JP5527959B2 - A heavy oil composition and method for producing the same - Google Patents

Description

  The present invention relates to a heavy fuel oil composition A widely used as a fuel for diesel engines other than those for land transportation, such as for agricultural and fishing, stationary power generation and construction equipment, and combustion equipment such as boilers. More specifically, the present invention relates to an A heavy oil composition excellent in filter oil permeability, in which sludge generated by precipitation or mixing of water does not cause clogging of the fuel filter.

  A heavy oil is a kind of heavy oil classified as No. 1 or No. 2 of JIS K 2205 “Heavy oil”, but most of its components are occupied by fractions such as straight-run gas oil, desulfurized gas oil and cracked gas oil. ing. Therefore, the residual carbon content of the 10% residual oil (hereinafter referred to as 10% residual oil) is excluded so that the A heavy oil after production is excluded from the light oil subject to Article 700-2, Paragraph 1, Item 1 of the Local Tax Law. A small amount of heavy fraction such as residual oil is added as a residual carbon content-giving substrate so that the amount of carbon) is more than 0.2% by mass.

In general, heavy fractions, which are residual carbon components, contain impurities such as asphaltene and resin corresponding to residual carbon, as well as trace amounts of metals, which are dry sludge. As a fine particle in the A heavy oil composition. It is generally known that sludge causes clogging in a filter, and methods for improving sludge stability or oil permeability have been proposed in order to reduce sludge. For example, Japanese Patent Application Laid-Open No. 2004-091676 discloses an A heavy oil composition having improved oil permeability by using a specific petroleum resin as a residual carbon content-imparting base material, and Japanese Patent Application Laid-Open No. 2007-231121. Discloses a heavy fuel oil composition in which dry sludge is reduced by blending specific fatty acid alkyl esters as a base material.
JP 2004-091676 A JP 2007-231121 A

  However, the use of specific petroleum resins as the residual carbon-imparting base material or the use of specific fatty acid alkyl esters as the base material requires that a specific manufacturing facility be newly installed or that a commercial product be purchased. This is not preferable because it increases the manufacturing cost as a result. Even if the amount of dry sludge is reduced, the problem that clogging or clogging may occur in the filter still remains in relation to free moisture, as will be described below.

  That is, fine dry sludge present in the heavy fuel oil composition A normally passes through the mesh of the fuel filter unless the amount thereof is excessively large, so that problems such as clogging the filter may occur. Often not. On the other hand, for example, when the amount of saturated water decreases due to temperature change of the A heavy oil composition during storage, and dissolved water is deposited, or when water is mixed due to condensation inside the storage tank. However, most of the free water can be easily separated and removed by a coalescer, etc., but some free water binds to fine dry sludge and floats in the composition and cannot be separated and removed by the coalescer. It will be a thing. When the particle diameter becomes larger than the mesh of the fuel filter, the fuel filter is often clogged.

  Therefore, in order to solve such a problem, it is necessary to reduce the dry sludge in the A heavy oil composition, but it is necessary to suppress moisture from being combined with the dry sludge. However, none of the prior arts including the above-mentioned document mentions a solution to the filter clogging problem caused by the combination of dry sludge and free water.

  Accordingly, an object of the present invention is to provide a heavy oil composition A that does not cause the problem of filter clogging caused by dry sludge being combined with free moisture, while using a residual carbon-imparted base material obtained in a normal petroleum refining process, and its production. It is to provide a method.

The present inventors conducted earnest research on elements that promote the bonding between moisture and dry sludge while using a residual carbon content-imparted base material obtained in a normal oil refining process in the A heavy oil composition. As a result, it has been found that when a residual carbon content-imparting base material having specific properties is used, the bond between moisture and dry sludge tends to be suppressed. The present invention is based on the new knowledge, that is, an atmospheric distillation residue obtained by atmospheric distillation of a Middle Eastern light crude oil, satisfying the following properties (1) to (4), A heavy oil composition comprising a residual carbon content-imparting substrate that suppresses bonding with dry sludge.
(1) Density is 0.95 g / cm ³ or less (2) Relative permittivity is 2.9 or less (3) Asphaltene content is 5 % by mass or less (4) Resin content is 6 % by mass or less

In the present invention, the residual carbon content-imparting substrate may be any material that imparts residual carbon . As the residual carbon-imparting base material, such as its atmospheric distillation and residue oil is used crude. In the present invention, the above (1) to (4) properties must be those which satisfy the, as such substrates, atmospheric Tomezan渣oil obtained light crude oil or these Middle East system It is.

