TWI826986B - Method for measuring catalyst concentration in slurry solution and continuous preparation method of hydrogenated petroleum resin using the same - Google Patents

Abstract

This invention relates to a method for measuring the catalyst concentration of a slurry solution by a simple process without stability problems, and a continuous preparation method of a hydrogenated petroleum resin using the same.

Description

Method for measuring catalyst concentration in slurry solution and continuous preparation method of hydrogenated petroleum resin using the method

The present invention relates to a method for measuring the catalyst concentration of a slurry solution through a simple process without stability problems, and a continuous preparation method of hydrogenated petroleum resin using this method. Cross-references to related applications

This application claims the rights and interests of Korean Patent Application No. 10-2021-0047646 filed with the Korean Intellectual Property Office on April 13, 2021, the entire content of which is incorporated herein by reference.

The operation method of the petroleum resin hydrogenation reactor is to use a high-temperature and high-pressure pump to stir the catalyst slurry solution in the reactor. However, if the solid catalyst content in the slurry solution exceeds the standard value, the pump may be damaged due to the strong stress of the fluidized bed. Damage or malfunction, so the hydrogenation reactor operation should be stopped.

Specifically, if the catalyst concentration is low, the hydrogenation performance may be reduced, and if the catalyst concentration is high, it may cause pump failure, so productivity may be reduced due to frequent shutdowns of operations. Therefore, operating the solid catalyst concentration in the slurry solution within a certain range to ensure the operational stability of the hydrogenation reactor is considered to be one of the important process technologies.

Common analyzers for measuring solid catalyst concentration can only be used under aqueous conditions, so there was a need to develop a novel method for measuring catalyst concentration in hydrogenation reactors including organic solvents.

At the same time, if the nickel-based catalyst used in the hydrogenation reactor is recovered through vacuum filtration, heat and flame may be generated due to the self-heating property of the catalyst, thereby reducing stability.

Therefore, there is a need to develop a novel method for measuring the solid catalyst concentration in the reactor through a safer and simpler process.

technical issues

The object of the present invention is to provide a method for measuring the catalyst concentration of a slurry solution through a simple process without stability problems.

Another object of the present invention is to provide a continuous preparation method of hydrogenated petroleum resin, which uses a method of measuring the catalyst concentration of the slurry solution. Technical solution

According to a specific example of the present invention, a method for measuring catalyst concentration in a slurry solution is provided, which includes the following steps: The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; The second cleaning uses alcohol to clean the first cleaned slurry solution; For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and The catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst is measured and is defined as the weight ratio of the catalyst solid content obtained after drying.

According to another specific example of the present invention, a continuous preparation method of hydrogenated petroleum resin is provided, including the following steps: introducing a slurry solution containing petroleum resin, a hydrogenation catalyst and a solvent and hydrogen and oxygen into a continuous slurry reactor to perform a continuous hydrogenation reaction , during the hydrogenation reaction, recover part of the slurry solution and measure the concentration of the hydrogenation catalyst in the slurry solution; introduce and discharge the hydrogenation catalyst periodically or non-periodically, so that the hydrogenation catalyst concentration is maintained at 2wt% to 2wt% based on the total weight of the slurry solution. 20wt%, in which the step of measuring the hydrogenation catalyst concentration includes the following steps: a) The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; b) The second cleaning uses alcohol to clean the first cleaning c) Use deionized water (DI water) to clean the second cleaned slurry solution for the third time; d) Dry the third cleaned slurry solution at 50°C to 70°C to obtain Catalyst solid content; and e) measuring the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, which concentration is defined as the weight ratio of the catalyst solid content obtained after drying. beneficial effect

According to the method of measuring the catalyst concentration in the slurry solution of the present invention, the catalyst concentration in the slurry solution can be measured in a safe and simple method after a multi-step cleaning process of the slurry solution using a specific solvent. In particular, the catalyst concentration in the slurry solution can be accurately measured without the need for separate calibration of the process.

Moreover, according to the continuous preparation method of hydrogenated petroleum resin of the present invention, by using the method of measuring the catalyst concentration in the slurry solution, the catalyst concentration can be effectively controlled and the operating efficiency of the reactor can be significantly improved.

While the invention is susceptible to various modifications and the invention may be taken in various forms, specific embodiments are described and explained in detail below. However, it should be understood that these are not intended to limit the present invention to the specific disclosure, and the present invention includes all modifications, equivalents, or substitutes thereof that do not depart from the spirit and technical scope of the present invention.

