KR101604669B1 - Production method of Tetrahydrotri(cyclopentadiene) using a heterogeneous solid acid catalyst - Google Patents

Abstract

The present invention relates to a process for preparing exo-tetrahydrotri (cyclopentadiene) which is easy to use as a raw material for a high-density liquid fuel which is a high-value-added fuel through isomerization of endo-tetrahydrotri (cyclopentadiene) . Specifically, by applying isomerization of endo-tetrahydrotri (cyclopentadiene) by applying zeolite as a heterogeneous solid acid catalyst, mesoporous aluminosilicate, heteropolyacid of cesium 12-tungstophosphate, etc., exo-tetrahydrotri (Cyclopentadiene). ≪ / RTI >

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for preparing an isomer of tetrahydrotri (cyclopentadiene) using a heterogeneous solid acid catalyst,

The present invention relates to a process for preparing an isomer of endo-tetrahydrotri (cyclopentadiene) using zeolite as a heterogeneous solid acid catalyst, mesoporous aluminosilicate, heteropolyacid of a cesium salt of 12-tungstophosphoric acid or the like.

Dicyclopentadiene (hereinafter also referred to as " DCPD ") is obtained by underwater cracking reaction of naphtha and gas oil produced after crude oil purification treatment. At present, DCPD is mainly used as a raw material for general petroleum resin products, but studies have been conducted to use it as a high-density liquid fuel having high added value in order to use it more efficiently.

High density liquid fuels are fuels that increase the amount of fuel loaded per unit volume in aircraft, missiles, rockets, etc., which have limited capacity. In order to be used as a high density liquid fuel, the density should be higher than kerosene (more than 0.8 g / ml) and the energy content should be high and the freezing point should be low (below -20 ℃). In order to have such a fuel characteristic, when the constituent component of the fuel is a cyclic structure composed of C ₃ , C ₄ , C _5, etc., it is structurally dense and has high strain energy and is advantageous as a constituent thereof.

In the case of JP-10 made from exo-tetrahydrodi (cyclopentadiene) (hereinafter also referred to as exo-THDCP) among high-density liquid fuels, due to its structural characteristics, high density and energy content (0.94 g / ml, 150,000 BTU / gal) and is currently being used as fuel for US Navy and Air Force missiles.

Interest in the development of fuel with higher density and energy content than that of JP-10 is recently increasing. In the case of tricyclopentadiene (hereinafter also referred to as " TCPD ") produced through the oligomerization of DCPD and cyclopentadiene (hereinafter also referred to as " CPD "), . The TCPD generated from DCPD has two double bonds, which are highly reactive and stabilize through hydrogenation to increase the possibility of use as a fuel.

However, the resulting tetrahydrotri (cyclopentadiene) (hereinafter referred to as "THTCPD") is solid at room temperature and is unlikely to be used as a fuel. In order to increase the possibility of use as a fuel of endo-tetrahydrotri (cyclopentadiene) (hereinafter also referred to as "endo-THTCPD"), it is necessary to convert it to an exo isomer via an isomerization reaction.

In the case of exo-tetrahydrotri (cyclopentadiene) (hereinafter also referred to as "exo-THTCPD") produced through the isomerization reaction, the density and energy content (1.04 g / ml, 160,000 BTU / gal), which is highly likely to be used as a high-density energy fuel.

Isomerization of Endo-THTCPD is converted to exo-THTCPD via Wagner-Meerwein rearrangement. Endo-THTCPD is produced by the Diels-Alder reaction of norbonyl and CPD of DCPD during the dimerization of DCPD and CPD and is the main component of THTCPD. The structure of THTCPD thus produced has both a norbornyl group and a cyclopentyl group at both ends as shown in Formula (1), and a norbornyl group is advantageous in the production of carbon cations, and isomerized by a carbon cation generated in the norbornyl group .

[Chemical Formula 1]

Until now, the isomerization of endo-THTCPD has only been carried out using homogeneous aluminum chloride (AlCl ₃ ) catalysts. AlCl ₃ catalysts are harmful to the environment as a harmful substance. In the case of the solvent used for the AlCl ₃ catalyst, a chloride-based solvent such as methylene chloride or ethylene chloride is used to cause additional problems .

In addition, AlCl ₃ , which acts as a homogeneous catalyst, requires a separate separation step after the reaction, thus reducing the economical efficiency of the process. Therefore, it is necessary to develop a heterogeneous solid catalyst suitable for isomerization of endo-THTCPD to overcome the above problems.

Korean Patent Publication No. 10-1040969

It is an object of the present invention to provide a method for producing exo-THTCPD by isomerizing endo-THTCPD using a heterogeneous solid acid catalyst such as zeolite, mesoporous alumina silicate, or heteropolyacid of 12-tungstophosphate cesium salt.