  In addition to the above (1) to (4), the A heavy oil composition of the present invention may contain a residual carbon content-imparting substrate that satisfies the metal content of 5 mass ppm or less. In addition, sodium, potassium, vanadium, nickel, iron, aluminum, silicon can be considered as the main metals included in the metal content, but other metals are included in the residual carbon content-giving substrate as well. Preferably not.

Method for producing heavy oil A composition of the present invention consists of atmospheric residue obtained by atmospheric distillation of Middle Eastern light crude oil, above the middle distillate base material (1) meets to (4), A residual carbon component-imparting base material that suppresses bonding between moisture and dry sludge is added. The residual carbon-imparting substrate added here may satisfy that the metal content is 5 mass ppm or less in addition to the above (1) to (4).

  The middle distillate base material of the present invention is a base material appropriately blended according to the properties required for the A heavy oil composition, excluding 10% residual charcoal, such as density, distillation properties, kinematic viscosity and sulfur content. It means each fraction having a boiling point range of about 150 to 400 ° C. obtained mainly by atmospheric distillation of crude oil or decomposition of heavy oil. Specifically, a straight-run kerosene fraction or cracked kerosene fraction having a boiling range of about 150 to 280 ° C, a straight-run kerosene fraction or cracked gas oil fraction having a boiling range of about 200 to 400 ° C, and hydrogen thereof. Such as hydrodesulfurized products.

  The A heavy oil composition of the present invention and the A heavy oil composition produced by the production method of the present invention are stored in comparison with the conventional A heavy oil composition while using the residual carbon content-imparting base material obtained in a normal petroleum refining process. The water sludge deposited or mixed during transportation or transportation and the dry sludge have low binding properties, and the fuel filter is hardly clogged.

As long as the density of the residual carbon content-providing base material blended in the A heavy oil composition of the present invention is 0.95 g / cm ³ or less, the effects of the present invention are satisfied as long as the above conditions (2) to (4) are satisfied. Can be obtained. When the density is higher than 0.95 g / cm ³ , the separation property between the dry sludge and the water in the A heavy oil composition is unfavorable even if other conditions are satisfied. Further, in order to further enhance the effect, preferably 0 . 94 g / cm ³ or less.

If the relative permittivity of the residual carbon content-providing base material blended in the A heavy oil composition of the present invention is 2.9 or less, the present invention is applicable as long as the above conditions (1), (3) and (4) are satisfied. The effect of can be obtained. If the relative permittivity is larger than 2.9 , the effect cannot be obtained even if other conditions are satisfied, which is not preferable .

If the asphaltene content of the residual carbon content-providing base material blended in the A heavy oil composition of the present invention is 5 % by mass or less, the present invention is used as long as the above conditions (1), (2) and (4) are satisfied. Although it is possible to obtain the effect, in order to enhance the effect, it is more preferably 3 mass% or less, and most preferably not more than 1 wt%.

If the resin content of the residual carbon content-providing base material blended in the A heavy oil composition of the present invention is 6 % by mass or less, the effects of the present invention are obtained as long as the above conditions (1) to (3) are satisfied. it is Ru can.

  Further, in addition to satisfying the above conditions (1) to (4) in addition to the residual carbon content-imparting base material, if the metal content is 5 mass ppm or less, mixing of moisture and dry sludge Is more difficult to generate. Furthermore, in order to further enhance the effect, the metal content is preferably 3 mass ppm or less, and most preferably 1 mass ppm or less.

