KR102424826B1 - Preparation method of hydrogenated petroleum resin - Google Patents

Abstract

The present invention relates to a method for producing a hydrogenated petroleum resin. More specifically, using a selective hydrogenation catalyst having excellent selectivity for olefin double bonds in petroleum resins, and through hydrogenation in a slurry reactor, hydrogenated petroleum resins exhibiting excellent color and thermal stability while having an aromatization degree of 10% or more It relates to a manufacturing method.

Description

Manufacturing method of hydrogenated petroleum resin {PREPARATION METHOD OF HYDROGENATED PETROLEUM RESIN}

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0065352 on June 3, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.

The present invention relates to a method for producing a hydrogenated petroleum resin. More specifically, through a selective hydrogenation reaction, it relates to a method for producing a hydrogenated petroleum resin exhibiting excellent color and thermal stability while having an aromatization degree of 10% or more.

In general, a hydrogenation or hydrogenation process for an organic compound is a reaction applied to reduce a specific functional group or convert an unsaturated compound into a saturated compound, such as ketones, aldehydes, imines, etc. It can be applied to various compounds, such as reducing a compound having the same unsaturated functional group to a compound such as alcohol or amine, or saturating the unsaturated bond of an olefin compound, and is commercially very important. one of the reactions.

Lower olefins (ie, ethylene, propylene, butylene and butadiene) and aromatics (ie, benzene, toluene and xylene) are basic intermediates widely used in the petrochemical and chemical industries. Thermal cracking, or steam pyrolysis, is the main type of process for forming these materials, typically 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. At this time, by thermally decomposing naphtha, etc., C4 fraction including ethylene, propylene, butane and butadiene, cracked gasoline (including benzene, toluene and xylene), cracked kerosene (C9 or higher fraction), cracked heavy oil (ethylene bottom oil) ) and hydrogen gas can be produced, and petroleum resin can be prepared by polymerization from oil and the like.

However, some petroleum resins contain a double bond of an aromatic moiety (hereinafter referred to as an 'aromatic double bond') and a double bond of an aliphatic moiety (hereinafter referred to as an 'olefin double bond'). If the content is high, the quality of the petroleum resin may deteriorate. At this time, if the olefin double bond is subjected to a hydrogenation process in which hydrogen is added, the quality can be improved, such as unsaturated double bonds are saturated and the color is brightened and the peculiar smell of petroleum resin is reduced.

In the hydrogenation reaction of such a petroleum resin, in order to control the content of aromatic double bonds, it is necessary to selectively hydrogenate the olefinic bonds of the resin. The selective hydrogenation reaction for such an olefinic double bond can be generally performed by contacting hydrogen and a reaction target to be hydrogenated with a noble metal catalyst such as palladium (Pd) or platinum (Pt). Such a noble metal catalyst is very expensive It is expensive and is the main cause of cost increase. However, when a metal other than a noble metal catalyst, for example, a nickel (Ni)-based catalyst is used, the aromatic double bond is hydrogenated together with the olefinic double bond, so that it is difficult to control the content of the aromatic double bond in the petroleum resin.

In order to solve the above problems, the present invention is to provide a method for producing a hydrogenated petroleum resin that exhibits excellent color and thermal stability while having an aromatization degree of 10% or more.

Accordingly, according to one embodiment of the present invention, it comprises the step of performing a hydrogenation reaction by adding a selective hydrogenation catalyst and hydrogen gas to a mixture of petroleum resin and a solvent, wherein the selective hydrogenation catalyst is nickel (Ni) and sulfur ( S) is a supported catalyst supported on a support, and the nickel is contained in an amount of 40 to 80% by weight based on the total weight of the selective hydrogenation catalyst. It provides a method for producing a hydrogenated petroleum resin of 20 or less.

In addition, according to another embodiment of the present invention, there is provided a hydrogenated petroleum resin prepared by the above manufacturing method, having an aromatization degree of 10% or more and an APHA value of 20 or less measured according to ASTM D1209.