Furthermore, the terminology used herein is for the purpose of explaining particular embodiments only and is not intended to limit the invention. A singular expression includes its plural expression unless this is expressly stated from the context or it is obvious that this is not intended. As used herein, the terms "comprising", "equipped with" or "having" are intended to indicate the presence of a feature, number, step, structural element or combination thereof, and they are not intended to exclude one or more other features, The presence or possibility of addition of quantities, steps, structural elements or combinations thereof.

In addition, when reference is made to each layer or element being formed "on" or "over" each layer or element, this means that each layer or element is formed directly on each layer or element, or Other layers or elements may be additionally formed between layers or on a body or a substrate.

The operation method of the petroleum resin hydrogenation reactor is to use a high-temperature and high-pressure pump to stir the catalyst slurry solution in the reactor. However, if the solid catalyst content in the slurry solution exceeds the standard value, the pump may be damaged due to the strong stress of the fluidized bed. Damage or malfunction, so the hydrogenation reactor operation should be stopped.

Therefore, the catalyst concentration in the slurry solution needs to be controlled within a certain range. In order to measure the catalyst concentration, ultrasonic waves have been used in the reactor or the slurry solution has been recovered from the reactor through vacuum filtration. However, if ultrasonic wave is used, it is carried out under aqueous conditions and is not suitable for slurries carried out under organic solvent conditions, and a calibration process is required to measure the concentration, so a separate measurement method is required for calibration. In addition, in the case of vacuum filtration, if a nickel-based catalyst is used, ignition may occur due to self-heating properties, so the stability may be significantly reduced.

In order to solve these problems, the inventors found that by using three different solvents to clean the slurry solution in stages, drying it under specific conditions and measuring the concentration, the catalyst concentration in the slurry solution can be accurately measured through a simple process. With the completion of the present invention, there are no problems such as combustion stability. Method for measuring catalyst concentration in slurry solutions

According to a specific example of the present invention, the method for measuring the catalyst concentration in the slurry solution includes the following steps: The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; The second cleaning uses alcohol to clean the first cleaned slurry solution; For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and The catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst is measured and is defined as the weight ratio of the catalyst solid content obtained after drying.

Each step is explained in detail below.

First, the petroleum resin slurry solution may include petroleum resin, hydrogenation catalyst and solvent.

Petroleum resin needs to be hydrogenated, and the type is not particularly limited. For example, it may include dicyclopentadiene (DCPD), C5 fraction, C8 fraction, C9 fraction or polymerization products thereof.

C5 fraction includes petroleum fractions, by-products and their combinations. It is obtained by pretreatment, distillation and polymerization of petroleum. It refers to C5 unsaturated hydrocarbons, such as cyclopentadiene, isoprene, piperylene and the like. ;C8 fraction includes petroleum fractions, by-products and their combinations. It is obtained by pretreatment, distillation and polymerization of petroleum. It refers to C8 unsaturated hydrocarbons, such as styrene, octene and the like; C9 fraction includes petroleum fractions, by-products and their combinations. The products and their combinations are obtained by preprocessing, distilling and polymerizing petroleum, and refer to C9 unsaturated hydrocarbons, such as vinyl toluene, indene and the like.

The hydrogenation catalyst may be a catalyst containing nickel (Ni) as an active metal. Specifically, the hydrogenation catalyst may be a catalyst carrying nickel (Ni) on a carrier, but is not limited thereto.

The supported catalyst may include, based on 100 parts by weight of the catalyst, 40 to 90 parts by weight of one or more materials selected from the group consisting of nickel (Ni), nickel oxide (NiO, Ni ₂ O ₃ ) and nickel peroxide (NiO ₂ ), and a carrier consisting of 10 to 60 parts by weight.

The active material can be derived from raw material precursors, such as nickel nitrate (Ni(NO ₃ ) ₂ ), nickel chloride (NiCl ₂ ), nickel sulfate (NiSO ₄ ), nickel acetate (Ni(Acetate) ₂ ), preferably using Nickel nitrate.

There is no specific limitation as long as the carrier is a compound commonly used in the art. For example, it can be one or more selected from silica (SiO ₂ ), diatomaceous earth, aluminum oxide (Al ₂ O ₃ ) and magnesium oxide. In this case When supported by a carrier, the catalyst can exhibit better catalytic activity due to the improved structural stability of the catalyst.

