continuous the step of hydrogenation;

The catalyst mixture in which the first hydrogenation catalyst and the second hydrogenation catalyst are contained is periodically or aperiodically introduced and discharged during the hydrogenation reaction such that, based on the total weight of the reaction solution including the petroleum resin and the solvent, there is a continuous slurry reaction The concentration of the total hydrogenation catalyst in the vessel including the first hydrogenation catalyst and the second hydrogenation catalyst is maintained at 0.5% by weight to 20% by weight, the first hydrogenation catalyst is a non-selective hydrogenation catalyst, and the second hydrogenation catalyst is a selective hydrogenation catalyst , The hydrogenated petroleum resin obtained by the continuous hydrogenation reaction has an APHA value of 25 or less as measured by ASTM D1209, and an aromaticity of 3% to 20% as measured by 1H-NMR.

In order to prepare petroleum resins including aromatic functional groups, it is very important to control the aromaticity of the final product through selective hydrogenation.

The selective hydrogenation reaction of petroleum resin refers to a reaction in which any one of an aromatic double bond and an olefinic double bond present in the petroleum resin is selectively hydrogenated. In order to prepare a high-quality petroleum resin having an excellent color while containing a desired content of aromatic groups, it is necessary to selectively hydrogenate only the olefinic double bond instead of the aromatic double bond.

When the hydrogenation reaction is carried out using a hydrogenation catalyst that is not selective for aromatic double bonds and olefinic double bonds, the reaction usually hydrogenates both aromatic double bonds and olefinic double bonds, so it is difficult to control both the aromatic hydrocarbon content and the olefin content in the final product. To improve color and thermal stability, when the olefinic double bonds are fully hydrogenated, the aromatic double bonds are also hydrogenated. As a result, the aromatic hydrocarbon content in the final product may be excessively reduced, in which case compatibility with the base polymer may be reduced. Conversely, when the hydrogenation reaction is carried out focusing on satisfying the aromaticity, there are problems of deterioration of color and thermal stability due to a large amount of residual olefinic double bonds.

As the selectivity for olefinic double bonds is higher, the content of aromatic double bonds, ie, the aromaticity of petroleum resins, may increase, which can be determined by 1H-NMR.

Additionally, the APHA value, which is an indicator of the color properties of petroleum resins, typically decreases, but not necessarily proportionally, as the selectivity to olefinic double bonds increases, and the APHA value can be determined according to ASTM D1209. With lower APHA values, the resin becomes a water-white resin with little color and odor, where the residual olefin content (NMR, % area) can be less than 0.1%.

In order to continuously prepare hydrogenated petroleum resins with specific aromaticity and APHA value, attempts have been made to change the type of hydrogenation catalyst. However, noble metal catalysts used to produce highly selective hydrogenation catalysts are very expensive and are the main reason for the increase in cost. When a metal other than a noble metal catalyst is used, such as a nickel (Ni)-based catalyst, the aromatic double bond is hydrogenated together with the olefinic double bond, so it is difficult to control the aromatic double bond content, APHA value, aromaticity, etc. of the petroleum resin. question.

Accordingly, as a method for continuously producing a hydrogenated petroleum resin, it was found that a catalyst mixture comprising a first hydrogenation catalyst and a second hydrogenation catalyst each having a different selectivity is introduced periodically or aperiodically to maintain the catalyst concentration in the reactor In the predetermined range, the hydrogenated petroleum resin with specific aromaticity and APHA value can be continuously prepared, and then the present invention is completed. The thus prepared hydrogenated petroleum resin has excellent compatibility with the base polymer, and its aromaticity and APHA value can be controlled according to its application. Accordingly, the hydrogenated petroleum resin can be applied to various adhesives and/or pressure-sensitive adhesives.

Meanwhile, a type of reactor widely used in the hydrogenation reaction commercially is a fixed bed reactor, which has an advantage of low operating cost in terms of operation. A fixed bed reactor is operated by passing a liquid feedstock with hydrogen from top to bottom or from bottom to top through a reactor comprising a catalyst bed packed with a hydrogenation catalyst to carry out the hydrogenation reaction. The catalyst bed of a fixed bed reactor is usually used after it has been filled with enough catalyst, which is sufficient for long-term use for a period of several months, a year or more.

However, as the hydrogenation reaction proceeds, the activity of the hydrogenation catalyst gradually decreases. At the beginning of the reaction, due to the high catalytic activity, a product with a low content of aromatic double bonds and excellent color can be obtained. When the catalytic activity gradually decreases with time and the conversion rate of the hydrogenation reaction gradually decreases, the content of aromatic double bonds increases, and there are problems that the color and thermal stability also deteriorate.

At the same time, various physical and chemical influences on the catalyst can cause a reduction in catalytic activity, for example, blockage or loss of catalytically active areas due to thermal, mechanical or chemical treatments. In addition, at the start of the reaction, since the reaction proceeds rapidly due to the high concentration of the raw materials, the reaction heat may partially accumulate to generate a hot spot. Sintering due to these hot spots further accelerates the reduction of catalytic activity. This reduction in catalytic activity results in a reduction in overall reactivity and in a reduction in the overall degree of hydrogenation, selectivity and purity of the hydrogenation product. Therefore, if the catalytic activity falls below a certain level, the packed catalyst should be replaced. In this case, since the catalyst cannot be replaced during the reaction in the fixed-bed reactor, the catalyst needs to be replaced after the reaction is completely stopped, which causes huge losses on an industrial scale. In addition, it is basically impossible to control the selectivity of the hydrogenation reaction by changing the type of catalyst during the reaction.

The present invention aims to solve the above-mentioned complex problems by using a mixture of a non-selective hydrogenation catalyst and a selective hydrogenation catalyst with high selectivity to olefin double bonds in the hydrogenation reaction of petroleum resin, and using a continuous slurry reactor instead of fixed The hydrogenation reaction is carried out in a bed reactor, and then high-quality hydrogenated petroleum resin satisfying both aromaticity and APHA value can be efficiently prepared.

In addition, since the type of the hydrogenation catalyst can be changed during the process, the selectivity of the hydrogenation reaction can be easily controlled as required.

Specifically, in the method for continuously preparing hydrogenated petroleum resin according to an embodiment of the present invention, petroleum resin, solvent, first hydrogenation catalyst, second hydrogenation catalyst and hydrogen are introduced into a continuous slurry reactor for continuous the hydrogenation reaction.