According to the production method of the present invention, by performing a hydrogenation reaction with high selectivity for the olefin double bond in a petroleum resin having both an aromatic double bond and an olefinic double bond, hydrogenation exhibiting excellent color and thermal stability while having an aromatization degree of 10% or more Petroleum resin can be produced.

Since the present invention may have various modifications and various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In addition, the terminology used herein is used only to describe exemplary embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "having" are intended to designate the presence of an embodied feature, step, component, or a combination thereof, but one or more other features or steps; It should be understood that the possibility of the presence or addition of components, or combinations thereof, is not precluded in advance.

In addition, in the present invention, when it is said that each component is formed "on" or "on" each component, it means that each component is directly formed on each component, or another component is each It means that it may be additionally formed between layers, on an object, or on a substrate.

Hereinafter, the manufacturing method of the hydrogenated petroleum resin of the present invention will be described in more detail.

According to an embodiment of the present invention, a method for producing a hydrogenated petroleum resin having an aromaticity of 10% or more and an APHA value of 20 or less measured according to ASTM D1209, a selective hydrogenation catalyst and and performing a hydrogenation reaction by introducing hydrogen gas, wherein the selective hydrogenation catalyst is a supported catalyst in which nickel (Ni) and sulfur (S) are supported on a carrier, and the nickel is 40 based on the total weight of the selective hydrogenation catalyst. to 80% by weight.

In order to manufacture a petroleum resin containing an aromatic functional group, a technique for controlling the color, degree of aromatization, and color value of the final product through a selective hydrogenation reaction is very important.

Selective hydrogenation in petroleum resin is a reaction in which hydrogen is selectively added to either an aromatic double bond or an olefinic double bond present in the petroleum resin. Rather, it is necessary to selectively perform the hydrogenation (hydrogenation) reaction only on the olefin double bond.

The higher the selectivity for the olefin double bond, the higher the content of the aromatic double bond of the petroleum resin, ie, the degree of aromatization, and the degree of aromatization can be measured by NMR.

In addition, the APHA value indicating the color characteristics of the petroleum resin is not necessarily proportional thereto, but may generally decrease as the selectivity for the olefin double bond increases, and the APHA value may be measured according to ASTM D1209. The lower the APHA value, the more colorless and transparent (water white) resin that has almost disappeared color and odor, in which case the remaining olefin content (NMR, %area) may be less than 0.1%.

In general, the hydrogenation reaction using a non-selective hydrogenation catalyst hydrogenates both the aromatic double bond and the olefinic double bond, so the degree of aromatization in the final product is high, but it contains an olefinic double bond, so there is a problem that color and thermal stability are lowered. . Conversely, when all olefin double bonds are hydrogenated to improve color and thermal stability, aromatic double bonds are also hydrogenated, so that the aromatic content in the final product is lowered to less than 10%.

Meanwhile, a conventionally widely used reactor type for hydrogenation reaction is a fixed bed reactor, and the fixed bed reactor has advantages of low investment and operating costs. The fixed-bed reactor is a method of performing a hydrogenation reaction by passing a liquid raw material inside a reactor including a catalyst bed filled with a hydrogenation catalyst from top to bottom or from bottom to top together with hydrogen. The catalyst bed of the fixed bed reactor is used by filling a sufficient amount of catalyst to be usable for a long period of time of several months or one year or more.

However, as the hydrogenation reaction proceeds, the activity of the hydrogenation catalyst is gradually decreased. Accordingly, at the beginning of the reaction, the catalyst activity is high, so a product with a low content of aromatic double bonds and excellent color can be obtained. There was a problem in that color and thermal stability were also decreased.

On the other hand, the decrease in catalytic activity is caused by various physical and chemical influences on the catalyst, for example, blockage of catalytically active sites or loss of catalytically active sites as a result of thermal, mechanical or chemical treatment. In addition, in the early stage of the reaction, the reaction proceeds rapidly and rapidly due to the high concentration of the reaction raw material, and the heat of reaction may be partially accumulated to create a hot spot. As sintering occurs by these hot spots, the degradation of the catalyst activity is further accelerated. This reduction in catalytic activity causes a decrease in overall reactivity and causes the overall degree of hydrogenation, selectivity, and purity of the hydrogenation reaction product to fall. In this case, since the catalyst cannot be replaced during the reaction in a fixed bed reactor, the reaction must be completely stopped and the catalyst must be replaced when the catalyst is replaced, resulting in many losses on an industrial scale. In addition, it is fundamentally impossible to change the type of catalyst in the middle of the reaction in order to control the selectivity of the hydrogenation reaction.

