JP2003105354A - Fuel oil base and gas oil and gas oil composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fuel oil base with a very low sulfur content for diesel engine, having improved low-temperature performances in the case of using an oil having a relatively low sulfur content such as GTL, hydrocracking oil, a light LGO, etc., and a gas oil composition containing the same. SOLUTION: This fuel oil base comprises a mixed base composed of a base A having >=0.35 gradient (X) of linear regression line obtained from the amount of 19-24C n-paraffin and <=15 wt.ppm sulfur content and a base B having >=0.3 wt.% amount (Y) of >=22C n-paraffin and <=15 wt.ppm sulfur content and has <=0.35 gradient (X) of the linear regression line, <=1.4 wt.% Y and <=15 wt.ppm sulfur content.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ultralow sulfur content fuel oil base material having good low temperature performance and a gas oil composition containing the same.

[0002]

2. Description of the Related Art In recent years, from the environmental point of view, PM (particulate matter) and NOx contained in exhaust gas of diesel automobiles.
Significant reductions in emissions of environmental pollutants such as (nitrogen oxides) and HC (hydrocarbons) are required. For this purpose, engine improvement, oxidation catalyst, NOx reduction catalyst, DP
The performance of diesel vehicles is being improved by post-processing devices such as F (diesel particulate filter). In order to effectively utilize the capacity of these post-treatment devices and maintain their durability, light oil is required to reduce the sulfur content. By the end of December 2004, the sulfur content was 50 pp.
It is obligatory to start supplying gas oil with a low sulfur content of m or less. In the future, in order to further improve the performance of post-treatment equipment, improve durability, and suppress the deterioration of fuel efficiency due to sulfur poisoning recovery, it is necessary to further reduce the sulfur content and produce ultra-low sulfur content gas oil. desired.

To produce ultra-low sulfur content gas oil, G
TL (Gas to Liquid), hydrocracked oil,
Alternatively, it is advantageous in manufacturing to use a fuel base material that originally has a very low sulfur content such as light LGO. GTL is a hydrocarbon compound produced by Fischer-Tropsch reaction from synthesis gas (CO, H ₂ ). The light oil base material is an oil having a 90% distillation temperature of 280 to 360 ° C., an oil having a high cetane number and containing almost no sulfur content. The hydrocracked oil is a distillate having an initial distillation temperature of 260 ° C. or higher obtained from an atmospheric distillation column and / or a reduced pressure gas oil distilled from the reduced pressure distillation column, having a hydrogen partial pressure of 100 to 250 kg / cm ² ,
LHSV 0.01-10.0, reaction temperature 350-45
Among the distillates produced by hydrotreating under the reaction condition of 0 ° C, it is a distillate oil having an initial distillation temperature of 260 ° C or higher and a 90% distillation temperature of 365 ° C or lower. An oil with a high cetane number and very low sulfur content. The lightened LGO is a fraction obtained by hydrodesulfurizing and refining a fraction having a 90% distillation temperature of 330 ° C. or lower obtained from an atmospheric distillation column by a predetermined method. Since this oil has a high cetane number, which is essential for diesel fuel, it has good ignitability and originally has a small amount of refractory desulfurization compounds, and therefore has an advantage that the sulfur content after desulfurization is very small.

However, since GTL and light LGO have a large content of n-paraffin, which is a component of wax,
The amount of wax deposited per unit temperature (wax deposition rate) is high, and when used in cold regions, a large amount of wax deposits at once due to a slight decrease in temperature, leading to filter clogging in the fuel supply system, poor starting and running. It may cause the engine to stop inside. Further, in the case of hydrocracked oil, especially when 90% distillation temperature is raised, n-
Since the paraffin content is large, the wax precipitation start temperature (cloud point) becomes high. Therefore, there is a problem in low-temperature performance in using these base materials as a fuel oil base material for producing an ultra-low sulfur gas oil composition.

[0005]

SUMMARY OF THE INVENTION The present invention is an ultra-low sulfur content diesel engine with improved low temperature performance when a relatively low sulfur oil such as GTL, hydrocracked oil, or light LGO is used. An object of the present invention is to provide a fuel oil base for use and a gas oil composition containing the same.

