KR20230174879A - Manufacturing method of alkylbicyclo[2.2.2]octanes and hydrocarbon fuel composition including the same - Google Patents

Abstract

The present invention relates to a method for producing alkylbicyclo[2.2.2]octane and a hydrocarbon fuel composition containing the same, wherein alkylbicyclo[2.2.2]octane can be produced in high yield under a hydrogenation reaction catalyst and a heteropoly acid catalyst. It can be used as sustainable aviation fuel by mixing it with existing fuel.

Description

Method for producing alkylbicyclo[2.2.2]octane and hydrocarbon fuel composition containing the same {MANUFACTURING METHOD OF ALKYLBICYCLO[2.2.2]OCTANES AND HYDROCARBON FUEL COMPOSITION INCLUDING THE SAME}

The present invention relates to a method for producing alkylbicyclo[2.2.2]octane and a hydrocarbon fuel composition containing the same.

High energy density hydrocarbon fuels are used as fuel for aircraft such as missiles and rockets with limited-sized fuel tanks based on their high volumetric net heat of combustion, but research on synthesis from renewable raw materials is limited. It is inadequate.

The volume-based net calorific value of hydrocarbons is expressed as the product of the gravimetric net heat of combustion and density, and research is being conducted to increase the density of hydrocarbons in order to synthesize high energy density hydrocarbons. In general, in the case of hydrocarbons, the density increases as the number of ring structures increases, and this is due to an increase in net calorific value based on volume. Therefore, research on ring-structured hydrocarbons as high energy density hydrocarbon fuels is attracting attention. However, as the ring structure is formed, the hydrogen to carbon (H/C) ratio decreases, so the net calorific value by weight decreases.

To compensate for the reduced H/C ratio caused by the ring structure, hydrocarbons containing a strained ring structure that can release additional strain energy during combustion have been designed. For example, a fuel that can generate additional ring strain energy during combustion has been developed by giving a cyclopropane structure through the Simmons-Smith cyclopropanation, but the limitation is that it is not a catalyst-mediated reaction. there was. As another example, research has been conducted to develop cage-type hydrocarbons, cubane and adamantane, as high energy density hydrocarbon fuels. Cuban and adamantane had limitations in that they had no utility as liquid fuels due to their abnormally high melting points.

Korean Patent Publication No. 2014-0023906

The purpose of the present invention is to provide a method for producing alkylbicyclo[2.2.2]octane in high yield using a hydrogenation reaction catalyst and a heteropoly acid catalyst.

The purpose of the present invention is to provide a hydrocarbon fuel composition containing alkylbicyclo[2.2.2]octane.

1. Method for producing a compound of Formula 3, comprising the step of hydrogenating a compound of Formula 1 or Formula 2 under a hydrogenation reaction catalyst and a heteropoly acid catalyst:

[Formula 1]

(R ₁ is H, CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH; R ₂ is CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH, or are connected to each other to form an ester group or anhydride group Can form a ring containing 3 to 8 carbon atoms)

[Formula 2]

(R is H, CO ₂ H, CO ₂ Me or CO ₂ Et)

[Formula 3]

(R ₁ and R ₂ are H or Me, respectively).

2. The method of producing a compound of Formula 3 in 1 above, wherein the hydrogenation reaction catalyst is one selected from the group consisting of Ni/C, Pt/C, Pd/C, Ru/C, Rh/C, and Cu/C.

3. In 1 above, the heteropoly acid catalyst is one selected from the group consisting of phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, and silicotungstic acid. Method for preparing a compound of formula (3).

4. In 1 above, the hydrogenation reaction catalyst and the heteropoly acid catalyst are each included in an amount of 40 to 60 parts by weight based on 100 parts by weight of the compound of Formula 1 or Formula 2.

5. The method for producing the compound of Formula 3 according to 1 above, wherein the hydrogenation is performed in a solvent containing a saturated hydrocarbon having 5 to 12 carbon atoms.

