TW202330652A - 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 a degree of hydrogenation according to application of the hydrogenated petroleum resin through a continuous hydrogenation reaction.

Description

Method for continuously preparing hydrogenated petroleum resin

[Cross-reference between related applications]

This application claims priority based on Korean Patent Application No. 10-2020-0172598 filed on December 10, 2020, and all the content disclosed in the Korean Patent Application Document is incorporated in this specification as a part of it.

The present invention relates to a method for continuously preparing hydrogenated petroleum resin, in particular to a method capable of easily controlling APHA value and degree of hydrogenation through continuous hydrogenation reaction according to the application of hydrogenated petroleum resin A method 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. ), aldehydes, imines and other unsaturated functional groups are reduced to alcohols, amines and other compounds, or the unsaturated bonds of olefinic compounds are saturated and hydrogenated Response is one of the very important ones in business.

Lower olefins (i.e., ethylene, propylene, butylene, and butadiene) and aromatic compounds (i.e., 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 the absence of oxygen. Feedstocks may include petroleum gas and distillates such as naphtha, kerosene and gas oil. In this regard, C4 petroleum fractions (petroleum fraction) including ethylene, propylene, butane (butane) and butadiene, pyrolysis gasoline (including benzene, toluene, and xylene) can be produced through thermal decomposition of naphtha, etc. ), C5 petroleum fractions including dicyclopentadiene (DCPD), cracked kerosene (petroleum fractions above C9), cracked heavy oil (ethylene bottom oil) and hydrogen, and can be prepared by polymerization from petroleum fractions Out of petroleum resin (petroleum resin).

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

In the hydrogenation reaction of this type 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. Selective hydrogenation of olefinic double bonds can generally be carried out by contacting hydrogen gas and the hydrogenation reaction host with a noble metal catalyst such as palladium (Pd), platinum (Pt), etc. Noble metal catalysts are very expensive and cause an increase in cost. However, 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, hydrogenation question of degree.

[technical problem]

In order to solve the above-mentioned problems, there is provided a method for continuously preparing hydrogenated petroleum resins capable of easily controlling the APHA value and the degree of hydrogenation according to the application of the hydrogenated petroleum resins.

[Technical solutions]

According to a specific example of the present invention, a kind of method for continuously preparing hydrogenated petroleum resin is provided, and described method comprises the following steps:

introducing petroleum resin, solvent, first hydrogenation catalyst (hydrogenation catalyst), second hydrogenation catalyst and hydrogen into a continuous slurry reactor (continuous slurry reactor) to carry out continuous hydrogenation reaction;

The catalyst mixture containing the first hydrogenation catalyst and the second hydrogenation catalyst is introduced and discharged periodically or aperiodically during the hydrogenation reaction, so that based on the total weight of the reaction solution including petroleum resin and solvent, there is a continuous slurry reaction maintaining a concentration of the total hydrogenation catalyst comprising the first hydrogenation catalyst and the second hydrogenation catalyst in the vessel at 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 a hydrogenation degree of 40% to 90% as measured by 1H-NMR.

[Invention effect]

According to the preparation method of the present invention, hydrogenated petroleum resin having excellent color and degree of hydrogenation 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 introducing and discharging the catalyst mixture containing the first hydrogenation catalyst and the second hydrogenation catalyst into and out of the continuous slurry reactor periodically or non-periodically during the hydrogenation reaction, the color and hydrogenation of the hydrogenated petroleum resin can be constantly maintained. degree.

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

The terminology used herein is for describing illustrative specific examples only and is not intended to limit the scope of the present invention. Unless the context clearly dictates otherwise, singular forms are intended to include plural forms. The terms "comprising", "comprising" and "having" used in this disclosure are used to indicate the existence of certain features, steps, components or combinations thereof, but do not exclude the presence of one or more different features, steps, components or combinations thereof. Possibility to exist or add.

In addition, in the present invention, when it is mentioned that an element is formed "on" or "over" another element, it means that each element is directly formed on another element, or may be additionally formed between a film layer, a body, or a substrate. form other components.

