JP2008201949A - Kerosene composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a kerosene composition produced by using, as a raw material base of kerosene, an atmospheric distillation residue, a vacuum distillation residue, a propane-deasphalted asphalt or LCO obtained from an FCC apparatus which are used as a heavy oil base heretofore, and having excellent storage stability. <P>SOLUTION: The kerosene composition contains a kerosene fraction obtained from a desulfurized and denitrified product of a mixed base material containing (A) a light cut obtained by the thermal cracking treatment of at least one material selected from (a) an atmospheric distillation residue of crude oil, (b) a vacuum distillation residue obtained by the vacuum distillation of the atmospheric distillation residue, (c) a propane-deasphalted asphalt obtained by the propane-deasphalting treatment of the vacuum distillation residue and (d) a bottom fraction of a fluidized catalytic cracker and (B) a light cycle oil obtained from a fluidized catalytic cracker at a volume ratio of 100:0 to 50:50, and 3-30 mg of an antioxidation agent based on 1 L of the composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a kerosene composition, and more specifically, atmospheric distillation residue, vacuum distillation residue, propane-desorbed asphalt, or fluid catalytic cracking device (hereinafter abbreviated as FCC device), which has been conventionally used as a heavy oil base material. It is related with the kerosene composition excellent in the storage stability which uses the light cycle oil (LCO) etc. which are obtained from the above as a raw material base material of kerosene.

At present, kerosene is used for lighting, heating, kitchen use, etc., and most of it is used in general households. Therefore, it is desirable that the kerosene has a certain range of sulfur content from the viewpoint of the indoor environment, smoke point and oxidation start temperature from the viewpoint of combustibility, and flash point and storage stability from the viewpoint of safety. In order to satisfy these conditions, conventionally, hydrorefined kerosene obtained by hydrotreating a fraction having a boiling range of 145 to 280 ° C. obtained by distilling crude oil has been used.
On the other hand, the demand for heavy oil is decreasing from the viewpoint of environmental improvement. As a result, effective use of atmospheric distillation residue, vacuum distillation residue, propane deasphalted asphalt, etc., used as a base material for heavy oil has become a problem. It is coming. In addition, since the LCO fraction obtained from the FCC apparatus has a low cetane number, a high olefin content and a high sulfur content, it is not suitable for a kerosene / light oil base material, and has been conventionally used as a heavy oil base material. As the demand for heavy oil declines, where to use it has become an issue.
By the way, the coker apparatus is an equipment capable of obtaining kerosene / light oil fraction from vacuum distillation residue, propane-desorbed asphalt, etc., but a base material obtained by mixing the LCO with the fraction obtained from the coker equipment. Even if the kerosene fraction is removed by distillation after desulfurization / denitrogenation treatment, there is a problem in stability.
On the other hand, as a method for producing kerosene considering changes in the demand structure of petroleum products in recent years, CAT (catalyst average temperature) 400 is selected from at least one selected from vacuum distilled light oil, catalytic cracked light oil, pyrolyzed light oil and degassed oil. There is disclosed a method for producing kerosene (see, for example, Patent Document 1), characterized by having a step of hydrocracking at a temperature not higher than ° C. and a step of recovering the kerosene fraction.
However, in this technology, as a raw material for kerosene, a pyrolysis gas oil obtained from a pyrolysis device such as a coker is cited, but in order to obtain this pyrolysis gas oil, the base material supplied to the pyrolysis device is mentioned. No mention is made.

JP 2003-105349 A

  Under such circumstances, the present invention uses an atmospheric distillation residue, a vacuum distillation residue, a propane deasphalted asphalt, or an LCO obtained from an FCC apparatus, which has been conventionally used as a heavy oil base material, as a raw material base material for kerosene. An object of the present invention is to provide a kerosene composition having excellent storage stability.

