JP2008266510A - Kerosene composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a kerosene composition which can mainly use a plant-originated fatty acid alkyl ester as a fuel to reduce loads on environments, and can improve combustibility to prevent the production of tars on a wick, when used in a wick type stove. <P>SOLUTION: This kerosene composition contains a fatty acid alkyl ester in an amount of 2 to 20 vol% based on the total amount of the composition, wherein the main component of the fatty acid alkyl ester is a fatty acid alkyl ester represented by general formula (I) (wherein, R<SP>1</SP>is a 5 to 9C hydrocarbon group; R<SP>2</SP>is a 1 to 4C hydrocarbon group). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a kerosene composition, and in particular, to a kerosene composition containing a specific fatty acid alkyl ester.

  In recent years, from the viewpoint of preventing global warming, it has been required to reduce carbon dioxide emissions from ordinary households and industries. Regarding the reduction of carbon dioxide emissions, technological development in fuel (oil) has been promoted, and the concept of carbon neutral (that is, those derived from plants among the fuel (oil) in the atmosphere in the life cycle) Therefore, fatty acid alkyl esters such as FAME (fatty acid methyl ester) obtained from plant-derived compounds, for example, vegetable oils and fats, are attracting attention.

  FAME is expected to be an alternative fuel to light oil because its properties are close to that of light oil, and so far, fuels composed of FAME and light oil compositions containing FAME are known (see, for example, Patent Document 1). However, from the viewpoint of preventing global warming and the like, it is preferable that the scope of application of FAME and other fatty acid alkyl esters is further expanded, and it is desired that they are used not only for alternative fuels of light oil but also for other fuel applications. . Examples of the other fuel include kerosene, which can be applied as a kerosene composition containing a fatty acid alkyl ester.

  Regarding combustion in a core-type stove, which is one of the methods of using kerosene, there has been known a problem derived from the properties of kerosene. That is, depending on the properties of kerosene, a tar content may be generated on the core, and the combustibility may be deteriorated. Further, when this tar generation progresses, the operation of a safety device such as a seismic resistance device becomes defective and the fire cannot be extinguished. There was a thing.

  With respect to the combustibility of kerosene, in recent years, a technique for improving the combustibility by defining the distillation properties of the kerosene composition and the content of sulfur and the like has been disclosed (Patent Document 2). However, there is still room for improvement regarding the combustibility of kerosene, and a kerosene composition having further excellent performance has been desired.

  Conventionally, it is thought that the addition of oxygen-containing compounds is effective in improving the flammability of kerosene, but even if the above fatty acid alkyl ester is simply added to the kerosene base, it is usually effective in improving flammability. On the contrary, the flammability tends to deteriorate.

JP-A-2005-23136 JP 2006-131710 A

  The present invention has been made under such circumstances, and it is possible to reduce the burden on the environment by using fatty acid alkyl esters derived mainly from plants as a fuel. An object of the present invention is to provide a kerosene composition that can improve combustibility and suppress the generation of tar content on the core when used in the above.

The present inventors have found that the above object can be achieved by specifying a fatty acid alkyl ester and blending it with a kerosene base material. The present invention has been completed based on such findings. That is, the present invention
[1] 2 to 20% by volume of fatty acid alkyl ester based on the total amount of the composition,
A kerosene composition in which the main component of the fatty acid alkyl ester is the fatty acid alkyl ester represented by the general formula (I);

(R ¹ represents a hydrocarbon group having 5 to 9 carbon atoms, and R ² represents a hydrocarbon group having 1 to 4 carbon atoms.)
[2] The kerosene composition according to the above [1], wherein the fatty acid alkyl ester is one or a mixture of two or more selected from methyl caproate, methyl caprylate, and methyl caprate,
[3] The kerosene composition according to the above [1] or [2], which satisfies the following conditions (1) to (5):
(1) 95 vol% distillation temperature is 215 to 270 ° C
(2) Sulfur content is 10 mass ppm or less (3) Flash point is 40 ° C. or more (4) Kinematic viscosity at 30 ° C. is 1.2 to 1.8 mm ² / s
(5) The amount of air injection gum is 2 mg / 100 mL or less.

  According to the present invention, a kerosene composition containing a specific fatty acid alkyl ester is provided. Since the kerosene composition of the present invention mainly uses fatty acid alkyl esters derived from plants as fuel, it is possible to reduce the burden on the environment, and when used in a core stove, It is possible to improve the combustibility and suppress the tar content generation on the core.

