JP2008024840A - Kerosene composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide low smell kerosene causing no uncomfortable feeling due to kerosene smell, when a user treats the kerosene, e.g., refuels an oil stove without increase of production cost. <P>SOLUTION: The kerosene composition has distillation characteristics of 135-170°C initial boiling point, 175-200°C 30% distillation temperature, 190-220°C 50% distillation temperature, 200-240°C 70% distillation temperature, 215-265°C 90% distillation temperature, 230-270°C 95% distillation temperature, wherein the composition has ≤50 mass ppm sulfur content and ≤20 vol.% aromatic hydrocarbon content, in the aromatic hydrocarbon content, the content of aromatic hydrocarbon having two and three or more rings is ≤2.0 vol.%, and in ≤175°C distillate, the rates of content of C8 and C9 benzene are ≤1 mass% 7C benzene, ≤9 mass% 8C benzene and ≤18 mass% 9C benzene and the vapor pressure is ≤5.0 kPa at 37.8°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to kerosene, and more particularly to a low-odor kerosene with a low odor.

The types and standards of kerosene currently used in oil stoves are shown in Japanese Industrial Standards (JIS K 2203). Among them, No. 1 kerosene is widely used for household heating equipment and the like. The kerosene fraction is mainly obtained by fractionating crude oil to a predetermined distillation property by atmospheric distillation. The obtained kerosene fraction is then hydrorefined by a hydrodesulfurization unit so that the sulfur content becomes a predetermined amount or less. Furthermore, in the kerosene production process, the flash point is adjusted to 40 ° C. or higher by evaporating light components with a stripper.
The quality of kerosene obtained in this way is controlled based on the standard shown in the above-mentioned JIS K 2203. However, as a non-standard quality in practice, odor when handling kerosene such as oil supply to oil stoves is handled. Is also an important factor in product quality. Therefore, a low odor with less hydrocarbon odor is desired.

  As a method for solving the above-mentioned problem of kerosene odor, there is a method of adding a deodorant to kerosene (for example, see Patent Document 1), a method of making kerosene with paraffins (for example, see Patent Document 2), and the like. . However, in the method of adding a deodorant to kerosene, the hydrocarbon odor cannot be completely removed, so that a substance having another odor is added to mask the hydrocarbon odor. The kerosene then retains the scent of other substances instead of the original hydrocarbon odor. Therefore, there was a problem of personal preference for odor and it was not very effective. In addition, the method of making kerosene with paraffins has a problem in that the manufacturing cost increases and the price of kerosene becomes high.

  Furthermore, there is also a high-performance kerosene excellent in handling that has solved the above problems (see, for example, Patent Document 3 and Patent Document 4). This kerosene regulates the reduction of high-boiling fractions and the amount of polycyclic aroma in order to suppress odors during combustion, and also reduces the amount of low-boiling fractions and the amount of total aromatic hydrocarbons in order to reduce odors during handling. Is specified. However, this kerosene needed to be drastically improved in its manufacturing process, such as extremely narrowing the range of available fractions for kerosene and further tightening hydrotreating conditions to reduce the aromatic components of the kerosene as a whole. For this reason, the manufacturing cost has increased, and there has been a problem that the price of kerosene becomes high.

Japanese Patent Publication No.54-32003 JP-A-63-150380 Japanese Patent Laid-Open No. 2-113092 Japanese Patent Laid-Open No. 3-182594

  In view of the above-described conventional situation, an object of the present invention is to provide kerosene with reduced odor without increasing the manufacturing cost.

  As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that the content and vapor pressure of specific components contained in kerosene greatly influence the hydrocarbon-based odor suppression of kerosene. And the knowledge that it became possible to suppress the odor of kerosene itself by optimizing the component concentration and vapor pressure. In addition, in kerosene that is compatible with sulfur-free products in recent years, we have determined that hydrogen sulfide remaining in a very small amount in kerosene fractions has a significant effect on odors, and have a process for accurately removing the hydrogen sulfide remaining in a very small amount. The knowledge that it becomes possible to suppress the odor of kerosene by applying was obtained, and the present invention was completed based on these findings. That is, the present invention provides a kerosene composition having the following characteristics.