[0006]

DISCLOSURE OF THE INVENTION In order to improve the low-temperature performance of oils obtained from low-sulfur content oils such as GTL, the present inventor has paid attention to the n-paraffin distribution contained in these oils and studied. It was As a result, it has a low sulfur content and 19 to 2 carbon atoms.
4 has a slope (X) of a linear regression line obtained from the n-paraffin content of 4 in a specific range, and a base material having an n-paraffin content of 22 or more carbon atoms (Y) in a specific range. It was found that an ultra-low sulfur content fuel oil base material excellent in low-temperature performance can be obtained by mixing at least two kinds of base materials of the above and adjusting X and Y of the mixed base materials to specific values.

In the present invention, the slope (X) of the linear regression line obtained from the content of n-paraffin having 19 to 24 carbon atoms is 0.
Substrate A having a sulfur content of 35 or more and a sulfur content of 15 ppm by weight or less
And a base material B having an n-paraffin content of 22 or more carbon atoms (Y) of 0.3% by weight or more and a sulfur content of 15 ppm by weight or less, and a slope of a linear regression line thereof. (X) is 0.35 or less, Y is 1.4 wt% or less, and the sulfur content is 15 wt ppm or less. The present invention also resides in a gas oil composition containing the fuel oil base as described above.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The fuel oil base material of the present invention has 1 carbon atoms.
The base material A having a sulfur content of 15 ppm by weight or less and the n-paraffin content having 22 or more carbon atoms (Y) specified by the slope (X) of the linear regression line obtained from the n-paraffin content of 9 to 24 Substrate B having a specified sulfur content of 15 ppm by weight or less
And a mixed base material including. Both the base A and the base B have a sulfur content of preferably 10 ppm by weight or less, and more preferably 5 ppm by mass or less. Here, the sulfur content means the content of the sulfur content measured by JIS K 2541 "Sulfur content test method" (hereinafter the same).

The slope (X) of the linear regression line and the carbon number 2
The n-paraffin content (Y) of 2 or more will be described. The slope (X) of the linear regression line is n− with 19 to 24 carbon atoms.
It is calculated from the paraffin content. Where n-
The paraffin content is a content quantified from a gas chromatograph operated with a non-polar column and an FID (hydrogen flame ionization detector) and operated under a predetermined temperature program,
A gas chromatograph is an analysis method for separating and quantitatively analyzing each composition by utilizing the physical properties (boiling point, polarity, etc.) of each composition in a sample. For example, the slope (X) of the linear regression line of a certain base material can be obtained as follows. First, n in the sample is analyzed by gas chromatography.
-Separate and measure the paraffin content as peaks with 19 to 24 carbon atoms. The obtained area of the n-paraffin having each carbon number is divided by the total area of all components including components other than the n-paraffin, and the content of the n-paraffin having each carbon number is determined in% by weight. Then, by plotting each of these contents with the Y-axis and the X-axis as the number of carbon atoms and obtaining a linear regression line for these plots, the slope X of the base material can be specified.

The content (total amount) (Y) of n-paraffins having 22 or more carbon atoms in a certain base material can be determined by the following method. That is, a non-polar column and an FID (hydrogen flame ionization detector) were attached, and the number of carbon atoms in the sample was 22 by a gas chromatograph operated under a predetermined temperature program.
The above n-paraffin component peaks are separately measured. The obtained area of the n-paraffin having each carbon number is divided by the total area of all components including components other than the n-paraffin, and the content of the n-paraffin having each carbon number is determined in% by weight. And (Y) can be obtained by summing up these contents.