6. In 1 above, the compound of Chemical Formula 1 is a method of producing a compound of Chemical Formula 3, which is a compound represented by the following Chemical Formula 1-1 or 1-2:

[Formula 1-1]

(R ₁ is H, CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH; R ₂ is CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH)

[Formula 1-2]

.

7. In 1 above, the compound of Chemical Formula 2 is a method of producing a compound of Chemical Formula 3, which is a compound represented by the following Chemical Formula 2-1:

[Formula 2-1]

(R is H, CO ₂ H, CO ₂ Me or CO ₂ Et).

8. In 1 above, the compound of Chemical Formula 3 is a compound represented by the following Chemical Formulas 3-1 to 3-4. Method for producing a compound of Chemical Formula 3:

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

.

9. The method for producing a compound of Formula 3 according to 1 above, further comprising reacting a compound of Formula 4 below with a compound of Formula 5 or Formula 6 to produce a compound of Formula 1 or Formula 2:

[Formula 4]

[Formula 5]

(R ₁ is H, CO ₂ H, CO ₂ Me or CO ₂ Et; R ₂ is CO ₂ H, CO ₂ Me or CO ₂ Et)

[Formula 6]

(R ₁ and R ₂ are CO ₂ H, CO ₂ Me or CO ₂ Et, respectively).

10. The method for producing a compound of Formula 3 in 9 above, wherein the compound of Formula 4 is α-phellandrene or α-terpinene.

11. The method of producing a compound of Formula 3 according to 9 above, wherein the compound of Formula 5 is one selected from the group consisting of acrylic acid, acrylic acid ester, maleic acid, and maleic acid ester.

12. The method for producing a compound of Formula 3 according to 9 above, wherein the compound of Formula 6 is fumaric acid or fumaric acid ester.

13. The method for producing a compound of Formula 3 according to 1 above, further comprising reacting a compound of Formula 4 and a compound of Formula 7 to produce a compound of Formula 1:

[Formula 4]

[Formula 7]

.

14. The method for producing a compound of Formula 3 according to 13 above, wherein the compound of Formula 4 is α-phellandrene or α-terpinene.

15. Hydrocarbon fuel composition comprising a compound of formula 3:

[Formula 3]

(In Formula 3, R ₁ and R ₂ are each H or Me).

16. In item 15 above, Jet A, Jet A-1, JP-8 (Jet Propellant-8), JP-10 (Jet Propellant-10), RJ-4 fuel, RJ-5 fuel, biodiesel and synthetic aviation fuel A hydrocarbon fuel composition further comprising one selected from the group consisting of.

The production method of the present invention can synthesize hydrocarbons with high density characteristics in high yield using a mixed catalyst.

The hydrocarbon fuel composition of the present invention can improve the insufficient density or combustion characteristics of conventional fuels by including high energy density hydrocarbons.

Figure 1 shows the results of analysis by gas chromatography-mass spectrometry (GC-MS) of an alkylbicyclo[2.2.2]octane mixture obtained by hydrogenating compounds of formulas 1 to 3 under a mixed catalyst.
Figure 2 shows the mass spectrum of alkylbicyclo[2.2.2]octane having 12 to 14 carbon atoms obtained by hydrogenating compounds of formulas 1 to 3 under a mixed catalyst.
Figure 3 is a graph showing the net calorific value by weight (NHOC _G ) and net calorific value by volume (NHOC _V ) according to the volume mixing ratio of the alkylbicyclo[2.2.2]octane mixture and Jet A-1 aviation fuel.
Figure 4 is a graph showing the density according to the volume mixing ratio of the alkylbicyclo[2.2.2]octane mixture and Jet A-1 aviation fuel.
Figure 5 is a graph showing the freezing point according to the volume mixing ratio of the alkylbicyclo[2.2.2]octane mixture and Jet A-1 aviation fuel.
Figure 6 is a graph showing the kinematic viscosity at temperature according to the volumetric mixing ratio of the alkylbicyclo[2.2.2]octane mixture and Jet A-1 aviation fuel.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for producing a compound of Formula 3, comprising the step of hydrogenating a compound of Formula 1 or Formula 2 below under a hydrogenation reaction catalyst and a heteropoly acid catalyst.

