JP2015183031A - Heavy oil a composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heavy oil A composition having excellent low temperature fluidity, which does not easily cause a filter clogging trouble under a use condition of winter season in cold area by letting a CFI (cold temperature flow improver) exhibit its effect to the maximum.SOLUTION: Provided is a heavy oil A composition in which is mixed any of an atmospheric distillation bottom obtained by processing crude oil by an atmospheric distillation apparatus, a vacuum distillation bottom obtained by further processing the atmospheric distillation bottom by a vacuum distillation apparatus, or an extract obtained from a lubricant production process. An asphaltene content contained in the atmospheric distillation bottom, vacuum distillation bottom, or extract is 1.0 mass% or less. An asphaltene content in the heavy oil A composition is 7.0 mg/L or more and 45.0 mg/L or less, and a clouding point of the composition is -10.0°C or less.

Description

  The present invention is an A heavy oil composition having excellent low-temperature fluidity, which is less likely to cause filter clogging troubles under use conditions in cold regions in winter by maximizing the effect of CFI (low-temperature fluidity improver). About.

A heavy oil is used as a fuel for various combustion equipment such as an internal combustion engine such as a diesel engine or a boiler that meets the requirements of JIS K 2205, Type 1 or No. 2. In general, heavy oil A is distinguished from light oil in terms of residual carbon among the four items (density, distillation properties, residual carbon content, flash point) that are not subject to the taxation of light oil collection tax stipulated in Article 700 of the Local Tax Law. Turn into. For this reason, A heavy oil is usually a straight-run kerosene (or desulfurized straight-run kerosene) obtained from an atmospheric distillation unit, a straight-run light diesel oil (or a desulfurized straight-run light diesel oil), and a light product obtained from a fluid catalytic cracker. Cycle oil, direct desulfurization oil obtained from direct desulfurization equipment, etc. are mixed, and in order to adjust the residual carbon content, atmospheric residual oil, reduced pressure residual oil, extract, etc. are mixed to leave 10% residual oil. It is produced so that the carbon content exceeds 0.2% by mass.
The extract here is a highly aromatic oil produced as a by-product in the step of removing the aromatic component in the lubricating oil using a solvent such as furfural, and its properties are 0.95 to 1.05 g / cm ³ , The kinematic viscosity at 100 ° C. is 5 to 100 mm ² / s, and the sulfur content is 0.5 to 5.0 mass%.

Engines and various combustion equipment that use A heavy oil as fuel have filters with openings of 5 to 250 μm in the fuel system and the like for the purpose of removing foreign substances in the fuel oil in order to protect the precision equipment at the later stage. Yes. However, when a device having such a filter is used in winter, the filter is likely to be clogged with the wax precipitated from the heavy oil A.
Therefore, in order to solve such problems, regarding the improvement of the filter clogging prevention performance of the A heavy oil composition, the increase in the kerosene fraction, the utilization of the dewaxing base material, the blending of the heavy oil (Patent Document 1), the residual oil Increases (Patent Document 2), addition of CFI (low temperature fluidity improver) (Non-Patent Document 1), and the like have been proposed.
However, the A heavy oil composition obtained by each of the above-mentioned methods has room for improvement in the following points, and it is still not possible to put it to practical use as an A heavy oil composition by simply applying any known method. That's not enough.
That is, when kerosene fraction is blended to produce winter grade A heavy oil, the blending amount is too large and the flash point becomes an obstacle, which is not effective in terms of safety. Even if a dewaxed base material is used, the amount of wax is too large to be used in cold regions in winter, and the low temperature performance cannot be satisfied. Increased blending of heavy oil leads to deterioration of the wax precipitation point (cloud point). Increasing the amount of residual oil increases the amount of dust in the combustion gas. In addition, the performance of CFI (low temperature fluidity improver) largely depends on the compatibility with the base material used, and simply adding it cannot sufficiently improve the filter clogging prevention performance of A heavy oil for cold regions in winter. .

  The filter clogging prevention performance of A heavy oil has been evaluated in the past with the clogging point (CFPP) measured by JIS K 2288 “Petroleum products-Diesel oil—Clogging point test method”. It is known that due to rapid cooling (about −40 ° C./hour), it is significantly different from the actual use conditions and is insufficient to serve as an index of the filter clogging point of heavy oil A (for example, non-patent document). 2).