The base material A used in the present invention has a slope (X) of the linear regression line obtained by the above method of 0.35 or more. X of the substrate A is preferably 0.4 or more, more preferably 0.5 or more. In addition, Y of the base material A
Is not particularly limited, but the fuel oil base material of the present invention is used as the base material A.
From the viewpoint of easy production by mixing the base material B with the base material B, the content is preferably 1.2% by weight or less, more preferably 1.1% by weight.
Or less, more preferably 1.0% by weight or less, and most preferably 0.8% by weight or less. The base material A used in the present invention is not particularly limited as long as X is 0.35 or more, but it is preferable to use GTL and lightened LGO from the viewpoint of a base material having a low sulfur content.
Further, the distillation property of the base material A is not particularly limited, but it is 9 from the viewpoint of eliminating difficult desulfurization compounds.
The 0% distillation temperature (T ₉₀ ) is preferably 370 ° C. or lower, more preferably 355 ° C. or lower, more preferably 340 ° C. or lower, most preferably 320 ° C. or lower, 280 ° C. or higher.

The substrate B used in the present invention has the above-mentioned carbon number of 22.
The above n-paraffin content (Y) is 0.3% by weight or more. Y of the base material B is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, further preferably 1.4% by weight or more, and most preferably 1.5% by weight.
That is all. Also, the slope (X) of the linear regression line of substrate B
Is not particularly limited, but the fuel oil base material of the present invention is used as the base material A.
It is preferably 0.35 or less, more preferably 0.3 or less, more preferably 0.2 or less, and most preferably 0.1 or less from the viewpoint of easy production by mixing and the base material B. The base material B used in the present invention is not particularly limited as long as Y is 0.3% by weight or more, but it is preferable to use hydrocracked oil from the viewpoint of a base material having a low sulfur content. preferable.

The fuel oil base material of the present invention is prepared by mixing the base material A and the base material B. Base material A and base material B
As for the mixing ratio with, X of the base material after mixing is 0.35 or less, Y
Is not particularly limited as long as it is 1.4% by weight or less, but the mixing ratio of the base material A is preferably 10 to 90% by volume, from the viewpoint that the gradual cooling cloud point can be further lowered. It is preferably 15 to 85% by volume, more preferably 20 to 80% by volume. X of mixed base material (fuel oil base material)
Is preferably 0.33 or less, and more preferably 0.3 or less. Further, Y of the mixed base material is preferably 1.3% by weight or less, more preferably 1.2% by weight or less, and most preferably 1.0% by weight or less. In this way, by mixing the specific base material A and the base material B so as to satisfy the specific conditions, the slow cooling cloud point of the fuel oil base material after the mixing is the base material A and the base material B before the mixing. It is possible to obtain a fuel oil base material having a lower low temperature performance than that of the slow cooling cloud point. Here, the gradual cooling cloud point means that the temperature is rapidly cooled to a position higher than the expected cloud point by a predetermined temperature, and then the gradual cooling mode is switched to the gradual cooling mode until the cloud point is detected.
It is the cloud point obtained by detecting in ° C. In addition to the above-mentioned points, the slow-cooling cloud point can be measured according to a usual cloud point measuring method, that is, according to JIS K2269.

The fuel oil base material of the present invention comprises the above base materials A and B.
Is included as an essential component, but other base materials may be included. Other base materials that can be mixed with the fuel oil base material of the present invention include, for example, hydrodesulfurized gas oil obtained by hydrodesulfurizing straight-run light oil in one step or multiple steps under more severe conditions than ordinary hydrorefining, Desulfurization Reduced pressure gas oil, reduced pressure heavy gas oil or catalytically cracked gas oil obtained by catalytically cracking desulfurized heavy oil to a high degree of desulfurization, catalytically cracked heavy naphtha, straight-run kerosene obtained by atmospheric distillation of crude oil, and straight-run kerosene as hydrogen Hydrorefining kerosene obtained by chemical refining, FT kerosene obtained by Fischer-Trobusch (FT) reaction from natural gas, cracked kerosene obtained by decomposing gas oil fraction obtained by atmospheric distillation of straight run crude oil Etc. can be mentioned. Depending on the properties required of the fuel oil base material after mixing (or the gas oil composition prepared using this base material), the blending ratio of these base materials can be appropriately selected so as to satisfy the properties. In particular, considering that the present invention aims to obtain a base material having an excellent low temperature performance with an ultra-low sulfur content, among them, X is 0.35 or less and Y is 1.4 wt% or less. It is preferable to use a base material of, for example, an ultra low sulfur compound of straight run kerosene (ultra low sulfur kerosene). For example, when the fuel oil base material of the present invention and the ultra-low sulfur kerosene are mixed, the ultra-low sulfur kerosene base material is 80% by volume or less in terms of the viscosity, the lubricity and the flash point of the light oil. It is preferable. The blending ratio of the ultra-low sulfur kerosene base material is selected so as to satisfy the light oil quality standard defined in JIS K2204.