[Formula 1]

R ₁ is H, CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH; R ₂ may be CO ₂ H, CO ₂ Me, CO ₂ Et, or CH ₂ OH, or may be connected to each other to form a ring having 3 to 8 carbon atoms including an ester group or an anhydride group.

[Formula 2]

R is H, CO ₂ H, CO ₂ Me or CO ₂ Et.

[Formula 3]

R ₁ and R ₂ are each H or Me.

In the production method of the present invention, hydrogenation may include a reaction to reduce the double bond or triple bond of an organic compound (hydrogenation) and a hydrotreating reaction to remove oxygen by reacting the organic compound with hydrogen.

The hydrogenation may be performed as a batch process, but is not limited thereto, and may also be performed in a semi-batch process, a semi-continuous process, or a continuous reactor.

The hydrogenation may be carried out under a hydrogenation reaction catalyst and a heteropoly acid catalyst.

The hydrogenation reaction catalyst may be used without limitation as long as it is commonly used in the art. For example, metal catalysts such as nickel (Ni), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) or copper (Cu) or the metal catalyst on a carrier such as carbon, silica, alumina, magnesia, etc. It may be a catalyst supporting, and specifically, it may be a Ni/C, Pt/C, Pd/C, Ru/C, Rh/C or Cu/C catalyst.

The heteropoly acid catalyst can be used without limitation as long as it is commonly used in the art. For example, phosphorus (P), silicon (Si), germanium (Ge), arsenic (As), boron (B), or cobalt (Co) are the central elements, and tungsten (W), molybdenum (Mo), and vanadium (V) are used as central elements. ) or a heteropoly acid catalyst with niobium (Nb) as a coordination element, specifically, phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, or silicotungstic acid ( silicotungstic acid) may be a catalyst.

The hydrogenation reaction catalyst and the heteropoly acid catalyst may be mixed.

The hydrogenation reaction catalyst and the heteropoly acid catalyst are used in an amount of 5 to 150 parts by weight, 10 to 130 parts by weight, 15 to 115 parts by weight, 20 to 100 parts by weight, 25 to 85 parts by weight, 30 to 70 parts by weight, and 40 parts by weight, respectively, based on 100 parts by weight of the reactant. It can be used in a ratio of 60 to 60 parts by weight, but is not limited thereto.

Additionally, the above two catalysts can be easily separated from the product after the hydrogenation reaction and can be reused.

Hydrogenation can be carried out under solvent.

The solvent may include, for example, a saturated hydrocarbon having 5 to 12 carbon atoms. The solvent may be liquid at room temperature. The saturated hydrocarbons include linear or branched chain and cyclic saturated hydrocarbons. Cyclic saturated hydrocarbons may be substituted or unsubstituted with straight or branched chains.

The solvent is, for example, n-pentane, iso-pentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane. Theine, normal-heptane, 2-methylhexane, 3-methylhexane, 2,4-dimethylpentane, 2,3-dimethylpentane, 2,2-dimethylpentane, 3,3- Monosaturated hydrocarbons such as dimethylpentane, 3-ethylpentane, 2,3,3-trimethylbutane, octane, normal-decane, cyclopentane, cyclohexane, and cyclooctane; Alternatively, it may be a mixed saturated hydrocarbon of at least two of the above single saturated hydrocarbons, such as petroleum ether. Specific examples may be n-pentane, n-hexane, or cyclohexane, in which case the solvent can be easily recovered and reused through a distillation process after hydrogenation. You can.

The solvent may be used in amounts of 0.01 to 0.9% (v/w), 0.03 to 0.8%, 0.05 to 0.7%, 0.08 to 0.6%, 0.1 to 0.5%, 0.15 to 0.4%, and 0.2 to 0.3% relative to the reactant. It is not limited to this.

In the production method of the present invention, the compound of Formula 1 may be a compound represented by the following Formula 1-1 or 1-2.

[Formula 1-1]

R ₁ is H, CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH; R ₂ may be CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH. Specifically, R ₁ and R ₂ may be CO ₂ Me or CH ₂ OH.