  The kerosene composition of the present invention has the general formula (I)

The fatty acid alkyl ester represented by these is contained. In the general formula (I), R ¹ represents a hydrocarbon group having 5 to 9 carbon atoms, and R ² represents a hydrocarbon group having 1 to 4 carbon atoms. By containing the fatty acid alkyl ester which is an oxygen-containing compound, the effect of improving combustibility can be obtained, and the generation of the tar content can be suppressed. When the carbon number of R ¹ is 4 or less, the flash point of the kerosene composition tends to decrease and there is a risk of explosion when ignited, etc. When the carbon number is 10 or more, the kinematic viscosity becomes high and the core type When used in a stove, a problem occurs in the fuel supply to the wick, and tar content is easily generated.

R ¹ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be linear or branched. On the other hand, R ² is a saturated hydrocarbon group, and examples thereof include a methyl group, an ethyl group, various propyl groups, and various butyl groups.

  Preferable examples of the fatty acid alkyl ester include methyl caproate, methyl caprylate, and methyl caprate.

  The fatty acid alkyl ester can be synthesized by a known reaction of a fatty acid (or a fatty acid derivative) and an alkyl alcohol. For example, in the presence of an alkali catalyst such as caustic soda, a fatty acid having 6 to 10 carbon atoms and 1 to 1 carbon atoms are synthesized. 4 can be synthesized by an esterification reaction with an alcohol.

  Specific examples of the fatty acid having 6 to 10 carbon atoms include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid and the like. Specific examples of the alkyl alcohol having 1 to 4 carbon atoms include methanol, Examples thereof include ethanol, propanol having a linear or branched chain, and butanol having a linear or branched chain.

  It is preferable to use a mixture of fatty acids having 6 to 10 carbon atoms, starting from oils and fats such as animal oils and vegetable oils, that is, triglycerides, and fatty acids obtained therefrom. When triglyceride is used as a raw material, a transesterification reaction between triglyceride and alkyl alcohol can be used. Specific examples of the raw animal oil include beef tallow, pork tallow, sheep fat, whale oil, fish oil, liver oil and the like. Specific examples of the raw vegetable oil include linseed oil, safflower oil, sunflower oil, soybean oil, corn oil, cottonseed oil. Sesame oil, olive oil, castor oil, peanut oil, coconut oil, palm kernel oil, palm oil, coconut oil, rapeseed oil, rice bran oil and the like. In addition, waste cooking oils of these animal and vegetable oils can also be used. Among the above, palm kernel oil and coconut oil are preferably used because they contain a large amount of triglyceride containing a fatty acid having a carbon number used in the present invention.

  In the method using triglyceride as a raw material as described above, a fatty acid alkyl ester composed of a fatty acid other than those having 6 to 10 carbon atoms may be produced. Therefore, it is preferable to carry out purification treatment in the fatty acid alkyl ester synthesis process. For example, the fatty acid alkyl ester used in the present invention can be obtained by purification of fatty acid or purification of fatty acid alkyl ester.

For the above reasons, in the present invention, the fatty acid alkyl ester represented by the general formula (I) may be contained as the main component of the fatty acid alkyl ester, and the general formula (I) may be used as long as the effects of the present invention are not hindered. The hydrocarbon group corresponding to R ¹ may contain a fatty acid alkyl ester having 4 or less carbon atoms or 10 or more carbon atoms. In the present specification, “main component” means 50% by volume or more based on the total amount of fatty acid alkyl ester. From the above viewpoint, the content of the fatty acid alkyl ester represented by the general formula (I) is preferably 80% by volume or more, more preferably 90% by volume or more, based on the total amount of the fatty acid alkyl ester.

  Fatty acid alkyl ester may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more fatty acid alkyl esters are used in combination, the fatty acid alkyl esters synthesized individually may be mixed, and two or more fatty acids (or fatty acid derivatives) and / or two or more alkyl alcohols may be mixed. May be used as a raw material.

  The fatty acid alkyl ester blended in the kerosene composition of the present invention preferably has a total acid value of 1.0 mgKOH / g or less. If the total acid value is 1.0 mgKOH / g or less, there is no possibility of deteriorating the properties of kerosene, and there is no possibility of adversely affecting the equipment. This total acid value is a value measured according to JIS K 2501 “Petroleum products and lubricants—neutralization number test method”.

  The content of the fatty acid alkyl ester is 2 to 20% by volume, preferably 5 to 20% by volume, based on the total amount of the composition. When the content of the fatty acid alkyl ester is less than 2% by volume, a sufficient effect cannot be obtained from the viewpoint of carbon neutral. On the other hand, if it exceeds 20% by volume, the kinematic viscosity tends to increase, and when used in a core-type stove, a problem occurs in the fuel supply to the core, and the tar content tends to be generated. Moreover, 15 volume% or more is preferable from a viewpoint of the improvement of combustibility by addition of an oxygen-containing compound.