Petroleum resins are subjects that require selective hydrogenation, for example, petroleum resins may include dicyclopentadiene (DCPD), C5 petroleum fractions, C8 petroleum fractions, C9 petroleum fractions, or polymers thereof. C5 petroleum fractions are petroleum fractions obtained by pretreatment, distillation, and polymerization of petroleum, its by-products, and combinations thereof. C5 petroleum fractions refer to cyclopentadiene, isoprene An unsaturated hydrocarbon having 5 carbon atoms such as isoprene and piperylene. C8 petroleum fractions are petroleum fractions obtained by pretreatment, distillation, and polymerization of petroleum, its by-products, and combinations thereof. C8 petroleum fractions refer to styrene, octane, etc. with 8 carbon atoms. atomic unsaturated hydrocarbons. C9 petroleum fractions are petroleum fractions obtained by pretreatment, distillation, and polymerization of petroleum, its by-products, and combinations thereof. C9 petroleum fractions refer to vinyltoluene, indene, etc., which have 9 carbon atoms. atomic unsaturated hydrocarbons.

In addition, as the solvent, saturated hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, undecane, Dodecane, cyclohexane, methylcyclohexane, etc., but the present invention is not limited thereto.

The solvent may be used in an amount of 40 to 80 parts by weight based on 100 parts by weight of the petroleum resin. When the amount of the solvent to be used is less than 40 parts by weight, there is a concern that the reactivity and process stability may decrease due to an increase in viscosity. When the amount of the solvent used exceeds 80 parts by weight, there are concerns that productivity decreases and solvent recovery energy increases. Preferably, based on 100 parts by weight of petroleum resin, the solvent can be used in an amount of more than 40 parts by weight, more than 50 parts by weight, or more than 60 parts by weight, and the solvent can use less than 80 parts by weight, or less than 75 parts by weight, or 70 parts by weight. amount below the serving size.

The mixing of the petroleum resin and the solvent can be carried out according to a common method, and in the present invention, it can be carried out in a continuous slurry reactor.

After mixing the petroleum resin with the solvent, the first hydrogenation catalyst, the second hydrogenation catalyst, and hydrogen are introduced into the continuous slurry reactor.

In the present invention, the first hydrogenation catalyst is a non-selective hydrogenation catalyst, and the second hydrogenation catalyst is a selective hydrogenation catalyst.

The classification of non-selective hydrogenation catalysts and selective hydrogenation catalysts is not an absolute criterion, but a relative criterion. For example, as two hydrogenation catalysts with different selectivity to olefin bonds, including catalyst a and catalyst b. When catalyst a is more selective for olefin bonds than catalyst b, catalyst a can be classified as a selective hydrogenation catalyst, while catalyst b can be classified as a non-selective hydrogenation catalyst. However, when two hydrogenation catalysts include catalyst a and catalyst c having a higher selectivity to olefin bonds than catalyst a, catalyst c can be classified as a selective hydrogenation catalyst and catalyst a can be classified as a non-selective hydrogenation catalyst.

According to an embodiment of the present invention, the first hydrogenation catalyst is a non-selective hydrogenation catalyst comprising nickel (Ni) as an active metal, wherein nickel is supported on a carrier. In other words, the metal component of the first hydrogenation catalyst may consist of nickel.

According to an embodiment of the present invention, the first hydrogenation catalyst includes nickel (Ni) as an active metal and copper (Cu) as a cocatalyst, wherein the nickel and copper are supported on a carrier.

In addition, the second hydrogenation catalyst is a selective hydrogenation catalyst comprising nickel (Ni) as an active metal and sulfur (S) as a co-catalyst, wherein nickel and sulfur are supported on a carrier.

According to an embodiment of the present invention, the second hydrogenation catalyst includes nickel (Ni) as an active metal and copper (Cu) and sulfur (S) as a co-catalyst, wherein the nickel, copper and sulfur are supported on a carrier.

Compared to the second hydrogenation catalyst, the first hydrogenation catalyst may be substantially free of sulfur (S).

Meanwhile, in the preparation process of the first hydrogenation catalyst, when the precursor compound of nickel or copper is a compound containing sulfur (S), a trace amount of sulfur may remain in the first hydrogenation catalyst unintentionally, But even in this case, it is classified as a non-selective hydrogenation catalyst. In other words, in the specification of the present invention, when the first hydrogenation catalyst contains substantially no sulfur or impurely contains a trace amount of sulfur, for example, the amount of sulfur contained is less than 0.5% by weight based on the total weight of the catalyst, Alternatively, the weight ratio of sulfur to nickel (S/Ni) is less than 0.005.

In general, nickel catalysts are known to have very low selectivity for aromatic double bonds and olefinic double bonds, making it difficult to use nickel catalysts in selective hydrogenation reactions. However, the second hydrogenation catalyst of an embodiment of the present invention contains sulfur as a co-catalyst, thereby showing high selectivity for olefinic double bonds. Specifically, by containing sulfur as a co-catalyst or by containing copper and sulfur as a co-catalyst, even if nickel is used, during the hydrogenation reaction of petroleum resin, the hydrogenation reaction rate of olefinic unsaturated bonds is maintained, and aromatic The rate of hydrogenation of unsaturated bonds is also greatly reduced. Thus, selective hydrogenation of olefinic unsaturated bonds is possible.

In addition, the carrier may specifically be one or more selected from silica (silica, SiO ₂ ), diatomite (diatomite), alumina (alumina, Al ₂ O ₃ ) and magnesium oxide (magnesia). When supported on such a carrier, the catalyst can exhibit better catalytic activity by improving the structural stability of the catalyst.

According to an embodiment of the present invention, the carrier is preferably silica, and the silica may have a surface area of 200 square meters per gram (m ² /g) to 400 m ² /g, and a pore size of 10 nanometers ( nm) to 30 nm porous supports. When porous silica having the above-mentioned properties is used as a support, catalytic activity and lifetime can be improved, and the effect of a high-efficiency process for separating products and catalysts can be optimally provided. In addition, by providing the silica support having a uniform particle size distribution, the effect of suppressing the fragmentation of the catalyst can be provided even during the high-speed rotation of the hydrogenation reaction.

In addition, according to an embodiment of the present invention, for the first hydrogenation catalyst and the second hydrogenation catalyst having the above components, the catalytic activity and selectivity can be further improved by controlling the content and physical properties of each component.