The present invention is to solve the above complex problems, and uses a catalyst capable of performing the hydrogenation reaction with high selectivity for olefin double bonds in the hydrogenation reaction of petroleum resin, and furthermore, a slurry reactor instead of a fixed bed reactor By performing a hydrogenation reaction using

Specifically, in the method for producing a hydrogenated petroleum resin according to an embodiment of the present invention, a petroleum resin, which is a hydrogenation reaction target, is mixed with a solvent, and a selective hydrogenation catalyst and gas gas are introduced thereto to perform a hydrogenation reaction.

The hydrogenation reaction target is a target for which selective hydrogenation is requested, for example, a petroleum resin (or non-hydrogenated petroleum resin) composed of C5 or C9 petroleum fractions and by-products and combinations thereof through distillation, pretreatment and polymerization.

In addition, as the solvent, a hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane, cyclohexane, methylcyclohexane, benzene, toluene, or xylene may be used, 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. If the amount of the solvent used is less than 40 parts by weight, there is a risk of a decrease in reactivity and process stability due to an increase in viscosity, and if it exceeds 80 parts by weight, there is a risk of a decrease in productivity and an increase in solvent recovery energy. Preferably, the solvent is 40 parts by weight or more, or 50 parts by weight or more, or 60 parts by weight or more, and the content of the solvent is 80 parts by weight or less, or 75 parts by weight or less, or 70 parts by weight or less with respect to 100 parts by weight of the petroleum resin. can be used as

The mixing of the petroleum resin and the solvent may be carried out according to a conventional method, and in the present invention, it is carried out in a slurry reactor.

After mixing the petroleum resin and the solvent, a selective hydrogenation catalyst is introduced into the reactor.

The selective hydrogenation catalyst includes nickel (Ni) as an active metal and sulfur (S) as a promoter, and the nickel and sulfur are supported catalysts supported on a carrier.

In the specification of the present invention, such a catalyst containing sulfur (S) together with nickel (Ni) is used as another nickel catalyst, for example, containing only nickel as an active metal and not including a cocatalyst, or nickel as an active metal. It is called "nickel-based selective hydrogenation catalyst" to distinguish it from catalysts containing other cocatalysts or compounds other than sulfur.

In general, nickel catalysts are known to be difficult to use for selective hydrogenation because their selectivity for olefin bonds is very low. However, the hydrogenation catalyst according to an embodiment of the present invention exhibits high selectivity for olefin double bonds by including sulfur as a co-catalyst. Specifically, by including sulfur as a co-catalyst, the hydrogenation reaction rate for aromatic unsaturated bonds is greatly reduced while maintaining the hydrogenation reaction rate for olefinic unsaturated bonds during hydrogenation of petroleum resins even when nickel is used, thereby selectively for olefinically unsaturated bonds. Hydrogenation is possible.

In addition, the support may specifically be at least one selected from silica (SiO ₂ ), alumina (Al ₂ O ₃ ), and magnesia, and when supported on such a support, better catalytic activity can be exhibited by improving the structural stability of the catalyst have.

In addition, according to one embodiment of the invention, in the nickel-based selective hydrogenation catalyst having the above configuration, the catalytic activity and selectivity can be further improved by controlling the content and physical properties of the constituent components.

Specifically, the selective hydrogenation catalyst may include nickel (Ni) in an amount of 40 to 80 wt% based on the total weight of the selective hydrogenation catalyst. If the nickel content is less than 40% by weight, the catalyst activity is lowered, and as a result, it is difficult to implement the APHA of the hydrogenated petroleum resin to 20 or less. In addition, when the nickel content exceeds 80% by weight, production is not easy, and there is a problem in that catalyst selectivity is lowered, and catalyst activity is lowered due to lower dispersibility. Preferably, nickel (Ni) is 40 wt% or more, or 50 wt% or more, or 55 wt% or more, or 60 wt% or more, 80 wt% or less, or 75 wt% or less, based on the total weight of the selective hydrogenation catalyst, Alternatively, it may be included in an amount of 70% by weight or less.