Hereinafter, the A heavy oil composition of the present invention and the production method thereof will be described in detail.
The A heavy oil composition of the present invention is selected from known light oil base materials such as straight-run kerosene fraction, straight-run light oil fraction, cracked light oil fraction, cracked kerosene fraction and hydrodesulfurized products thereof. It can be obtained by adding a residual carbon content-imparting base material having specific properties to one or more kinds (corresponding to the middle distillate base material of the present invention). Here, the straight-run kerosene fraction and the straight-run light oil fraction can be obtained by atmospheric distillation of crude oil. The cracked light oil fraction and cracked kerosene fraction can be obtained by catalytic cracking, thermal cracking, hydrocracking, etc. of heavy oil. In addition, in order to reduce the sulfur content of the cracked gas oil fraction and cracked kerosene fraction in advance, an indirect desulfurization method or direct desulfurization is performed before heavy oil is subjected to catalytic cracking, thermal cracking, hydrocracking, etc. Hydrodesulfurization treatment such as a method can be performed. In addition, the light hydrocarbon fraction produced by the desulfurization reaction can also be used as a cracked light oil fraction and a cracked kerosene fraction. Usually, these fractions are blended and used so as to have desired properties, for example, density, distillation properties, sulfur content and kinematic viscosity are in a desired range.

In order to satisfy the tax law provisions for fuel oil classified as A heavy oil, the residual carbon content-giving base material has a 10% residual carbon of the A heavy oil composition more than 0.2% by mass as described above. (1) density is 0.95 g / cm ³ or less, (2) relative dielectric constant is 2.9 or less, (3) asphaltene content is 5 mass% or less, (4 ) The resin content must satisfy the properties of 6 % by mass or less. Such substrates, for example, an atmospheric Tomezan渣oil obtained from such light crude oil of Middle East.

<Example 1>
Atmospheric distillation residue obtained by atmospheric distillation of Middle East light crude oil as a residual carbon content-giving base material with 69.6% by volume of straight-run gas oil fraction (GO), 30.0% by volume of cracked gas oil (LCO) A heavy oil composition satisfying JIS K 2205 was prepared by blending 0.4% by volume of oil (LSLR) .
<Comparative Example 1>
It is obtained by atmospheric distillation and vacuum distillation of Middle Eastern medium crude oil as a residual carbon content-giving base material with 69.8% by volume of straight-run gas oil fraction (GO), 30.0% by volume of cracked gas oil (LCO). The A heavy oil composition satisfying JIS K 2205 was prepared by blending 0.2% by volume of the vacuum distillation residue oil (MSSR) obtained.
<Comparative example 2>
Boiling point of about 300, obtained by catalytic cracking of vacuum gas oil as raw material as a residual carbon content-giving base material, with 69.7% by volume of straight-run gas oil fraction (GO), 30.0% by volume of cracked gas oil (LCO) A heavy oil composition satisfying JIS K 2205 was prepared by blending 0.3% by volume of a mixture of heavy cycle oil and slurry oil (HCO / SL) in the range of ˜550 ° C.
<Comparative Example 3>
Atmospheric distillation obtained by atmospheric distillation of heavy crude oil as a base material for residual carbon content, 69.7% by volume of straight gas oil fraction (GO), 30.0% by volume of cracked gas oil (LCO) A heavy oil composition satisfying JIS K 2205 was prepared by blending 0.3% by volume of residual oil (HSLR).
<Reference example>
As a reference example, a composition containing 70.0% by volume of a straight-run gas oil fraction (GO) and 30.0% by volume of cracked gas oil (LCO) was prepared without blending a residual carbon content-imparting base material.

Example 1, the properties of the blended residual carbon-imparting base material in a ratio Comparative Examples 1 to Comparative Example 3 shown in Table 1. Each measurement was performed as follows.
<Relative permittivity>
Measured by the mutual induction bridge method in the dielectric constant test in JIS K 6911 “General Test Method for Thermosetting Plastics”.
<Density>
Measured according to JIS K 2249 “Crude oil and petroleum products—Density test method” vibration type density test method.
<Sulfur content>
JIS K 2541-4 “Crude oil and petroleum products—Sulfur content test method” Measured by a radiation excitation method.
<Residual carbon content>
JIS K 2270 “Crude oil and petroleum products—residual carbon content test method” was measured by a micro method.
<Ash content>
JIS K 2272 “Crude oil and petroleum products—ash and sulfate ash test method” Measured by the ash test method.
<Nitrogen content>
JIS K 2609 “Crude oil and petroleum products—nitrogen content test method” Measured by the chemiluminescence method.
<Metal content>
Measured according to Petroleum Institute Standard JPI-5S-62-2000 “Petroleum Products-Metal Content Test Method”. As a test method, for the measurement of aluminum (Al), silicon (Si), iron (Fe), nickel (Ni), vanadium (V), ICP-luminescence method, for the measurement of sodium (Na), potassium (K) Atomic absorption was employed.
<Saturated, Aroma, Resin, Asphaltene>
It was measured by thin layer chromatography / hydrogen flame ionization detector method using Iatroscan MK-5 (product name, manufactured by Yatron Co., Ltd.).