Specifically, the first hydrogenation catalyst may include nickel (Ni) in an amount of 40 wt % to 80 wt % based on the total weight of the first hydrogenation catalyst. When the amount of nickel is less than 40% by weight, catalytic activity may decrease, resulting in difficulty in obtaining a hydrogenated petroleum resin having an APHA value of 25 or less. In addition, when the amount of nickel exceeds 80% by weight, preparation is not easy, and there is a problem that catalytic activity is lowered due to low dispersibility. Preferably, based on the total weight of the first hydrogenation catalyst, the content of nickel may be more than 40% by weight, more than 50% by weight, more than 55% by weight or more than 60% by weight, and the content of nickel may be less than 80% by weight, 75% by weight or more. % by weight or less or 70% by weight or less.

In addition, when the first hydrogenation catalyst further includes copper (Cu) as a co-catalyst, the content of copper (Cu) may be 0.1 wt % to 5 wt % based on the total weight of the first hydrogenation catalyst. When the amount of copper is less than 0.1% by weight, the reduction degree and dispersibility of nickel may decrease, and thus the catalytic activity may decrease. When the amount of copper exceeds 5% by weight, the dispersibility may decrease, and thus there is a problem that the catalytic activity may decrease. Preferably, based on the total weight of the first hydrogenation catalyst, the content of copper may be more than 0.1% by weight, more than 0.3% by weight, more than 0.5% by weight, or more than 0.7% by weight, and the content of copper may be less than 5% by weight, 4% by weight or more. wt % or less, 3 wt % or less, or 2 wt % or less.

Specifically, the second hydrogenation catalyst may include nickel in an amount of 40 wt % to 80 wt % based on the total weight of the second hydrogenation catalyst. When the amount of nickel is less than 40% by weight, catalytic activity may decrease, resulting in difficulty in obtaining a hydrogenated petroleum resin having an APHA value of 25 or less. In addition, when the amount of nickel is more than 80% by weight, preparation is not easy, catalyst selectivity may be lowered, and catalytic activity may be lowered due to lowered dispersibility. Preferably, based on the total weight of the second hydrogenation catalyst, the content of nickel may be more than 40% by weight, more than 50% by weight, more than 55% by weight or more than 60% by weight, and the content of nickel may be less than 80% by weight, 75% by weight or more. % by weight or less or 70% by weight or less.

In addition, the second hydrogenation catalyst may include sulfur as a co-catalyst in an amount of 0.5 wt % to 20 wt % based on the total weight of the second hydrogenation catalyst. When the sulfur content is less than 0.5 wt %, the selective catalytic activity may decrease, and when the sulfur content exceeds 20 wt %, the dispersibility may decrease, so there is a problem that the selective catalytic activity decreases. Catalytic activity may decrease. Preferably, based on the total weight of the second hydrogenation catalyst, the content of sulfur may be more than 0.5% by weight, more than 1% by weight, more than 3% by weight, or more than 4% by weight, and the content of sulfur may be less than 20% by weight, 10% by weight or more. wt % or less, 8 wt % or less, 7 wt % or less, or 5 wt % or less.

In addition, when the second hydrogenation catalyst further includes copper (Cu) as a co-catalyst, the content of copper (Cu) may be 0.1 wt % to 5 wt % based on the total weight of the second hydrogenation catalyst. When the amount of copper is less than 0.1 wt %, the selective catalytic activity may decrease, and when the amount of copper is more than 5 wt %, the dispersibility may decrease, and thus there is a problem that the selective catalytic activity decreases. Preferably, based on the total weight of the second hydrogenation catalyst, the content of copper may be 0.1 wt% or more, 0.3 wt% or more, 0.5 wt% or more, or 0.7 wt% or more, and the copper content may be 5 wt% or less, 4 wt% or more. wt % or less, 3 wt % or less, or 2 wt % or less.

In addition, in the second hydrogenation catalyst, the weight ratio of sulfur to nickel (S/Ni) may be 0.01 to 0.3.

When the above weight ratio is satisfied while including nickel and sulfur, the selectivity to olefinic double bonds can be further improved. When the weight ratio of sulfur to nickel is less than 0.01, the selective catalytic activity may decrease. When the weight ratio of sulfur to nickel is more than 0.3, the dispersibility may decrease, and thus there is a problem that the selective catalytic activity may decrease. More preferably, the weight ratio of sulfur to nickel may be 0.01 or more, 0.015 or more, 0.02 or more, or 0.025 or more, and the weight ratio of sulfur to nickel may be 0.3 or less, 0.2 or less, 0.1 or less, 0.08 or less, or 0.06 or less.

In addition, the first hydrogenation catalyst and the second hydrogenation catalyst may include the support in an amount of 10 wt % to 50 wt % based on the total weight of each of the first hydrogenation catalyst and the second hydrogenation catalyst. When the amount of the carrier is less than 10% by weight, the improvement effect due to the carrier is insufficient. When the amount of the carrier is more than 50 wt %, it is understood that the catalytic activity may decrease due to the relatively decreased contents of the active metal and the co-catalyst. Preferably, based on the total weight of the catalyst, the content of the carrier can be more than 10% by weight, more than 20% by weight or more than 30% by weight, and the content of the carrier can be less than 50% by weight, less than 45% by weight or less than 40% by weight .

In addition, regarding the first hydrogenation catalyst and the second hydrogenation catalyst, the average crystal size of nickel may be 1 nm to 10 nm, preferably 1 nm or more, 3 nm or more, or 5 nm or more, and the average crystal size of nickel The crystal size can be below 10 nanometers, below 8 nanometers, or below 7 nanometers. When the average crystal size of nickel falls within the above range, excellent catalytic activity can be obtained.

In addition, the average particle size (D ₅₀ ) of the first hydrogenation catalyst and the second hydrogenation catalyst may be 5 micrometers (μm) to 50 micrometers. More specifically, the average particle diameter (D ₅₀ ) may be 5 micrometers or more, 6 micrometers or more, or 7 micrometers or more, respectively, and the average particle diameter (D ₅₀ ) may be 50 micrometers or less, 40 micrometers or less, 30 micrometers or less, or 25 micrometers, respectively. below microns.

When the particle size distributions of the first hydrogenation catalyst and the second hydrogenation catalyst fall within the above range, excellent catalytic activity can be obtained due to the high dispersibility of the catalysts in the reaction solution.

In the present invention, the average particle diameter (D ₅₀ ) represents the particle diameter at the 50% point of the cumulative particle diameter distribution according to the particle diameter when analyzing the particle diameter distribution, and can be measured using a laser diffraction method. Specifically, the catalyst powder to be tested was dispersed in distilled water as a dispersion medium, and then introduced into a laser diffraction particle size analyzer (instrument name: Malvern Instrument Ltd., model: Mastersizer 2000). The particle size distribution can be calculated by measuring the difference in diffraction pattern according to particle size as the particles pass through the laser beam.