The hydrogenation catalyst may further contain cocatalysts, other additives and the like as necessary, without specific limitations.

The average size of the active material is not particularly limited, for example, it may be 1 nm to 10 nm, preferably 1 nm or greater, or 3 nm or greater, or 5 nm or greater, 10 nm or less, or 8 nm or less, or 7 nm or less. When the average size of the active material is within the above range, more excellent catalytic activity can be exhibited.

Saturated hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane and the like can be used as solvents, but the present invention does not Limited to this.

The amount of solvent may be 40 to 80 parts by weight based on 100 parts by weight of petroleum resin. If the amount of solvent is less than 40 parts by weight, the viscosity may increase, so reactivity and process stability may decrease. If it is more than 80 parts by weight, productivity may decrease and solvent recovery energy may increase. Preferably, the amount of solvent can be 40 parts by weight or more, or 50 parts by weight or more, or 60 parts by weight or more, and 80 parts by weight or less, or 75 based on 100 parts by weight of petroleum resin. parts by weight or less or 70 parts by weight or less.

The mixing of petroleum resin and solvent can be carried out by common methods.

According to a specific example of the present invention, the method includes the step of using a saturated hydrocarbon solvent to first clean the petroleum resin slurry solution containing the hydrogenation catalyst.

This step removes residual petroleum resin on the surface of the recovered catalyst, thereby improving the efficiency of the catalyst stabilization process in the subsequent second and third cleaning steps, thereby reducing the final recovered catalyst solids after drying in the process of measuring the concentration of the slurry solution. Errors in contents.

The hydrocarbon solvent used in the first cleaning step can be specifically selected from the group consisting of pentane, hexane, heptane, nonane, decane, undecane, dodecane, cyclohexane and methylcyclohexane. One or more of them, preferably cyclohexane.

The amount of hydrocarbon solvent is not specifically limited, and the amount can be 2-3 times the weight of the slurry solution to be measured.

The cleaning step is performed by a common method. For example, it can be performed by introducing the slurry solution to be measured into a container including filter paper, introducing the cleaning solvent into the container, and introducing the slurry solution into the container, so that the slurry solution is Clean. The cleaning step can be performed 1-3 times, preferably 2-3 times. In this case, it is repeated by the same method.

As long as the filter paper can filter the catalyst solid content, there is no specific limit. For example, PTFE filter paper with a pore size of 0.3㎛-5.0㎛ can be used, but is not limited to this.

Next, the method includes the step of washing the first washed slurry solution a second time with alcohol.

In the first cleaned slurry solution, the saturated hydrocarbon solvent used as the cleaning liquid remains. In the second cleaning step, the corresponding solvent component is removed by using alcohol for the second cleaning, so that the subsequent Deionized water is used in the third cleaning step to improve the efficiency of the catalyst stabilization process.

If the second cleaning step using alcohol is omitted, even if deionized water is used for cleaning with residual organic solvent, the deionized water may not contact the catalyst surface due to the nature of the solvent, making it difficult to achieve catalyst stabilization.

The alcohol used in the second cleaning step can be one or more selected from the group consisting of C1-10 primary alcohol, C1-10 secondary alcohol and C1-10 tertiary alcohol. For example, methanol, ethanol, propanol, butyl alcohol can be used. Alcohol, hexanol and the like, preferably ethanol, 2-propanol, 1-hexanol, 2-methyl-2-propanol and the like can be used.

The amount of alcohol used is not specifically limited, and the amount of solvent used can be 2-3 times the weight of the slurry solution to be measured.

The cleaning step is performed by the same method as the first cleaning step. Specifically, the alcohol used in the second cleaning step can be introduced into the container containing the first cleaned slurry solution, so that the slurry solution Be cleansed. The cleaning step can be performed 1 to 3 times, preferably 2 to 3 times. In this case, the same method is repeated.

Next, the method includes washing the second washed slurry solution a third time using a deionized water (DI water) step.

In the third cleaning step, by performing the third cleaning with deionized water, the active material (such as nickel) may come into contact with water. Therefore, the surface of the active material may be deactivated in the form of hydrates, thereby causing the drying process to fail. Combustion due to the self-heating properties of the active material can be prevented, enabling stable measurement of the catalyst weight. Through this process, the catalyst concentration can ultimately be measured more accurately and more stably.