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

The method for continuously preparing hydrogenated petroleum resin according to a specific example of the present invention is characterized in that the method includes introducing petroleum resin, solvent, a first hydrogenation catalyst, a second hydrogenation catalyst and hydrogen into a continuous slurry reactor for continuous A step of a hydrogenation reaction; wherein the catalyst mixture comprising the first hydrogenation catalyst and the second hydrogenation catalyst is periodically or non-periodically introduced and discharged during the hydrogenation reaction so that based on the total weight of the reaction solution including the petroleum resin and the solvent, there is The concentration of the total hydrogenation catalyst comprising the first hydrogenation catalyst and the second hydrogenation catalyst in the continuous slurry reactor is maintained at 0.5% to 20% by weight; the first hydrogenation catalyst is a non-selective hydrogenation catalyst, and the second hydrogenation catalyst It is a selective hydrogenation catalyst; and the hydrogenated petroleum resin obtained by the continuous hydrogenation reaction has an APHA value of 25 or less according to ASTM D1209, and a hydrogenation degree of 40% to 90% according to 1H-NMR.

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

The selective hydrogenation reaction of petroleum resin refers to a reaction for selectively hydrogenating any one of aromatic double bonds and olefinic double bonds present in petroleum resins. In order to prepare high-quality petroleum resins, it is necessary to selectively hydrogenate only olefinic double bonds instead of aromatic double bonds.

When the hydrogenation reaction is performed using a hydrogenation catalyst that is not selective for aromatic double bonds and olefinic double bonds, the reaction usually hydrogenates both aromatic and olefinic double bonds. Therefore, although the final product has a high degree of hydrogenation, there are problems of color and thermal stability deterioration due to olefinic double bonds. Conversely, when the olefinic double bonds are fully hydrogenated, the aromatic double bonds are also hydrogenated in order to improve color and thermal stability. As a result, the aromatic content in the final product may be excessively reduced, in which case compatibility with the base polymer may be reduced.

Therefore, when fully hydrogenating olefinic double bonds, it is not easy to control the degree of hydrogenation to control the content of aromatic double bonds.

In addition to the selectivity for aromatic double bonds and olefinic double bonds, a hydrogenation catalyst with high catalytic activity for hydrogenation can increase the overall degree of hydrogenation, which can be measured by 1H-NMR.

In addition, when the selectivity for olefinic double bonds increases, the APHA value used to indicate the color properties of petroleum resins usually decreases, but not necessarily proportional to this, and the APHA value can be determined according to ASTM D1209. As the APHA value gets lower, the resin becomes a water-white resin with almost no color and odor, in which the residual olefin content (NMR, % area) can be less than 0.1%.

In order to continuously prepare hydrogenated petroleum resins with specific hydrogenation degree and APHA value, people try to change the type of hydrogenation catalyst. However, the noble metal catalysts used to produce highly selective hydrogenation catalysts are very expensive and are the main reason for the cost increase. When metals other than noble metal catalysts are used, such as nickel (Ni)-based catalysts, the aromatic double bonds are hydrogenated together with the olefin double bonds, so there is a problem that it is difficult to control the aromatic double bond content, APHA value, degree of hydrogenation, etc. of the petroleum resin. question.

Accordingly, as a method for continuously preparing hydrogenated petroleum resins, it was found that when periodically or non-periodically introducing a catalyst mixture comprising a first hydrogenation catalyst and a second hydrogenation catalyst each having a different selectivity to maintain the catalyst concentration in the reactor When the predetermined range, can continuously prepare the hydrogenated petroleum resin with specific degree of hydrogenation and APHA value, and then complete the present invention. The hydrogenated petroleum resin thus prepared has excellent compatibility with the base polymer, and its degree of hydrogenation 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, the type of reactor widely used commercially for hydrogenation reaction is a fixed bed reactor (fixed bed reactor), which has the advantage of low running cost in terms of operation. The fixed-bed reactor operates in such a way that a liquid raw material passes through a reactor including a catalyst bed filled with a hydrogenation catalyst from the upper part to the lower part or from the lower part to the upper part together with hydrogen gas to perform a hydrogenation reaction. The catalyst bed of a fixed bed reactor is usually used after being filled with enough catalyst, which is sufficient for long-term use for several months, a year or longer.

However, as the hydrogenation reaction proceeds, the activity of the hydrogenation catalyst will gradually decrease. At the beginning of the reaction, due to the high catalytic activity, a product with low aromatic double bond content 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 the aromatic double bond increases, and there are problems of poor color and thermal stability.