In order to accomplish the above object, the present invention relates to a method for producing exo-THTCPD through isomerization of endo-THTCPD on a solventless condition at 200 ° C to 300 ° C. The present invention also relates to a method for producing exo-THTCPD by applying a catalyst such as Y zeolite, mesoporous aluminosilicate, and cetarium salt of 12-tungstophosphate cesium salt in heterogeneous solid acid catalysts to the isomerization of the endo-THTCPD .

In the present invention, in the isomerization of endo-THTCPD with exo-THTCP at 200 ° C. to 300 ° C. under no solvent conditions, a catalyst such as Y zeolite, mesoporous aluminosilicate, heteropolyacid of cesium 12- , And solved the problem of environmentally harmful problem due to the use of the conventional homogeneous AlCl ₃ catalyst and solvent. Also, it is possible to simplify the process facilities and shorten the manufacturing time by the necessity of the separation process, which is an advantage of the heterogeneous catalyst The same process improvement can be expected.

In the present invention, as a reaction catalyst for isomerizing endo-THTPD to exo-THTCPD at high temperature, a catalyst having heat resistance even at a high temperature of 200 to 300 DEG C, specifically Y zeolite, mesoporous alumina silicate, cesium 12- Heteropoly acid of salt or the like is used. The catalyst was prepared as follows.

Y zeolite of Zeolyst Internationl (USA) was used as the zeolite catalyst of the present invention, and the Si / Al molar ratio of Y zeolite was 15, 30, 40. In order to remove the residual structure forming material, (hereinafter also referred to as " HY zeolite ").

The Al-MCM-41 catalyst among the mesoporous alumina silicates used in the present invention was prepared using the sol-gel method. In the case of the Al-MCM-41 catalyst, tetraethyl orthosilicate (hereinafter also referred to as "TEOS") was used as the silicon precursor and aluminum sulfate was used as the aluminum precursor. As the structure forming material, cetyltrimethylammonium Cetyltrimethyl ammonium bromide (hereinafter, also referred to as " CTAB ") and an aqueous ammonia solution as a precipitant. For the preparation of Al-MCM-41, the aluminum precursor aqueous solution was thoroughly mixed with the CTAB aqueous solution, and the silicon precursor of Si / Al ratio to be prepared was mixed and stirred for 1 hour. Then, the pH was adjusted to 10.5 using an aqueous ammonia solution, Lt; / RTI > The resulting precipitate is washed and filtered using distilled water, dried at 70 ° C for 12 hours, pulverized and calcined at 550 ° C for 6 hours in an air atmosphere to obtain a catalyst.

The Al-SBA-15 catalyst among the mesoporous alumina silicates used in the present invention was prepared by post grafting.

SBA-15 was prepared by using TEOS as a silicon precursor and using Pluronic P123 (poly (ethyleneglycol) -block-poly (ethylene glycol) -block-poly (ethylene glycol)] as a structure forming material.

SBA-15 is prepared by first adding TEOS to an aqueous solution of Pluronic P123, which is a structure-forming material, completely dissolved in an aqueous hydrochloric acid solution, stirring at 35 DEG C for 20 hours, and then standing at 80 DEG C for 24 hours. Then, the precipitate was washed with water and ethanol, filtered, dried at 110 ° C for 12 hours, pulverized and then calcined at 550 ° C for 6 hours in an air atmosphere. The resulting powder was dispersed in anhydrous hexane, and then aluminum isopropoxide was added thereto. The aluminum isopropoxide was added to the Si / Al solution for 24 hours. The resulting mixture was washed with hexane, filtered and dried at 100 ° C. Lt; RTI ID = 0.0 > 550 C < / RTI > for 6 hours to obtain a catalyst.

The heteropoly acid of the cesium salt of 12-tungstophosphate was prepared by ion exchange method. The heteropolyacid of 12-tungstophosphate cesium salt is dissolved in distilled water, and a cesium salt such as cesium nitrate (CsNO ₃ ) aqueous solution is mixed and stirred. The solution is allowed to stand overnight. The resulting suspension is dried on a rotary evaporator Followed by calcining at 300 DEG C for 2 hours to obtain a catalyst.

Hereinafter, a method for producing exo-THTCPD through the isomerization reaction of endo-THTCPD using the catalysts will be described in detail.

As the isomerization catalyst for isomerization of endo-THTCPD to exo-THTCPD at high temperature in the present invention, heteropolyacids such as HY zeolite, Al-MCM-41, Al-SBA-15 and 12- do.

In the present invention, the high-temperature isomerization reactor is composed of a batch reactor equipped with, for example, a pressure gauge, a thermometer, a heating heater, and a condensing tank.

In the exemplary batch reactor that can be used in the present invention, the isomerization reaction catalyst is charged and endo-THTCPD, which is a reactant, is added, and then the reactor is completely sealed to prevent contact with air. And the reaction experiment was carried out.

Hereinafter, the present invention will be described in more detail with reference to comparative examples and examples according to the present invention. However, the present invention is not limited by these examples.