[Formula 1-2]

In the production method of the present invention, the compound of Formula 2 may be a compound represented by the following Formula 2-1.

[Formula 2-1]

R may be H, CO ₂ H, CO ₂ Me or CO ₂ Et.

In the production method of the present invention, the compound of Formula 3 may be a compound represented by the following Formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

The compound of Formula 3 may be a hydrocarbon with 12 to 14 carbon atoms having 2 to 4 alkyl groups with bicyclo[2.2.2]octane as the basic skeleton.

The hydrogenation reaction temperature of the production method of the present invention is 100 to 450°C, 120 to 430°C, 140 to 400°C, 150 to 380°C, 160 to 350°C, 180 to 300°C, 190 to 280°C, 195 to 260°C, It may be 200 to 250°C, but is not limited thereto.

For example, if an alcohol functional group is present in the compound of Formula 1 or 2, the reaction can be performed at 160 to 240°C, preferably 180 to 220°C, and if a carbonyl functional group is present in the compound of Formula 1 or 2 In this case, the reaction may be performed at 210 to 290°C, preferably 230 to 270°C.

The hydrogenation reaction is performed at a hydrogen partial pressure of 0.1 to 100 bar, 0.5 to 90 bar, 1 to 80 bar, 2 to 70 bar, 3 to 60 bar, 5 to 50 bar, 7 to 40 bar, 9 to 35 bar, 10 to 30 bar. , can be performed at 12 to 25 bar, 15 to 20 bar, but is not limited thereto.

The hydrogenation reaction may be performed for 0.5 to 50 hours, 1 to 40 hours, 2 to 35 hours, 3 to 30 hours, 3.5 to 25 hours, 4 to 20 hours, and 4 to 15 hours, but is not limited thereto.

For example, when an alcohol functional group is present in the compound of Formula 1 or 2, the reaction time is 0.5 to 25 hours, 1 to 20 hours, 1.5 to 15 hours, 2 to 10 hours, 3 to 8.5 hours, 3.5 to 7 hours, 4 to The hydrogenation reaction can be carried out for 5 hours, and if a carbonyl function is present in the compound of formula 1 or 2, 4 to 30 hours, 4.5 to 25 hours, 5 to 20 hours, 5.5 to 18 hours, 6 to 15 hours. , the hydrogenation reaction can be performed for 6.5 to 13 hours, 8 to 12 hours, and 9 to 11 hours.

The production method of the present invention may further include the step of producing a compound of Formula 1 or Formula 2 by reacting a compound of Formula 4 below with a compound of Formula 5 or Formula 6.

[Formula 4]

[Formula 5]

R ₁ is H, CO ₂ H, CO ₂ Me or CO ₂ Et; R ₂ is CO ₂ H, CO ₂ Me or CO ₂ Et.

[Formula 6]

R ₁ and R ₂ are CO ₂ H, CO ₂ Me or CO ₂ Et, respectively.

The compound of Formula 4 may be a monoterpene with a conjugated cyclohexadiene structure. For example, it may be α-phellandrene or α-terpinene.

α-Phellandrene or α-terpinene may be obtained naturally or synthetically. The synthesis is carried out by acid catalysts such as aluminum chloride, phosphoric acid or silica-aluminum oxide solid acids to form α-pinene, β-pinene, limonene and terpinolene. Alternatively, γ-terpinene or the like may be isomerized into a conjugated cyclohexadiene structure.

Compounds of formulas 5 and 6 may be acids or esters having 3 to 8 carbon atoms and containing 1 to 2 carboxyl groups. Formula 5 may be, for example, acrylic acid, maleic acid, acrylic acid ester or maleic acid ester including dimethyl maleate, and Formula 6 may be, for example, fumaric acid or fumaric acid including dimethyl fumarate. It could be an ester.

The reaction commonly used in the art can be used without limitation as long as it produces a ring-shaped molecule made of carbon. For example, it may be a Diels-Alder reaction, in which case the compound of Formula 4 is a conjugated diene, and the compounds of Formulas 5 and 6 are dienophiles. It is used as.