At the same time, various physical and chemical influences on the catalyst can cause a decrease in catalytic activity, for example, blockage or loss of catalytically active areas due to heat treatment, mechanical treatment or chemical treatment. In addition, at the beginning of the reaction, since the reaction proceeds rapidly due to the high concentration of the raw materials, the heat of reaction may be partially accumulated to generate a hot spot. The reduction in catalytic activity is further accelerated due to sintering of these hot spots. This decrease in catalytic activity can lead to a decrease in overall reactivity and to a decrease in the overall degree of hydrogenation, selectivity, and purity of the hydrogenated product. Therefore, if the catalytic activity drops below a certain level, the packed catalyst should be replaced. At this time, since the catalyst cannot be replaced during the reaction in the fixed-bed reactor, the catalyst needs to be replaced only after the reaction is completely stopped, causing a huge loss on an industrial scale. In addition, it is basically impossible to change the type of catalyst during the reaction to control the selectivity of the hydrogenation reaction.

The present invention aims to solve the above-mentioned complex problems, using a mixture of non-selective hydrogenation catalysts and selective hydrogenation catalysts with high selectivity to olefin double bonds in the hydrogenation of petroleum resins, and adopting continuous slurry reactors instead of fixed The hydrogenation reaction is carried out in a bed reactor, and then a high-quality hydrogenated petroleum resin that satisfies both the degree of hydrogenation and the 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 in a specific example of the present invention, petroleum resin, solvent, first hydrogenation catalyst, second hydrogenation catalyst and hydrogen are introduced into a continuous slurry reactor for continuous hydrogenation reaction.

Petroleum resins are the subject of 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 their combinations. C5 petroleum fractions refer to cyclopentadiene, isoprene Unsaturated hydrocarbons (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 their combinations. C8 petroleum fractions refer to styrene (styrene), octene (octane), etc. with 8 carbons Atoms of unsaturated hydrocarbons. C9 petroleum fractions are petroleum fractions obtained by pretreatment, distillation, and polymerization of petroleum, its by-products and their combinations. C9 petroleum fractions refer to vinyltoluene, indene, etc. with 9 carbons Atoms of 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 parts by weight to 80 parts by weight based on 100 parts by weight of the petroleum resin. When the amount of the solvent is less than 40 parts by weight, there is concern that the reactivity and process stability will decrease due to the increase in viscosity. When the amount of the solvent used exceeds 80 parts by weight, there is a concern 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 be used in an amount of less than 80 parts by weight, or less than 75 parts by weight, or 70 parts by weight less than one serving.

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 the petroleum resin is mixed 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 standard, but a relative standard. For example, as two hydrogenation catalysts having different selectivities for olefin bonds, catalyst a and catalyst b are included. When catalyst a is more selective for olefinic 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 the two hydrogenation catalysts include catalyst a and catalyst c having a higher selectivity for olefin bonds than catalyst a, catalyst c may be classified as a selective hydrogenation catalyst and catalyst a may 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 the nickel is supported on a carrier. In other words, the metal component of the first hydrogenation catalyst may consist of nickel.

According to another 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 the nickel and sulfur are supported on a carrier.

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

The first hydrogenation catalyst may substantially not contain sulfur (S) compared to the second hydrogenation catalyst.

Meanwhile, in the preparation process of the first hydrogenation catalyst, when the precursor compound (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 does not substantially contain 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 , or 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 to aromatic double bonds and olefinic double bonds, making it difficult to use nickel catalysts in selective hydrogenation reactions. However, the second hydrogenation catalyst of one specific example of the present invention contains sulfur as a co-catalyst, thereby exhibiting high selectivity for olefinic double bonds. Specifically, by including sulfur as a co-catalyst or by including copper and sulfur as a co-catalyst, even when nickel is used, aromatic unsaturated The hydrogenation reaction rate of the bond will also be greatly reduced. Thus, selective hydrogenation of olefinic unsaturation is possible.

In addition, the carrier may specifically be one or more selected from silicon dioxide (silica, SiO ₂ ), diatomite (diatomite), aluminum oxide (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 a specific example of the present invention, the carrier is preferably silica, which may have a surface area of 200 square meters per gram (m ² /g) to 400 m ² /g, and a pore diameter of 10 nanometers ( nm) to 30 nm porous supports. When the porous silica having the above characteristics is used as a carrier, it can improve the catalytic activity and lifetime, and can optimally provide the effect of a high-efficiency process for separating the product from the catalyst. In addition, by providing a silica carrier with a uniform particle size distribution, it is possible to provide an effect of suppressing catalyst fragmentation even during high-speed rotation of a hydrogenation reaction.

