KR102098856B1 - Method for preparing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene using ruthenium catalyst - Google Patents

Abstract

The present invention relates to a method for manufacturing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene. More specifically, the present invention relates to a method for manufacturing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene by using a catalyst on which ruthenium is carried on regular mesoporous silica.

Description

Method for preparing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene using ruthenium catalyst

The present invention relates to a method for preparing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene using a catalyst supporting ruthenium on regular mesoporous silica.

High-energy-density fuel has attracted much attention as a fuel for aircraft with limited volumes such as missiles and rockets due to its high energy content and excellent stability. Dicyclopentadiene and tricyclopentadiene are dense and additional due to their compact structure. It is an ideal high energy density fuel candidate because it causes strain energy. Exo-tetrahydrodicyclopentadiene (exo-THDCPD), which is used as a high energy density fuel that must have a high energy content and low freezing point, has low density (0.94 g / ml) and low calorific value (142,000 Btu / gal). And efforts are being made to improve the calorific value. Recently, tricyclopentadiene is being developed as a strong candidate among polycyclic hydrocarbons that can be used as a high energy density fuel.

Dicyclopentadiene is a raw material that can be produced from the C ₅ fraction of the existing petrochemical process, and it is applied as a high energy density fuel such as Tetrahydrotricyclopentadiene (THTCPD) when an appropriate small polymerization / isomerization catalytic reaction process is applied. can do. It is known that exo-THTCPD has a freezing point, calorific value, and density of -40 ^o C or less, 160,000 BTU / gal, and 1.04 g / ml, respectively, and is excellent as a high energy density fuel.

Cyclopentadiene purified and separated from the C ₅ fraction of the petrochemical process is not thermodynamically stable and thus exists as endo-dicyclopentadiene. After converting endo-dicyclopentadiene to exo-dicyclopentadiene after isomerization, hydrogenation process produces exo-tetrahydrodicyclopentadiene (exo-THDCPD), which can be used as a high energy density fuel. have.

Tetrahydrotricyclopentadiene production can be produced through a two-step process from cyclopentadiene and dicyclopentadiene. The first is the Diels-Alder addition reaction for the dimerization of cyclopentadiene and dicyclopentadiene. In order to have storage stability as fuel, there must be no double bond in the molecular bond, so the C = C double bond held in the hydrogenation reaction in step 2 is converted into the single bond form of CC and converted from tricyclopentadiene. Tetrahydrotricyclopentadiene is prepared.

The first reaction, the dimerization of dicyclopentadiene and cyclopentadiene, is a C = C double bond in the norbonyl ring and cyclopentyl among the two double bonds present in dicyclopentadiene. According to which of the C = C double bonds, cyclopentadiene reacts, it is classified into NB addition or CP addition reaction. More than 96% of the raw material dicyclopentadiene exists in the endo form, and the norbonyl double bond is more reactive than the cyclopentyl double bond, so the NB addition reaction proceeds preferentially over the CP addition reaction. Therefore, the resulting tricyclopentadiene is obtained with an NB additive having an endo-exo-endo type stereochemical structure. When the endo-exo-endo type tricyclopentadiene undergoes an isomerization reaction, an exo-exo-exo type tricyclopentadiene (exo-TCPD) is obtained. Tetrahydrotricyclopentadiene, which has undergone hydrogenation using Endo-exo-endo type tricyclopentadiene or exo-exo-exo type tricyclopentadiene as a raw material, can be used as a high energy density fuel.

Hydrogenation reactions known for the production of tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene include the preparation of tetrahydrotricyclopentadiene from tricyclopentadiene using a catalyst carrying nickel on a Kiselguhr support. Although the technology is known from U.S. Patent No. 4401837, there is a disadvantage that the reaction time is long due to low activity of the catalyst. In addition, a technique for preparing tetrahydrotricyclopentadiene from tricyclopentadiene using a palladium-boron / gamma-alumina catalyst is known from Catalysis Communications 8, 571-575 (2007), but expensive palladium is used as a catalyst. Therefore, it is necessary to lower the price of the catalyst.

As a result, the present inventors tried to solve the above-mentioned problems, and, as a result, hydrogenated dicyclopentadiene and tricyclopentadiene using a catalyst supporting ruthenium on regular mesoporous silica to tetrahydrodicyclopentadiene and tetra The present invention was completed by confirming that hydrotricyclopentadiene can be prepared.

Accordingly, an object of the present invention is to provide a method for preparing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene.

A method of preparing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene to achieve the above object is to use a catalyst in which ruthenium is supported on regular mesoporous silica. It consists of a method for producing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene.

Hereinafter, the present invention will be described in detail.

As described above, the present invention is to prepare tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene using a catalyst in which ruthenium is supported on regular mesoporous silica. It's about how.