There is no specific limit on the amount of deionized water used, and the amount used can be 2-3 times the weight of the slurry solution to be measured.

The cleaning step is performed by the same method as the first and second cleaning steps. Specifically, the deionized water for the third cleaning can be introduced into the container containing the second cleaned slurry solution. , let the slurry solution be cleaned. The cleaning step can be performed 1 to 3 times, preferably 2 to 3 times. In this case, the same method is repeated.

Then, the method includes the step of drying the third washed slurry solution at 50°C to 70°C to obtain the catalyst solid content.

Through the drying process of 50°C to 70°C, the residual organic solvent and excess moisture in the slurry solution can be effectively removed without modifying the catalyst. The better drying temperature is 55°C to 65°C.

There is no specific limit to the drying time. It can be carried out within the above temperature range for 10 to 120 minutes to fully remove the residual organic solvent and excess moisture. It is preferably carried out for 30 to 60 minutes.

The method of the drying process is not particularly limited and can be carried out by methods commonly used in the art, for example, it can be carried out in a convection oven.

Through the drying process, the organic solvent and excess moisture in the slurry solution can be effectively removed.

Next, the method includes the step of measuring the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, the concentration being defined as the weight ratio of the catalyst solid content obtained after drying.

Specifically, the catalyst concentration in the slurry solution can be measured according to the following mathematical formula 1.

[Mathematical formula 1] Catalyst concentration in slurry solution (wt%) = (C-B)/A x 100 A: Weight of petroleum resin slurry solution used for measurement B: Weight of filter paper and drying dish before use C: Weight of dried filter paper and drying dish including recovered catalyst solid content

As mentioned above, if the catalyst concentration in the slurry solution is measured through the first, second and third cleaning steps under specific solvents and specific conditions, the petroleum resin slurry residues can be effectively removed while the activity can be The material is stable in hydrate form, so the catalyst concentration in the slurry solution can be accurately measured by a very simple method.

At the same time, if the method of measuring the catalyst concentration in the slurry solution is applied to the continuous production method of hydrogenated petroleum resin using a slurry reactor, the catalyst concentration of the reactor can be effectively controlled, thereby stably maintaining the operation of the reactor. Continuous preparation method of hydrogenated petroleum resin

According to another specific example of the present invention, a continuous preparation method of hydrogenated petroleum resin is provided, which uses a method of measuring the catalyst concentration in the slurry solution.

Specifically, the method consists of the following steps: The slurry solution containing petroleum resin, hydrogenation catalyst and solvent, and hydrogen and oxygen are introduced into the continuous slurry reactor to perform continuous hydrogenation reaction, Recovering a portion of the slurry solution during the hydrogenation reaction and measuring the concentration of the hydrogenation catalyst in the slurry solution; and Periodically or non-periodically introduce and discharge the hydrogenation catalyst so that the concentration of the hydrogenation catalyst is maintained at 2wt% to 20wt% based on the total weight of the slurry solution, The steps for measuring the hydrogenation catalyst concentration include the following steps: a) The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; b) Use alcohol to clean the first cleaned slurry solution for the second cleaning; c) For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; d) Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and e) Measure the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, which concentration is defined as the weight ratio of the catalyst solid content obtained after drying.

First, the method includes the step of introducing a slurry solution containing petroleum resin, a hydrogenation catalyst and a solvent, and hydrogen and oxygen into a continuous slurry reactor to perform a continuous hydrogenation reaction,

The types and contents of the petroleum resin, hydrogenation catalyst and solvent in the slurry solution are as mentioned above, so they will not be described again.

Hydrogenation catalysts can be mixed with solvents or petroleum resins and introduced.

By using a slurry reactor to disperse catalyst particles in the reaction solution and allow it to react continuously, a certain amount of fresh catalyst can be introduced periodically or non-periodicly during the reaction, and the catalyst can be discharged at the same time, so it is easy to control the reactor Catalyst content. As a result, the activity of the catalyst can be kept constant. When additional fresh catalyst is introduced, the catalyst and solvent can be mixed and introduced in separate reactors.

As for the reactor, specifically, depending on the mixing method, an autoclave type reactor equipped with a stirrer or a loop type reactor that mixes the reaction fluid while circulating may be used.

Subsequently, hydrogenation reaction is performed while introducing hydrogen and oxygen into the continuous slurry reactor.