In addition, according to a specific example 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, the catalytic activity may decrease, making it difficult to obtain 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 of lowering catalytic activity 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 less. % 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 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, dispersibility may decrease, and thus there is a problem that 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 less, 3% by weight or less, or 2% by weight 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, the catalytic activity may decrease, making it difficult to obtain 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, the preparation is not easy, the selectivity of the catalyst may be reduced, and the catalytic activity may be reduced due to the reduction of dispersibility. Preferably, based on the total weight of the second hydrogenation catalyst, the content of nickel may be 40% by weight or more, 50% by weight or more, 55% by weight or more or 60% by weight or more, and the content of nickel may be 80% by weight or less, 75% by weight or less. % by weight or less or 70% by weight or less.

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

In addition, when the second hydrogenation catalyst further includes copper (Cu) as a co-catalyst, the content of copper 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% by weight, the selective catalytic activity may decrease, and when the amount of copper is greater than 5% by weight, the dispersibility may decrease, so there is a problem of decreased selective catalytic activity. Preferably, based on the total weight of the second 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 less, 3% by weight or less, or 2% by weight or less.

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

When the above weight ratio is satisfied while nickel and sulfur are contained, the selectivity to olefinic double bonds can be further improved. When the weight ratio of sulfur to nickel is less than 0.01, selective catalytic activity may decrease. When the weight ratio of sulfur to nickel is greater 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 greater than 0.01, greater than 0.015, greater than 0.02, or greater than 0.025, and the weight ratio of sulfur to nickel may be less than 0.3, less than 0.2, less than 0.1, less than 0.08, or less than 0.06.

In addition, the first hydrogenation catalyst and the second hydrogenation catalyst may include the carrier 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 support is greater than 50% by weight, it is understood that the catalytic activity may decrease due to the relative decrease in the content of the active metal and 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 can be 1 nm to 10 nm, preferably 1 nm or more, 3 nm or more or 5 nm or more, and the average nickel crystal size The crystal size may be below 10 nm, below 8 nm, or below 7 nm. 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, 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. Micron or less.

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 high dispersibility of the catalysts in the reaction solution.

In the present invention, the average particle diameter (D ₅₀ ) means 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, which was 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 the diffraction pattern according to the particle size when the particles pass through the laser beam.

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

Alternatively, when the first hydrogenation catalyst additionally includes copper, the precursor compound of nickel and the precursor compound of copper are mixed in a solvent to prepare a precursor solution, and then the carrier is suspended in the precursor solution to precipitate nickel and copper in the carrier.

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

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 may be used.

As the copper precursor compound, one or a mixture of two or more selected from copper nitrates, acetates, sulfates, chlorides, and hydroxides 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 preparation of the first hydrogenation catalyst, sulfur may remain in the catalyst. It is preferable to remove as much of this sulfur as possible by washing with copious amounts of distilled water during the washing process of the catalyst preparation by the deposition-precipitation method.

Place the precursor solution in a precipitation vessel and raise the temperature to 50°C to 120°C with stirring. Next, a pH adjuster (pH adjuster) is added to the precursor solution at elevated temperature 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 adjusting agent 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 hours to 24 hours.

Afterwards, 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 atmosphere. The activated supported catalyst is fixed using a nitrogen mixed gas containing 0.1 vol% to 20 vol% of oxygen to prepare a catalyst powder.

In addition, according to a specific example of the present invention, it may further include a step of sintering the dried catalyst in air before reducing the dried catalyst under the hydrogen gas environment. Those skilled in the art may selectively perform the step of sintering in air as needed, and may perform the step 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 also contains copper, a precursor compound of nickel, a precursor compound of copper, and a 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 form Precipitates nickel, copper and sulfur in the carrier.

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

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 copper precursor compound, one or a mixture of two or more selected from copper nitrates, acetates, sulfates, chlorides, and hydroxides 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 (sulfur dioxide, SO ₂ ) or sulfur trioxide (sulfur trioxide, SO ₃ ) can be used, Sodium sulfide is preferably 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 individually introduced.

Place the precursor solution in a precipitation vessel and raise the temperature to 50°C to 120°C with stirring. Next, a pH adjuster is 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 were prepared. The pH adjusting agent may include sodium carbonate or sodium bicarbonate as a precipitating agent.