(1) Initial distillation point 135-170 ° C, 30% distillation temperature 175-200 ° C, 50% distillation temperature 190-220 ° C, 70% distillation temperature 200-240 ° C, 90% distillation temperature 215-265 ° C 95% distillation temperature of 230 to 270 ° C., a sulfur content of 50 mass ppm or less, a total aromatic hydrocarbon content of 20 vol% or less, in the total aromatic hydrocarbon content The content of aromatic hydrocarbons of 2 and 3 or more rings is 2.0 vol% or less, and the content ratio of C7, C8 and C9 benzene in the fraction of 175 ° C. or less is 1 mass% or less for C7 benzene, C8 benzene Is 9 mass% or less, C9 benzene is 18 mass% or less, and the vapor pressure at 37.8 ° C. is 5.0 kPa or less.
(2) The kerosene composition according to (1) above, wherein the kerosene composition has a hydrogen sulfide concentration in a generated gas at 25 ° C. of 1 volppm or less.

  The kerosene composition of the present invention is a low odor kerosene that does not cause discomfort due to kerosene odor when consumers handle kerosene, such as refueling an oil stove, without an increase in cost such as a large production process improvement. Can be provided and is very useful.

Hereinafter, the contents of the present invention will be described in more detail.
The distillation properties of the kerosene composition in the present invention are as follows: initial boiling point 135-170 ° C, 30% distillation temperature 175-200 ° C, 50% distillation temperature 190-220 ° C, 70% distillation temperature 200-240 ° C, 90%. % Distillation temperature 215 to 265 ° C., 95% distillation temperature 230 to 270 ° C., preferably initial distillation point 140 to 170 ° C., 30% distillation temperature 180 to 200 ° C., 50% distillation temperature 195 to 220. C., 70% distillation temperature of 205-240.degree. C., 90% distillation temperature of 220-260.degree. C., and 95% distillation temperature of 240-270.degree. An initial boiling point of 170 ° C. or lower is preferable because it is unlikely to cause problems such as difficulty in ignition. If the initial boiling point is 135 ° C. or higher, the flash point is less likely to be low, and it is less likely that the flash point is below 40 ° C., which is the flash point standard value of kerosene defined in JIS K 2203. A 30% distillation temperature of 175 ° C. or higher is preferable because there are few distillates at 175 ° C. or lower containing light hydrocarbon components and the odor of kerosene itself can be suppressed. A 30% distillation temperature of 200 ° C. or lower is preferable because the ignitability is improved. Furthermore, if the 50% distillation temperature is 220 ° C., the 70% distillation temperature is 240 ° C., the 90% distillation temperature is 265 ° C., and the 95% distillation temperature is 270 ° C. or less, the ignition is easy and steady combustion is reached. It is preferable because it does not take time until If a 50% distillation temperature is 190 ° C, a 70% distillation temperature is 200 ° C, a 90% distillation temperature is 215 ° C, and a 95% distillation temperature is 230 ° C or higher, a core-type / radial oil stove is used. At this time, it is preferable because a stable combustion state can be maintained in which the combustion cylinder is kept in a red-heated state without letting out the flame from the upper part of the combustion cylinder, and the fire is easily extinguished when extinguishing.

Moreover, the sulfur content contained in the kerosene composition in the present invention is 50 mass ppm or less, preferably 10 mass ppm or less called “sulfur free”, and more preferably 1 mass ppm or less called “sulfur zero”. By reducing the sulfur content to 50 mass ppm or less and reducing it further, it is possible to suppress odors and the like derived from sulfur-based hydrocarbon compounds like conventional kerosene. It is also preferable from the viewpoint.
In the present invention, the distillation property can be measured by the atmospheric pressure distillation test of JIS K 2254, and the sulfur content can be measured by the microcoulometric titration method of JIS K 2541.

  In the kerosene composition of the present invention, the total aromatic hydrocarbon content is 20 vol% or less, preferably 18 vol% or less. If the total aromatic hydrocarbon content is within 20 vol%, the smoke point is high, and therefore the combustibility is poor and the possibility of causing soot is low, which is preferable. In addition, the content rate (composition rate) of the total aromatic hydrocarbon content here is obtained based on JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method (HPLC)” It is done.

In the kerosene composition of the present invention, the content of aromatic hydrocarbons of 2 or more rings is 2.0 vol% or less, preferably 1.0 vol% or less of the total aromatic content of 20 vol%. If the content of the aromatic hydrocarbons of 2 or more rings is less than 2.0 vol%, the odor is weak and the combustibility is good, so there is little possibility of causing soot, which is preferable.
Here, the content ratio of the bicyclic aromatic hydrocarbon content and the tricyclic or higher aromatic hydrocarbon content can be determined based on the above-mentioned JPI-5S-49-97.