The fuel oil base material of the present invention is prepared by using an ordinary GTL, light LGO, or hydrocracked oil according to the present invention so as to meet the properties and compositions of the respective base materials, and then finalize these. It can be obtained by preparing it according to the base material having the properties and composition specified in the above. The order of mixing during preparation is also not particularly limited.

The gas oil composition of the present invention has an ultralow sulfur content by optionally adding known additives such as a cetane number improver, a detergent and a lubricity improver to the above fuel oil base stock. Although a gas oil composition having excellent low-temperature performance can be easily obtained, it is preferable that the following properties be satisfied. The sulfur content of the light oil composition is 15 ppm by weight or less, preferably 10 ppm by weight or less, more preferably 5 ppm by weight or less, and most preferably 1 ppm by weight or less. When the sulfur content is 15 ppm by weight or more, the degree of poisoning of the aftertreatment catalyst is not so different from that of diesel oil having a sulfur content of 50 ppm by weight.

The distillation properties of the light oil composition are preferably as follows. 90% distillation point (T ₉₀ ): 280 to 360 ° C. Here, the distillation property means a value measured according to JIS K 2254 “Petroleum products-Distillation test method”.
The T ₉₀ of the light oil composition is preferably 280 ° C. or higher, more preferably 290 ° C. or higher, more preferably 295 ° C. or higher, more preferably 300 ° C. or higher from the viewpoint of ensuring the lubricity of the fuel injection pump and the fuel injection valve. is there. On the other hand, from the viewpoint of not increasing the PM concentration in the exhaust gas, T ₉₀ is preferably 360 ° C. or lower, more preferably 355 ° C. or lower, and further preferably 350 ° C. or lower.

The kinematic viscosity of the light oil composition is preferably 2.7 mm ² / s or more at 30 ° C. in No. 1 and No. 1, preferably 2.5 mm ² / s or more in No. 2, and preferably 2 in No. 3. 0.0 mm ² / s or more, preferably 1.7 m for Special 3
It is at least m ² / s. When the kinematic viscosity of each light oil is less than the above value, the light oil composition may cause poor lubrication in the fuel injection pump, resulting in severe wear of the pump and insufficient atomization of the fuel.

The flash point is preferably 45 ° C. or higher.
If the temperature is 45 ° C or lower, the storage stability may be insufficient.

By mixing the fuel oil base material of the present invention with another base material, the fuel oil base material can be used as a fuel for fuel cells and a heavy fuel oil A by being mixed with an appropriate base material in addition to the above light oil composition. can do.

[0021]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

As shown in Table 1, base materials for ultra-low sulfur gas oil compositions (A-1, A-2, A-3, B-) having general properties.
1 and C) were prepared. C is an extremely low sulfur content kerosene.

[0023]

[Table 1]

(Examples 1 to 10 and Comparative Example 1) The obtained base materials were blended in the blending ratios shown in Table 2, and the gas oil composition of the present invention (Examples 1 to 10) and the gas oil composition for comparison were prepared. (Comparative Example 1) was prepared. The mixed base materials X and Y indicate the slope of the linear regression line and the n-paraffin content of 22 or more carbon atoms for the base materials after mixing, respectively.