Afterwards, washing, filtering and fixing steps can be performed in the same manner as in 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 the form of powder, particle or granule, preferably powder.

The thus-prepared first hydrogenation catalyst and the second hydrogenation catalyst were introduced into a continuous slurry reactor for hydrogenation, and a petroleum resin solution to be hydrogenated was introduced through separate pipes 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 reactor, in which catalyst particles dispersed in a reaction solution react continuously, a predetermined amount of fresh catalyst can be introduced periodically or non-periodically during the reaction, and the catalyst can be discharged at the same time. 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 degree of hydrogenation 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 a reaction liquid in circulation may be used according to a mixing method.

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

The temperature during the hydrogenation reaction may be from 150°C to 350°C, preferably above 150°C or above 200°C and below 300°C. In addition, the pressure may be from 20 bar to 100 bar, preferably above 20 bar or above 50 bar and below 100 bar. When the temperature is lower than 150°C or the pressure is lower than 20 bar during the hydrogenation reaction, the reaction may not take place sufficiently. When the reaction temperature is higher than 350°C or the pressure is higher than 100 bar, overreaction may occur and by-products may be produced.

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 a specific example of the present invention may further include a step: before introducing hydrogen, purging the chamber containing the first hydrogenation catalyst and the second hydrogenation catalyst with an inert gas such as nitrogen or argon or a reducing gas such as hydrogen Mixture and slurry reactor for petroleum resin solution. 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 can be performed according to the usual method, and can be repeated once or more than twice.

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

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

The continuous slurry reactor is operated by injecting the catalyst slurry into the reactor at high speed by using a high temperature and high pressure pump. Therefore, it is important to operate the reactor under the process conditions where the operational stability and reaction efficiency are balanced with each other. From this point of view, when the concentration of the catalyst is less than 0.5% by weight, the efficiency of the hydrogenation reaction may decrease. When the concentration of the catalyst is too high exceeding 20% by weight, 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 decrease.

Preferably, the catalyst mixture can 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% by weight or more, 1% by weight or more, or 2% by weight based on the total weight of the petroleum resin solution above, above 3% by weight, or above 5% by weight, and the concentration of the total hydrogenation catalyst is maintained at below 20% by weight, below 10% by weight, or below 8% by weight.

In addition, the catalyst mixture including the first hydrogenation catalyst and the second hydrogenation catalyst may be introduced into the continuous slurry reactor multiple times to maintain the above-mentioned concentration, and may be introduced or discharged periodically or non-periodically.

"Periodic introduction" refers to the first time point (T1) of introducing the catalyst mixture, the second time point (T2) of introducing the catalyst mixture, the third time point (T3) of introducing the catalyst mixture, the introduction of the catalyst mixture The time interval between the n-1th time point (Tn-1) of the catalyst mixture and the nth time point (Tn) of introducing the catalyst mixture is the same, for example, the time between T1 and T2, the time between T2 and T3 , Tn-1 and Tn are all the same.

"Aperiodic introduction" refers to the first time point (T1) of introducing the catalyst mixture, the second time point (T2) of introducing the catalyst mixture, the third time point (T3) of introducing the catalyst mixture, and the introduction of the catalyst mixture. The time interval between the n-1 time point (Tn-1) of the mixture and the n-th time point (Tn) of introducing the catalyst mixture is different from each other, for example, the time between T1 and T2, the time 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 1:99 or more, 3:97 or more, 5:95 or more, 10:90 or more, 15:85 or more, 20:80 or more, or 30:90 or more. More than 70, and the weight ratio can be less than 99:1, less than 97:3, less than 95:5, less than 90:10, less than 85:15, less than 80:20, 70:30, less than 60:40 or 50:50 Below, but the present invention is not limited thereto.

According to a specific example of the present invention, after introducing the first hydrogenation catalyst and the second hydrogenation catalyst for the first time, the first hydrogenation catalyst and the second hydrogenation catalyst in the form of a mixture may be introduced periodically or non-periodically at an interval of 1 hour to 24 hours. dihydrogenation catalyst.