In addition, the selective hydrogenation catalyst may include 0.1 to 20% by weight of sulfur (S) as a cocatalyst based on the total weight of the selective hydrogenation catalyst. If the content of the sulfur is less than 0.1% by weight, the selective catalytic activity may be reduced, and if it is more than 20% by weight, the dispersibility may deteriorate and the selective catalytic activity may be lowered. Preferably at least 0.1 wt%, or at least 0.5 wt%, or at least 1 wt%, or at least 3 wt%, or at least 4 wt%, and not more than 20 wt%, or at least 10 wt%, relative to the total weight of the selective hydrogenation catalyst % or less, or 7% by weight or less, or may be included in an amount of 5% by weight or less.

In addition, in the nickel-based selective hydrogenation catalyst, the molar ratio of the sulfur to 1 mol of the nickel (molar ratio of S/Ni) may be 0.03 to 0.5. By including nickel and sulfur to satisfy the above molar ratio, selectivity for olefin double bonds may be further improved. If the molar ratio of S/Ni is less than 0.03, the selective catalytic activity may be reduced, and if the molar ratio exceeds 0.5, the dispersibility may be lowered and the selective catalytic activity may be lowered. More preferably, the molar ratio of S/Ni may be 0.03 or more, or 0.05 or more, or 0.1 or more, or 0.12 or more, and may be 0.5 or less, or 0.35 or less, or 0.3 or less, or 0.2 or less, or 0.15 or less.

In addition, the selective hydrogenation catalyst may include a carrier in an amount of 10 to 50% by weight based on the total weight of the selective hydrogenation catalyst. When the carrier content is less than 10% by weight, the improvement effect due to the inclusion of the carrier is not sufficient, and when it exceeds 50% by weight, there is a risk of lowering the catalyst activity due to a relative decrease in the content of active metal and cocatalyst. Preferably, the carrier is included in an amount of 10 wt% or more, or 20 wt% or more, or 30 wt% or more, and 50 wt% or less, or 45 wt% or less, or 40 wt% or less, based on the total weight of the selective hydrogenation catalyst. can do

In addition, in the nickel-based selective hydrogenation catalyst, the average crystal size of the nickel may be 1 to 10 nm, preferably 1 nm or more, or 3 nm or more, or 5 nm or more, 10 nm or less, or 7 nm or less. . When the average crystal size of the nickel is within the above range, it may exhibit better catalytic activity.

In addition, the selective hydrogenation catalyst may have an average particle size of 1 to 20 μm, preferably 1 μm or more, or 3 μm or more, or 5 μm or more, and 20 μm or less, or 10 μm or less, or 7 μm or less. can When the average particle size of the catalyst is within the above range, better catalytic activity may be exhibited.

The nickel-based selective hydrogenation catalyst may be prepared by mixing a nickel compound and a sulfur raw material in a solvent to prepare a precursor solution, suspending the carrier in the precursor solution, and precipitating nickel and sulfur on the carrier.

When describing the method for preparing the nickel-based selective hydrogenation catalyst in more detail, first, a carrier and a nickel precursor are dissolved in distilled water to prepare a precursor solution. In this case, the nickel precursor may include nickel or metal salts such as nitrate, acetate, sulfate, and chloride of nickel, and most preferably, nickel chloride may be used.

The precursor solution is placed in a precipitation vessel and heated to 50 to 120° C. while stirring. Next, a solution containing a pH adjuster and a sulfur raw material is injected into the elevated temperature precursor solution for 30 minutes to 2 hours to precipitate, thereby forming a supported catalyst on which nickel and sulfur are supported. As the sulfur raw material, one or a mixture of two or more selected from copper nitrate, acetate, sulfate, chloride and hydroxide may be used.