The first hydrogenation catalyst described above can be prepared by mixing a precursor compound of nickel with a solvent to prepare a precursor solution, and suspending the support in the precursor solution to precipitate nickel in the support.

Alternatively, when the first hydrogenation catalyst further includes copper, a precursor solution is prepared by mixing a precursor compound of nickel and a precursor compound of copper in a solvent, and then the carrier is suspended in the precursor solution to precipitate nickel and copper in the carrier.

More specifically, the carrier and the nickel precursor compound were first dissolved in distilled water to prepare a precursor solution. When the first hydrogenation catalyst further includes copper, a precursor compound of copper may further be included.

At this time, the precursor compound of nickel may include nickel or a metal salt thereof, such as nickel nitrate, acetate, sulfate, chloride, and the like. Preferably, nickel chloride or nickel sulfate can be used.

As the precursor compound of copper, one or a mixture of two or more selected from the group consisting of nitrates, acetates, sulfates, chlorides and hydroxides of copper can be used. Preferably, copper sulfate can be used.

Meanwhile, when sulfate is used as a precursor compound of nickel or a precursor compound of copper during the preparation of the first hydrogenation catalyst, sulfur may remain in the catalyst. This sulfur is preferably removed as much as possible by washing with a large amount of distilled water in the washing process of the catalyst preparation process by the deposition-precipitation method.

The precursor solution was placed in a precipitation vessel and the temperature was raised to 50°C to 120°C with stirring. Next, a pH adjuster was added to the elevated temperature precursor solution for 30 minutes to 2 hours to induce precipitation. Thus, nickel supported catalysts are produced, or nickel and copper supported catalysts are produced. The pH adjuster may include sodium carbonate or sodium hydrogen carbonate as a precipitator.

The supported catalyst is washed and filtered, then dried at 100°C to 200°C for 5 to 24 hours.

After that, the dried catalyst is activated by reduction at a temperature of 200°C to 500°C, preferably 300°C to 450°C, under a hydrogen gas atmosphere. The activated supported catalyst is immobilized using a nitrogen mixed gas containing 0.1 vol % to 20 vol % of oxygen to prepare a catalyst powder.

In addition, according to an embodiment of the present invention, it may further comprise a step of sintering the dried catalyst in air before reducing the dried catalyst under a hydrogen gas atmosphere. Those skilled in the art can selectively carry out the step of sintering in air as needed, and it can be carried out at a temperature of 200°C to 500°C.

In addition, the above-mentioned second hydrogenation catalyst can be prepared by mixing a precursor compound of nickel and a precursor compound of sulfur in a solvent to prepare a precursor solution, and suspending the carrier in the precursor solution to precipitate nickel and sulfur in the carrier. preparation.

Alternatively, when the second hydrogenation catalyst further contains copper, the precursor compound of nickel, the precursor compound of copper and the precursor compound of sulfur are mixed in a solvent to prepare a precursor solution, and then the carrier is suspended in the precursor solution to Precipitated nickel, copper and sulfur in the support.

More specifically, the carrier, the precursor compound of nickel and the precursor compound of sulfur are first dissolved in distilled water to prepare a precursor solution. When the second hydrogenation catalyst further contains copper, a precursor compound of copper may be further contained.

At this time, the precursor compound of nickel may include nickel or a metal salt thereof, such as nickel nitrate, acetate, sulfate, chloride, and the like. Preferably, nickel chloride or nickel sulfate can be used.

As the precursor compound of copper, one or a mixture of two or more selected from the group consisting of nitrates, acetates, sulfates, chlorides and hydroxides of copper can be used. Preferably, copper sulfate can be used.

As the precursor compound of sulfur, sodium sulfide (Na ₂ S), sodium hydrosulfide (NaHS), sulfur dioxide (SO ₂ ) or sulfur trioxide (SO ₃ ) can be used, Preferably, sodium sulfide can be used.

Meanwhile, when sulfate is used as the precursor compound of nickel or the precursor compound of copper, the precursor compound of sulfur may not be separately introduced.

The precursor solution was placed in a precipitation vessel and the temperature was raised to 50°C to 120°C with stirring. Next, a pH modifier was added to the elevated temperature precursor solution for 30 minutes to 2 hours to induce precipitation. Thus, nickel and sulfur supported catalysts or nickel, copper and sulfur supported catalysts are prepared. The pH adjusting agent may include sodium carbonate or sodium bicarbonate as a precipitating agent.

Afterwards, the washing, filtering and fixing steps can be carried out in the same manner as the preparation of the first hydrogenation catalyst.

However, the preparation method is only an example, and the present invention is not limited thereto.

The first hydrogenation catalyst and the second hydrogenation catalyst may be in powder form or granular form, preferably in powder form.

The first hydrogenation catalyst and the second hydrogenation catalyst thus prepared are introduced into a continuous slurry reactor for hydrogenation, and a petroleum resin solution as an object of hydrogenation is introduced through a separate pipe connected to the reactor, and then mixed with each other.

In this regard, the first hydrogenation catalyst and the second hydrogenation catalyst may be introduced after being mixed with a solvent or a petroleum resin solution.

By using the above-mentioned slurry type reactor in which the catalyst particles dispersed in the reaction solution are continuously reacted, a predetermined amount of fresh catalyst can be introduced periodically or aperiodically during the reaction, while the catalyst can be discharged. Therefore, the catalyst content in the reactor can be easily controlled. As a result, the activity and selectivity of the catalyst can remain unchanged. In addition, the aromaticity can be controlled by controlling the input amount of the first hydrogenation catalyst and the second hydrogenation catalyst, and the color and thermal stability of the prepared hydrogenated petroleum resin can be easily improved. As the reactor, an autoclave type reactor equipped with a stirrer or a loop type reactor capable of mixing the reaction liquid in circulation can be used according to the mixing method.

Subsequently, hydrogen gas was introduced into the continuous slurry reactor for hydrogenation reaction.

The temperature during the hydrogenation reaction may be 150°C to 350°C, preferably 150°C or higher or 200°C or higher and 300°C or lower. Furthermore, the pressure may be 20 bar to 100 bar, preferably 20 bar or more or 50 bar or more and 100 bar or less. When the temperature during the hydrogenation reaction is lower than 150°C or the pressure is lower than 20 bar, the reaction may not occur sufficiently. When the reaction temperature is higher than 350°C or the pressure is higher than 100 bar, overreaction and by-products may occur.