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

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

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

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

In the preparation method of a specific example of the present invention, because 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, therefore, when the catalytic activity When it decreases as the hydrogenation reaction progresses, or when it is necessary to control the degree of hydrogenation of the product, there is no need to stop the reaction even if the catalyst needs to be replaced or introduced. In addition, because the catalyst introduced in the reaction process can be changed, 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 degree of hydrogenation can be controlled at 40% to 90% according to the application. At the same time, hydrogenated petroleum resins with excellent color and thermal stability can be prepared. Specifically, the degree of hydrogenation of the hydrogenated petroleum resin prepared according to the preparation method may be above 40%, above 45%, above 50%, above 55% or above 60%, and the degree of hydrogenation may be below 90% or below 85%. , less than 80%, less than 75%, or less than 70%, as 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 the APHA value may be, for example, 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 may be applied to pressure-sensitive adhesives and/or adhesives because it has a specific range of hydrogenation degree 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 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: The first hydrogenation catalyst (A)

Add 40 grams (g) of porous silicon dioxide 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 the precipitation container, and raise the temperature to 80° under stirring c. After reaching 80°C, 1,500 ml of a solution containing 262 grams of sodium carbonate was completely introduced within 1 hour using a syringe pump. After the precipitation was completed, the pH of the slurry was 7.6, the slurry was washed with about 30 liters (L) of distilled water, filtered, and then dried at 100° C. for 8 hours or more using a drying oven. The product was subdivided and then sintered at 300°C in air. Subsequently, the product was subdivided and then reduced for activation at 400 °C under a hydrogen gas atmosphere. The activated catalyst was immobilized with nitrogen mixed gas containing 1 vol% oxygen to prepare a hydrogenation catalyst.

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

The average particle size (D ₅₀ ) of the catalyst was 7.5 microns.

Preparation Example 2: Second Hydrogenation Catalyst (B)

40 grams 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 of distilled water were added to the precipitation vessel, and the temperature was raised to 80° C. under stirring. After reaching 80°C, 1,500 ml of a 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, filtered, and then dried at 100° C. for 8 hours or more using a drying oven. The product was subdivided and then sintered at 300°C in air. Subsequently, the product was subdivided and then reduced for activation at 400 °C under a hydrogen gas atmosphere. The activated catalyst was immobilized with a nitrogen gas mixture containing 1 vol% oxygen to prepare a selective hydrogenation catalyst.

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

The average particle size (D ₅₀ ) of the catalyst was 8.1 microns.

Preparation Example 3: The third hydrogenation catalyst (C)

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

Preparation Example 4: The 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: The fifth hydrogenation catalyst (E)

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

The characteristics 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/Nickel (S/Ni) Weight%/weight% (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 ingredients of each of Preparation Examples 1 to 5.

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

<Example of hydrogenation reaction>

Using each of the catalysts prepared in Preparation Examples 1 to 5, the following hydrogenation reactions were carried out.

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), the 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 added at 1.0% by weight based on the total weight of petroleum resin and solvent amount introduced into the reactor. After the reactor was connected, it was purged three times with 5 kilograms per square centimeter (kg/cm ² ) of nitrogen (N ₂ ) and three times with hydrogen (H ₂ ).

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

After the start of the continuous hydrogenation reaction, the degree of hydrogenation of the product gradually increases as the catalyst in the reactor loses its activity. When the degree of hydrogenation of the product reached 65%, the hydrogenation catalyst (A) of Preparation Example 1 and the selective hydrogenation catalyst (B) of Preparation Example 2 were mixed in a weight ratio of 20:80, and then based on petroleum resin and The total weight of the solvent, which was introduced in an amount of 0.15% by weight. Afterwards, the hydrogenation catalyst (A) of Preparation Example 1 and the selective hydrogenation catalyst (B) of Preparation Example 2 were mixed in a weight ratio of 20:80, and then based on the total weight of petroleum resin and solvent in the reactor, every 5 hours It was introduced 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/expelling 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% by weight based on the total weight of the petroleum resin and the solvent in the reactor to 2.0% by weight.

Example 2

Carry out the hydrogenation reaction in the same manner as in Example 1, and the difference is that when the degree of hydrogenation of the reaction product reaches 45%, the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (B) of Preparation Example 2 are Mixed at a weight ratio of 5:95, 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 3

Carry out the hydrogenation reaction in the same manner as in Example 1, and the difference is that when the degree of hydrogenation of the reaction product reaches 55%, the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (B) of Preparation Example 2 are 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

Carry out the hydrogenation reaction in the same manner as in Example 1, and the difference is that when the degree of hydrogenation of the reaction product reaches 85%, the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (B) of Preparation Example 2 are 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, based on the total weight of petroleum resin and solvent, the catalyst mixture was introduced into the reactor in an amount of 7.0% by weight, and, during the reaction, based on the total weight of petroleum resin and solvent in the reactor, The concentration of the catalyst mixture comprising hydrogenation catalyst (A) and hydrogenation catalyst (B) is maintained at 7.0% by weight to 9.0% by weight.