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

Thereafter, the method may further include the step of reducing and activating the dried catalyst at a temperature of 200 to 500° C., preferably 300 to 450° C. in a hydrogen atmosphere, and the activated supported catalyst contains 0.1 to 20% oxygen A powder catalyst can be prepared by passivation with a nitrogen mixed gas.

However, the manufacturing method is merely an example, and the present invention is not limited thereto.

The nickel-based selective hydrogenation catalyst may be in the form of powder, particles, or granules, preferably in the form of a powder.

When the nickel-based selective hydrogenation catalyst prepared as described above is used as a catalyst for hydrogenation reaction alone for petroleum resin, the degree of aromatization of the reaction product may show a high selectivity similar to that of the noble metal catalyst.

According to another embodiment of the present invention, a hydrogenation catalyst (hereinafter referred to as a 'second hydrogenation catalyst') having a different selectivity from the selective hydrogenation catalyst during the hydrogenation reaction may be further included.

Specifically, a selective hydrogenation catalyst comprising nickel and copper (Cu) as a co-catalyst; selective hydrogenation catalysts comprising noble metals; and one or more of a non-selective hydrogenation catalyst of nickel metal, wherein the noble metal is one selected from the group consisting of palladium (Pd), platinum (Pt), ruthenium (Ru), and rhodium (Rh). More than that.

In addition, when the second hydrogenation catalyst is mixed and used, the input amount is not particularly limited because it may vary depending on the desired degree of aromatization of the product, but for example, 0.1 to 10 parts by weight based on 1 part by weight of the selective hydrogenation catalyst. can be used by

The hydrogenation catalyst thus prepared is put into the slurry reactor for the hydrogenation reaction, and the petroleum resin, which is the object of the hydrogenation reaction, is added and mixed through a separate pipe connected to the reactor.

By using a slurry-type reactor in which catalyst particles are dispersed and reacted in the reaction solution as described above, a certain amount of new catalyst can be periodically injected during the reaction and a certain amount of catalyst can be discharged at the same time, so that the catalyst content in the reactor can be controlled. Easy. As a result, the activity and selectivity of the catalyst can always be kept constant. In addition, by controlling the amount of the hydrogenation catalyst with high selectivity, the hydrogenation reaction for the aromatic double bond can be minimized and the hydrogenation for the olefin double bond can be maximized, so that the color and thermal stability of the hydrogenated petroleum resin produced can be easily improved. . Specifically, the reactor may be an autoclave-type reactor equipped with a stirrer or a loop-type reactor in which the reaction fluid is circulated and mixed according to a mixing method.

In addition, the introduction of the hydrogenation catalyst into the slurry reactor may be adopted without limitation in any way, such as one-time, periodic, aperiodic, or continuous.

In addition, the hydrogenation catalyst may be added in an amount of 0.2 to 10 parts by weight based on 100 parts by weight of the petroleum resin as the hydrogenation reaction target. If the input amount of the hydrogenation catalyst is too small, catalytic activity may not be properly expressed, and if the input amount is too large, productivity may be lowered compared to the input amount. Preferably, the hydrogenation catalyst is 0.2 parts by weight or more, or 1 part by weight or more, or 3 parts by weight or more, or 5 parts by weight or more, and the content is 10 parts by weight or less, or 8 parts by weight or less based on 100 parts by weight of the petroleum resin. can be put into

In addition, a solvent may be further added during the mixing, and in this case, the hydrocarbon-based solvent as described above may be used as the solvent.

Then, hydrogen gas is introduced into the reactor to perform a hydrogenation reaction.

The hydrogenation temperature may be 150 to 250 °C, preferably 150 °C or higher, or 200 °C or higher, and 250 °C or lower. In addition, the pressure may be 20 to 100 bar, preferably 20 bar or more, or 50 bar or more, and may be 100 bar or less. When the temperature during the hydrogenation reaction is less than 150 ° C or the pressure is less than 20 bar, there is a fear that a sufficient reaction may not occur, and when the reaction temperature exceeds 250 ° C or the pressure exceeds 100 bar, overreaction and side reactants are generated There is a risk of

In addition, hydrogen gas may be continuously introduced so that the reaction pressure is kept constant during the hydrogenation reaction.