The temperature during the hydrogenation reaction may be 150°C to 350°C, preferably 150°C or higher, or 200°C or higher and 300°C or lower. And, the pressure may be 20 bar to 100 bar, preferably 20 bar or higher, or 50 bar or higher, and 100 bar or lower. If the hydrogenation reaction temperature is lower than 150°C or the pressure is lower than 20 bar, sufficient reaction may not occur. If the reaction temperature is higher than 350°C or the pressure is higher than 100 bar, there is concern about excessive reaction and the production of by-products. Furthermore, hydrogen can be introduced continuously so that the reaction pressure can be constantly maintained during the hydrogenation reaction.

And, a step of purging the inside of the slurry reactor including the mixture of the hydrogenation catalyst and the petroleum resin with an inert gas (such as nitrogen, argon and the like) or a reducing gas (such as hydrogen) before adding the hydrogen gas. Preferably, a process of purging with an inert gas (such as nitrogen) and then purging with hydrogen can be performed. Among them, the purging process can be carried out according to common methods, and can be repeated once or twice.

Also, during mixing, a solvent may be additionally introduced, wherein a hydrocarbon-based solvent as described above may be used as the solvent.

Next, the method includes the steps of recovering a portion of the slurry solution during the hydrogenation reaction and measuring the concentration of the hydrogenation catalyst in the slurry solution.

Specifically, during the hydrogenation reaction, a portion of the slurry solution in the reactor is recovered, and the catalyst concentration in the slurry solution is measured through the following steps a), b), c), d) and e). a) The first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; b) Use alcohol to clean the first cleaned slurry solution for the second cleaning; c) For the third cleaning, use deionized water (DI water) to clean the second cleaned slurry solution; d) Dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content; and e) Measure the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, which concentration is defined as the weight ratio of the catalyst solid content obtained after drying.

Steps a), b), c), d) and e) are the same as those described in the method of measuring the catalyst concentration in the slurry solution, and therefore will not be described again.

Next, the method includes the steps of periodically or non-periodically introducing and discharging the hydrogenation catalyst to maintain the concentration of the hydrogenation catalyst at 2 to 20 wt% based on the total weight of the slurry solution.

The concentration derived according to the above method of measuring the concentration of the hydrogenation catalyst can be regarded as the total concentration in the slurry solution. According to the derived concentration, the hydrogenation catalyst can be introduced and discharged periodically or non-periodically to control the concentration.

Since the continuous slurry reactor is operated by using a high-temperature and high-pressure pump to stir the catalyst slurry in the reactor, it is important to operate under process conditions that balance operational stability and reaction efficiency. In this regard, if the catalyst concentration is lower than 2 wt%, the hydrogen reaction efficiency may be reduced, while if the catalyst concentration is greater than 20 wt%, the strong stress on the fluidized catalyst bed may cause pump damage or failure. Therefore the work may become difficult and productivity may decrease.

Also, the hydrogenation catalyst is introduced into the continuous slurry reactor multiple times to maintain the above concentration, and is introduced and discharged periodically or non-periodically.

The term "periodic introduction" refers to the time interval between the time when the hydrogenation catalyst is introduced for the first time (T1), the time when the hydrogenation catalyst is introduced for the second time (T2), the time when the hydrogenation catalyst is introduced for the third time (T3), and the time when the hydrogenation catalyst is introduced for the third time (T3). The time interval between the time when the hydrogenation catalyst is introduced for the n-1 time (Tn-1) and the time when the hydrogenation catalyst is introduced for the nth time (Tn), that is, the time between T1 and T2, the time between T2 and T3 and Tn The times between -1 and Tn are all the same.

The term "aperiodic introduction" refers to the time interval between the time when the hydrogenation catalyst is introduced for the first time (T1), the time when the hydrogenation catalyst is introduced for the second time (T2), and the time when the hydrogenation catalyst is introduced for the third time (T3). The time interval between the time when the hydrogenation catalyst is introduced for the n-1th time (Tn-1) and the time when the hydrogenation catalyst is introduced for the nth time (Tn), that is, the time between T1 and T2, the time between T2 and T3 and The times between Tn-1 and Tn are different from each other.

The term "discharge" refers to the transfer of the slurry solution of the hydrogenation catalyst from the reactor into a sampling vessel that can be individually depressurized and cooled by operating a valve. In the sampling container, the first slurry solution and hydrogen gas coexist. By introducing a coolant into the cooling dish tube to cool the reaction solution, and then operating the valve of the sampling container to discharge the hydrogen gas, a measurement sample at normal temperature and pressure is obtained.

