KR101035715B1 - Compounds of bicyclohepatane typed , Cetane number improver containing thereof and Fuel oil - Google Patents

Abstract

The present invention relates to a bicycloheptane-based compound, a cetane number improver and a fuel oil comprising the same, and more particularly, to a cetane number improver including a novel bicycloheptane-based compound and a fuel oil including the cetane number improver composition. The cetane number improver of the present invention is less toxic than conventional cetane number improvers, has excellent stability, and can greatly increase the fuel efficiency of fuel oil by greatly improving the cetane number of fuel oils such as diesel.

Cetane number, bicycloheptane

Description

Compounds of bicyclohepatane typed, Cetane number improver containing varying fuel and fuel oil}

The present invention relates to a novel bicycloheptane-based compound, to use as a cetane number improver comprising the compound, and to a fuel oil comprising the same.

In general, the cetane number of DC diesel obtained by distillation from crude oil is about 50, so there is no problem in the use of high-speed diesel engine.However, in case of diesel oil produced by high-tantan gasoline by contact distribution of diesel oil, the cetane number is 30-40. It is low and the ignition property is bad, and the use of the cetane number improver for improving the combustion performance of a fuel is calculated | required.

Cetane number improvers are decomposed during fuel combustion, producing free radicals, preventing ignition delays, and helping diesel engines start up easier. It also functions to reduce the soot of the exhaust gas. Conventional cetane number improvers include aliphatic nitrate compounds, aliphatic peroxides, aldehydes, ketones, ethers, esters, metal oxides, aliphatic hydrocarbons and the like. Among these, the aliphatic peroxide is rarely used because it has a high risk of explosion and may adversely affect the fuel. In addition, other existing cetane number improvers other than the aliphatic nitrate compounds have a disadvantage in that the amount of cetane improvement is low, so that the amount of the cetane is increased.

As cetane number enhancers, the aliphatic nitrates typically use nitrate compounds of unsubstituted aliphatic or substituted aliphatic or cycloaliphatic alcohols having about 2-10 carbon atoms. Alkyl groups included in such aliphatic nitrate compounds may be linear or branched, saturated or unsaturated alkyl groups.

Examples of aliphatic nitrate compounds include methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, t-butyl Nitrate, n-amyl nitrate, n-hexyl nitrate, n-heptyl nitrate, sec-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate And latex, n-decyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate and isopropylcyclohexyl nitrate. Also, for example, alkoxy substituted aliphatic alcohols such as 2-ethoxyethyl nitrate, 2- (2-ethoxyethoxy) ethyl nitrate, 1-methoxypropyl nitrate or 4-ethoxybutyl nitrate Nitrate is also suitable, and diol nitrates such as 1,6-hexamethylene dinitrate are also suitable. As the cetane number enhancer at present, the most widely used aliphatic nitrate compound is 2-ethylhexyl nitrate (EHN). However, aliphatic nitrate compounds are toxic and poor in stability, causing environmental problems, and thus new cetane number improvers are needed. In addition, in the case of peroxides, Di-tert-butyl peroxide was developed in the 1940's, but is rarely used because it may have an adverse effect on explosion risk and fuel. The development of environmentally friendly and stable new structure of peroxide cetane number improver is needed.

Accordingly, the present inventors have conducted extensive research to develop a cetane number improver having a high cetane number improving effect and a low explosion risk, and found that a bicycloheptane-based compound having a specific structure has an effect of improving the cetane value of fuel oil. The invention was completed.

An object of the present invention is to provide a novel compound having an effect of improving cetane number.

Another object of the present invention is to provide a novel cetane number improver.

Another object of the present invention is to provide a fuel oil of a novel composition having excellent cetane number.

This invention solves the subject of this invention by providing the bicycloheptane type compound represented by following General formula (1) which has a cetane number improvement effect.

In Formula 1, R ¹ is a hydrogen atom or OR; R ² is a hydrogen atom or —ONO ₂ ; Or R ¹ and R ² is Can combine to form a five-membered hydrocarbon ring, At this time, the hydrocarbon ring One to three substituents selected from OR and -ONO ₂ may be substituted; R is a hydrogen atom or a C ₁ to C ₁₂ linear or branched saturated or unsaturated alkyl group.

In addition, the present invention solves the problems of the present invention by providing a use of the bicycloheptane-based compound represented by the formula (1) as a cetane number improver.

Moreover, this invention solves the subject of this invention by providing the fuel oil containing the cetane number improver mentioned above.