In addition, the manufacturing method according to an embodiment of the present invention purges the inside of the slurry reactor including the mixture of the hydrogenation catalyst and the petroleum resin before the introduction of the hydrogen gas with an inert gas such as nitrogen, argon, or a reducing gas such as hydrogen. It may further include the step of Preferably, after purging with an inert gas such as nitrogen, a process of purging with hydrogen may be performed. In this case, the purge process may be performed according to a conventional method, and may be repeatedly performed once or twice or more.

In the manufacturing method according to an embodiment of the present invention, since the hydrogenation reaction proceeds in the above-described slurry reactor, it is necessary to replace or add a catalyst in order to control the aromatization of the product or decrease in catalytic activity as the hydrogenation reaction proceeds. Since the input catalyst can be changed without stopping the reaction even when there is a continuous reaction, the catalytic activity can be kept constant, so that the efficiency of the hydrogenation reaction can be dramatically improved.

According to the manufacturing method of the present invention as described above, it is possible to prepare a hydrogenated petroleum resin having an aromatization degree of 10% or more and exhibiting excellent color and thermal stability. Specifically, the hydrogenated petroleum resin prepared according to the manufacturing method may have an aromatization degree measured by NMR analysis of 10% or more, or 12% or more, and less than 30%, or 25% or less, or 20% or less or 15% or less, or 14% or less.

In addition, the hydrogenated petroleum resin may have an APHA value measured according to ASTM D1209 of 20 or less, or 17 or less, or 15 or less. In addition, the lower the APHA value, the more preferable, so the lower limit is not particularly limited, but may be, for example, 5 or more, or 10 or more.

In addition, the hydrogenated petroleum resin may have a color level of 13 or more, 15 or less, or 14 or less, measured by a Gardner colorimeter after aging at 180° C. for 72 hours.

On the other hand, the hydrogenated petroleum resin prepared according to an embodiment of the present invention can be used as a pressure-sensitive adhesive and/or adhesive due to the high degree of aromatization and excellent color and thermal stability as described above.

Accordingly, according to another embodiment of the present invention, the hydrogenated petroleum resin prepared by the above-described manufacturing method has an aromatization degree of 10% or more and an APHA value of 20 or less measured according to ASTM D1209, more specifically, an aromatization degree of 10% or more, and less than 30%, or less than 25%, or less than 20% or less than 15%, or less than 14%, and an APHA value measured according to ASTM D1209 of less than or equal to 20, or less than 17, or less than 15, and not more than 5 , or 10 or more, and having a color level of 13 or more and 15 or less, or 14 or less as measured by a Gardner colorimeter after aging at 180° C. for 72 hours, a hydrogenated petroleum resin is provided.

Furthermore, according to another embodiment of the present invention, there is provided a pressure-sensitive adhesive, or adhesive, comprising the above-described hydrogenated petroleum resin.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples, but these are intended to help a specific understanding of the invention and the scope of the present invention is not limited by Examples or Comparative Examples.

<Preparation example of hydrogenation catalyst>

Preparation Example 1: Hydrogenation Catalyst (A)

1 g of porous silica powder having a surface area of 200 m ² /g and a pore size of 28 nm and 50 ml of a solution of nickel chloride (243 g/l nickel) dissolved in distilled water was placed in a precipitation vessel, and the temperature was raised to 80° C. with stirring. After reaching 80°C, 40 ml of a solution containing sodium carbonate (175 g/l) and sodium sulfide (15 g/l) was injected using a syringe pump within 1 hour. After the precipitation was completed, the pH of the slurry was 7.7, which was washed and filtered with about 1.5 L of distilled water, and then dried at 120° C. for 12 hours or more using a drying oven. After subdivision, it was activated by reducing it to a temperature of 400° C. in a hydrogen atmosphere. The activated catalyst was passivated using a nitrogen mixed gas containing 1% oxygen to prepare a nickel-based selective hydrogenation catalyst.