According to a specific example of the present invention, after the hydrogenation catalyst is introduced for the first time, the hydrogenation catalyst may be introduced periodically or non-periodically at intervals of 1 to 24 hours.

Also, the hydrogenation catalyst introduced for the first time and the hydrogenation catalyst introduced later during the reaction may have the same or different nickel and support contents (wt%) within the range that satisfies the above properties.

In periodic introduction and non-periodic introduction, there is no specific limit on the number of introductions (n) of the hydrogenation catalyst, as long as it is 2 or more times, the hydrogenation catalyst can be introduced multiple times according to production needs to perform the hydrogenation reaction.

Moreover, the time interval for introducing the hydrogenation catalyst is not limited, and can be controlled within 1 to 24 hours as needed, for example.

As mentioned above, according to the preparation method of a specific example of the present invention, the catalyst concentration in the slurry solution after the first, second and third cleaning steps is measured in a specific solvent and under specific conditions, because no catalyst will be produced It is safe due to natural ignition, and the catalyst concentration of the slurry solution can be accurately measured by a very simple method. Moreover, since the hydrogenation reaction is carried out by introducing the hydrogenation catalyst, the concentration of the hydrogenation catalyst is maintained constant in the continuous slurry reactor. Therefore, even if the catalyst needs to be replaced or added according to the progress of the hydrogenation reaction to control the catalytic activity, there is no need to stop the reaction. Changing the catalyst introduced in the middle allows the reaction to proceed continuously and maintain the catalytic activity constantly, thereby significantly improving the efficiency of the hydrogenation reaction.

The functions and effects of the present invention will be explained in detail below through specific embodiments of the present invention. However, these embodiments are only used to illustrate the present invention and do not determine the scope of rights of the present invention thereby. [ Examples and Comparative Examples ]

Synthesis Example 1 : Hydrogenation catalyst of synthesis

Place a 1.875 mL solution of 37.5 g porous silica powder and nickel nitrate (297.3 g/L) in distilled water into a precipitation vessel, and raise the temperature to 80°C while stirring. After reaching 80°C, use a syringe pump to introduce 1.500 mL of sodium carbonate (174.6 g/L) solution into the precipitation vessel within 1 hour. After completing the precipitation, the solution pH is 7.5, wash and filter with about 5L distilled water, and then dry in an oven at 120°C for more than 8 hours. It is subdivided and then reduced and activated at 400°C in a hydrogen atmosphere. The activated catalyst was passivated using a nitrogen gas mixture containing 1% oxygen, thereby preparing a hydrogenation catalyst.

Example 1

98.0 g of a petroleum resin solution prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 was mixed with 2.0 g of a hydrogenation catalyst to prepare a petroleum resin slurry solution, which was introduced into the slurry solution at 1,600 A 500 mL CSTR (Continuous Stirred Tank Reactor) type continuous slurry reactor stirred by RPM was used as the raw material. After fixing the reactor, purge it 3 times with 5 kg/cm ² _N and 3 times with H ₂ .

The temperature in the reactor was raised to 230°C, and then the reactor was pressurized to a reaction pressure of 80 bar, and the hydrogenation reaction was carried out for 1 hour. Also, in order to maintain the reaction pressure at 80 bar during the hydrogenation reaction, hydrogen gas was continuously supplied.

After the reaction for 1 hour, the petroleum resin slurry solution was transferred from the reactor to a separate sampling container, then cooled to room temperature (about 25°C) and reduced to atmospheric pressure (about 1 atm) to obtain 12 g of petroleum resin slurry. Solution sample. The obtained sample was placed in a drying dish with filter paper (PTFE filter paper) of a vacuum filter placed on it, and filtration was started. On a drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Next, 30 g of ethanol each time was introduced 3 times for the second cleaning step. Next, 30 g of deionized water was introduced three times each time for the third cleaning step to stabilize the catalyst activity. After completing the first, second and third cleaning steps, take out the dry drying dish, place it in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dry it at 60°C for 30 minutes to obtain the solid content of the catalyst things.