Japanese Patent Laid-Open No. 9-333583 JP-A-7-97581

Koji Nomura, “Science of Marine Fuel”, 1994, P164-166 “Petroleum Society Standards, Standard Method for Testing Low Temperature Fluidity of Heavy Fuel Oil A (Actual Machine Simulation Method)”, JPI-5S-47-96, P6-7

  An object of the present invention is to provide an A heavy oil composition that does not cause clogging (clogging trouble) of a filter with wax even under use conditions in a cold region in winter.

  As a result of intensive studies to solve the above problems, the present inventors have determined the asphaltene content of the residual coal-adjusted base material to be blended with the A heavy oil composition, the asphaltene content and the cloud point in the A heavy oil composition. In the case of the range, the present inventors have found that the filter clogging due to wax does not occur even in the use condition in a cold region in the winter, and the present invention has been completed.

  That is, the present invention is an atmospheric distillation residue obtained by treating crude oil with an atmospheric distillation device, a vacuum distillation residue obtained by further treating an atmospheric distillation residue with a vacuum distillation device, or a lubricating oil production process. Any one of the extracts obtained from the above, the asphaltene content contained in these atmospheric distillation residue, vacuum distillation residue, or extract is 1.0% by mass or less, and the concentration of asphaltenes in the heavy fuel oil composition A Is 7.0 mg / L or more and 45.0 mg / L or less, and a cloud point is -10.0 degrees C or less, It is related with A heavy oil composition characterized by the above-mentioned.

Moreover, this invention relates to the said A heavy oil composition characterized by satisfy | filling the following (1)-(5).
(1) Cetane index is 40.0 or more (2) Sulfur content is 1% by mass or less (3) Aromatic content is 20.0% by volume or more (4) Addition amount of CFI (low temperature fluidity improver) is 500 mg / L or less (5) 10% residual carbon content is 0.21 mass% or more and 0.6 mass% or less

  In the present invention, either the above atmospheric distillation residue or the vacuum distillation residue is 0.10% by volume or more and 0.50% by volume or less with respect to the total amount of the A heavy oil composition, or the extract is the A heavy oil composition. The A heavy oil composition as described above, which is blended in an amount of 1.15% by volume to 3.00% by volume based on the total amount of the product.

  Further, the present invention provides an atmospheric distillation residue obtained by treating crude oil with an atmospheric distillation device, a vacuum distillation residue obtained by further treating an atmospheric distillation residue with a vacuum distillation device, or a lubricating oil production process. Any one of the extracts obtained from the above, the asphaltene content contained in these atmospheric distillation residue, vacuum distillation residue, or extract is 1.0% by mass or less, and the concentration of asphaltenes in the heavy fuel oil composition A Is 7.0 mg / L or more and 45.0 mg / L or less, and a cloud point is -10.0 degrees C or less, It is related with the manufacturing method of A heavy oil composition characterized by the above-mentioned.

Moreover, this invention relates to the manufacturing method of the said A heavy oil composition characterized by the A heavy oil composition satisfy | filling the following (1)-(5).
(1) Cetane index is 40.0 or more (2) Sulfur content is 1% by mass or less (3) Aromatic content is 20.0% by volume or more (4) Addition amount of CFI (low temperature fluidity improver) is 500 mg / L or less (5) 10% residual carbon content is 0.21 mass% or more and 0.6 mass% or less

  In the present invention, either the above atmospheric distillation residue or the vacuum distillation residue is 0.10% by volume or more and 0.50% by volume or less with respect to the total amount of the A heavy oil composition, or the extract is the A heavy oil composition. The present invention relates to the method for producing the A heavy oil composition as described above, which is blended in an amount of 1.15% by volume to 3.00% by volume based on the total amount of the product.

