JP2011195759A - Method for manufacturing fuel oil c - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a fuel oil C which is reduced in the concentration of hydrogen sulfide contained in a base material for use in fuel oil C.SOLUTION: The method comprises adding 0.01-2.0 vol.%, based on the fuel oil C whole amount, of water to a fuel oil C base material selected from the bottom oil obtained from an atmospheric distillation apparatus, the bottom oil obtained from a vacuum distillation apparatus, the residual oil obtained from a bottom oil desulfurization apparatus, the residual oil obtained from a fluid catalytic cracking, and the extracted oil.

Description

  The present invention relates to a method for producing C heavy oil, and more particularly to a method for producing C heavy oil in which the concentration of hydrogen sulfide contained in a C heavy oil base material is reduced and the amount of hydrogen sulfide generated from C heavy oil is reduced.

C heavy oil is widely used as fuel for external combustion equipment such as boilers, diesel equipment fuel for large ships and power generation, and combustion equipment such as gas turbines.
As base materials for producing C heavy oil, atmospheric residual oil (column bottom oil (AR) obtained from an atmospheric distillation apparatus), residual oil desulfurized heavy oil, vacuum residual oil (column bottom oil obtained from a vacuum distillation apparatus) (VR)), slurry oil, extract oil, and the like, and if necessary, an appropriate amount of viscosity adjusting oil (cutter material) is blended to produce C heavy oil. Among these C heavy oil base materials, the possibility of containing hydrogen sulfide is relatively high in particularly heavy vacuum residue. Hydrogen sulfide is toxic, and hydrogen sulfide staying in a ship's hatch may become higher than expected, and it is desired to reduce the concentration of hydrogen sulfide for safety.
In order to reduce the hydrogen sulfide concentration in the C heavy oil base, chemicals are also used mainly in the United States, but the chemicals are expensive and not always economically optimal for continuous use.
In Patent Document 1 (Japanese Patent No. 36060895) and Patent Document 2 (Japanese Patent Laid-Open No. 2002-146364), the sulfur content is reduced by hydrotreating heavy oil using a hydrodesulfurization catalyst. A method for reducing the sulfur content in heavy oil is usually performed. By reducing the sulfur content, the generation of hydrogen sulfide is suppressed to some extent. However, some types of crude oil are prone to generate hydrogen sulfide, and even though the hydrogen content can reduce the sulfur content to some extent, the hydrogen sulfide content may not be reduced. It was difficult to reduce the concentration to a satisfactory level, and the type of crude oil to be processed by the atmospheric distillation apparatus and the mixing ratio of various crude oils had to be restricted.
Therefore, even if crude oil, which is prone to generate hydrogen sulfide, is treated with an atmospheric distillation device, the generation of hydrogen sulfide can be suppressed, and even if C heavy oil manufactured using various C heavy oil base materials is used for ships, it is a hatch. A C heavy oil capable of suppressing the concentration of staying hydrogen sulfide is desired.
From the above background, development of a method capable of reducing the hydrogen sulfide concentration in C heavy oil and the amount of hydrogen sulfide generated from C heavy oil at low cost is desired.

Japanese Patent No. 36008095 JP 2002-146364 A

  This invention is made | formed in view of such a situation, and it aims at providing the method which can reduce the hydrogen sulfide in C heavy oil base material.

  The reason why hydrogen sulfide is dissolved in C heavy oil is that the bottom oil (AR) obtained from the atmospheric distillation apparatus, the bottom oil (VR) obtained from the vacuum distillation apparatus, and the residual oil obtained from the residual oil desulfurization apparatus (RDS bottom), the possibility that it is relatively contained in the residual oil (slurry oil) obtained from the fluid catalytic cracker, and the hydrogen sulfide concentration in the bottom oil by lowering the bottom temperature of the vacuum distillation unit It is presumed that hydrogen sulfide is generated by the thermal decomposition reaction at the bottom part of each apparatus such as a vacuum distillation apparatus. In general, this thermal decomposition reaction can be moderated to some extent. However, if a vacuum distillation apparatus is used as an example, it is constantly sulfided without sacrificing the yield of vacuum gas oil, such as by lowering the furnace outlet temperature. It is difficult to suppress the production of hydrogen.