Example 1, the ratio Comparative Examples 1 to Comparative Example 3 and Reference Example were measured as described below. The results are shown in Table 2.
<10% carbon residue>
After adjusting 10% residual coal according to JIS K 2270 “Crude Oil and Petroleum Products—Residual Carbon Content Test Method”, measurement was performed by a micro method.
<Moisture + sludge content (centrifugation test)>
In the separatory funnel, 100 ml of the A heavy oil composition of the example or the comparative example or the composition of the reference example is taken, and 3 ml of water (volume ratio 100: 3 with the A heavy oil composition or the composition of the reference example) is mixed therein. The mixture was shaken for 30 minutes and then transferred to a graduated test tube for centrifugation. Centrifugation was performed for 120 minutes in accordance with “Test method for insoluble matter in used lubricating oil” of JPI-5S-18-80. Then, the volume of the mixed layer of water and sludge formed immediately above the water layer formed at the bottom of the scale test tube is measured, and this is compared to the total volume of the A heavy oil composition and water after centrifugation. Set the volume ratio of the mixed layer to ``
Calculated as “moisture + sludge mixing ratio”. In addition, Shaker SA31 (product name, Yamato Chemical Co., Ltd.) is used for shaking, the stroke is 40 mm, and the shaking speed is 22 per minute.
5 times.

As is apparent from the results in Table 2, the water + sludge mixing ratio is high in the A heavy oil composition of Comparative Examples 1 to 3, whereas it is low in the A heavy oil composition of Example 1. It can be seen that the mixed layer of moisture and sludge has a tendency to be difficult to generate. And from Table 1, as for the residual carbon content provision base material used for Example 1, all are (1) density 0.95g / cm < ³ > or less, (2) relative dielectric constant 2.9 or less, ( 3) The asphaltene content is 5 % by mass or less, and (4) the resin content is 6 % by mass or less. On the other hand, the residual carbon content-imparting base material used in Comparative Examples 1 to 3 does not satisfy all these conditions, and tends to easily generate a mixed layer of moisture and sludge. Was confirmed.

Note that the moisture + sludge content is different from the moisture content. In the reference example, a mixed layer of moisture and sludge is not generated. Therefore, in the centrifuge test for obtaining the above moisture + sludge content, a residual carbon content-imparting substrate including a factor of dry sludge apart from moisture. It was confirmed that the impact of. Therefore, the above centrifugation test can be said to be an effective test in measuring the binding property between moisture and dry sludge.

Claims (2)

An atmospheric distillation residue oil obtained by atmospheric distillation of a Middle Eastern light crude oil, a residual carbon content-imparting base material that satisfies the following properties (1) to (4) and suppresses the bond between moisture and dry sludge A heavy oil composition characterized by containing.
(1) Density is 0.95 g / cm ³ or less (2) Relative permittivity is 2.9 or less (3) Asphaltene content is 5 % by mass or less (4) Resin content is 6 % by mass or less This is an atmospheric distillation residue oil obtained by atmospheric distillation of middle east light crude oil on the middle distillate base material, satisfies the following properties (1) to (4), and suppresses the bond between moisture and dry sludge. A method for producing a heavy fuel oil composition comprising adding a residual carbon content-imparting base material.
(1) Density is 0.95 g / cm ³ or less (2) Relative permittivity is 2.9 or less (3) Asphaltene content is 5 % by mass or less (4) Resin content is 6 % by mass or less