Furthermore, hydrogen can be introduced continuously, so that the reaction pressure is kept constant during the hydrogenation reaction.

In addition, the preparation method according to an embodiment of the present invention may further include a step of: purging the catalyst including the first hydrogenation catalyst and the second hydrogenation catalyst with an inert gas such as nitrogen and argon or a reducing gas such as hydrogen before introducing the hydrogen. Slurry reactors for mixtures and petroleum resin solutions. Preferably, after purging with an inert gas such as nitrogen, the process of purging with hydrogen may be performed. At this time, the purging process may be carried out according to the usual method, or may be repeated once or twice or more.

In addition, a solvent may be further introduced during mixing, and the solvent in this case may be the above-mentioned hydrocarbon solvent.

In the method for continuously producing a hydrogenated petroleum resin of the present invention, the catalyst mixture including the first hydrogenation catalyst and the second hydrogenation catalyst may be introduced periodically or aperiodically so that the total amount based on the reaction solution including the petroleum resin and the solvent is By weight, the concentration of the total hydrogenation catalyst comprising the first hydrogenation catalyst and the second hydrogenation catalyst is maintained at 0.5 wt % to 20 wt %.

The continuous slurry reactor is operated by injecting the catalyst slurry into the reactor at a high speed using a high temperature and high pressure pump, therefore, it is important to operate the reactor under process conditions in which operational stability and reaction efficiency are balanced with each other. From this point of view, when the concentration of the catalyst is lower than 0.5 wt %, the efficiency of the hydrogenation reaction may decrease. When the concentration of the catalyst is too high beyond 20 wt %, the pump may be damaged or malfunction due to strong stress in the catalyst fluidized bed, and thus may be difficult to operate and productivity may be reduced.

Preferably, the catalyst mixture may be introduced such that the concentration of the total hydrogenation catalyst comprising the first hydrogenation catalyst and the second hydrogenation catalyst is maintained at 0.5 wt% or more, 1 wt% or more, 2 wt% based on the total weight of the petroleum resin solution above, 3 wt % or more, or 5 wt % or more, and the concentration of the total hydrogenation catalyst is maintained at 20 wt % or less, 10 wt % or less, or 8 wt %.

Additionally, the catalyst mixture comprising the first hydrogenation catalyst and the second hydrogenation catalyst may be introduced into the continuous slurry reactor multiple times to maintain the above concentrations, and may be introduced or withdrawn periodically or aperiodically.

"Introduced periodically" means the first time point (T1) of the catalyst mixture introduction, the second time point (T2) of the catalyst mixture introduction, the third time point (T3) of the catalyst mixture introduction, the catalyst mixture introduction The time interval between the n-1th time point (Tn-1) and the nth time point (Tn) of the introduction of the catalyst mixture are all the same, such as the time between T1 and T2, the time between T2 and T3 , the time between Tn-1 and Tn are the same.

"Introduced aperiodically" means the first time point (T1) of the catalyst mixture introduction, the second time point (T2) of the catalyst mixture introduction, the third time point (T3) of the catalyst mixture introduction, the catalyst mixture introduction The time interval between the n-1th time point (Tn-1) of the mixture and the nth time point (Tn) of the introduction of the catalyst mixture is different from each other, such as the time between T1 and T2, between T2 and T3 , the time between Tn-1 and Tn are different from each other.

According to a specific example of the present invention, the catalyst mixture may include the first hydrogenation catalyst and the second hydrogenation catalyst in a weight ratio of 1:99 to 99:1, and may be mixed in various weight ratios within the above range as required. For example, the weight ratio of the first hydrogenation catalyst to the second hydrogenation catalyst may be greater than 1:99, greater than 3:97, greater than 5:95, greater than 10:90, greater than 15:85, greater than 20:80, or greater than 30: 70 or more, and the weight ratio can be 99:1 or less, 97:3 or less, 95:5 or less, 90:10 or less, 85:15 or less, 80:20 or less, 70:30, 60:40 or less or 50:50 Below, but the present invention is not limited to this.

According to a specific example of the present invention, after the first hydrogenation catalyst and the second hydrogenation catalyst are introduced for the first time, the first hydrogenation catalyst and the second hydrogenation catalyst in the form of a mixture are periodically or aperiodically introduced at intervals of 1 hour to 24 hours. Dihydrogenation catalyst.

When introduced periodically or aperiodically, the number of times (n) of introduction of the catalyst mixture is not particularly limited as long as it is two or more, and the hydrogenation reaction can be performed by the number of times necessary for introducing the catalyst mixture into production. In addition, the catalyst mixture can be withdrawn from the reactor as needed in order to maintain a constant APHA value and aromaticity.

In addition, the time interval for introducing the catalyst mixture can be adjusted as required, for example, within 1 hour to 24 hours, but the present invention is not limited thereto.

Additionally, for the first introduction and subsequent introductions, the amount of the catalyst mixture per introduction may be from 0.001 wt % to 1 wt % based on the total weight of the reaction solution including the petroleum resin and solvent present in the slurry reactor . When the amount of the catalyst mixture introduced each time is less than 0.001 wt %, the interval between introductions of the catalyst mixture may become too short to maintain a constant aromaticity, and thus the process efficiency may be reduced and may not be practical. When the amount of the catalyst mixture introduced at a time exceeds 1 wt %, it may be difficult to maintain the aromaticity within a predetermined range due to a rapid increase in activity.

At the same time, in order to maintain the target aromaticity of the hydrogenated petroleum resin and the APHA value without significant deviation, for example, maintain the aromaticity and the APHA value within the range of ±15% of the target value, preferably within the range of ±10%, more preferably Within the range of ±5%, in the continuous hydrogenation reaction process, the amount of the catalyst mixture introduced each time and the time interval of the introduction can be appropriately controlled.

In the production method of an embodiment of the present invention, since the hydrogenation reaction is carried out by introducing the first hydrogenation catalyst and the second hydrogenation catalyst while maintaining their total concentration in the continuous slurry reactor, when the catalytic activity is When it decreases as the hydrogenation reaction progresses, or when the aromaticity of the product needs to be controlled, it is not necessary to stop the reaction even if the catalyst needs to be replaced or introduced. In addition, since the catalyst introduced in the reaction process can be changed, the continuous reaction can be carried out, and the catalytic activity can be continuously maintained, thereby significantly improving the efficiency of the hydrogenation reaction.