The kerosene composition of the present invention preferably has the following properties.
Although there is no restriction | limiting in particular about the density in 15 degreeC, From a viewpoint of a fuel consumption rate, it is preferable that it is 0.780 g / cm < ³ > or more, and it is more preferable that it is 0.790-0.830 g / cm < ³ >. The density is a value measured according to JIS K2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The flash point is preferably 40 ° C. or higher, more preferably 43 ° C. or higher, from the viewpoint of safety. The flash point is a value measured according to JIS K2265 “Tag sealed flash point test method”.
The kinematic viscosity at 30 ° C. is preferably 1.2 to 1.8 mm ² / s. If it is less than 1.2 mm ² / s, combustible vapor is generated at room temperature, and there is a risk of ignition due to static electricity or the like. On the other hand, if it exceeds 1.8 mm ² / s, trouble is likely to occur in the fuel supply to the core, and tar generation is promoted.
It is preferable that the amount of air injection gum is 2 mg / 100 mL or less. When it exceeds 2 mg / 100 mL, tar generation at the initial stage of combustion tends to be promoted. The air injection gum amount is a value measured according to JIS K2261 “Petroleum products—automobile gasoline and aviation fuel oil—existing gum test method—injection evaporation method”.
The sulfur content is preferably 10 mass ppm or less, more preferably 6 mass ppm or less, from the viewpoint of suppressing the amount of SOx generated when burned with a core-type stove or fan heater. The sulfur content is a value measured according to JIS K2541 “Crude oil and petroleum products—Sulfur content test method”.
The nitrogen content is preferably 5 mass ppm or less, more preferably 3 mass ppm or less, from the viewpoint of suppressing the amount of NOx generated when burned with a core-type stove or fan heater. The nitrogen content is a value measured by a chemiluminescence method.
The smoke point is preferably 25 mm or more, and more preferably 26 mm or more, from the viewpoint of suppressing the generation of soot when using a core-type stove. The smoke point is a value measured according to JIS K2537.
The Saybolt color is preferably +27 or more. The Saybolt color is a value measured according to JIS K2580.
The copper plate corrosion is preferably 1 or less from the viewpoint of suppressing corrosion of combustion equipment. The copper plate corrosion is a value measured according to JIS K2531.

The kerosene composition of the present invention preferably has the following distillation properties.
Initial boiling point (IBP): 140-165 ° C
10 vol% distillation temperature (T _10): 160~190 ℃
30 volume% distillation temperature (T _30): 170~200 ℃
50 volume% distillation temperature (T _50): 180~220 ℃
70 volume% distillation temperature (T _70): 190~240 ℃
90 volume% distillation temperature (T _90): 210~265 ℃
95% by volume distillation temperature (T ₉₅ ): 215 to 270 ° C.
Distillation end point (EP): 230-280 ° C
The initial boiling point (IBP) is preferably 140 ° C. or higher, more preferably 145 ° C. or higher, from the viewpoint of preventing adverse effects on safety due to lowering of the flash point. On the other hand, from the viewpoint of ignition characteristics at low temperatures, it is preferably 165 ° C. or lower, more preferably 160 ° C. or lower.
T ₁₀ is preferably not less than 162 ° C., more preferably not less than 165 ° C. from the viewpoint of preventing undesired effects on safety due to a decrease in flash point and reducing odor during refueling, while ignition characteristics at low temperatures are preferred. From this viewpoint, it is preferably 185 ° C. or lower, more preferably 180 ° C. or lower.
T ₃₀ is preferably 172 ° C. or higher, more preferably 175 ° C. or higher, from the viewpoint of odor reduction and calorific value at the time of refueling, while preferably 195 ° C. or lower, more preferably, from the viewpoint of ignition characteristics at low temperatures. Is 190 ° C. or lower.
Moreover, from the viewpoint of the balance between the calorific value and the combustibility, T ₅₀ is preferably 182 to 210 ° C., more preferably 185 to 205 ° C., and T ₇₀ is preferably 192 to 230 ° C., more preferably 195 to was 225 ° C., T ₉₀ is preferably two hundred twelve to two hundred and sixty ° C., more preferably from two hundred and fifteen to two hundred fifty-five ° C..
T _95, when burned in wick-type stove, from the viewpoint of preventing the problem remains the kerosene unburnt in the core occurs, preferably 270 ° C. or less, more preferably 268 ° C. or less, 265 ° C. The following is more preferable. On the other hand, from the viewpoint of calorific value, 220 ° C. or higher is preferable, and 225 ° C. or higher is more preferable.
The distillation end point (EP) is preferably 280 ° C. or lower, more preferably 275 ° C. or lower, from the viewpoints of stability and flammability. On the other hand, from the viewpoint of preventing deterioration of the fuel consumption rate when burned with an oil fan heater, 232 ° C. or higher is preferable, and 235 ° C. or higher is more preferable.
The distillation property is a value measured according to JIS K2254 “Evaporation Test Method”.