In Comparative Example 1, 15 g of the reaction product endo-THTCPD, 30 g of 1,2-dichloroethane as a solvent and 0.75 g of aluminum chloride (AlCl ₃ ) as a homogeneous catalyst were fed into a 100 ml batch reactor The temperature of the reactor was selected at 25 ^° C and the reaction was carried out for 6 hours.

In Examples 1 to 4, 5.4 g of HY zeolite catalyst was charged into a batch reactor of 100 ml capacity, 27 g of endo-THTCPD as a reaction product was charged, and the temperature of the reactor was raised to 200 ° C., 250 ° C., 275 ° C. and 300 ° C., respectively And the reaction was carried out for 6 hours each.

In another Example 5, 5.4 g of Al-MCM-41 catalyst was charged in a 100 ml batch reactor and 27 g of endo-THTCPD as a reactant was charged. After the temperature of the reactor was raised to 275 ° C, .

In another Example 6, 5.4 g of Al-SBA-15 catalyst was charged in a 100 ml batch reactor and 27 g of endo-THTCPD as a reactant was charged. After the temperature of the reactor was raised to 275 ° C, .

In another example 7, 5.4 g of a heteropolyacid catalyst of 12-tungstophosphate cesium salt was charged in a 100 ml batch reactor and 27 g of endo-THTCPD as a reactant was charged. After the temperature of the reactor was raised to 275 캜, Reaction experiments were carried out.

After each reaction, quantitative analysis of the product obtained by gas chromatography equipped with flame ionization detector (FID) was performed. The results of the analysis are shown in Table 1.

division catalyst Reaction raw material reaction
Temperature
( ^o C) reaction
time
(hr) exo-THTCPD yield
(weight%) repeat
use work
Ease anatomy
Hazard Comparative Example 1 AlCl ₃ THTCPD 25 6 59.5 Impossible Bad
① Formation of corrosive viscous material during reaction
②Chloride type solvent use is necessary greatness
(LD ₅₀ = 38 mg / kg) Example 1 HY THTCPD 200 6 24.8 possible
(Can be reused more than 2 times) Good
① No particle shape change during reaction
② No solvent required Very low
(LD ₅₀ = no data available) Example 2 HY THTCPD 250 6 30.0 Example 3 HY THTCPD 275 6 44.6 Example 4 HY THTCPD 300 6 26.5 Example 5 Al-MCM-41 THTCPD 275 6 36.9 Example 6 Al-SBA-15 THTCPD 275 6 31.8 Example 7 CsHPA THTCPD 275 6 16.0

Note) HY: HY zeolite

Al-MCM-41: Self-manufactured

Al-SBA-15: self-made

_{CsHPA: Cs 2 .5 H 0 .5} PW 12 O 40 (12- tungstophosphoric acid cesium salt of heteropoly acid): Production itself

In the isomerization reaction product of Table 1, the yield of exo-THTCPD is expressed as the weight percentage of the total amount of exo-THTCPD converted to other substances including exo-THTCPD. Although not shown in Table 1 above, the endo-THTCPD conversion rate in the present invention can be calculated as the weight percentage of endo-THTCPD in terms of the total amount of conversion of endo-THTCPD to other substances including exo-THTPD.

As shown in Table 1, in the present invention, the reaction yield of converting endo-THTCPD to exo-THTCPD through isomerization reaction is as follows: AlCl ₃ It is possible to confirm the applicability of heterogeneous solid acid catalyst isomerization which is advantageous in terms of reusability, ease of operation and harmfulness to human body although it is 75% lower than that of the catalyst. Based on these results, it is possible to identify reaction conditions suitable for the preparation of exo-THTCPD by the isomerization reaction of endo-THTCPD using a heterogeneous solid acid catalyst.

The present invention is based on the discovery that the exo-THTCPD isomer of endo-THTCPD can be prepared by isomerization of endo-THTCPD using a heterogeneous solid acid catalyst to improve environmental problems of conventional homogeneous catalysts And can be used for process improvement by the necessity of separation process and the like.

Claims (9)

Exo-tetrahydrotri (cyclopentadiene) isomerization reaction was carried out by isomerization of endo-tetrahydrotri (cyclopentadiene) using Al-SBA-15 as a heterogeneous solid acid catalyst as an isomerization catalyst. Tri (cyclopentadiene).
delete The process for preparing exo-tetrahydrotri (cyclopentadiene) according to claim 1, wherein the amount of the isomerization catalyst is 20 wt% based on the total weight of the reaction product.
The process according to claim 1, wherein the isomerization reaction is carried out in a batch reactor.
The process according to claim 1, wherein the isomerization reaction is carried out at a reaction temperature of 200 to 300 ° C.
The process according to claim 1, wherein the isomerization reaction has a reaction time of 6 hours.
7. An exo-tetrahydrotri (cyclopentadiene) composition prepared by the process according to any one of claims 1 to 6.
A composition for preparing exo-tetrahydrotri (cyclopentadiene) comprising an endo-tetrahydrotri (cyclopentadiene) and a heterogeneous solid acid catalyst as an active ingredient Al-SBA-15. delete