As described above, since CFPP cannot accurately evaluate the filter clogging prevention performance of the A heavy oil composition, the evaluation of the filter clogging prevention performance of the A heavy oil composition of the present invention is evaluated by the corrected clogging point test method. did. The corrected clogging point means a value measured by the correction method 4 described in the explanation of “Petroleum Society Standard JPI-5S-47-96, Low Temperature Fluidity Test Method for Heavy Oil A”.
In the present invention, good filter clogging prevention performance means that the correction clogging point is −25 ° C. or lower. This is because, as a result of analyzing the results of AMeDAS in Hokkaido from 1996 to February 2007, the temperature with an appearance frequency of 1% was −25 ° C.

  The A heavy oil composition of the present invention has a specific range of asphaltene content of the residual coal-adjusted base material blended in the A heavy oil composition, and the asphaltene content and cloud point in the A heavy oil composition. A heavy oil composition that does not cause clogging (clogging trouble) of the filter with wax even under the use conditions in FIG.

2 is a photograph of wax crystals of Example 1. 2 is a photograph of wax crystals of Example 12. FIG. 2 is a photograph of wax crystals of Comparative Example 1.

  The present invention is described in detail below.

  A heavy oil composition of the present invention comprises an atmospheric distillation residue obtained by treating crude oil with an atmospheric distillation device, a vacuum distillation residue obtained by further treating an atmospheric distillation residue with a vacuum distillation device, or lubrication. It is obtained by blending any of the extracts obtained from the oil production process.

In the present invention, the atmospheric distillation residual oil, the vacuum distillation residual oil or the asphaltene content in the extract to be blended in the heavy fuel oil composition A as a residual carbon adjusting base material needs to be 1.0% by mass or less, 0.8 mass% or less is preferable and 0.6 mass% or less is more preferable.
Here, the asphaltene content means a value obtained in accordance with IP143 “Asphaltene content test method”.

In the present invention, when either atmospheric distillation residue or atmospheric distillation residue is used, the blending ratio may be 0.10% by volume or more and 0.50% by volume or less with respect to the total amount of A heavy oil composition. It is preferably 0.15% by volume or more and 0.45% by volume or less, more preferably 0.20% by volume or more and 0.45% by volume or less.
In addition, when the extract is used, the blending ratio is preferably 1.15% by volume or more and 3.00% by volume or less, and 1.20% by volume or more and 2.50% by volume or less based on the total amount of the heavy oil composition A. Is more preferable, and more preferably 1.30% by volume or more and 2.50% by volume or less.

The asphaltene content in the heavy oil composition A of the present invention needs to be 7.0 mg / L or more and 45.0 mg / L or less, preferably 7.5 mg / L or more and 43.0 mg / L or less, More preferably, it is 5 mg / L or more and 42.0 mg / L or less. Asphaltenes have a large molecular weight and are polar substances containing nitrogen, oxygen, etc., and thus have a crystal nucleation effect and disperse wax. However, if the asphaltene content exceeds a certain amount, it adsorbs with CFI (low temperature fluidity improver) and deactivates the wax dispersing action of both the asphaltene content and CFI.
Here, the asphaltene concentration in the heavy fuel oil composition A refers to the asphaltene content of the blended residual charcoal adjustment base material according to IP143 “Testing method for asphaltene content”, and the amount of asphaltene contained in 1 liter of heavy fuel oil composition 1L. Means the calculated value.

The cloud point of the heavy oil composition A of the present invention is required to be -10.0 ° C or lower from the viewpoint of satisfying properties other than low-temperature performance, and is -15.0 ° C or higher and -10.0 ° C or lower. Preferably, it is -14.0 ° C or higher and -10.0 ° C or lower, more preferably -13.0 ° C or higher and -10.0 ° C or lower.
The cloud point here means a value obtained in accordance with JIS K 2269 “Pour point of crude oil and petroleum product and cloud point test method of petroleum product”.