As a result of intensive studies, the inventors of the present invention have developed a method for producing C heavy oil in which the hydrogen sulfide concentration in the C heavy oil base material obtained by refining crude oil is reduced and the amount of hydrogen sulfide generated from the C heavy oil is reduced. The headline and the present invention have been completed.
That is, the present invention is a C heavy oil having a reduced hydrogen sulfide concentration and a generated hydrogen sulfide amount, characterized in that water is added to a C heavy oil base in an amount of 0.01 to 2.0% by volume based on the total amount of C heavy oil. It relates to the manufacturing method.
In the present invention, the C heavy oil base material is obtained from a bottom oil obtained from an atmospheric distillation apparatus, a bottom oil obtained from a vacuum distillation apparatus, a residual oil obtained from a residual oil desulfurization apparatus, and a fluid catalytic cracking apparatus. The present invention relates to the method for producing C heavy oil as described above, which is selected from residual oil and extract oil.
Furthermore, the present invention has a kinematic viscosity at 50 ° C. of 30 to 3000 mm ² / s, a flash point of 60 ° C. or higher, a density at 15 ° C. of 0.90 to 1.01 g / cm ³ , and a sulfur content of 4.5 mass%. The present invention relates to C heavy oil produced by the above-described method, which is as follows.

  By the method of the present invention, it is possible to reduce the hydrogen sulfide concentration in the C heavy oil base material obtained by refining crude oil, and to produce C heavy oil having a low hydrogen sulfide concentration and a reduced amount of generated hydrogen sulfide. Is possible.

Hereinafter, the present invention will be described in detail.
The method for producing C heavy oil of the present invention is characterized by adding a specific amount of water to a C heavy oil base material.

  As the C heavy oil base material, the bottom oil obtained from the atmospheric distillation apparatus, the bottom oil obtained from the vacuum distillation apparatus, the residual oil obtained from the residual oil desulfurization apparatus, the residual oil and extract obtained from the fluid catalytic cracking apparatus At least one C heavy oil base selected from oil is used. These C heavy oil bases may be used alone or in combination of two or more.

  Here, the tower bottom oil obtained from the atmospheric distillation apparatus is a residual oil obtained by distilling crude oil at an atmospheric pressure with an atmospheric distillation apparatus (also referred to as an atmospheric residue). The tower bottom oil obtained from the vacuum distillation apparatus is a residual oil obtained by distilling atmospheric residual oil under reduced pressure using a vacuum distillation apparatus (also referred to as vacuum residual oil). The residual oil obtained from the residual oil desulfurization apparatus is a residual oil obtained when the atmospheric residual oil or the vacuum residual oil is desulfurized in the residual oil desulfurization apparatus. The residual oil obtained from the fluid catalytic cracker is a residual oil obtained by cracking residual oil obtained from the residual oil desulfurizer with a fluid catalytic cracker (also referred to as slurry oil). Extract oil is an aromatic component that is not suitable for lubricating oil among the fractions extracted from the vacuum distillation apparatus for lubricating oil raw material by solvent extraction.

In addition, for the purpose of adjusting the viscosity of the C heavy oil base material, an appropriate amount of viscosity adjusting oil (also referred to as a cutter material) can be mixed with the C heavy oil base material as necessary.
Examples of the viscosity adjusting oil include straight run light oil obtained from an atmospheric distillation apparatus, cracked light oil obtained from a fluid catalytic cracking apparatus, and the like. The blending ratio of the viscosity adjusting oil is appropriately determined depending on the kinematic viscosity of the C heavy oil base material used and the viscosity adjusting oil itself so as to match the desired kinematic viscosity of the C heavy oil.