According to the preparation method of the present invention, the aroma degree can be controlled at 3% to 20% according to the application. At the same time, hydrogenated petroleum resins with excellent color and thermal stability can be prepared. Specifically, the aromaticity of the hydrogenated petroleum resin prepared according to the preparation method may be more than 3%, more than 4% or more than 5%, and the aromaticity may be less than 20%, less than 18%, less than 15%, less than 14% , 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, or 7% or less, which are determined by 1H NMR analysis.

In addition, the APHA value of the hydrogenated petroleum resin may be 25 or less, 20 or less, 15 or less, 14 or less, 13 or less, 12 or less, or 11 or less, which is measured according to ASTM D1209. Also, the lower the APHA value, the better. Therefore, the lower limit of the APHA value is not particularly limited, and examples of the APHA value may be 1 or more, 2 or more, 3 or more, 5 or more, 6 or more, 7 or more, 8 or more, or 9 or more.

Meanwhile, the hydrogenated petroleum resin prepared according to an embodiment of the present invention can be applied to a pressure-sensitive adhesive and/or adhesive because it has a specific range of aromaticity and excellent color.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, these Examples and Comparative Examples are provided only for a better understanding of the present invention, but the scope of the present invention is not limited thereto.

<Preparation Example of Hydrogenation Catalyst>

Preparation Example 1: First Hydrogenation Catalyst (A)

Add 40 grams (g) of porous silica powder with an average particle size of 7 microns, 491 grams of nickel sulfate, 6 grams of copper sulfate, and 2,000 milliliters (ml) of distilled water into a precipitation vessel, and raise the temperature to 80° with stirring C. After reaching 80°C, a 1,500 ml solution containing 262 grams of sodium carbonate was completely introduced within 1 hour using a syringe pump. After the precipitation was complete, the pH of the slurry was 7.6, the slurry was washed with about 30 liters (L) of distilled water and filtered, and then dried at 100°C for 8 hours or more using a drying oven. The product was subdivided and then sintered in air at 300°C. Subsequently, the product was subdivided and then activated by reduction at 400°C under a hydrogen gas atmosphere. The activated catalyst was immobilized using a nitrogen mixed gas containing 1 vol % of oxygen to prepare a hydrogenation catalyst.

In the fixed catalyst, the nickel (Ni) content was 62.3 wt %, the copper (Cu) content was 0.86 wt %, the sulfur (S) content was 0.3 wt %, and the average size of the nickel crystals was determined to be 4.2 wt %, based on the total weight of the catalyst. nanometers. Sulfur (S) is a residual impurity from nickel sulfate and copper sulfate.

The average particle size ( _D50 ) of the catalyst was 7.5 microns.

Preparation Example 2: Second Hydrogenation Catalyst (B)

40 g of porous silica powder with an average particle size of 7 microns, 491 g of nickel sulfate, 6 g of copper sulfate, and 2,000 ml of distilled water were added to a precipitation vessel, and the temperature was raised to 80°C with stirring. After reaching 80°C, a 1,500 ml solution containing 262 grams of sodium carbonate and 32 grams of sodium sulfide was completely introduced within 1 hour using a syringe pump. After the precipitation was completed, the pH of the slurry was 7.5, the slurry was washed with about 30 liters (L) of distilled water and filtered, and then dried at 100°C for 8 hours or more using a drying oven. The product was subdivided and then sintered in air at 300°C. Subsequently, the product was subdivided and then activated by reduction at 400°C under a hydrogen gas atmosphere. The activated catalyst was immobilized using a nitrogen gas mixture containing 1 vol% oxygen to prepare a selective hydrogenation catalyst.

In the fixed catalyst, based on the total weight of the catalyst, the nickel (Ni) content was 63.3 wt %, the copper (Cu) content was 0.87 wt %, the sulfur (S) content was 2.5 wt %, and the average size of the nickel crystals was determined to be 4.7 wt % nanometers.

The average particle size ( _D50 ) of the catalyst was 8.1 microns.

Preparation Example 3: Third Hydrogenation Catalyst (C)

A hydrogenation catalyst was prepared in the same manner as in Preparation Example 1 except that copper sulfate as a raw material for catalyst preparation was not added.

Preparation Example 4: Fourth Hydrogenation Catalyst (D)

A hydrogenation catalyst was prepared in the same manner as in Preparation Example 2, except that copper sulfate as a catalyst preparation raw material was not added.

Preparation Example 5: Fifth Hydrogenation Catalyst (E)

A hydrogenation catalyst was prepared in the same manner as in Preparation Example 2, except that porous silica powder having an average particle diameter of 20 μm was used, and copper sulfate as a catalyst preparation raw material was not added.

The properties of the catalysts of Preparation Examples 1 to 5 are summarized and shown in Table 1 below.

[Table 1] part unit Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 catalyst name A B C D E Nickel crystal size Nanometer (nm) 4.2 4.7 5.1 5.3 4.8 Nickel (Ni) Weight % (wt.%) 62.3 63.3 64.2 64.5 63.8 Copper (Cu) Weight % (wt.%) 0.86 0.87 - - - Sulfur (S) Weight % (wt.%) 0.3 2.5 0.3 2.6 2.6 Sulfur/Ni (S/Ni) wt%/wt% (wt.%/wt.%) 0.0048 0.039 0.0047 0.040 0.041 Silicon dioxide (SiO ₂ ) Weight % (wt.%) 19.2 18.9 18.8 19.0 19.1 Average particle size (D ₅₀ ) Micron (μm) 7.5 8.1 7.3 7.6 20.1

*Nickel (Ni), copper (Cu), and sulfur (S) may exist in the form of oxides, so oxygen (O) is included in the balance other than the components of each of Preparation Examples 1 to 5.

**The catalysts of Preparative Examples 1 and 3 contain trace amounts of sulfur derived from nickel sulfate.

<Example of hydrogenation reaction>

The following hydrogenation reactions were performed using each of the catalysts prepared in Preparation Examples 1 to 5.

Example 1

In a 500 mL-CSTR (continuous stirred tank reactor) type continuous slurry reactor with a high stirring speed of 1,600 RPM (revolutions per minute), as a raw material was introduced at a weight ratio of 60:40. Non-hydrogenated petroleum resin (dicyclopentadiene petroleum resin, Hanwha Solutions Corp.) and solvent Exxsol™ D40 (EXXONMOBIL CHEMICAL). Then, the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (B) of Preparation Example 2 were mixed in a weight ratio of 20:80, and then mixed in a weight ratio of 1.0% by weight based on the total weight of the petroleum resin and the solvent. introduced into the reactor. After connecting the reactor, it was purged 3 times with 5 kilograms per square centimeter (kg/cm ² ) nitrogen (N ₂ ) and 3 times with hydrogen (H ₂ ).