The catalyst concentration in the slurry solution can be measured according to the following mathematical formula 1. [Mathematical formula 1] Catalyst concentration in slurry solution (wt%) = (C-B)/A x 100 A: Weight of petroleum resin slurry solution used for measurement B: Weight of filter paper and drying dish before use C: Weight of dried filter paper and drying dish including recovered catalyst solid content

Example 2

The catalyst concentration in the slurry solution was measured by the same method as Example 1, except that 96.0 g of petroleum prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 The resin solution and 4.0 g of hydrogenation catalyst were mixed to prepare a petroleum resin slurry solution.

Example 3

The catalyst concentration in the slurry solution was measured by the same method as Example 1, except that 92.0 g of petroleum prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 The resin solution and 8.0 g of hydrogenation catalyst were mixed to prepare a petroleum resin slurry solution.

Example 4

The catalyst concentration in the slurry solution was measured by the same method as Example 1, except that 85.0 g of petroleum prepared by mixing petroleum resin (prepared by Hanwha Solutions) and cyclohexane in a ratio of 60:40 The resin solution and 15.0 g of hydrogenation catalyst were mixed to prepare a petroleum resin slurry solution.

Example 5

The catalyst concentration in the slurry solution was measured by the same method as in Example 1, except that the same content of 1-hexyl alcohol was used instead of ethanol in the second cleaning step.

Example 6

The catalyst concentration in the slurry solution was measured by the same method as in Example 1, except that the same content of 2-propanol was used instead of ethanol in the second cleaning step.

Example 7

The catalyst concentration in the slurry solution was measured by the same method as in Example 1, except that the same content of 2-methyl-2-propanol was used instead of ethanol in the second cleaning step.

Comparative Example 1

12 g of the petroleum resin slurry solution of Example 1 was introduced into a drying dish on which the filter paper (PTFE filter paper) of the vacuum filter was placed, and filtration was started. On the drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Then, the drying dish was taken out, placed in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dried at 60° C. for 30 minutes, in which rapid heating occurred during the drying period, so the catalyst could not be recovered.

Comparative Example 2

12 g of the petroleum resin slurry solution of Example 1 was introduced into a drying dish on which the filter paper (PTFE filter paper) of the vacuum filter was placed, and filtration was started. On the drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Next, 30 g of ethanol each time was introduced three times for the second cleaning step. Then, the drying dish was taken out, placed in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dried at 60° C. for 30 minutes, in which rapid heating occurred during the drying period, so the catalyst could not be recovered.

Comparative Example 3

12 g of the petroleum resin slurry solution of Example 1 was introduced into a drying dish on which the filter paper (PTFE filter paper) of the vacuum filter was placed, and filtration was started. On the drying dish, introduce 30 g of cyclohexane 3 times each time for the first cleaning step. Next, 30 g of deionized water was introduced three times each time to perform the second cleaning step. Then, the drying dish was taken out, placed in a convection oven (Ajeon Heating Industries, Convection oven (G2D)), and dried at 60° C. for 30 minutes, in which rapid heating occurred during the drying period, so the catalyst could not be recovered.

Experimental examples 1

The measured catalyst concentrations and errors in the slurry solutions according to the Examples and Comparative Examples are shown in Table 1 below.

【Table 1】 Catalyst content in the samples used (wt%) Catalyst content in recovered samples (wt%) Error range(%) Example 1 2 2.14 7.0 Example 2 4 4.13 3.25 Example 3 8 8.65 8.12 Example 4 15 15.21 1.4 Example 5 2 2.12 6.0 Example 6 2 2.10 5.0 Example 7 2 2.16 8.0 Comparative Example 1 2 Unable to measure - Comparative Example 2 2 Unable to measure - Comparative Example 3 2 Unable to measure -

As confirmed by the data in Table 1, according to the method of measuring the catalyst concentration in the slurry solution of the present invention, the catalyst concentration in the slurry solution can be measured by a simple method. In particular, based on the actual catalyst content in the slurry solution, the error range is less than 10%, thus confirming that when this method is applied to a continuous slurry reactor, the measurement method of catalyst concentration is highly accurate and, therefore, does not require a separate calibration process. .

Meanwhile, if the first, second and third cleaning steps of the present invention are not completely performed in the comparative example, the catalyst concentration cannot be measured due to heat during the drying process.