In the kerosene composition of the present invention, the content ratio of C7, C8 and C9 benzene in the fraction of 175 ° C. or less, C7 benzene is 1 mass% or less, preferably 0.8 mass% or less, C8 benzene is 9 mass% or less, preferably 7 mass% or less, C9 benzene is 18 mass% or less, preferably 17 mass% or less. It is preferable to set the specific ratio to suppress the odor of kerosene itself.
Conventionally, it has been known that kerosene itself has a strong odor when the distillation temperature contains a fraction of less than 170 ° C., and that the odor is strong when the content of aromatic hydrocarbon components is large. However, when the distillation temperature contains many fractions of less than 170 ° C., it is difficult to suppress the hydrocarbon-based odor of kerosene simply by reducing the aromatic component content in the entire kerosene. I understood that.

In the present invention, it is most effective for the suppression of odor to specify an aromatic hydrocarbon component having a carbon number of C7 to C9 as a substance that causes odor and to specify its content in a fraction of 175 ° C. or lower. I found out.
That is, even when there are many fractions at 175 ° C. or less, if there are few aromatic hydrocarbon components having C7 to C9 carbon atoms and many aliphatic hydrocarbon components, the odor of kerosene itself can be suppressed. I understood. This is considered to be due to the masking effect due to the fact that the aliphatic hydrocarbon compound is higher than the aromatic hydrocarbon compound at the same boiling point fraction, that is, the threshold concentration at which the type of odor can be discriminated. .
Therefore, by setting the content ratio of these components in fractions of 175 ° C. or lower as described above, the odor intensity during handling is suppressed, and unpleasant petroleum odor is suppressed even when refueling oil stoves and the like. can do.

  In addition, the content rate of C7 benzene, C8 benzene, and C9 benzene here is analyzed by gas chromatograph method (GC), and it follows JIS K 2536-2 petroleum product-component test method (how to obtain all components by gas chromatograph). Analyze and calculate the total fraction below 1,2,3-trimethylbenzene with a boiling point of 175 ° C, and further add the contents of each C7 benzene compound to give C7 benzene, which contains each C8 benzene compound. After adding the amount to C8 benzene and adding the content of each C9 benzene compound to C9 benzene, finally divide each C7 benzene, C8 benzene, and C9 benzene by the total fraction of 175 ° C or less. The respective content ratios are obtained.

  Here, C7 benzene refers to toluene. C8 benzene is at least one of ethylbenzene, o-xylene, m-xylene, and p-xylene, and C9 benzene is iso-propylbenzene, n-propylbenzene, 1-methyl-2-ethyl-benzene. 1-methyl-3-ethyl-benzene, 1-methyl-4-ethyl-benzene, and 1,2,3-methylbenzene, 1,2,4-methylbenzene, 1,3,5-methylbenzene Show at least one.

  In addition, the present inventor obtained new knowledge that hydrogen sulfide remaining in kerosene greatly affects the odor of the entire kerosene composition, while studying to suppress the odor of kerosene. It was. As a method of suppressing the odor caused by this ultra-small amount of residual hydrogen sulfide, the hydrogen sulfide in the product oil is removed by stripping using steam while managing the hydrogen sulfide in the produced oil at a low concentration of ppb level. And a method of removing by alkali cleaning such as caustic soda, a nitrogen purge operation, and the like, and it is preferable to carry out these methods to remove ultra trace residual hydrogen sulfide.

  In the kerosene composition of the present invention, the hydrogen sulfide concentration in the generated gas at 25 ° C. of the kerosene composition is preferably 1 volppm or less from the viewpoint of suppressing odor. More preferably, it is 0.5 volppm or less. More preferably, it is 0.2 volppm or less. In this way, the hydrogen sulfide remaining in kerosene is reduced to a very low level of ppb, and the odor derived from sulfur is eradicated by reducing the hydrogen sulfide concentration in the generated gas at 25 ° C. of the kerosene composition. Can do.

  Here, the hydrogen sulfide concentration in the generated gas at 25 ° C. of the kerosene composition here was measured after putting a sample at 25 ° C. ± 5 ° C. into a 500 ml 1000 ml glass bottle with a cap and shaking the bottle vigorously for 30 seconds. The bottle is allowed to stand, and a gas suction unit with a hydrogen sulfide gas detector tube (minimum scale: 0.2 volppm, maximum scale: 2 volppm) is used to suck a predetermined amount of gas in the gas phase and measure the hydrogen sulfide concentration. Is.