This step may include lactonizing the material produced by the reaction.

The production method of the present invention may further include the step of reacting a compound of Formula 4 below with a compound of Formula 7 to produce a compound of Formula 1.

[Formula 4]

[Formula 7]

The compound of Formula 4 may be within the above-mentioned range.

The reaction may be a reaction within the above-mentioned range.

The present invention relates to a hydrocarbon fuel composition comprising a compound of formula (3).

[Formula 3]

R ₁ and R ₂ are each H or Me.

The fuel composition of the present invention can be used as gasoline, diesel, LPG, aviation gasoline, jet fuel, rocket propellant, etc., and specifically, can be used as aviation fuel such as aviation gasoline or jet fuel.

The composition may further include conventionally used fuels such as petroleum-derived diesel fuel, aviation fuel, and liquid hydrocarbon rocket propellant. For example, diesel fuel, kerosene, aviation fuel such as Jet A, Jet A-1, JP-8 (Jet Propellant-8), JP-10 (Jet Propellant-10), RJ-4 fuel, RJ-5 fuel. It may include liquid hydrocarbon rocket propellants, biodiesel, or synthetic aviation fuel.

The fuel composition may include a mixture of the compound of Formula 3 and a conventionally used fuel within a range that satisfies all the physical properties required for each fuel depending on the use of the fuel. For example, the compound of Formula 3 and conventional fuel may be included in a ratio of 1:4 to 3:1, preferably 1:3 to 3:2, but are not limited thereto. For more detailed properties, please refer to the ASTM D7566 appendix. For example, diesel fuel, kerosene, aviation fuel such as Jet A, Jet A-1, JP-8 (Jet Propellant-8), JP-10 (Jet Propellant-10), RJ-4 fuel, RJ-5 Liquid hydrocarbon rocket propellants such as fuel, biodiesel or synthetic aviation fuel, specifically Jet A, Jet A-1, JP-8 (Jet Propellant-8), JP-10 (Jet Propellant-10), RJ- It can be mixed with 4 fuel, RJ-5 fuel, more specifically Jet A-1, but is not limited thereto.

Hereinafter, the present invention will be described in detail with reference to examples.

Example 1. Synthesis of alkylbicyclo[2.2.2]octane

To confirm the yield of the product (alkylbicyclo[2.2.2]octane, ABCOs) of the catalyst mixture, comparative experiments (Reactions 1 to 3) were conducted under different catalyst conditions. In each reaction, one of the compounds of Formulas I to III below was used as a reactant, and the reaction conditions are described in detail below.

[Formula Ⅰ]

[Formula Ⅱ]

[Formula Ⅲ]

(1) Experimental method

1) Reaction 1

Without adding a catalyst, 100 mg of the compound of Formula I and 20 mL of cyclohexane were added to a 50 mL high-temperature and high-pressure batch reactor at a hydrogen pressure of 15 bar and a reaction temperature of 250°C, and stirred at 600 rpm for 4 hours. While doing so, a hydrogenation reaction was performed.

2) Reaction 2

At a hydrogen pressure of 15 bar and a reaction temperature of 250°C, 50 mg of hydrogenation catalyst (Pd/C), 100 mg of the compound of Formula I, and 20 mL of cyclohexane were added to a 50 mL batch reactor for high temperature and high pressure, and hydrogenation was performed while stirring at 600 rpm for 4 hours. A treatment reaction was performed.

3) Reaction 3

At a hydrogen pressure of 15 bar and a reaction temperature of 250°C, 50 mg of heteropoly acid (phosphotungstic acid, HPW), 100 mg of the compound of formula I, and 20 mL of cyclohexane were added to a 50 mL high-temperature and high-pressure batch reactor and incubated at 600 rpm for 4 hours. Hydrogenation reaction was performed while stirring.