As the A heavy oil base material used in the present invention, straight-run kerosene (or desulfurized straight-run kerosene) obtained by treating crude oil with an atmospheric distillation apparatus, straight-run light diesel oil (or desulfurized straight-run light diesel oil) And light cycle oil obtained from a fluid catalytic cracking device, direct degassing light oil obtained from a direct desulfurization device, and the like. In the present invention, these may be used alone or in combination of two or more.
Furthermore, to adjust the residual carbon content, the atmospheric pressure residue obtained by treating crude oil with an atmospheric distillation device, the vacuum residue obtained by further treating the atmospheric distillation residue with a vacuum distillation device, and the production of lubricating oil Extracts obtained from the process are mixed and mixed so that the residual carbon content of 10% residual oil exceeds 0.2% by mass.
In addition, the above-mentioned atmospheric residue, reduced-pressure residue and extract are produced by ordinary production methods, and are obtained by treating ordinary crude oil with an atmospheric distillation apparatus. Aroma in a lubricating oil using a solvent such as a furfural in a normal lubricating oil production process It is an extract obtained from the process of removing a group.

  The proportion of straight-run kerosene that can be blended in the A heavy oil composition of the present invention is preferably 40.0% by volume or less, more preferably 38.0% by volume or less from the viewpoint of flash point, and 25.0% by volume or less. Most preferred.

The A heavy oil composition of the present invention needs to satisfy JIS Class 1 heavy oil standards. The JIS class 1 standard is a standard that satisfies “class 1” defined in JIS K 2205 “heavy oil”. Specifically, the flash point is 60 ° C. or more, the pour point is 5 ° C. or less, and the residual carbon content is 4% by mass or less. The kinematic viscosity at 50 ° C. is 20 mm ² / s or less, the sulfur content is 2.0 mass% or less, the water content is 0.3 volume% or less, and the ash content is 0.05 mass% or less.

The flash point of the heavy oil composition A of the present invention needs to be 60 ° C. or higher of JIS Class 1 heavy oil standard. Furthermore, it is preferable that it is 62 degreeC or more from a viewpoint of safety | security.
In the present invention, the flash point means a value obtained in accordance with JIS K 2265 “How to determine the flash point”.

The pour point of the heavy oil composition A of the present invention needs to satisfy JIS Class 1 heavy oil standard of 5 ° C. or lower. Furthermore, from the viewpoint of low temperature performance, it is preferably −40 ° C. or lower, and more preferably −45 ° C. or lower.
Here, the pour point means a value obtained in accordance with JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

The residual carbon content in the heavy oil composition A of the present invention needs to satisfy 4 mass% or less, which is a JIS class 1 heavy oil standard. Furthermore, it is preferably 3% by mass or less, more preferably 2% by mass or less, from the viewpoint of reducing fine particles and PM and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine.
Here, the residual carbon content means a value obtained in accordance with JIS K 2270 “Crude oil and petroleum products—How to determine the residual carbon content”.

Although there is no restriction | limiting in particular about 10% residual carbon content of A heavy oil composition of this invention, From a viewpoint of "the residual carbon content of 10% residual oil 0.2 mass% or more" which is a tax exemption condition of A heavy oil on tax law It is preferable that it is 0.21 mass% or more. On the other hand, it is preferable that it is 0.6 mass% or less from a viewpoint of the filter clogging prevention by sludge.
Here, the 10% residual carbon content means a value obtained in accordance with JIS K 2270 “Crude oil and petroleum products—How to determine the residual carbon content”.

The kinematic viscosity at 50 ° C. of the A heavy oil composition of the present invention is preferably 3.0 mm ² / s or less, and more preferably 2.8 mm ² / s or less. When the kinematic viscosity at 50 ° C. is larger than 3.0 mm ² / s, the resistance in the fuel injection system increases, the injection system becomes unstable, and the concentrations of NOx and PM in the exhaust gas increase.
Here, the kinematic viscosity means a value obtained in accordance with JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.

The sulfur content of the A heavy oil composition of the present invention is preferably 1% by mass or less from the viewpoint of reducing fine particles and PM and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine.
Here, the sulfur content means a value obtained in accordance with JIS K2541 “Crude oil and petroleum products—sulfur content test method”.

The aromatic content of the A heavy oil composition of the present invention is preferably 20.0% by volume or more, more preferably 25.0% by volume or more, from the viewpoints of solubility and storage stability of the residual coal base material, and 30% 0.0% by volume or more is more preferable.
Here, the aromatic content means a value obtained in accordance with JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method”.