Example 6

Based on the total weight of petroleum resin and solvent, the catalyst mixture was introduced into the reactor in an amount of 7.0% by weight, and when the degree of hydrogenation of the reaction product reached 65%, the hydrogenation catalyst (C) of Preparation Example 3 and Preparation Example 4 The hydrogenation catalyst (D) was mixed in a weight ratio of 20:80, and then introduced in an amount of 0.15% by weight every 5 hours based on the total weight of petroleum resin and 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% by weight to 9.0% by weight.

Example 7

Based on the total weight of petroleum resin and solvent, the catalyst mixture was introduced into the reactor in an amount of 7.0% by weight, and when the degree of hydrogenation of the reaction product reached 65%, the hydrogenation catalyst (C) of Preparation Example 3 and Preparation Example 5 The hydrogenation catalyst (E) was mixed in a weight ratio of 20:80, and then introduced in an amount of 0.15% by weight every 5 hours based on the total weight of petroleum resin and 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% by weight to 9.0% by weight.

Example 8

Based on the total weight of petroleum resin and solvent, the catalyst mixture was introduced into the reactor in an amount of 7.0% by weight, and when the degree of hydrogenation of the reaction product reached 65%, the hydrogenation catalyst (A) of Preparation Example 1 and Preparation Example 2 The hydrogenation catalyst (B) was mixed in a weight ratio of 30:70, and then introduced in an amount of 0.20% by weight every 8 hours based on the total weight of petroleum resin and 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% by weight to 9.0% by weight.

Comparative example 1

Carry out the hydrogenation reaction in the same manner as in Example 1, except that when the degree of hydrogenation of the reaction product reaches 65%, only the hydrogenation catalyst (A) of Preparation Example 1 is introduced, and based on the total amount of petroleum resin and solvent in the reactor weight, which is introduced in an amount of 0.15% by weight.

Comparative example 2

Carry out the hydrogenation reaction in the same manner as in Example 1, except that when the degree of hydrogenation of the reaction product reaches 65%, only the hydrogenation catalyst (A) of Preparation Example 1 is introduced, and based on the total amount of petroleum resin and solvent in the reactor weight, which is introduced in an amount of 0.05% by weight.

<Experimental Example>

The hydrogenation degree and APHA value of the examples and comparative examples were measured according to the following methods, and the results are shown in Table 2 below.

After the start of the hydrogenation reaction, each hydrogenated petroleum resin as a product of the hydrogenation reaction was taken out, and the degree of hydrogenation and the APHA value thereof were measured.

(1) Determination of degree of hydrogenation (%)

Each of the petroleum resins of Examples and Comparative Examples before and after the hydrogenation reaction was dissolved in a deuterated chloroform (CDCl ₃ ) solvent at a concentration of 2.5% by weight for 1H-NMR analysis (600 megahertz (MHz)). The degree of hydrogenation (%) is obtained as Equation 1 below.

[Formula 1]

Degree of hydrogenation (%)=(1-The total amount of hydrogen contained in the aromatic group (aromatic group) and olefin group (olefin group) in the petroleum resin after hydrogenation/the aromatic group and olefin in the petroleum resin before hydrogenation The total amount of hydrogen contained in the group)×100

In Equation 1, the amount of hydrogen contained in the aromatic group in the petroleum resin is determined from 6.0 ppm relative to the internal standard (TMS: 0 ppm) of tetramethylsilane (TMS) in 1H NMR analysis. The amount of hydrogen contained in olefin groups in petroleum resins is measured from the ratio of the area ratio of the peak area of hydrogen bonded to aromatic hydrocarbons that appears in the aromatic region to the 9.0 ppm region, specifically at 4.0 The area ratio of the hydrogen peak appearing in the olefin region in the region from ppm to 6.0 ppm is measured by the number of protons obtained.