4) Reaction 4

In a high-temperature, high-pressure batch reactor with a capacity of 50 mL at a hydrogen pressure of 15 bar and a reaction temperature of 200°C, 50 mg of hydrogenation catalyst (Pd/C), 50 mg of heteropolyacid (phosphotungstic acid, HPW), 100 mg of the compound of formula I, and cyclohexane. Hydrogenation reaction was performed by adding 20 mL and stirring at 600 rpm for 4 hours.

5) Reaction 5

In a high-temperature, high-pressure batch reactor with a capacity of 50 mL at a hydrogen pressure of 15 bar and a reaction temperature of 220°C, 50 mg of hydrogenation catalyst (Pd/C), 50 mg of heteropolyacid (phosphotungstic acid, HPW), 100 mg of the compound of formula I, and cyclohexane. Hydrogenation reaction was performed by adding 20 mL and stirring at 600 rpm for 4 hours.

6) Reaction 6

In a high-temperature, high-pressure batch reactor with a capacity of 50 mL at a hydrogen pressure of 15 bar and a reaction temperature of 220°C, 50 mg of hydrogenation catalyst (Pd/C), 50 mg of heteropolyacid (phosphotungstic acid, HPW), 100 mg of compound of formula II, and cyclohexane. Hydrogenation reaction was performed by adding 20 mL and stirring at 600 rpm for 4 hours.

7) Reaction 7

In a 50 mL high-temperature and high-pressure batch reactor at a hydrogen pressure of 15 bar and a reaction temperature of 230°C, 50 mg of hydrogenation catalyst (Pd/C), 50 mg of heteropolyacid (phosphotungstic acid, HPW), 100 mg of compound of formula II, and cyclohexane. Hydrogenation reaction was performed by adding 20 mL and stirring at 600 rpm for 10 hours.

8) Reaction 8

In a high-temperature, high-pressure batch reactor with a capacity of 50 mL at a hydrogen pressure of 15 bar and a reaction temperature of 200°C, 50 mg of hydrogenation catalyst (Pd/C), 50 mg of heteropolyacid (phosphotungstic acid, HPW), 100 mg of compound of formula III, and cyclohexane. Hydrogenation reaction was performed by adding 20 mL and stirring at 600 rpm for 4 hours.

9) Reaction 9

At a hydrogen pressure of 15 bar and a reaction temperature of 230°C, 100 mg of the compound of formula II and 20 mL of cyclohexane were added to a 50 mL high-temperature and high-pressure batch reactor, and 50 mg of hydrogenation catalyst (Pd/C) and heteropoly acid (phosphotungstic acid, HPW) 50 mg was reused and a hydrogenation reaction was performed while stirring at 600 rpm for 10 hours.

(2) Experiment results

The hydrocarbon yield in each reaction was analyzed using the internal standard method of Gas Chromatography-Flame Ionization Detector (GC-FID) using n-decane as an internal standard. The column was DB-5ms, helium was used at a flow rate of 2 mL/min as a carrier gas, and the oven temperature was 40°C for 2 minutes, the temperature was raised to 320°C at 7°C/min for 40 minutes, and 320°C for 2 minutes. analyzed during.

Reactant types, solvents, and reactions of Reactions 1 to 3 (comparative experiment), in which a hydrogenation reaction was carried out under conditions in which two catalysts or one catalyst was absent, and in Reactions 4 to 9, in which a hydrogenation reaction was carried out in the presence of two catalysts. Hydrocarbon yields according to reaction conditions such as temperature and reaction time are shown in Table 1.

division reactant catalyst menstruum Hydrogen pressure (bar) reaction temperature
(℃) reaction time
(city) Hydrocarbon yield (%) reaction 1 Chemical formula Ⅰ - cyclohexane 15 250 4 0 reaction 2 Chemical formula Ⅰ PD/C cyclohexane 15 250 4 0 reaction 3 Chemical formula Ⅰ Pd/C-HPW cyclohexane 15 250 4 0 reaction 4 Chemical formula Ⅰ Pd/C-HPW cyclohexane 15 200 4 40.7 reaction 5 Chemical formula Ⅰ Pd/C-HPW cyclohexane 15 220 4 54.9 reaction 6 Formula II Pd/C-HPW cyclohexane 15 220 4 65.5 reaction 7 Formula II Pd/C-HPW cyclohexane 15 230 10 100.8 reaction 8 Formula III Pd/C-HPW cyclohexane 15 200 4 99.3 reaction 9 Formula II Pd/C-HPW (reusable) cyclohexane 15 230 10 101.3