The internal temperature of the reactor was raised to 230°C, and then the hydrogenation reaction was carried out under the reaction pressure to 90 bar. Furthermore, in order to keep the reaction pressure at 90 bar during the hydrogenation reaction, hydrogen will be introduced continuously.

After the continuous hydrogenation reaction begins, the aromaticity of the product increases gradually with the deactivation of the catalyst in the reactor. When the aromaticity of the product reaches 9%, the hydrogenation catalyst (A) of Preparation Example 1 and the selective hydrogenation catalyst (B) of Preparation Example 2 are mixed in a weight ratio of 20:80, and then the petroleum resin and solvent in the reactor are mixed. , was added in an amount of 0.15% by weight. After that, the hydrogenation catalyst (A) of Preparation Example 1 and the selective hydrogenation catalyst (B) of Preparation Example 2 were mixed at a weight ratio of 20:80, and then based on the total weight of the petroleum resin and the solvent in the reactor, every 5 hours It was added in an amount of 0.15% by weight. The catalyst was introduced a total of 3 times, and the reaction was carried out for 20 hours. During the reaction, the hydrogenation reaction was continuously performed while introducing/extracting the catalyst so that the concentration of the catalyst mixture containing the hydrogenation catalyst (A) and the hydrogenation catalyst (B) was maintained at 1.0 wt % based on the total weight of the petroleum resin and the solvent in the reactor to 2.0 wt%.

Example 2

The hydrogenation reaction was carried out in the same manner as in Example 1, except that when the aromaticity of the reaction product reached 15%, the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (B) of Preparation Example 2 were replaced by A weight ratio of 5:95 was mixed and then introduced in an amount of 0.20% by weight based on the total weight of petroleum resin and solvent in the reactor.

Example 3

The hydrogenation reaction was carried out in the same manner as in Example 1, except that when the aromaticity of the reaction product reached 12%, the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (B) of Preparation Example 2 were replaced by Mixed in a weight ratio of 10:90, it was then introduced in an amount of 0.20% by weight based on the total weight of petroleum resin and solvent in the reactor.

Example 4

The hydrogenation reaction was carried out in the same manner as in Example 1, except that when the aromaticity of the reaction product reached 3%, the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (B) of Preparation Example 2 were replaced by A weight ratio of 33.3:66.7 was mixed and then introduced in an amount of 0.10% by weight based on the total weight of petroleum resin and solvent in the reactor.

Example 5

The hydrogenation reaction was carried out in the same manner as in Example 1, except that the catalyst mixture was introduced into the reactor in an amount of 7.0% by weight based on the total weight of the petroleum resin and the solvent, and, during the reaction, based on the petroleum resin and the solvent in the reactor The concentration of the catalyst mixture comprising the hydrogenation catalyst (A) and the hydrogenation catalyst (B) is maintained at 7.0% to 9.0% by weight of the total weight of .

Example 6

The catalyst mixture was introduced into the reactor in an amount of 7.0% by weight based on the total weight of the petroleum resin and the solvent, and when the aromaticity of the reaction product reached 9%, the hydrogenation catalyst (C) of Preparation Example 3 and Preparation Example 4 were prepared The hydrogenation catalyst (D) was mixed in a weight ratio of 20:80 and then introduced in an amount of 0.15 wt % every 5 hours based on the total weight of the petroleum resin and the solvent in the reactor. The hydrogenation reaction was carried out in the same manner as in Example 1, except that, during the reaction, the concentration of the catalyst mixture comprising the hydrogenation catalyst (C) and the hydrogenation catalyst (D) was maintained at 7.0 wt% to 9.0 wt%.

Example 7

The catalyst mixture was introduced into the reactor in an amount of 7.0% by weight based on the total weight of the petroleum resin and the solvent, and when the aromaticity of the reaction product reached 9%, the hydrogenation catalyst (C) of Preparation Example 3 and Preparation Example 5 were prepared The hydrogenation catalyst (E) was mixed in a weight ratio of 20:80 and then introduced in an amount of 0.15 wt % every 5 hours based on the total weight of the petroleum resin and the solvent in the reactor. The hydrogenation reaction was carried out in the same manner as in Example 1, except that, during the reaction, the concentration of the catalyst mixture comprising the hydrogenation catalyst (C) and the hydrogenation catalyst (E) was maintained at 7.0 wt% to 9.0 wt%.

Example 8

The catalyst mixture was introduced into the reactor in an amount of 7.0% by weight based on the total weight of the petroleum resin and the solvent, and, when the aromaticity of the reaction product reached 9%, the hydrogenation catalyst (A) of Preparation Example 1 and Preparation Example 2 were combined The hydrogenation catalyst (B) was mixed in a weight ratio of 30:70, and then introduced in an amount of 0.20 wt % every 8 hours based on the total weight of the petroleum resin and the solvent in the reactor. The hydrogenation reaction was carried out in the same manner as in Example 1, except that, during the reaction, the concentration of the catalyst mixture comprising the hydrogenation catalyst (A) and the hydrogenation catalyst (B) was maintained at 7.0 wt% to 9.0 wt%.

Comparative Example 1

The hydrogenation reaction was carried out in the same manner as in Example 1, except that when the aromaticity of the reaction product reached 9%, only the hydrogenation catalyst (A) of Preparation Example 1 was introduced, and based on the total amount of petroleum resin and solvent in the reactor. weight, it was introduced in an amount of 0.15% by weight.

Comparative Example 2

The hydrogenation reaction was carried out in the same manner as in Example 1, except that when the aromaticity of the reaction product reached 9%, only the hydrogenation catalyst (A) of Preparation Example 1 was introduced, and based on the total amount of petroleum resin and solvent in the reactor. weight, it was introduced in an amount of 0.05% by weight.

<Experimental Example>

The aromaticity and APHA value of Examples and Comparative Examples were measured according to the following methods, respectively, and the results are shown in Table 2 below.

After the hydrogenation reaction started, each hydrogenated petroleum resin that was a product of the hydrogenation reaction was taken out, and its aromaticity and APHA value were measured.