(2) Determination of APHA value

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

[Table 2] part Degree of Hydrogenation (%) APHA value 5 hours 10 hours 15 hours 20 hours 5 hours 10 hours 15 hours 20 hours Example 1 67.8 62.5 68.7 61.2 6 6 7 6 Example 2 40.4 48.2 45.3 47.1 8 7 6 5 Example 3 54.2 57.1 53.3 58.3 5 4 3 4 Example 4 88.2 81.2 86.4 80.5 5 4 2 2 Example 5 63.9 65.1 63.5 66.7 5 4 5 7 Example 6 64.3 65.9 63.1 64.3 6 5 6 6 Example 7 63.5 65.9 62.7 65.1 5 4 5 6 Comparative example 1 63.1 73.3 81.6 94.1 7 3 1 1 Comparative example 2 63.5 67.7 61.3 69.2 6 18 27 41

[table 3] part Degree of Hydrogenation (%) APHA value 8 hours 16 hours 24 hours 32 hours 8 hours 16 hours 24 hours 32 hours Example 8 66.7 62.4 66.3 63.1 3 4 3 2

Please refer to Table 2 and Table 3, the APHA value measured according to ASTM D1209 of the hydrogenated petroleum resin obtained by the present invention is 25 or less, and the hydrogenation degree measured according to 1H-NMR ranges from 40% to 90%, which means that even if the hydrogenation reaction is continuous The APHA value and degree of hydrogenation of the hydrogenated petroleum resin are still kept constant without significant deviation.

In Comparative Example 1, neither the degree of hydrogenation nor the APHA value was kept constant during the reaction period. In Comparative Example 2, although the degree of hydrogenation was maintained, 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, said method comprising the following steps: introducing a petroleum resin, a solvent, a first hydrogenation catalyst, a second hydrogenation catalyst and hydrogen into a continuous slurry reactor to carry out a continuous hydrogenation reaction; The catalyst mixture containing the first hydrogenation catalyst and the second hydrogenation catalyst is introduced and discharged periodically or aperiodically during the hydrogenation reaction, so that based on the reaction solution including the petroleum resin and the solvent , the concentration of the total hydrogenation catalyst comprising the first hydrogenation catalyst and the second hydrogenation catalyst present in the continuous slurry reactor 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; 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 a hydrogenation degree of 40% to 90% as measured by 1H-NMR. The method of claim 1, wherein the catalyst mixture is introduced at an interval of 1 hour to 24 hours after the first introduction of the first hydrogenation catalyst and the second hydrogenation catalyst. The method according to 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 according to 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 amount of the catalyst mixture introduced each time is 0.001 wt. based on the total weight of the reaction solution comprising the petroleum resin and the solvent present in the slurry reactor % to 1% by weight. The method according to claim 1, wherein the first hydrogenation catalyst is a catalyst supported by nickel or a catalyst supported by nickel and copper. The method according to claim 1, wherein the second hydrogenation catalyst is a catalyst supported by nickel and sulfur or a catalyst supported by nickel, copper and sulfur. 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 according to claim 1, wherein the crystal size of the nickel in the first hydrogenation catalyst and the second hydrogenation catalyst is independently 1 nm to 10 nm. The method according to claim 1, wherein the petroleum resin comprises dicyclopentadiene, C5 petroleum fractions, C8 petroleum fractions, C9 petroleum fractions or polymers thereof. The method as claimed in claim 1, wherein the solvent is selected from pentane, hexane, heptane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane and its Mixture of saturated hydrocarbon solvents. The method as claimed in 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 as described in claim 1, wherein the degree of hydrogenation determined by 1H-NMR is calculated by the following equation 1: [Formula 1] Degree of hydrogenation (%)=(1-the total amount of hydrogen contained in aromatic groups and olefin groups in petroleum resin after hydrogenation/the total amount of hydrogen contained in aromatic groups and olefin groups in petroleum resin before hydrogenation )×100 In said Equation 1, the amount of hydrogen contained in the aromatic group in the petroleum resin is obtained from specifically in 1H NMR analysis relative to the internal standard (TMS: 0 ppm) which is tetramethylsilane (TMS) in The amount of hydrogen contained in olefin groups in petroleum resins is measured by the ratio of the area of the peak area of hydrogen bonded to aromatic hydrocarbons that appears in the aromatic region from 6.0 ppm to 9.0 ppm to the number of protons obtained. Specifically, The area ratio of the hydrogen peak appearing in the olefin region in the 4.0 ppm to 6.0 ppm region is measured by the number of protons obtained.