Such a cetane number improver of the present invention has a high cetane number improving effect of fuel oil and a low explosion risk, and a fuel oil including the cetane number improver composition of the present invention has excellent combustion efficiency.

Hereinafter, the present invention will be described in detail.

Bicycloheptane-based compound represented by the formula (1) characterized by the present invention is a novel compound, it is included in the fuel oil has the effect of improving the cetane number. That is, its structural features to the bicyclo heptane-based compound represented by Formula 1 of the present invention as claimed comprises a -ONO ₂ in the molecule structure, -ONO ₂ is formed when the combustion fuel oil, free radical Thereby increasing ignition.

To more specifically illustrate the bicycloheptane-based compound represented by the formula (1), it may be represented by the formula (1a), 1b, 1c, and 1d.

In Chemical Formulas 1a to 1d, R is a hydrogen atom or a C ₁ to C ₁₂ linear or branched saturated or unsaturated alkyl group.

In the bicycloheptane compound represented by Formula 1, preferably R is a C ₁ ~ C ₁₂ linear or branched saturated or unsaturated alkyl group, more preferably C ₂ ~ C ₁₀ linear or branched Alkyl group. And compounds in which R is ethyl, butyl, ethylbutyl, 2-ethylhexyl or octyl are particularly preferred, and when R is a branched alkyl group, substituents include ethyl, n-propyl, isopropyl, allyl, n-butyl , Isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, sec-heptyl, n-octyl, 2-ethylhexyl, sec-octyl, n-nonyl, n-decyl, cyclo It is preferable that it is 1 type chosen from pentyl, cyclohexyl, methylcyclohexyl, and isopropylcyclohexyl.

On the other hand, the present invention is characterized by a cetane number improver comprising a bicycloheptane compound represented by the formula (1). As the cetane number improver, the bicycloheptane compound represented by Formula 1 may be used as a single compound or a mixture of two or more compounds.

On the other hand, the present invention is characterized by a fuel oil containing a cetane number improver containing a bicycloheptane-based compound represented by the formula (1). In this case, the bicycloheptane-based compound may be added to the fuel oil as it is, but may be dissolved in the inert, stable hydrocarbon organic solvent and added to the fuel oil. As the hydrocarbon organic solvent, at least one selected from diethyl ether, tetrahydrofuran and methyl t-butyl ether is preferably used. In addition, in the case where the organic solvent is further added and used, it is preferable to use 30 to 300 parts by weight based on 100 parts by weight of the bicycloheptane-based compound.

The bicycloheptane-based compound represented by the formula (1) included in the fuel oil as a cetane number improver is preferably in a concentration of 50 to 5,000 ppm in terms of the performance of the cetane number. The type of the fuel oil is not particularly limited, but is preferably used for diesel fuel oil.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by the following examples.

Synthesis Example Synthesis of Bicycloheptane Compound

Synthesis Example 1.

(R=옥틸)

(R = octyl)

Into a 250 mL round bottom flask, add 10 g (1 equivalent) of norbornylene and 50 mL of THF, stir for 30 minutes under Ice Base, and add a small amount of 25 g of m-Chloroperoxybenzoic acid. The solution dissolved in THF was slowly added dropwise and reacted using a dropping funnel. After completion of the reaction, the solid was filtered and distilled under reduced pressure to remove THF, and it was confirmed by ¹ H-NMR measurement that 10.5 g (90% yield) of norbornyl epoxide was obtained.

¹ H-NMR δ in (CDCl ₃ , ppm): 0.65 (1H, CH), 1.15 (2H, CH ₂ ), 1.27 (1H, CH), 1.42 (2H, CH ₂ ), 2.40 (2H, CH ₂ ) , 3.31 (2H, 2 CH).

Into a 100 mL round bottom flask, 4.6 g of the previously synthesized norbornyl epoxide and 16.3 g of 1-octanol were added, stirred at a reaction temperature of 80 to 100 ^° C. for about 30 minutes, and then 2 drops of sulfuric acid was added. As the reaction proceeded, the color of the reactant changed to pale yellow and reacted for 8 hours. After the reaction was completed, the reaction was dissolved in ethyl acetate, neutralized with NaHCO ₃ aqueous solution, the organic layer was separated and distilled under reduced pressure to remove the solvent to obtain 9.8 g of octyloxy norbornyl alcohol (98% yield). 5 g of octyloxy norbornyl alcohol and 10 g of nitric acid were quantified in a 100 mL round bottom flask, stirred at room temperature for 30 minutes, an ice base was installed, and 4 g of sulfuric acid was slowly added dropwise. The reaction temperature was increased as the reaction proceeded, and the temperature of the reactant was lowered to room temperature, followed by stirring for about 1 hour. After the reaction was completed, the reaction product was dissolved in ethyl acetate, neutralized with NaHCO ₃ aqueous solution, the organic layer was recovered and the solvent of the organic layer was removed to obtain 5.5 g (yield 93%) of the desired bicycloheptane compound. . The structure of the prepared bicycloheptane-based compound was confirmed as follows by using ¹ H-NMR and FT-IR.