The hydrocarbon yield in Table 1 above was determined considering the following. Depending on the type of oxygen functional group in the reactant, hydrogenation, hydrodecarboxylation, and hydrodeoxygenation reactions are involved during the hydrogenation process, resulting in differences in the number of carbons in the product. When there is a carbonyl functional group in the reactant, the hydrodecarboxylation reaction is more dominant than the hydrogenation reaction under the above hydrogen partial pressure conditions, so that the carbon number of the product decreases during hydrogenation treatment.

[Scheme 1]

Accordingly, as shown in Scheme 1, if the reactant is a compound of Formula I or Formula II, alkylbicyclo[2.2.2]octane having 12 or 13 carbon atoms, and alkylbicyclo[2.2.2]octane having 14 carbon atoms if the reactant is a compound of Formula III. 2.2.2] Octane can be synthesized theoretically, and the hydrocarbon yield in Table 1 was calculated based on its theoretical yield.

As shown in Table 1, alkylbicyclo[2.2.2]octane could not be obtained in reactions 1 to 3, which were conditions in which two catalysts or one catalyst were missing in the hydrogenation reaction, and the hydrogenation catalyst (Pd/ It was confirmed that alkylbicyclo[2.2.2]octane could be obtained in reactions 4 to 9 when a catalyst physically mixed with C) and heteropoly acid (HPW) was used.

The severity of the hydrogenation reaction may vary depending on the oxygen functional group contained in the reactant, and even when the heterogeneous catalyst (Pd/C-HPW) is reused as in reaction 9, the yield of alkylbicyclo[2.2.2]octane is low. It was confirmed that the catalyst was maintained and could be recovered and reused.

The alkylbicyclo[2.2.2]octane mixture having 12 to 14 carbon atoms synthesized through reactions 4 to 9 was analyzed by gas chromatography-mass spectrometry (GC-MS) (FIG. 1) to confirm the respective mass spectra. As a result (Figure 2), alkylbicyclo[2.2.2]octane with 12 carbon atoms has m/z = 166, 123, and alkylbicyclo[2.2.2]octane with 13 carbon atoms has m/z = 180, 137. In alkylbicyclo[2.2.2]octane with 14 carbon atoms, characteristic peaks were detected at m/z = 194, 151.

Example 2. Confirmation of physical properties of aviation fuel mixture containing alkylbicyclo[2.2.2]octane

The alkylbicyclo[2.2.2]octane mixture (ABCOs) synthesized through reactions 4 to 9 of Example 1 was mixed with Jet A-1, a known aviation fuel, to obtain net calorific value, density, freezing point, and Kinematic viscosity was confirmed.

The Jet A-1:ABCOs volume mixing ratio used to confirm the physical properties of aviation fuel is shown in Table 2.

division One 2 3 4 Jet A-1 100 75 50 0 ABCOs 0 25 50 100

(1) As a result of measuring the net calorific value based on weight (NHOC _G ) and net calorific value based on volume (NHOC _V ) of the above mixtures (Figure 3), Jet A-1 must be satisfied as aviation fuel even if ABCOs are mixed up to a volume ratio of 50%. It was found that the lower limit of net calorific value based on weight, 42.8 MJ/kg, was satisfied, and the net calorific value based on volume was confirmed to increase as the volume ratio of mixed ABCOs increased.

(2) As a result of measuring the density of the above mixtures (FIG. 4), even if ABCOs were mixed up to a volume ratio of 50%, the density was within the range of 0.775 g/mL to 0.84 g/mL, which is the density range of Jet A-1 that must be satisfied as aviation fuel. It was confirmed that it had density.

(3) As a result of measuring the freezing points of the above mixtures (FIG. 5), it was confirmed that even if ABCOs were mixed up to a volume ratio of 50%, it did not exceed -47°C, which is the upper freezing point limit of Jet A-1, which must be satisfied as aviation fuel.