(1) Determination of aroma (%)

The hydrogenated petroleum resins of the hydrogenation reaction products of the Examples and Comparative Examples were dissolved in a deuterated chloroform (CDCl ₃ ) solvent at a concentration of 2.5% by weight to conduct 1H-NMR analysis (600 megahertz (MHz)). As shown in Equation 1 below, the degree of aromaticity (%) is obtained from the ratio of the number of protons in the aromatic region to the total number of hydrogens (protons) in the polymer.

[Equation 1]

In Equation 1, Ar _A is from the 6.0 ppm (parts per million) to 9.0 ppm region specifically in 1H NMR analysis relative to an internal standard (TMS: 0 ppm) for tetramethylsilane (TMS) The number of protons obtained from the area ratio of the peaks of hydrogen bonded to aromatic hydrocarbons appearing in the aromatic region, O _A is the area ratio of the peaks of hydrogen appearing in the olefin region, specifically in the 4.0 ppm to 6.0 ppm region The number of protons obtained, Al _A is the number of protons obtained from the area ratio of the peaks of hydrogen bonded to aliphatic hydrocarbons appearing in the aliphatic region specifically in the 0.1 ppm to 4.0 ppm region.

(2) Determination of APHA value

According to ASTM D1209, the APHA values of the hydrogenated petroleum resins, which are the hydrogenation reaction products of the Examples and Comparative Examples, were measured.

[Table 2] part Aromaticity (%) APHA value 5 hours 10 hours 15 hours 20 hours 5 hours 10 hours 15 hours 20 hours Example 1 8.8 9.1 8.7 9.0 6 6 7 6 Example 2 15.2 14.9 15.1 15.0 8 7 6 5 Example 3 12.1 12.3 11.9 12.2 5 4 3 4 Example 4 3.0 3.5 3.7 3.6 5 4 2 2 Example 5 9.2 8.9 9.3 8.5 5 4 5 7 Example 6 9.1 8.7 9.4 9.1 6 5 6 6 Example 7 9.3 8.7 9.5 8.9 5 4 5 6 Comparative Example 1 9.4 6.8 4.3 2.1 7 3 1 1 Comparative Example 2 9.4 9.0 9.3 9.6 6 18 27 41

[table 3] part Aromaticity (%) APHA value 8 hours 16 hours 24 hours 32 hours 8 hours 16 hours 24 hours 32 hours Example 8 8.5 9.6 8.6 9.4 3 4 3 2

Please refer to Table 2 and Table 3. The hydrogenated petroleum resin obtained by the present invention has an APHA value of 25 or less according to ASTM D1209 and an aromaticity of 3% to 20% according to 1H-NMR, which means that even if the hydrogenation reaction is continuously carried out, The APHA value and aromaticity of the hydrogenated petroleum resin remained unchanged without obvious deviation.

In Comparative Example 1, neither the aromaticity nor the APHA value was maintained continuously during the reaction period. In Comparative Example 2, although the aromaticity remained unchanged, the APHA value increased and the target color could not be satisfied.

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Claims (13)

A method for continuously preparing hydrogenated petroleum resin, the method comprises the following steps: introducing a petroleum resin, a solvent, a first hydrogenation catalyst, a second hydrogenation catalyst and a hydrogen into a continuous slurry reactor to carry out a continuous hydrogenation reaction; The catalyst mixture in which the first hydrogenation catalyst and the second hydrogenation catalyst are contained is periodically or aperiodically introduced and discharged during the hydrogenation reaction, so that a reaction solution based on the petroleum resin and the solvent is included The total weight of the total hydrogenation catalyst present in the continuous slurry reactor comprising the first hydrogenation catalyst and the second hydrogenation catalyst is maintained at a concentration of 0.5% to 20% by weight; the first hydrogenation catalyst is a non-selective hydrogenation catalyst, and the second hydrogenation catalyst is a selective hydrogenation catalyst; and The hydrogenated petroleum resin obtained by the continuous hydrogenation reaction has an APHA value of 25 or less as measured by ASTM D1209, and an aromaticity of 3% to 20% as measured by 1H-NMR. The method of claim 1, wherein the catalyst mixture is introduced at intervals of 1 hour to 24 hours after the first introduction of the first hydrogenation catalyst and the second hydrogenation catalyst. The method of claim 1, wherein the catalyst mixture comprises the first hydrogenation catalyst and the second hydrogenation catalyst in a weight ratio of 1:99 to 99:1. The method of claim 1, wherein the first hydrogenation catalyst and the second hydrogenation catalyst are introduced after being mixed with the solvent or the petroleum resin. The method of claim 1, wherein the catalyst mixture is introduced in an amount of 0.001 weight per introduction based on the total weight of the reaction solution including the petroleum resin and the solvent present in the slurry reactor % to 1% by weight. The method of claim 1, wherein the first hydrogenation catalyst is a nickel-supported catalyst or a nickel and copper-supported catalyst. The method of claim 1, wherein the second hydrogenation catalyst is a catalyst supported by nickel and sulfur on a carrier or a catalyst in which nickel, copper and sulfur are supported on a carrier. The method according to claim 1, wherein the average particle diameters of the first hydrogenation catalyst and the second hydrogenation catalyst are respectively 5 microns to 50 microns. The method of claim 1, wherein the crystal size of nickel in the first hydrogenation catalyst and the second hydrogenation catalyst is each independently 1 nm to 10 nm. The method of claim 1, wherein the petroleum resin comprises dicyclopentadiene, C5 petroleum fraction, C8 petroleum fraction, C9 petroleum fraction, or polymers thereof. The method of claim 1, wherein the solvent is selected from the group consisting of pentane, hexane, heptane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane and the like A mixture of saturated hydrocarbon solvents. The method of claim 1, wherein the hydrogenation reaction is carried out at a temperature of 150°C to 350°C and a pressure of 20 bar to 100 bar. The method of claim 1, wherein the aromaticity determined according to 1H-NMR is calculated by the following equation 1: [Equation 1]

In the Equation 1, Ar _A is from the aromatic region specifically in the 6.0 ppm to 9.0 ppm region relative to an internal standard that is tetramethylsilane (TMS) (TMS: 0 ppm) in 1H NMR analysis The number of protons obtained from the area ratio of the peaks of hydrogen bonded to aromatic hydrocarbons that appear, _OA is the number of protons obtained from the area ratio of the peaks of hydrogen appearing in the olefin region, specifically in the 4.0 ppm to 6.0 ppm region , Al _A is the number of protons obtained from the area ratio of the peaks of the aliphatic hydrocarbon-bonded hydrogen appearing in the aliphatic region specifically in the 0.1 ppm to 4.0 ppm region.