Although there is no restriction | limiting in particular in the nitrogen content of A heavy oil composition of this invention, From a viewpoint of NOx reduction in exhaust gas, 0.02 mass% or less is preferable, and 0.015 mass% or less is more preferable.
Here, the nitrogen content means a value measured according to JIS K 2609 “Crude oil and petroleum products—Test method for nitrogen content”.

The water | moisture content of A heavy oil composition of this invention needs to satisfy | fill 0.3 volume% or less which is a JIS class 1 heavy oil specification. Furthermore, 0.2% by volume or less is preferable and 0.1% by volume or less is more preferable from the viewpoint of rust of equipment, storage tank, and fuel piping. In addition, from the viewpoint of filter clogging due to condensation of free water, 0.03% by volume or less is most preferable.
Here, the moisture means a value obtained in accordance with JIS K 2275 “Crude oil and petroleum products—moisture test method”.

The ash content of the A heavy oil composition of the present invention needs to satisfy 0.05 mass% or less, which is a JIS class 1 heavy oil standard. Furthermore, from the viewpoint of fine particles and PM reduction, it is preferably 0.04% by mass or less, and more preferably 0.03% by mass or less.
Here, ash means a value obtained in accordance with JIS K 2272 “Crude oil and petroleum products—Test method for ash and sulfate ash”.

The cetane index of the A heavy oil composition of the present invention is preferably 40.0 or more, more preferably 43.0 or more, and further preferably 45.0 or more from the viewpoint of combustibility.
Here, the cetane index means a value obtained in accordance with JIS K 2204-1192 “light oil”.

The density at 15 ° C. of the heavy oil composition A of the present invention is not particularly limited, but is preferably 0.800 g / cm ³ or more and 0.9100 g / cm ³ or less. If it is less than 0.800 g / cm ³ , the calorific value per capacity decreases, and combustion becomes unstable. On the other hand, if it exceeds 0.9100 g / cm ³ , the ignitability deteriorates and the generation of soot increases and the combustion becomes unstable.
Here, the density means a value obtained in accordance with JIS K 2249 “Crude oil and petroleum products—Determination of density—”.

The distillation properties of the A heavy oil composition of the present invention are not particularly limited, but usually those satisfying the following properties are preferred.
10 vol% distillation temperature (T10): 180-280 ° C
50 volume% distillation temperature (T50): 240-340 degreeC
90 vol% distillation temperature (T90): 280-380 ° C
Here, the distillation property means a value measured according to JIS K 2254 “Petroleum products—Distillation test method”.

CFI (low temperature fluidity improver) can be mix | blended with the A heavy oil composition of this invention.
As CFI, polymer-type additives such as ethylene-vinyl acetate copolymer and ethylene-α-olefin copolymer, oil-soluble dispersion-type additives, alkersuccinic acid, and the like can be used. The amount of CFI added is not particularly limited and may not be added, but when added, it is preferably 500 mg / L or less from the viewpoint of storage stability. Moreover, in order to enlarge the low temperature performance improvement effect, 150 mg / L or more is preferable and 300 mg / L or more is more preferable.

  In addition to CFI (low temperature fluidity improver), an additive may be added to the A heavy oil composition of the present invention as necessary. The additives herein include cetane number improvers, antioxidants, discriminating agents, stabilizers, dispersants, metal deactivators, microbial disinfectants, combustion aids, antistatic agents, colorants, and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Examples 1-12 and Comparative Examples 1-3)
Using various main base materials having the properties shown in Table 1, they were blended at a volume ratio shown in Table 2 to prepare Samples A and B before blending with a residual coal adjusted base material. Properties of the prepared samples A and B are shown in Table 2. Next, samples A and B in Table 2 were blended with a predetermined amount of various residual coal adjusting base materials and CFI (low temperature fluidity improver) shown in Table 3, so that the examples described in Table 4 and A of the comparative example A heavy oil composition was prepared. For CFI, an ethylene-vinyl acetate copolymer was used.