  The vapor pressure at 37.8 ° C. of the kerosene composition in the present invention is 5.0 kPa or less, preferably 4.5 kPa or less. In addition, 37.8 degreeC is the measurement temperature of the vapor pressure by JIS specification. By suppressing the vapor pressure at 37.8 ° C. of the kerosene composition to 5.0 kPa or less, the high vapor pressure component from the kerosene composition, that is, the release of hydrogen sulfide, which has a great influence on odor, to the atmosphere is suppressed. It is possible to eradicate the odor derived from the sulfur content. In addition, the vapor pressure in 37.8 degreeC of a kerosene composition here can be measured by the crude oil and fuel oil-vapor pressure test method-Reed method shown by JISK2258.

  Although the manufacturing method of the kerosene composition in this invention is not specifically defined, it can obtain by refine | purifying various raw materials so that it may have the property prescribed | regulated by mixing a commercially available solvent or this invention. For example, a kerosene fraction obtained by atmospheric distillation of crude oil or a desulfurized kerosene obtained by desulfurizing them can be used. Furthermore, a direct desulfurized kerosene fraction obtained from a direct desulfurization apparatus, a kerosene fraction obtained by hydrocracking heavy oil or residual oil, and the like can be used, and are not particularly limited. As described above, the method for producing the kerosene composition of the present invention is not particularly limited, but in its production, stripping using steam for removing hydrogen sulfide in the product oil to the ppb level, caustic soda, etc. It is preferable to perform alkali cleaning or purging with nitrogen for a predetermined time.

  In the kerosene composition of the present invention, various fuel oil additives can be appropriately added as necessary. The fuel oil additives include phenolic and amine antioxidants, metal deactivators such as Schiff compounds and thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, succinimides, and polyalkyls. Detergents such as amines and polyetheramines, anti-icing agents such as polyhydric alcohols and ethers thereof, organic acid alkali metals and alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants And known fuel oil additives such as antistatic agents such as cationic surfactants and amphoteric surfactants, and rust inhibitors such as alkenyl succinates. These can be added alone or in combination. Moreover, the addition amount of these fuel oil additives can be suitably set as needed.

  The kerosene composition of the present invention can be preferably used for so-called consumer heaters, such as various petroleum stoves, petroleum fan heaters, or oil-type water heaters, and further, direct-fired food drying fuel, industrial It can be preferably used in various applications such as fuel for fuel, fuel for oil engines, and solvent.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in more detail, this invention is not limited to these Examples.
In Examples and Comparative Examples, the flash point, distillation properties, sulfur content, and smoke point were measured according to the method defined in JIS K 2203.
Further, the odor test was performed by the following odor intensity measurement and odor sensory test.
[Measurement of odor intensity]
A sample of kerosene is collected on a 1 ml aluminum dish and allowed to stand in a glass odor bottle with a volume of 2.5 l, and the odor is volatilized at room temperature of 25 ° C. One minute later, the odor intensity was started with an odor sensor (OD-85 manufactured by Riken Keiki Co., Ltd.), and the odor intensity 10 minutes after the odor intensity was stabilized was measured.
[Odor sensory test]
The same various kerosene used for the measurement of the odor intensity by the odor sensor was used to obtain the odor intensity from the odor sensory test by 15 subjects. In this test, 500 ml of sample oil is put into a 1000 ml glass container with a stopper, shaken vigorously for 30 seconds, the stopper is opened, and after 5 seconds, the sample is smelled, and the odor intensity is shown in Table 1. Judgment was made using a rating scale. Here, the correlation between the odor intensity obtained from the odor sensor and the 6-step odor intensity rating scale shown in Table 1 is shown as a graph in FIG.

  In the present invention, the odor sensor display of 1000 or less in the odor intensity measurement and the 6-stage odor intensity rating scale of 3 or less were determined as the target low-odor kerosene.

Example 1
A straight-run kerosene fraction having a boiling point range of 149 to 289 ° C. obtained by atmospheric distillation of Middle Eastern crude oil under the conditions of WABT 320 ° C., hydrogen partial pressure 5.5 MPa, liquid space velocity (LHSV) 3.0 h ⁻¹ Of kerosene having a boiling point range of 148.5 to 275.5 ° C. and a sulfur content of 6 mass ppm, in which purging with nitrogen was performed for a predetermined time, and the hydrogen sulfide concentration in the gas generated from kerosene was 0.2 volppm. Composition A was obtained. Table 2 shows the properties of the obtained kerosene composition A and the odor test results.