¹ H-NMR δ in (CDCl ₃ , ppm): 0.81 (3H, CH ₃ ), 0.98 (1H, CH), 1.17 (10H, 5CH ₂ ), 1.42 (4H, 2CH ₂ ), 1.71 (1H, CH) , 1.83 (1H, CH), 2.05 (2H, OH ₂ ), 2.15 (2H, CH ₂ ), 3.37 (2H, CH ₂ ), 3.52 (2H, CH ₂ ), 3.88 (1H, CH).

Synthesis Example 2.

(R=옥틸)

(R = octyl)

3.71 g of bicycloheptadiene and 50 mL of MC were added to a 250 mL round bottom flask, and stirred for 30 minutes under an ice base. A solution of 13.9 g of m-chloroperoxybenzoic acid in a small amount of MC was added to a titrator. Was slowly added dropwise and reacted. After completion of the reaction, the solid was filtered and distilled under reduced pressure to remove MC to obtain 4 g (yield 91%) of norbornyl diepoxide and the structure was confirmed by ¹ H-NMR measurement.

¹ H-NMR δ in (CDCl ₃ , ppm): 1.35 (2H, CH ₂ ), 2.12 (2H, 2CH), 3.01 (4H, 4CH).

In a 100 mL round bottom flask, 1.6 g of the previously synthesized norbornel diepoxide and 5.1 g of 1-octanol were added, stirred at a reaction temperature of 80 to 100 ^° C. for about 30 minutes, and then 2 drops of sulfuric acid was added. As the reaction proceeded, the color of the reactant changed to pale yellow and reacted for 8 hours. After the reaction was completed, the reactant was dissolved in ethyl acetate, neutralized with NaHCO ₃ aqueous solution, the organic layer was separated and distilled under reduced pressure to remove the solvent, and 3.5 g (98% yield) of dioctyloxy norbornyl dialcohol was obtained. Obtained.

4 g of synthesized dioctyloxy norbornyl dialcohol and 10 g of nitric acid were quantified, and stirred at room temperature for 30 minutes. Then, an ice base was installed and 4 g of sulfuric acid was slowly added dropwise thereto. The reaction temperature was increased as the reaction proceeded, and the temperature of the reactant was lowered to room temperature, followed by stirring for about 1 hour. After the reaction was completed, the reaction was dissolved in ethyl acetate and neutralized with NaHCO ₃ aqueous solution, the organic layer was recovered and the solvent of the organic layer was removed to obtain 4.5 g (yield 93%) of the desired bicycloheptane compound. The structure of the prepared bicycloheptane-based compound was confirmed as follows by using ¹ H-NMR and FT-IR.

¹ H-NMR δ in (CDCl ₃ , ppm): 0.90 (6H, 2CH ₃ ), 1.24 (20H, 10CH ₂ ), 1.31 (2H, CH ₂ ), 1.42 (4H, 2CH ₂ ), 1.92 (2H, 2CH ), 2.05 (2H, 2OH), 2.92 (2H, 2CH), 3.82 (4H, 2CH ₂ ), 4.03 (2H, 2CH ₂ )

Synthesis Example 3.

(R=옥틸)

(R = octyl)

8.9 g of exo-tricyclo [5.2.1.0/2,6/] dec-8-ene} and THF 10 in a 100 mL round bottom flask. After adding mL and stirring to dissolve, the THF solution in which 23 g of m-chloroperoxybenzoic acid was dissolved was slowly added dropwise and reacted using a titrator. After completion of the reaction, the solid was filtered and distilled under reduced pressure to remove THF, and then 9.5 g (yield 95%) of exo-tricyclo [5.2.1.0/2,6/] dec-8-ene epoxide was obtained, which was ¹ H. It was confirmed as follows using -NMR.