(Filter clogging prevention performance)
The filter clogging prevention performance was evaluated by the correction method 4 described in the explanation of “Petroleumological Society Standard JPI-5S-47-96, A Heavy Oil Low Temperature Fluidity Test Method”. The acceptance criterion was −25 ° C. or lower. This is because, as a result of analyzing the results of AMeDAS in Hokkaido from 1996 to February 2007, the temperature with an appearance frequency of 1% was −25 ° C.

(Take photo of wax crystal)
50 mL of A heavy oil composition was sampled in a test tube having a diameter of 25 mm and a length of 200 mm, and after sealing the mouth of the test tube, the “Petroleum Society Standard JPI-5S-47-96, Low Temperature Fluidity Test Method for A Heavy Oil” It was cooled to −25 ° C. by the cooling method of correction method 4 described in the explanation. After cooling, the test tube port was opened, a cooled sample was collected using a Pasteur pipette, dropped onto a preparation, and magnified 1000 times using an optical microscope. In addition, the said operation | work was implemented in the low temperature thermostat. Examples and Comparative Examples of the present invention are represented, and images of Examples 1 and 12 and Comparative Example 1 are shown in FIGS.

  As is apparent from the results in Table 4, it can be seen that all of the A heavy oil compositions of Examples 1 to 12 according to the present invention have excellent filter clogging prevention performance. On the other hand, Comparative Examples 1 to 3 in which the asphaltene content of the A heavy oil composition and the alfalten content of the residual coal-adjusted base material blended in the A heavy oil composition are not within the specified range have poor filter clogging prevention performance. This result is attributed to whether or not the wax crystals are dispersed as shown in FIGS.

Claims (6)

  Of atmospheric distillation residue obtained by treating crude oil with an atmospheric distillation device, vacuum distillation residue obtained by further treating atmospheric distillation residue with a vacuum distillation device, or extract obtained from a manufacturing process of lubricating oil Any one of them, the asphaltene content in these atmospheric distillation residue, vacuum distillation residue, or extract is 1.0% by mass or less, and the asphaltene concentration in the heavy oil A composition is 7.0 mg / L A heavy oil composition having a cloud point of -10.0 ° C. or lower and a lower limit of 45.0 mg / L or lower. The A heavy oil composition according to claim 1, wherein the following (1) to (5) are satisfied.
(1) Cetane index is 40.0 or more (2) Sulfur content is 1% by mass or less (3) Aromatic content is 20.0% by volume or more (4) Addition amount of CFI (low temperature fluidity improver) is 500 mg / L or less (5) 10% residual carbon content is 0.21 mass% or more and 0.6 mass% or less   Either the above atmospheric distillation residue or the vacuum distillation residue is 0.10% by volume or more and 0.50% by volume or less based on the total amount of the A heavy oil composition, or the extract is 1% based on the total amount of the A heavy oil composition. 3. A heavy oil composition according to claim 1 or 2, which is blended in an amount of 15% by volume or more and 3.00% by volume or less.   Of atmospheric distillation residue obtained by treating crude oil with an atmospheric distillation device, vacuum distillation residue obtained by further treating atmospheric distillation residue with a vacuum distillation device, or extract obtained from a manufacturing process of lubricating oil Any one of them, the asphaltene content in these atmospheric distillation residue, vacuum distillation residue, or extract is 1.0% by mass or less, and the asphaltene concentration in the heavy oil A composition is 7.0 mg / L It is 45.0 mg / L or less above, and a cloud point is -10.0 degrees C or less, The manufacturing method of A heavy oil composition characterized by the above-mentioned. The method for producing an A heavy oil composition according to claim 4, wherein the A heavy oil composition satisfies the following (1) to (5).
(1) Cetane index is 40.0 or more (2) Sulfur content is 1% by mass or less (3) Aromatic content is 20.0% by volume or more (4) Addition amount of CFI (low temperature fluidity improver) is 500 mg / L or less (5) 10% residual carbon content is 0.21 mass% or more and 0.6 mass% or less Either the above atmospheric distillation residue or the vacuum distillation residue is 0.10% by volume or more and 0.50% by volume or less based on the total amount of the A heavy oil composition, or the extract is 1% based on the total amount of the A heavy oil composition. The method for producing an A heavy oil composition according to claim 4 or 5, wherein the blending amount is 15 volume% or more and 3.00 volume% or less.