In the catalyst according to the present invention, the regular mesoporous silica has regularly aligned mesopores, and is faster to the active point in the catalyst pores compared to other supports that are irregularly aligned through the regularly aligned mesopores. It has a material diffusion effect, thereby increasing catalytic activity.

The mesoporous silica is not particularly limited as long as it is a mesoporous silica used in the field, but KIT-6 and SBA-15 of the series of KIT (Korea Advanced Institute of Science and Technology) and SBA (Santa barbara Amorphous) It can be used as mesoporous silica.

As the mesoporous silica, KIT-6 or SBA-15 is produced by the combination between surfactant micelles and silicate species, the KIT-6 being silica having mesopores having cubic structure, and the silica having mesopores having hexagonal structure. SBA-15 can adjust the pore diameter through the surfactant micelle, and the mesoporous silica is useful as a catalyst support because of its large surface area, and has the advantage of easy mass transfer of molecules with large pore diameters.

In the present invention, the catalyst uses a ruthenium catalyst carrying ruthenium on mesoporous silica, which is any one selected from KIT-6 or SBA-15.

A ruthenium was used on a regular mesoporous silica support KIT-6 or SBA-15 support using a loading method. The catalyst supporting ruthenium on the KIT-6 support used in the present invention is a support having regular mesopores having a pore size of 5 to 9 nm, and a surface area of 450 m ² / g to 520 m ² / g. In addition, the catalyst supporting ruthenium on the SBA-15 support used in the present invention is a support having mesopores having a pore size of 6 to 9 nm, and a surface area of 400 m ² / g to 500 m ² / g. Since the catalyst in which ruthenium is supported on the regular mesoporous silica used in the present invention has mesopores having a pore size of 5 to 9 nm, diffusion of dicyclopentadiene and tricyclopentadiene into the catalyst pores is fast, so that the surface within the catalyst pores It has the advantage of being easy to reach the active point.

According to one embodiment of the present invention, when carrying ruthenium on the KIT-6, it is preferable to use 0.5% to 5.0% by weight of ruthenium, and when carrying ruthenium on the SBA-15 When the weight% of the ruthenium is less than 0.5% by weight, the effect as a catalyst tends not to appear, and when it exceeds 5.0% by weight, the surface area and pore size of the catalyst decreases, so that the effect as a catalyst does not appear and the price of the catalyst increases. Tend to

According to an embodiment of the present invention, 31.85 g of ruthenium nitrate (1.5 wt%), which is a kind of ruthenium precursor, is quantified and mixed in 400 ml of distilled water. Examples of the ruthenium precursor are selected from ruthenium nitrate, ruthenium chloride and ruthenium acetylacetonate. 10 g of mesoporous silica support KIT-6 or SBA-15 was added to the solution prepared above, and ruthenium was supported by an impregnation method using a rotary vacuum evaporator. Then, after sufficiently drying in an oven at 100 ° C, calcination is performed at 550 ° C for 3 hours to obtain a catalyst carrying ruthenium on mesoporous silica.

The catalyst thus obtained may be used in the form of a powdered catalyst as it is or in the form of pellets by mixing a binder to promote a hydrogenation reaction using dicyclopentadiene and tricyclopentadiene as reactants. The conditions for molding into pellets are as follows.

The catalyst in the form of powder was mixed with methyl cellulose, an organic binder, and distilled water was mixed to knead. The dough is prepared by using a hydraulic piston extruder to prepare a pellet type catalyst, cut into a certain length, dried, and then fired at 650 ° C. The calcined catalyst is reduced in a hydrogen atmosphere. The catalyst was introduced into a fixed bed catalytic reactor and reduced by flowing hydrogen at a flow rate of 30 mml / min for 2 hours at 450 ° C, and then lowered to room temperature. Then, after blocking hydrogen and flowing nitrogen, an oxygen and nitrogen mixed gas having an oxygen concentration of 5% was flowed for 10 minutes at a flow rate of 105 cc / min to passivation.

The catalyst in which ruthenium is supported on the regular mesoporous silica can be applied to the hydrogenation reaction of dicyclopentadiene and tricyclopentadiene under the following reaction conditions. In the present invention, the hydrogenation reaction of dicyclopentadiene and tricyclopentadiene is performed at a reaction temperature of 100 to 140 ° C, preferably 110 to 130 ° C, in a batch reactor equipped with a catalyst basket, wherein the reaction temperature is less than 100 ° C. When the reaction activity is lowered and the temperature exceeds 130 ° C, the yields of tetrahydrodiscitropentadiene and tetrahydrotrisitlopentadiene decrease because the reactants are converted to polymer materials through polymerization. In addition, the amount of the catalyst is 1 to 20 wt%, preferably 5 to 15 wt%, compared to the reactants, the activity is low at less than 1 wt%, and when it exceeds 20 wt%, the viscosity of the slurry composed of the reactant and the catalyst mixture is too large to react Driving is not easy.