¹ H-NMR δ in (CDCl ₃ , ppm): 1.22 (8H, 4CH ₂ ), 1.65 (2H, 2CH), 2.06 (1H, CH), 2.27 (2H, CH ₂ ), 3.30 (1H, CH), 3.47 (1 H, CH).

Into a 100 mL round bottom flask, 5.4 g of the exo-tricyclo [5.2.1.0/2,6/] dec-8-ene epoxy and 13.9 g of octanol were added and stirred at a reaction temperature of 80 to 110 ^° C. for about 30 minutes. Then, 2 drops of sulfuric acid was added. As the reaction proceeded, the color of the reactant was changed to light yellow and reacted for 9 hours. After completion of the reaction, the reaction product was dissolved in ethylene acetate, neutralized with NaHCO ₃ aqueous solution, the organic layer was separated and distilled under reduced pressure to remove the solvent, followed by octyloxy exo-tricyclo [5.2.1.0/2,6/ ] 9.4 g (94% yield) of Deck-8-ene alcohol were obtained.

5 g of octyloxy exo-tricyclo [5.2.1.0/2,6/] dec-8-ene alcohol and 10 g of nitric acid were quantified into a 100 mL round bottom flask, and stirred at room temperature for 30 minutes, followed by an ice base. Was added and slowly added dropwise 4 g of sulfuric acid. The reaction temperature was increased as the reaction proceeded, and when the temperature of the reactant was lowered to room temperature, the reaction temperature was stirred for about 1 hour. After the reaction was completed, the reaction was dissolved in ethylene acetate, neutralized with NaHCO ₃ aqueous solution, the organic layer was recovered and the solvent was removed, to obtain 5.2 g (yield 90%) of the desired bicycloheptane-based compound. The octyloxy exo-tricyclo [5.2.1.0/2,6/] dec-8-ene nitro compound was identified as follows using ¹ H-NMR and FT-IR.

¹ H-NMR δ in (CDCl ₃ , ppm): 0.81 (3H, CH ₃ ), 1.18 (14H, 7CH ₂ ), 1.45 (6H, 2CH ₂ , 2CH), 1.81 (1H, CH), 1.95 (3H, OH ₂ , CH), 2.19 (2H, CH ₂ ), 3.40 (2H, CH ₂ ), 3.60 (1H, CH), 3.72 (1H, CH).

Synthesis Example 4.

(R=옥틸)

(R = octyl)

Into a 100 mL round bottom flask, add 8.1 g of 4,7-methano-3a, 4,7,7-tetrahydroindene and 10 mL of THF to 4,7-Methano-3a, 4,7,7-tetrahydroindene. After stirring and dissolving, THF solution in which 35 g of m-chloroperoxybenzoic acid was dissolved was slowly added dropwise using a titrator to react. After completion of the reaction, the solid was filtered and distilled under reduced pressure to remove THF, and then 9.2 g (yield 92%) of 4,7-methano-3a, 4,7,7-tetrahydroindene epoxide was obtained. This was ¹ H-NMR. It was confirmed as follows using.

¹ H-NMR δ in (CDCl ₃ , ppm): 0.81 (1H, CH), 1.37 (1H, CH), 1.76 (2H, 2CH), 2.42 (2H, CH ₂ ), 2.55 (1H, CH), 2.67 (1H, CH), 3.17 (2H, 2CH), 3.35 (1H, CH), 3.50 (1H, CH).

3.7 g of the 4,7-methano-3a, 4,7,7-tetrahydroindene epoxide and 27.8 g of octanol were added to a 100 mL round bottom flask, and the reaction temperature was maintained at 90 to 115 ^° C. for about 30 minutes. After stirring, 2 drops of sulfuric acid was added. As the reaction proceeded, the color of the reactant was changed to light yellow and reacted for 9 hours. After completion of the reaction, the reaction product was dissolved in ethylene acetate, neutralized with NaHCO ₃ aqueous solution, the organic layer was separated and distilled under reduced pressure to remove the solvent, octyloxy 4,7-methano-3a, 4,7,7 8.9 g (98% yield) of tetrahydroindene alcohol were obtained.