Based on the total weight of the catalyst, the content of nickel in the passivated catalyst was 62.5 wt%, the content of sulfur was 4.5 wt%, and the content of the silica carrier was 33 wt%, the sulfur/nickel molar ratio was 0.13, the nickel The average crystal size of the catalyst was measured to be 5.1 nm and the average particle size of the catalyst was 5 μm.

Preparation Example 2: Hydrogenation Catalyst (B)

A 5% Pd/Carbon powder catalyst (5R452, manufactured by Johnson Matthey) was prepared.

Preparation Example 3: Hydrogenation Catalyst (C)

Ni powder catalyst was prepared.

<Hydrogenation reaction example>

Hydrogenation reaction was carried out as follows using the catalysts prepared in Preparation Examples 1 to 3.

Example 1

1L of 1L of 1,600RPM high-speed stirring batch type reactor, non-hydrogenated petroleum resin (DCPD polymerized petroleum resin) as a raw material and Exxsol™ D40 (EXXONMOBIL CHEMICAL Co., Ltd.) are added in a weight ratio of 60:40, and then the preparation example 1 The prepared catalyst (A) was put into the reactor, and after the reactor was connected, it was purged three times with N ₂ of 5 kg/cm ² , and purged three times with H ₂ , and the reactor pressure was set to 10 bar. At this time, the catalyst (A) was added in an amount of 8 parts by weight based on 100 parts by weight of the non-hydrogenated petroleum resin.

As shown in Table 1 below, after raising the temperature in the reactor to 250 °C, the hydrogenation reaction was performed by pressurizing the reaction pressure to 90 bar. In addition, in order to maintain the reaction pressure at 90 bar during the hydrogenation reaction, hydrogen was continuously supplied.

Example 2

In Example 1, the hydrogenation reaction was carried out in the same manner as in Example 1, except that the hydrogenation catalyst (A) of Preparation Example 1 and the hydrogenation catalyst (C) of Preparation Example 3 were mixed in a weight ratio of 10:90. carried out.

Comparative Example 1

A 0.5% Pd Pellet type catalyst is used as a catalyst, and a fixed bed reactor is used instead of a slurry reactor, and the reaction temperature in the reactor is 250° C., the pressure is 90 bar, and the residence time in the reactor is 2 hours. The hydrogenation reaction was performed in the same manner as in Example 1.

Comparative Example 2

As shown in Table 1 below, the hydrogenation reaction was carried out in the same manner as in Example 1, except that the catalyst (B) prepared in Preparation Example 2 was used instead of the catalyst (A) in Preparation Example 1 as a catalyst. was performed.

Comparative Example 3

As shown in Table 1 below, the hydrogenation reaction was carried out in the same manner as in Example 1, except that the catalyst (C) prepared in Preparation Example 3 was used instead of the catalyst (A) in Preparation Example 1 as a catalyst. was performed.

<Experimental example>

For the hydrogenation reaction of Examples and Comparative Examples, selectivity tests for olefin bonds were performed according to the following method, and the results are shown in Table 1 below.

(1) Measurement of Aromaticity (%)

After dissolving the reactants of the hydrogenation reaction of Examples and Comparative Examples at a concentration of 2.5 wt % in the solvent CDCl ₃ , 1H-NMR analysis (600 MHz) was performed, and as in Equation 1 below, total hydrogen (proton) of the polymer Aromaticity (%) was calculated from the ratio of the number of protons in the aromatic region to the number.

[Equation 1]

In Equation 1, Ar _A is the number of protons obtained from the area ratio of hydrogen peaks bonded to aromatic hydrocarbons, which appear in the aromatic region, specifically 6.0 to 9.0 ppm region, and _OA is the olefin region , specifically, the number of protons obtained from the area ratio of the hydrogen peaks appearing in the 4.0 to 6.0 ppm region, and Al _A is the hydrogen peak bonded to the aliphatic hydrocarbon, which appears in the aliphatic region, specifically 0.1 to 4.0 ppm region. is the number of protons obtained from the area ratio of .

(2) APHA value measurement

APHA values were measured according to ASTM D1209 for the reactants of the hydrogenation reaction of Examples and Comparative Examples.