In the method of the present invention, the method for adding water to the C heavy oil base is not particularly limited,
For example, it is desirable to use a method such as adding water in a temperature condition where water does not boil, or using a mixer to ensure mixing of water and oil.
In addition, when using a viscosity adjusting oil for adjusting the viscosity of the C heavy oil base material, water may be added to the mixed oil of the C heavy oil base material and the viscosity adjusting oil. You may add water and mix this with C heavy oil base material.
The amount of water added must be 0.01% by volume or more based on the total amount of C heavy oil. In order to reduce the hydrogen sulfide concentration more efficiently, 0.02% by volume or more is preferable, and 0.05% by volume. % Or more, more preferably 0.1% by volume or more, still more preferably 0.2% by volume or more, and most preferably 0.5% by volume or more.
On the other hand, an excessive amount of water to be added is not preferable in terms of the quality of C heavy oil as a product, and is required to be 2.0% by volume or less, and preferably 1.5% by volume or less. .2% by volume or less is more preferable, and 1.0% by volume or less is most preferable. When the amount of water in C heavy oil is more than 2.0% by volume, the water is deposited in the form of ice in the winter, which is not preferable because it tends to cause metal corrosion and filter clogging.

  In the method of the present invention, by adding a predetermined amount of water to the C heavy oil base material, the hydrogen sulfide concentration of the C heavy oil base material is reduced, the hydrogen sulfide concentration as the C heavy oil is reduced, and generated from the C heavy oil. The reason why the C heavy oil in which the amount of hydrogen sulfide to be reduced is obtained is not clear, but the hydrogen sulfide contained in the C heavy oil base material is dissolved in water having higher solubility than the oil and dissociates into ions. In addition, it is presumed that the hydrogen sulfide concentration is reduced due to either the fact that dissolved hydrogen sulfide is changed into hydrogen and sulfur in water.

The kinematic viscosity at 50 ° C. of C heavy oil obtained by the method of the present invention (hereinafter referred to as C heavy oil of the present invention) is required to be 3000 mm ² / s or less from the viewpoint of combustion failure, and is 2800 mm ² / s. preferably s or less, more preferably at most 2600 mm ² / s, and most preferably not more than 2500 mm ² / s. When the kinematic viscosity at 50 ° C. is higher than 3000 mm ² / s, combustion failure tends to occur, which is not preferable.
Moreover, the kinematic viscosity at 50 ° C. of the C heavy oil of the present invention needs to be 30 mm ² / s or more, preferably 70 mm ² / s or more, more preferably 120 mm ² / s or more, Most preferably, it is 160 mm ² / s or more.
The kinematic viscosity in the present invention means a value obtained according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.

The flash point of the C heavy oil composition of the present invention is required to be 60 ° C. or higher, preferably 65 ° C. or higher, and most preferably 70 ° C. or higher, from the viewpoint of safety in handling. .
In addition, the flash point in the present invention means a value measured by a pen schema ruten sealing method according to JIS K 2265 “How to obtain a flash point—Part 3: Pen schema rutens sealing method”.

The density at 15 ° C. of the heavy C oil of the present invention needs to be 0.90 g / cm ³ or more from the viewpoint of the calorific value, preferably 0.91 g / cm ³ or more, and 0.92 g / cm ^3. Most preferably, it is cm ³ or more. When the density at 15 ° C. is less than 0.90 g / cm ³ , the calorific value per capacity becomes small, which is not preferable.
The density at 15 ℃ of C heavy oil of the present invention, from the viewpoint of combustion failure, must be at 1.01 g / cm ³ or less, preferably 1.00 g / cm ³ or less, 0. Most preferably, it is 99 g / cm ³ or less. When the density at 15 ° C. is larger than 1.01 g / cm ³ , combustion failure tends to occur, which is not preferable.
In addition, the density in this invention means what represents the value obtained based on JISK2249 "crude oil and petroleum products-density test method and density / mass / capacity conversion table".

The sulfur content of C heavy oil of the present invention is required to be 4.5% by mass or less from the viewpoint of the environment, preferably 4.2% by mass or less, and 4.0% by mass or less. Is more preferable, and most preferably 3.5% by mass or less. When the sulfur content exceeds 4.5% by mass, there is a concern about deterioration of exhaust gas from the engine.
In addition, in this invention, a sulfur content means the value measured by JISK2541 "Crude oil and petroleum products-sulfur content test method".