Example 2
A kerosene fraction having a boiling range of 149 to 289 ° C. obtained by atmospheric distillation of Middle Eastern crude oil under conditions of WABT 320 ° C., hydrogen partial pressure 4.5 MPa, liquid space velocity (LHSV) 3.0 h ⁻¹ Kerosene composition having a boiling point range of 149.0 to 273.5 ° C. and a sulfur content of 2 mass ppm, desulfurization treatment, followed by purging with nitrogen for a predetermined time, and setting the hydrogen sulfide concentration in the generated gas of kerosene to 0.2 volppm Product B was obtained. Table 2 shows the properties of the obtained kerosene composition B and the odor test results.

Comparative Example 1
A kerosene fraction having a boiling point range of 149 to 289 ° C. obtained by atmospheric distillation of Middle Eastern crude oil under conditions of WABT 315 ° C., hydrogen partial pressure 5.5 MPa, liquid space velocity (LHSV) 3.0 h ⁻¹ A kerosene composition C having a boiling point range of 159 to 281 ° C. and a sulfur content of 10 mass ppm is obtained by performing desulfurization treatment and subsequently purging with nitrogen for a predetermined time to set the hydrogen sulfide concentration in the generated gas of kerosene to 0.2 volppm. It was. The properties of the obtained kerosene composition C and the odor test results are shown in Table 2.

Comparative Example 2
The crude oil was distilled at atmospheric pressure in the same manner as in Example 2 and desulfurized under the same conditions, followed by purging with nitrogen for a slightly shorter time than in Example 1, and the hydrogen sulfide concentration in the gas generated from kerosene was 1.0 volppm. A kerosene composition D having a boiling point range of 152 to 260 ° C. and a sulfur content of 2 mass ppm was obtained. Table 2 shows the properties of the obtained kerosene composition D and the odor test results thereof.

Comparative Example 3
A kerosene fraction having a boiling range of 149 to 289 ° C. obtained by atmospheric distillation of Middle Eastern crude oil under conditions of WABT 320 ° C., hydrogen partial pressure 3.0 MPa, liquid space velocity (LHSV) 5.2 h ⁻¹ A kerosene composition having a boiling point range of 151.5 to 274.0 ° C. and a sulfur content of 8 mass ppm, desulfurization treatment, followed by purging with nitrogen for a predetermined time, and setting the hydrogen sulfide concentration in the generated gas of kerosene to 0.2 volppm Product E was obtained. Table 2 shows the properties of the obtained kerosene composition E and the odor test results thereof.

Comparative Example 4
In the same manner as in Comparative Example 3, the crude oil was distilled at atmospheric pressure, desulfurized under the same conditions, and then purged with nitrogen was carried out for a shorter time than in Example 1, so that the hydrogen sulfide concentration in the gas generated from kerosene was 2 volppm. A kerosene composition F having a boiling point range of 148.5 to 283.0 ° C and a sulfur content of 17 mass ppm was obtained. The properties of the obtained kerosene composition F and the odor test results are shown in Table 2.

  As can be seen from Table 2, when the C7 to C9 benzene in the fraction of 175 ° C. or lower was not reduced and the vapor pressure was high, odor suppression was insufficient. Further, when the aromatic component was not reduced as a whole, particularly when the hydrogen sulfide concentration was high, the odor was detected strongly. Further, even when the fraction at 175 ° C. or lower was less than that of the Examples, the suppression of odor was insufficient unless C7 to C9 benzene in the fraction at 175 ° C. or lower was reduced.

It is a graph which shows the correlation with the odor sensor display of various kerosene, and a 6-step odor intensity rating scale.

Claims (2)

  Initial distillation point 135-170 ° C, 30% distillation temperature 175-200 ° C, 50% distillation temperature 190-220 ° C, 70% distillation temperature 200-240 ° C, 90% distillation temperature 215-265 ° C, 95% It has a distillation property at a distillation temperature of 230 to 270 ° C., has a sulfur content of 50 mass ppm or less, has a total aromatic hydrocarbon content of 20 vol% or less, and 2 and 3 in the total aromatic hydrocarbon content. The aromatic hydrocarbon content in the ring or higher is 2.0 vol% or less, and the content ratio of C7, C8 and C9 benzene in the fraction of 175 ° C. or lower is 1 mass% or less for C7 benzene and 9 mass% for C8 benzene. Hereinafter, C9 benzene is 18 mass% or less, and the vapor pressure in 37.8 degreeC is 5.0 kPa or less, The kerosene composition characterized by the above-mentioned.   The kerosene composition according to claim 1, wherein the kerosene composition has a hydrogen sulfide concentration in a generated gas at 25 ° C of 1 volppm or less.

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