(4) As a result of measuring the kinematic viscosity of the mixtures at each temperature (FIG. 6), even if ABCOs were mixed up to a volume ratio of 25%, the upper limit standard that must be satisfied as aviation fuel at -40℃ was 12mm ² /s. It was satisfied, and it was confirmed that even when ABCOs were mixed up to a volume ratio of 50%, the upper limit standard of 8mm ² /s at -20℃ was satisfied.

Claims (16)

A method for producing a compound of Formula 3, comprising the step of hydrogenating a compound of Formula 1 or Formula 2 below under a hydrogenation reaction catalyst and a heteropoly acid catalyst:
[Formula 1]

(R ₁ is H, CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH; R ₂ is CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH, or are connected to each other to form an ester group or anhydride group Can form a ring containing 3 to 8 carbon atoms)
[Formula 2]

(R is H, CO ₂ H, CO ₂ Me or CO ₂ Et)
[Formula 3]

(R ₁ and R ₂ are H or Me, respectively).
The method of claim 1, wherein the hydrogenation reaction catalyst is one selected from the group consisting of Ni/C, Pt/C, Pd/C, Ru/C, Rh/C, and Cu/C.
The method of claim 1, wherein the heteropoly acid catalyst has a chemical formula selected from the group consisting of phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, and silicotungstic acid. Method for preparing the compound of 3.
The method of claim 1, wherein the hydrogenation reaction catalyst and the heteropoly acid catalyst are each included in an amount of 40 to 60 parts by weight based on 100 parts by weight of the compound of Formula 1 or Formula 2.
The method of claim 1, wherein the hydrogenation is performed in a solvent containing a saturated hydrocarbon having 5 to 12 carbon atoms.
The method of claim 1, wherein the compound of Formula 1 is a compound represented by the following Formula 1-1 or 1-2:
[Formula 1-1]

(R ₁ is H, CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH; R ₂ is CO ₂ H, CO ₂ Me, CO ₂ Et or CH ₂ OH)
[Formula 1-2]
.
The method of claim 1, wherein the compound of Formula 2 is a compound represented by the following Formula 2-1: Method for producing a compound of Formula 3:
[Formula 2-1]

(R is H, CO ₂ H, CO ₂ Me or CO ₂ Et).
The method of claim 1, wherein the compound of Formula 3 is a compound represented by the following Formulas 3-1 to 3-4:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]
.
The method of claim 1, further comprising reacting a compound of Formula 4 with a compound of Formula 5 or Formula 6 to produce a compound of Formula 1 or Formula 2:
[Formula 4]

[Formula 5]

(R ₁ is H, CO ₂ H, CO ₂ Me or CO ₂ Et; R ₂ is CO ₂ H, CO ₂ Me or CO ₂ Et)
[Formula 6]

(R ₁ and R ₂ are CO ₂ H, CO ₂ Me or CO ₂ Et, respectively).
The method of claim 9, wherein the compound of Formula 4 is α-phellandrene or α-terpinene.
The method of claim 9, wherein the compound of Formula 5 is one selected from the group consisting of acrylic acid, acrylic acid ester, maleic acid, and maleic acid ester.
The method of claim 9, wherein the compound of Formula 6 is fumaric acid or fumaric acid ester.
The method of claim 1, further comprising reacting a compound of Formula 4 with a compound of Formula 7 to produce a compound of Formula 1:
[Formula 4]

[Formula 7]
.
The method of claim 13, wherein the compound of Formula 4 is α-phellandrene or α-terpinene.
Hydrocarbon fuel composition comprising a compound of formula 3:
[Formula 3]

(R ₁ and R ₂ are H or Me, respectively).
The method of claim 15, comprising Jet A, Jet A-1, JP-8 (Jet Propellant-8), JP-10 (Jet Propellant-10), RJ-4 fuel, RJ-5 fuel, biodiesel and synthetic aviation fuel. A hydrocarbon fuel composition further comprising one selected from the group.