Experimental examples 2

In a 500 mL CSTR (Continuous Stirred Tank Reactor) type continuous slurry reactor capable of stirring at 1,600 RPM, petroleum resin feedstock and cyclohexane solvent in a weight ratio of 60:40 are introduced into the reactor, and then the hydrogenation catalyst is Introduce the reactor, fix the reactor, and then flush with 5 kg/ ^cm of N ₃ times and H ₃ times. Among them, the introduction amount of the hydrogenation catalyst is 4.0wt% based on the total weight of the petroleum resin and solvent.

After the temperature in the reactor was raised to 230°C, the pressure was increased to a reaction pressure of 80 bar, and the hydrogenation reaction was carried out for 1 hour. Also, in order to maintain the reaction pressure at 80 bar during the hydrogenation reaction, hydrogen gas was continuously supplied.

For a 12 g petroleum resin slurry solution sample, the catalyst concentration was measured according to the method of Experimental Example 1 Example 1.

Next, the degree of change in the measured catalyst concentration is judged, and the catalyst is introduced/discharged from the reactor after the continuous hydrogenation reaction is started so that the catalyst concentration is maintained at ±0.5 wt% of the initial catalyst concentration.

Then, in order to measure the catalyst concentration in the slurry solution from the above reactor at intervals of 3 hours, recover the slurry solution sample to derive the catalyst concentration change, and accordingly introduce/discharge the catalyst into the reactor so that the catalyst concentration is maintained at the initial catalyst concentration. ±0.5wt%.

The catalyst was introduced/discharged 5 times in total, and the reaction was carried out for a total of 15 hours.

Experimental Example 2 demonstrates that by applying the method for measuring the catalyst concentration in the slurry solution of the present invention to a continuous slurry reactor, the catalyst concentration can be effectively controlled during a total reaction period of 15 hours, thereby effectively performing the reaction.

【Table 2】 Catalyst concentration (wt%) 3 hours 6 hours 9 hours 12 hours 15 hours Experimental Example 2 4.1 3.8 4.2 4.0 4.3

without

without

Claims (7)

A method for measuring the catalyst concentration in a slurry solution, which includes the following steps: the first cleaning uses a saturated hydrocarbon solvent to clean the petroleum resin slurry solution containing the hydrogenation catalyst; the second cleaning uses alcohol to clean the first cleaned slurry material solution; use deionized water (DI water) for the third cleaning to clean the second cleaned slurry solution; dry the third cleaned slurry solution at 50°C to 70°C to obtain the catalyst solid content ( content); and measure the catalyst concentration of the petroleum resin slurry solution containing the hydrogenation catalyst, which concentration is defined as the weight ratio of the catalyst solid content obtained after drying, in which the first cleaning step, the second cleaning step and the third Each cleaning step is performed independently 1 to 3 times. The method of measuring the catalyst concentration in the slurry solution of claim 1, wherein the hydrogenation catalyst is a catalyst carrying nickel (Ni) on a carrier. The method for measuring the catalyst concentration in the slurry solution of claim 1, wherein the petroleum resin contains dicyclopentadiene (DCPD), C5 fraction, C8 fraction, C9 fraction or polymerization products thereof. The method of measuring the catalyst concentration in the slurry solution of claim 1, wherein the saturated hydrocarbon solvent is selected from the group consisting of pentane, hexane, heptane, nonane, decane, undecane, dodecane, and cyclohexane One or more of the group consisting of methylcyclohexane. The method of measuring the catalyst concentration in the slurry solution of claim 1, wherein the alcohol is one or more selected from the group consisting of C1-10 primary alcohol, C1-10 secondary alcohol and C1-10 tertiary alcohol. The method of measuring the catalyst concentration in the slurry solution of claim 1, wherein the drying step is carried out for 10 to 120 minutes. A continuous preparation method of hydrogenated petroleum resin. The method includes the following steps: introducing a slurry solution containing petroleum resin, hydrogenation catalyst and solvent, and hydrogen and oxygen into the continuous slurry reaction process. A reactor is used to perform a continuous hydrogenation reaction, to recover a portion of the slurry solution during the hydrogenation reaction and to measure the concentration of the hydrogenation catalyst in the slurry solution; and to periodically or non-periodically introduce and discharge the hydrogenation catalyst so that the concentration of the hydrogenation catalyst Maintained at 2 wt% to 20 wt% based on the total weight of the slurry solution, wherein the step of measuring the concentration of the hydrogenation catalyst includes the method of measuring the catalyst concentration in the slurry solution as claimed in claim 1.