As a result of intensive studies to achieve the above object, the present inventors have obtained by pyrolyzing at least one selected from specific heavy oils obtained from each device of an oil refinery plant. In a kerosene fraction obtained from desulfurized and denitrogenated oil of a mixed base material containing a light fraction and a light cycle oil (LCO) obtained from an FCC unit in a specific proportion, an antioxidant is added in a specific proportion. It has been found that the purpose can be achieved by the kerosene composition contained. The present invention has been completed based on such findings.
That is, the present invention
(1) (a) an atmospheric distillation residue of crude oil, (b) a vacuum distillation residue obtained by subjecting the atmospheric distillation residue to a vacuum distillation treatment, and (c) a propane degassing treatment of the vacuum distillation residue. Light fraction (A) obtained by pyrolyzing at least one selected from among propane deasphalted asphalt and (d) bottom fraction of fluid catalytic cracker, and light obtained from fluid catalytic cracker 3-30 mg of antioxidant per liter of kerosene fraction obtained from desulfurized and denitrogenated oil of mixed base material containing cycle oil (B) at a volume ratio of 100: 0 to 50:50, and 1 L of the composition A kerosene composition, and (2) a kerosene according to (1), further comprising 0.1 to 98% by volume of desulfurized straight-run kerosene based on the total amount of the composition Composition,
Is to provide.

  According to the present invention, an atmospheric distillation residue, a vacuum distillation residue, propane deasphalted asphalt, or LCO obtained from an FCC apparatus, which has been conventionally used as a heavy oil base material, is used as a raw material base material for kerosene. A kerosene composition having excellent storage stability can be provided.

The kerosene composition of the present invention is a light product obtained by pyrolyzing at least one selected from heavy oils represented by the following (a) to (d) obtained from each device of an oil refinery plant. Obtained from desulfurized and denitrogenated oil of mixed base material containing fraction (A) and light cycle oil (LCO) (B) obtained from fluid catalytic cracker at a volume ratio of 100: 0 to 50:50 3 to 30 mg of antioxidant is contained per 1 L of the obtained kerosene fraction and the composition.
Next, the kerosene composition of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a process diagram showing an example of a method for producing a kerosene composition of the present invention.

In the present invention, as heavy oil to be supplied to the coker 4 and pyrolyzed, (a) atmospheric distillation residue of crude oil, (b) vacuum distillation residue obtained by subjecting the atmospheric distillation residue to vacuum distillation (C) Propane deasphalted asphalt obtained by subjecting the vacuum distillation residue to propane deblocking treatment and (d) at least one selected from the bottom fraction of a fluid catalytic cracking apparatus is used.
Specifically, the atmospheric distillation residue (AR) of the crude oil (a) refers to a residue obtained by supplying crude oil to the atmospheric distillation apparatus 1 and performing an atmospheric distillation treatment. The vacuum distillation residue (VR) of (b) refers to a residue obtained by supplying the atmospheric distillation residue (AR) of (a) to the vacuum distillation apparatus 2 and performing distillation under reduced pressure.
Further, (c) propane deasphalted asphalt (PDAS) refers to asphalt obtained by supplying the reduced-pressure distillation residue (VR) of (b) to the propane deburring apparatus 3 and propane deburring treatment.
On the other hand, the bottom fraction (CLO) of the FCC unit (d) is the FCC unit 5 with a mixture of straight-run heavy gas oil, vacuum gas oil, propane debris, atmospheric distillation residue, crude oil, etc. This refers to the catalytic cracking residue oil obtained by supplying and fluidizing catalytic cracking treatment, and is heavier than the later-described light cycle oil (LCO) coming out of the FCC unit 5.
In the present invention, (a), (b), (c) and (d) may be used alone as heavy oil to be supplied to the coker 4 and subjected to pyrolysis, or two or more may be used as appropriate. You may use it in combination.