In a 100 mL round bottom flask, 4.1 g of the octyloxy 4,7-methano-3a, 4,7,7-tetrahydroindene alcohol and 10 g of nitric acid were quantitated and stirred at room temperature for 30 minutes, followed by ice- The base was installed and 4 g of sulfuric acid was slowly added dropwise and reacted. The reaction temperature was increased as the reaction proceeded, and the reaction was stirred for about 1 hour while maintaining the temperature of the reactant. After completion of the reaction, the reaction was dissolved in ethylene acetate and neutralized with NaHCO ₃ aqueous solution, the organic layer was recovered and the solvent was removed to obtain 4.6 g (yield 92%) of the desired bicycloheptane compound. The structure of the prepared bicycloheptane compound was confirmed by ¹ H-NMR and FT-IR.

¹ H-NMR δ in (CDCl ₃ , ppm): 0.82 (6H, 2CH ₃ ), 1.27 (20H, 5CH ₂ ), 1.45 (8H, 2CH ₂ , 4CH), 1.81 (1H, CH), 2.01 (2H, OH ₂ ), 1.28 (1H, CH), 3.25 (4H, 2CH ₂ ), 3.59 (2H, CH ₂ ), 4.10 (2H, 2CH).

EXAMPLES Preparation of Cetane Number Enhancer Composition

Examples 1 to 10 and Comparative Examples 1 to 2

After preparing a cetane number improver composition with a composition as shown in Table 1, and added to the diesel fuel oil (SK, ULSD) so that the bicycloheptane-based compound to 1,000 ppm, ASTM D 6890: 2007 method (Standard Test The cetane number of fuel oil was measured using the Method for Determination of Ignition Delay and Derived Cetane Number (DCN) of Diesel Fuel Oils by Combustion in a Constant Volume Chamber.

In addition, Comparative Example 1 is SK's ULSD diesel fuel, and Comparative Example 2 is a 2-ethyl-hexyl nitrate compound.

As shown in Table 1, in the case of Comparative Example 1 which is an existing diesel fuel, it can be confirmed that the cetane number is lower than the fuel oil using the cetane number improver of Examples 1 to 10 of the present invention. In addition, it can be confirmed that the cetane number of the fuel oil using the cetane number improver of the present invention is superior to that of Comparative Example 2, which is a fuel oil using an existing nitrate-based cetane number improver having a risk of explosion.

Claims (9)

A bicycloheptane compound represented by Formula 1 below; [Formula 1]

In Formula 1, R ¹ is a hydrogen atom or OR; R ² is a hydrogen atom or —ONO ₂ ; Or R ¹ and R ² is Can combine to form a five-membered hydrocarbon ring, At this time, the hydrocarbon ring One to three substituents selected from OR and -ONO ₂ may be substituted; R is a hydrogen atom or a C ₁ to C ₁₂ linear or branched saturated or unsaturated alkyl group. According to claim 1, Bicycloheptane compound selected from Formula 1a to Formula 1d; [Formula 1a]

[Chemical Formula 1b]

[Formula 1c]

≪ RTI ID = 0.0 &

In Chemical Formulas 1a to 1d, R is a hydrogen atom or a C ₁ to C ₁₂ linear or branched saturated or unsaturated alkyl group. The bicycloheptane compound according to claim 1, wherein R is an alkyl group selected from ethyl, butyl, ethylbutyl, 2-ethylhexyl, and octyl. A cetane number improver comprising a bicycloheptane-based compound represented by Formula 1 below; [Formula 1]

In Formula 1, R ¹ is a hydrogen atom or OR; R ² is a hydrogen atom or —ONO ₂ ; Or R ¹ and R ² is Can combine to form a five-membered hydrocarbon ring, At this time, the hydrocarbon ring One to three substituents selected from OR and -ONO ₂ may be substituted; R is a hydrogen atom or a C ₁ to C ₁₂ linear or branched saturated or unsaturated alkyl group. [Claim 5] The cetane number improver according to claim 4, wherein the bicycloheptane-based compound is a single compound or a mixture selected from Formulas 1a to 1d; [Formula 1a]

[Chemical Formula 1b]

[Formula 1c]

≪ RTI ID = 0.0 &

In Chemical Formulas 1a to 1d, R is a hydrogen atom or a C ₁ to C ₁₂ linear or branched saturated or unsaturated alkyl group. 6. The cetane number improver according to claim 5, wherein R is an alkyl group selected from ethyl, butyl, ethylbutyl, 2-ethylhexyl and octyl. A fuel oil comprising the cetane number improver of claim 4. 8. The fuel oil according to claim 7, wherein the bicycloheptane compound is contained at a concentration of 50 to 5,000 ppm. 8. The fuel oil according to claim 7, wherein the fuel oil is diesel fuel oil.