The APHA value is proportional to the olefin content in the petroleum resin and increases as the number of olefin bonds increases, and the APHA value of the petroleum resin before hydrogenation was 1,500.

(3) Thermal stability evaluation (Ga# at 180℃, 72 hours)

It was evaluated according to ASTMD1544.

Specifically, after measuring 10 g of a sample in a test tube, aging was performed in an oven at 180° C. for 72 hours, and then evaluated by a Gardner color scale. Gardner color has a total of 18 levels of color. In Gardner Color, the color most similar to the color of the aged resin was found with the naked eye and the level of the color was recorded.

Hydrogenation Catalyst Type degree of aromatization
(%) APHA value Ga#
(at 180°C, 72 hours) Example 1 A 14 15 14 Example 2 A+C 10 10 13 Comparative Example 1 B (fixed bed reactor) 9.5 25 17 Comparative Example 2 B 15 25 16 Comparative Example 3 C One 10 12

Referring to Table 1, it was confirmed that, when manufactured by the manufacturing method according to the present invention, the degree of aromatization can be increased to 10% or more while the APHA value is as low as 20 or less. In addition, the hydrogenated petroleum resin of Examples prepared by the manufacturing method according to the present invention exhibited improved color and thermal stability while having a high degree of aromatization of 10% or more.

Claims (17)

It comprises the step of performing a hydrogenation reaction by adding a selective hydrogenation catalyst and hydrogen gas to a mixture of a petroleum resin and a solvent,
The selective hydrogenation catalyst is a supported catalyst in which nickel and sulfur are supported on a support, and the nickel is contained in an amount of 40 to 80% by weight based on the total weight of the selective hydrogenation catalyst,
A method for producing a hydrogenated petroleum resin having an aromatization degree of 10 to 15%, an APHA value of 10 to 20 measured according to ASTM D1209, and a color step of 13 to 15 measured by a Gardner colorimeter after aging at 180° C. for 72 hours.
According to claim 1,
The molar ratio of sulfur to 1 mole of nickel is 0.03 to 0.5, the manufacturing method.
According to claim 1,
The carrier comprises silica, alumina, magnesia, or a mixture thereof.
According to claim 1,
The content of the carrier is 10 to 50% by weight based on the total weight of the selective hydrogenation catalyst.
According to claim 1,
The selective hydrogenation catalyst is used in an amount of 0.2 to 10 parts by weight based on 100 parts by weight of the petroleum resin.
According to claim 1,
In the hydrogenation reaction, a selective hydrogenation catalyst comprising nickel and copper; selective hydrogenation catalysts comprising noble metals; and at least one hydrogenation catalyst selected from the group consisting of a non-selective hydrogenation catalyst for nickel metal is further added.
7. The method of claim 6,
The hydrogenation catalyst is included in an amount of 0.1 to 10 parts by weight based on 1 part by weight of the selective hydrogenation catalyst.
According to claim 1,
The solvent is a hydrocarbon solvent selected from the group consisting of pentane, hexane, heptane, nonane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and mixtures thereof.
According to claim 1,
The solvent is used in an amount of 40 to 80 parts by weight based on 100 parts by weight of the petroleum resin.
According to claim 1,
wherein the hydrogenation reaction is carried out in a slurry reactor.
11. The method of claim 10,
The slurry reactor is an autoclave-type reactor equipped with a stirrer or a loop-type reactor in which the reaction fluid is circulated and mixed.
According to claim 1,
The hydrogenation reaction is carried out at a temperature of 150 to 250 °C, and a pressure of 20 to 100 bar, the manufacturing method.
According to claim 1,
The hydrogenation reaction is carried out while continuously introducing hydrogen gas so that the reaction pressure is maintained during the reaction.
It is prepared by the manufacturing method according to claim 1, the degree of aromatization is 10 to 15%, the APHA value measured according to ASTM D1209 is 10 to 20, and the color step measured by a Gardner colorimeter after aging at 180° C. for 72 hours 13 to 15, hydrogenated petroleum resin.
delete A pressure-sensitive adhesive comprising the hydrogenated petroleum resin according to claim 14.
An adhesive comprising the hydrogenated petroleum resin according to claim 14.