  Although it does not specifically limit regarding the manufacturing method of the kerosene composition of this invention, It can obtain by mixing the said fatty-acid alkylester with a desulfurization straight-run kerosene fraction and / or another hydrocarbon fraction. The desulfurized straight kerosene fraction can be obtained by hydrodesulfurizing a straight kerosene fraction obtained by atmospheric distillation of crude oil. In the above production method, the conditions for hydrodesulfurization of the straight-run kerosene fraction are not particularly limited to the conditions that sufficient desulfurization is performed, and may be carried out by the same treatment as a normal kerosene hydrodesulfurization treatment. . Examples of the other hydrocarbon fractions include hydrocracked kerosene base materials, GTL oil synthesized by a Fischer-Tropsch reaction, and the like.

  A known fuel oil additive can be added to the kerosene composition of the present invention as necessary. Known fuel oil additives include, for example, antioxidants, metal deactivators, anti-icing agents, corrosion inhibitors, antistatic agents, colorants, discriminating agents, deodorants and the like. These additives can be used alone or in combination of two or more. The addition amount can be arbitrarily determined, but the addition amount of each additive is usually 0.2% by mass or less, preferably 0.02% by mass or less based on the total amount of the kerosene composition. is there.

  Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Various measurements were performed by the following methods.
Sulfur content: measured according to JIS K2541.
Flash point: Measured according to JIS K2265.
Kinematic viscosity (30 ° C.): Measured according to JIS K2283.
Air injection gum amount: Measured according to JIS K2261. In this test, about 0.3 g of gauze was placed in a test beaker, 50 mL of a test sample (kerosene composition) was added, and the weight increase of gauze after jetting air at 10 ° C. for 10 hours at 200 ° C. Was measured as the amount of air-jet gum.

Examples 1-8
Kerosene base material [95% by volume distillation temperature 252.0 ° C, 50% by volume distillation temperature 195.0 ° C, flash point 43.0 ° C, kinematic viscosity (30 ° C) 1.341 mm ² / s, sulfur content 6 mass ppm] and a fatty acid alkyl ester (methyl caproate, methyl caprylate, methyl caprate) so as to have the composition and blending amount (capacity part) shown in Table 1 to obtain a kerosene composition. The evaluation results are shown in Table 2. In addition, a capacity | capacitance part is a value in 15 degreeC.

Reference Example 1 and Comparative Examples 1-3
In the same manner as in Examples 1 to 8, a kerosene base and a fatty acid alkyl ester (methyl butyrate, methyl laurate) were blended so as to have the composition and blending amount (capacity part) described in Table 1, and a kerosene composition was prepared. Obtained. The evaluation results are shown in Table 2.

The kerosene compositions of Examples 1 to 8 have a flash point equivalent to that of kerosene containing no fatty acid alkyl ester and a 30 ° C. kinematic viscosity. Therefore, the same usage method as conventional kerosene can be applied to the kerosene composition containing the fatty acid alkyl ester of the present invention. Moreover, reduction of the burden with respect to an environment is achieved by using the kerosene composition containing a fatty-acid alkylester. Furthermore, as shown by the amount of air-injected gum, the kerosene composition of the present invention has a tar content suppressing effect.
On the other hand, the kerosene composition of Comparative Example 1 containing methyl butyrate is not suitable for use as kerosene because of its low flash point. Moreover, in the kerosene compositions of Comparative Examples 2 and 3 containing methyl laurate, the tar content generation is promoted.

  According to the present invention, a kerosene composition containing a specific fatty acid alkyl ester is provided. Since the kerosene composition of the present invention mainly uses fatty acid alkyl esters derived from plants as fuel, it is possible to reduce the burden on the environment, and when used in a core stove, Combustibility can be improved and tar content generation on the core can be suppressed.

Claims (3)

2 to 20% by volume of fatty acid alkyl ester based on the total amount of the composition,
The main component of the fatty acid alkyl ester is the general formula (I)

(R ¹ represents a hydrocarbon group having 5 to 9 carbon atoms, and R ² represents a hydrocarbon group having 1 to 4 carbon atoms.)
A kerosene composition which is a fatty acid alkyl ester represented by   The kerosene composition according to claim 1, wherein the fatty acid alkyl ester is one or a mixture of two or more selected from methyl caproate, methyl caprylate, and methyl caprate. The kerosene composition according to claim 1 or 2, wherein the following conditions (1) to (5) are satisfied.
(1) 95 vol% distillation temperature is 215 to 270 ° C
(2) Sulfur content is 10 mass ppm or less (3) Flash point is 40 ° C. or more (4) Kinematic viscosity at 30 ° C. is 1.2 to 1.8 mm ² / s
(5) Air injection gum amount is 2mg / 100mL or less