[0025]

[Table 2]

The following slow cooling cloud point test was conducted on each gas oil composition. The cloud point improvement effect was evaluated according to the following formula. The evaluation results are shown in Table 3. The cloud point improvement effect is shown to be better as L is larger in the following formula. L = M−N M = a × m / 100 + b × (100−m) / 100 L: Cloud point improvement effect level M: Cloud point of base material A, cloud point of base material B and blending of fuel oil base material Cloud point a of fuel oil base material or gas oil composition expected from the ratio a: Cloud point of base material A (or mixture of base material A) b: Cloud point of base material m: Base material A (or base material A) Mixture) and the base material B (or the mixture of the base material A) when the base material B is 100% by volume (volume%) N: Cloud point of the fuel oil base material or gas oil composition of the present invention

(Slow cooling cloud point test conditions) Rapid cooling mode (3 ° C./min): From room temperature to expected cloud point + 10 ° C. Slow cooling mode (0.5 ° C./min): Expected cloud point + 10 ° C. to cloud point detection (Gas chromatographic analysis conditions) Apparatus: Shimadzu GC-17A Column: Silica-based non-polar column (inner diameter 0.25 mm x length 30 m) Split ratio: 100: 1 Carrier gas: Helium Carrier gas flow rate: 1 mL / min Detector: Hydrogen flame ionization detector temperature gradient: 140 ° C → (8 ° C / min) → 360 ° C
(Hold 3 minutes)

[0028]

[Table 3]

From the results shown in Table 3, as shown in Examples 1 to 10, the specific base material defined by the linear regression line according to the present invention and the specific content defined by the specific n-paraffin were specified. The cloud point can be improved in the case of a gas oil prepared by using a fuel base material containing the base material of On the other hand, as seen in Comparative Example 1, when the blending ratio of the base material A and the X or Y of the mixed base material are out of the ranges specified in the present invention, only the cloud point same as the expected value can be obtained. Therefore, it can be seen that the cloud point improvement effect cannot be obtained.

(Examples 11 to 16) The gas oil composition of the present invention (mixed base material) and the base material C of Table 1 were mixed and the gas oil composition of the present invention having the composition shown in Table 4 (Examples) was mixed. 11-16) were prepared.

[0031]

[Table 4]

The light oil compositions of Examples 11 to 16 thus obtained were subjected to the slow cooling cloud point test in the same manner as above. The test results are shown in Table 5.

[0033]

[Table 5]

From the results shown in Table 5, the fuel base material prepared by further adding kerosene to the mixed base material of the specific base material A and base material B used for the preparation of the fuel oil base material of the present invention was used. It can be seen that even in the case of the conventional light oil composition, a light oil composition having good low temperature performance can be obtained.

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, low sulfur content can be obtained by using low sulfur content oil such as GTL, light LGO, and hydrocracked oil which have a relatively high paraffin content and cannot obtain sufficient low temperature performance. It is possible to obtain a fuel oil base material for a diesel engine, which has a high content and improved low-temperature performance. Therefore, the gas oil composition prepared by using the fuel oil base material of the present invention can be provided as a gas oil composition that is particularly excellent in low-temperature startability and low-temperature drivability and is compatible with high performance of diesel vehicles.

Claims (7)

[Claims] 1. A base material A having a slope (X) of 0.35 or more and a sulfur content of 15 ppm by weight or less and a linear regression line obtained from the content of n-paraffin having 19 to 24 carbon atoms and 22 carbon atoms. The above n-paraffin content (Y) is 0.3% by weight.
As described above, the mixed base material contains the base material B having a sulfur content of 15 ppm by weight or less, the slope (X) of the linear regression line is 0.35 or less, and Y is 1.4% by weight or less, and the sulfur content is Is 15 ppm by weight or less. 2. The base material A has X of 0.35 or more and Y of 1.4.
The fuel oil base material according to claim 1, wherein the base material B has an X content of 0.35 or less and a Y content of 0.3 weight% or more. 3. The fuel oil base material according to claim 1, wherein the mixing volume ratio of the base material A is 10 to 90% by volume. 4. The substrate A is Gas to Liquid.
The fuel oil base material according to any one of claims 1 to 3, which is (GTL). 5. The fuel oil base material according to claim 1, wherein the base material A is a lightened LGO. 6. The fuel oil base material according to claim 1, wherein the base material B is a hydrocracked oil. 7. A gas oil composition containing the fuel oil base material according to any one of claims 1 to 6.