In the present invention, the coker 4 for thermally decomposing at least one heavy oil selected from the above (a) to (d) is not particularly limited, and any one of conventionally known cokers can be used. Can be used properly. For example, a delayed coker or a fluid coker is used. Among these cokers, the use of delayed cokers accounts for the majority. This is because the coke of the delayed coker is agglomerated and has high utility value due to the superior physical properties due to its crystal structure, and the delayed coker is simple in structure and operation, and also operates as a bisbreaker. This is because it has advantages such as being able to.
As reaction conditions for the delayed coker, the temperature is usually about 450 to 530 ° C., preferably 480 to 510 ° C., and the pressure is usually about 1 MPa or less, preferably 0.2 to 0.6 MPa.
In the present invention, after the heavy oil is pyrolyzed by the coker 4, the remaining light distillate from which the heavy light oil fraction (CHGO) is removed [naphtha fraction ( CN), light light oil fraction (CLGO)] and light cycle oil (LCO) obtained from the FCC unit 5 are mixed so that the volume ratio of the light fraction to LCO is 100: 0 to 50:50. The obtained base material is supplied to the hydrotreating device 6 and subjected to desulfurization and denitrogenation treatment. Further, coke is taken out from the coker 4.
If the content ratio of the light fraction and LCO in the mixed base material is within the above range, the reaction conditions for desulfurization and denitrogenation treatment become mild, the hydrogen consumption can be reduced, and the life of the hydrotreating catalyst can be reduced. It can be long and economical. Moreover, the stability of the fraction after the treatment is good and advantageous. A preferred content ratio is 95: 5 to 50:50 by volume ratio.
In addition, LCO obtained from the FCC apparatus is rich in olefins and aromatics, so has a low cetane number and is unsuitable for kerosene / light oil bases, and has been used mainly as a heavy oil base. .

When at least one heavy oil selected from the above (a) to (d) is pyrolyzed using a coker, impurities such as metals and asphaltenes contained in the heavy oil Can be concentrated in product coke and decomposed into middle distillates, but the cracked oil contains unstable olefins. For the purpose of a kerosene composition, the olefins are preferably hydrogenated.
The hydrotreating device 6 can desulfurize and denitrogenate the mixed base material of the light fraction from the coker 4 and the LCO from the FCC unit 5 and can hydrogenate the olefins in the mixed base material. Any apparatus may be used, and desulfurization and denitrogenation are performed by hydrotreating (hydrorefining). Although there is no restriction | limiting in particular as such an apparatus, For example, after performing the hydrogenation process of the olefins in a mixed base material in a 1st reaction tower using a multistage reaction tower, it is a 2nd reaction tower. The mixed base material may be desulfurized or denitrogenated, and then denitrified or desulfurized in a third reaction tower. Alternatively, after the olefins in the mixed base material are hydrogenated in the first reaction tower, the mixed base material is desulfurized in the second reaction tower provided with the desulfurization catalyst filling zone and the denitrification catalyst filling zone. The treatment and the denitrification treatment may be performed simultaneously. In addition, there is no restriction | limiting in particular about the installation order of each reaction tower.
In the present invention, the mixed base material is desulfurized and denitrogenated in the hydrotreating apparatus 6 in this way, and then a naphtha fraction, a kerosene fraction and a light oil fraction are taken out by distillation. it can.

In the present invention, the target kerosene composition is obtained by adding 3 to 30 mg of antioxidant per 1 L of the composition to the kerosene fraction. When the addition amount of the antioxidant is less than 3 mg, the storage stability is insufficient, and when it exceeds 30 mg, the effect of improving the storage stability is hardly exhibited for the amount, which is economically disadvantageous. The preferable addition amount of the antioxidant is 5 to 15 mg per liter of the composition.
The antioxidant is not particularly limited as long as it is usually used for fuel oil, and any of phenol-based antioxidants and amine-based antioxidants can be used.

  Examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4,6-tri-tert-butylphenol. 2,6-di-tert-butyl-4-hydroxymethylphenol; 2,6-di-tert-butylphenol; 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-butyl-4 -(N, N-dimethylaminomethyl) phenol; 2,6-di-tert-amyl-4-methylphenol; n-octadecyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate A monocyclic phenol, 4,4′-methylenebis (2,6-di-tert-butylphenol); Pyridenebis (2,6-di-tert-butylphenol); 2,2′-methylenebis (4-methyl-6-tert-butylphenol); 4,4′-bis (2,6-di-tert-butylphenol); 4 4,4′-bis (2-methyl-6-tert-butylphenol); 2,2′-methylenebis (4-ethyl-6-tert-butylphenol); 4,4′-butylidenebis (3-methyl-6-tert- Butylphenol); 2,2′-thiobis (4-methyl-6-tert-butylphenol); polycyclic phenols such as 4,4′-thiobis (3-methyl-6-tert-butylphenol).

On the other hand, examples of amine-based antioxidants include diphenylamine-based compounds, specifically, diphenylamine and monooctyldiphenylamine; monononyldiphenylamine; 4,4′-dibutyldiphenylamine; 4,4′-dihexyldiphenylamine; -Dioctyldiphenylamine; 4,4'-dinonyldiphenylamine;tetrabutyldiphenylamine;tetrahexyldiphenylamine; tetraoctyldiphenylamine: alkylated diphenylamine having a C3-C20 alkyl group such as tetranonyldiphenylamine, and naphthylamine type , Specifically α-naphthylamine; phenyl-α-naphthylamine, further butylphenyl-α-naphthylamine; hexylphenyl-α-naphthylamine; Cycloalkenyl -α- naphthylamine; and alkyl-substituted phenyl -α- naphthylamine having 3 to 20 carbon atoms such as nonylphenyl -α- naphthylamine.
In the present invention, one type of the phenol-based antioxidant may be used, two or more types may be used in combination, and one type of the amine-based antioxidant may be used. The above may be used in combination, and further, one or more phenolic antioxidants and one or more amine antioxidants may be used in combination.

In the kerosene composition of the present invention, the desulfurized straight-run kerosene can be contained in a proportion of 0.1 to 98% by volume, preferably 30 to 95% by volume, based on the total amount of the composition. The desulfurized straight-run kerosene refers to kerosene obtained by desulfurizing straight-run kerosene obtained by distilling crude oil with a hydrotreating apparatus or the like.
[Properties of kerosene composition]
The kerosene composition of the present invention preferably has the following properties.
First, there is no particular limitation on the density at 15 ° C., from the viewpoint of fuel consumption rate, is preferably 0.780 g / cm ³ or more, and more preferably 0.790~0.830g / cm ³ . The density is a value measured according to JIS K 2249 “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 K 2265 “Tag sealed flash point test 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 K 2541 “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 23 mm or more, more preferably 24 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 K 2580.
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 K 2513.

<Distillation properties>
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% by volume distillation temperature (T ₅₀ ): 180-220 ° C.
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 the 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 K 2254 “Evaporation Test Method”.

<120 ° C accelerated deterioration test>
The 120 degreeC accelerated deterioration test was done by the method shown below, and Saybolt color (measured by JIS K2580) and the amount of real gum (measured by JIS K2261) were measured.
120 ° C accelerated deterioration test method:
200 mL of the sample and iron pieces (6 × 6 × 0.3 mm) are placed in a glass tube equipped with a cooling tube and an air blowing tube. The container is immersed in a constant temperature bath at 120 ° C., and dry air is blown in at a rate of 5 L / h for 2 hours.
With respect to various characteristics of the sample after the accelerated deterioration test, it is preferable that the Sevolt color is +28 or more. The actual gum amount is preferably 0.5 mg / 100 mL or less, and more preferably 0.1 mg / 100 mL or less.
The kerosene composition of the present invention uses, as a raw material base material for kerosene, an LCO obtained from an atmospheric distillation residue, a vacuum distillation residue, a propane deasphalted asphalt, or an FCC device, which has been conventionally used as a heavy oil base material. It has excellent storage stability and is an advantageous petroleum product that responds to changes in the demand structure of petroleum products in recent years, such as a decrease in demand for heavy oil.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The properties of kerosene and LCO in each example were measured according to the following method.
(1) Measurement of density, flash point, sulfur content, nitrogen content, smoke point, Saybolt color, copper plate corrosion and distillation properties, and 120 ° C. accelerated deterioration test were carried out according to the methods described in the specification.
(2) Doctor test A doctor test was performed according to JIS K2276.
Production Example 1
As a heavy oil, the vacuum distillation residue was supplied to a delayed coker and pyrolyzed under conditions of a temperature of 480 ° C. and a pressure of 0.17 MPa. Subsequently, the obtained pyrolysis oil was subjected to distillation treatment to obtain a light fraction from which a heavy gas oil fraction (CHGO) was removed.