In the present invention, the hydrogenation reaction of dicyclopentadiene and tricyclopentadiene is reacted for 30 minutes to 24 hours, preferably 1 to 12 hours under the above reaction conditions in a batch reactor equipped with a catalyst basket. Since the reaction activity is low and a polymer having a large molecular weight is generated in a large amount at 24 hours or more, it is not preferable because a solid product is produced.

The manufacturing method of the present invention as described above, the hydrogenation reaction of dicyclopentadiene and tricyclopentadiene through a ruthenium catalyst to efficiently produce tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene, which are high energy density fuels. There is an effect that can be done.

Hereinafter, the present invention will be described in more detail through examples, but the scope of the present invention is not limited thereto.

Comparative example

Filled with 4.0 g of Ru (1.5 wt%) / Kieselguhr catalyst pellets into a catalyst basket mounted in a 120 ml batch reactor, 40 g of a mixture containing 40% by weight of dicyclopentadiene and tricyclopentadiene, respectively, and hydrogen The reaction experiment was performed by pressing. At this time, Kieselguhr used as a catalyst support is an amorphous silica obtained from a diatom sediment and is widely used as a support for a catalyst for a hydrogenation reaction. The temperature of the reactor was maintained at 120 ° C and the reaction pressure was 10 bar. 6 hours after the start of the reaction, the reaction products were analyzed using a gas chromatograph, and the conversion rates of the dicyclopentadiene and tricyclopentadiene hydrogenation reactions were 23.1% and 11.9%, respectively.

Example 1

In the comparative example, a reaction experiment was performed under the same conditions, except that 4.0 g of Ru (1.5 wt%) / KIT-6 catalyst pellet was filled. As a result of analyzing the reaction product 6 hours after the start of the reaction using a gas chromatograph, the conversion rates of dicyclopentadiene and tricyclopentadiene hydrogenation reactions were 68.7% and 47.8%, respectively.

Example 2

In the comparative example, a reaction experiment was performed under the same conditions, except that 4.0 g of Ru (1.5 wt%) / SBA-15 catalyst pellet was filled. As a result of analyzing the reaction product 6 hours after the start of the reaction using a gas chromatograph, the conversion rates of dicyclopentadiene and tricyclopentadiene hydrogenation reactions were 78.1% and 60.6%, respectively.

Table 1 summarizes the reaction results of preparing dihydropentacyclodiediene and tetrahydrotricyclopentadiene by hydrogenating dicyclopentadiene and tricyclopentadiene according to Examples and Comparative Examples of the present invention.

division catalyst catalyst
shape reaction
Temperature
(℃) reaction
time
(h) DCPD conversion rate (%) TCPD conversion rate (%) Comparative example Ru (1.5 wt%) / Kieselguhr pellet 120 6 23.1 11.9 Example 1 Ru (1.5 wt%) / KIT-6 pellet 120 6 68.7 47.8 Example 2 Ru (1.5 wt%) / SBA-15 pellet 120 6 78.1 60.6

※ DCPD: Dicyclopentadiene

※ TCPD: Tricyclopentadiene

As shown in Table 1, it was confirmed that when the catalysts of Examples 1 and 2 according to the present invention were used, it was effective in increasing the conversion rate of the tricyclopentadiene hydrogenation reaction.

Claims (6)

In the method for producing tetrahydrodicitropentadiene and tetrahydrotricyclopentadiene by hydrogenating a mixture of dicyclopentadiene and tricyclopentadiene using a catalyst supporting ruthenium on a mesoporous silica support,
The mesoporous silica support is any one selected from KIT-6 or SBA-15,
In the case of a catalyst supporting ruthenium on the KIT-6, the pore size is 5 to 9 nm, and the surface area of the catalyst is 450 m ² / g to 520 m ² / g, or in the case of a catalyst supporting ruthenium on the SBA-15 The pore size is 6 to 9 nm, and the surface area of the catalyst is 400 m ² / g to 500 m ² / g, wherein the method for producing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene is characterized. delete The method for preparing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene according to claim 1, wherein the ruthenium loading amount of the catalyst supporting ruthenium on the mesoporous silica support is 0.5 to 5.0% by weight. The method of claim 1, wherein the hydrogenation reaction is 30 minutes to 24 hours of reaction time, characterized in that tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene. The method for preparing tetrahydrodicyclopentadiene and tetrahydrotricyclopentadiene according to claim 1, wherein the hydrogenation reaction has a reaction temperature of 100 to 140 ° C. delete