C heavy oil of the present invention comprises various additives such as a cetane number improver, an antioxidant, a stabilizer, a dispersant, a metal deactivator, a microbial disinfectant, a combustion aid, an antistatic agent, a discriminating agent, and a colorant. Can also be contained.
As the above-mentioned additive, one synthesized according to a conventional method may be used, or a commercially available additive may be used. In addition, the additive currently marketed may have diluted the active ingredient which contributes to the effect which the additive aimed at with the appropriate solvent. When using a commercially available additive in which the active ingredient is diluted, it is preferable to add the commercially available additive so that the properties in C heavy oil satisfy the above-mentioned conditions. The addition amount is arbitrary, but it is usually 0.5% by mass or less, preferably 0.2% by mass or less, based on the total amount of C heavy oil.

  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 to 10 and Comparative Examples 1 to 3]
(1) Preparation of C heavy oil Samples of C heavy oil of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared by the following method.

(2) Preparation of hydrogen sulfide measurement sample in oil (in liquid phase) and measurement of hydrogen sulfide concentration C heavy oil base material or mixed oil of C heavy oil base material and viscosity adjusting oil was collected in a 1 L can, and 60 After warming to 0 ° C., transfer to the 500 ml bottle for 300 ml and seal immediately. A predetermined amount of water corresponding to the desired water addition concentration (volume%) is added to the bottle, sealed again and stirred for 2 minutes, then immersed in a constant temperature bath at 60 ° C. for 30 minutes, and about 250 g in a separable flask. Collect. However, the subsequent operation is performed without adding water to the samples for Comparative Examples 1 to 3.
Using the sample obtained above, the hydrogen sulfide concentration in the oil (in the liquid phase) was measured according to IP 399 “Determination of hydrogen sulphide in fuel oils”.
The results are shown in Table 1.

(3) Preparation of hydrogen sulfide measurement sample in gas phase and measurement of hydrogen sulfide concentration Collect C heavy oil base material or mixed oil of C heavy oil base material and viscosity adjusting oil in 1 L can and heat to 60 ° C After that, it is transferred to a 500 ml bottle for 250 ml and immediately sealed. A predetermined amount of water corresponding to a desired water addition concentration (volume%) is added to the bottle, and the bottle is sealed again and stirred for 2 minutes, and then immersed in a thermostat at 60 ° C. for 20 minutes. However, the subsequent operation is performed without adding water to the samples for Comparative Examples 1 to 3.
Using the sample obtained above, the hydrogen sulfide concentration in the gas phase was measured according to ASTM D5705 “Standard Test Method for Measurement of Hydrogen Sulfide in the Vapor Phase Above Residual Fuel Oils”.
The results are shown in Table 1.

(4) Evaluation of hydrogen sulfide concentration measurement results The hydrogen sulfide concentration measurement results in the oil (in the liquid phase) and in the gas phase were evaluated based on the residual ratio based on the case where water was not added. As a reference, the same type of base material was evaluated as 100 in the case of oil (in liquid phase) and 1.00 in the case of gas phase. In addition, about Examples 1-6, it evaluated by the comparison with Comparative Example 3 about Comparative Example 1 about Examples 1-10, Comparative Example 2 about Examples 7-8, and Examples 9-10.
As is clear from the results in Table 1, the hydrogen sulfide concentrations in the oil (in the liquid phase) and in the gas phase of Examples 1 to 10 according to the present invention are the same type of groups as compared with Comparative Examples 1 to 3. In the comparison of materials, it can be seen that the hydrogen sulfide concentration is greatly reduced.

  According to the present invention, C heavy oil in which the hydrogen sulfide concentration of the C heavy oil base material is reduced can be produced, which is extremely useful industrially.

Claims (3)

  A method for producing C heavy oil in which the concentration of hydrogen sulfide and the amount of generated hydrogen sulfide are reduced, wherein water is added to a C heavy oil base material in an amount of 0.01 to 2.0% by volume based on the total amount of C heavy oil.   C base oil base oil obtained from atmospheric distillation equipment, bottom oil obtained from vacuum distillation equipment, residual oil obtained from residual oil desulfurization equipment, residual oil and extract oil obtained from fluid catalytic cracking equipment It is chosen from these, The manufacturing method of C heavy oil of Claim 1 characterized by the above-mentioned. The kinematic viscosity at 50 ° C. is 30 to 3000 mm ² / s, the flash point is 60 ° C. or more, the density at 15 ° C. is 0.90 to 1.01 g / cm ³ , and the sulfur content is 4.5 mass% or less. C heavy oil produced by the method according to claim 1 or 2.