Comparative Example 1
A mixed base material composed of 57% by volume of the light fraction from the delayed coker obtained in Production Example 1 and 43% by volume of light cycle oil (LCO) obtained from the FCC unit was hydrotreated according to a conventional method, After denitrification, a kerosene fraction was obtained by distillation. Table 1 shows the properties of this kerosene fraction (hereinafter referred to as the LCO-containing kerosene fraction).
Example 1
To the LCO-containing kerosene fraction obtained in Comparative Example 1, an antioxidant (chemical name: 2,6-ditertiary butyl-4-methylphenol) was added so as to be 10 mg per liter of the composition, A kerosene composition was prepared. The properties of this kerosene composition are shown in Table 1.
Example 2
The same antioxidant used in Example 1 was added to 10 mg per liter of the composition in a mixture comprising 50% by volume of the LCO-containing kerosene fraction obtained in Comparative Example 1 and 50% by volume of desulfurized straight-run kerosene. It was added so that a kerosene composition was prepared. The properties of this kerosene composition are shown in Table 1.

Reference example 1
Table 1 shows the properties of the LCO used in Comparative Example 1.
Reference example 2
Table 1 shows the properties of commercial kerosene.

[note]
1) Kerosene fraction containing LCO: A mixed base material consisting of 57% by volume of light fraction from delayed coker and 43% by volume of LCO from FCC unit was hydrotreated, desulfurized and denitrogenated, and then distilled. It refers to the kerosene fraction obtained.
2) Antioxidant: 2,6-ditertiary butyl-4-methylphenol

  As can be seen from Table 1, Examples 1 and 2 in which an antioxidant was added to an LCO-containing kerosene fraction or a mixture of an LCO-containing kerosene fraction and a desulfurized straight-run kerosene added an antioxidant. It is clear that the storage stability is superior to Comparative Example 1 that is not.

  In the kerosene composition of the present invention, an atmospheric distillation residue, a vacuum distillation residue, propane deasphalted asphalt, or LCO obtained from an FCC apparatus, which has been conventionally used as a heavy oil base material, is used as a raw material base material for kerosene. And is excellent in storage stability.

It is process drawing which shows one example of the method of manufacturing the kerosene composition of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Atmospheric distillation apparatus 2 Vacuum distillation apparatus 3 Propane removal apparatus 4 Coker 5 FCC apparatus 6 Hydrogenation processing apparatus

Claims (2)

  (A) Atmospheric distillation residue of crude oil, (b) Vacuum distillation residue obtained by subjecting the atmospheric distillation residue to vacuum distillation, (c) Propane removal obtained by subjecting the vacuum distillation residue to propane degassing treatment A light fraction (A) obtained by pyrolyzing at least one selected from the asphalt and (d) bottom fraction of a fluid catalytic cracker, and a light cycle oil (B) obtained from a fluid catalytic cracker ) In a ratio of volume ratio of 100: 0 to 50:50, and contains 3 to 30 mg of antioxidant per 1 L of kerosene fraction obtained from desulfurized and denitrogenated oil of mixed base material and composition Kerosene composition characterized by the above.   The kerosene composition according to claim 1, further comprising desulfurized straight-run kerosene in a proportion of 0.1 to 98% by volume based on the total amount of the composition.

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