JP5153289B2 - A heavy oil composition - Google Patents

Description

  The present invention relates to a heavy fuel oil composition A used for diesel engines other than those for automobiles, such as internal combustion engines for agriculture and fisheries, stationary power generation diesel engines, construction machinery engines, and the like.

  Catalytic cracking devices are widely used as a process for obtaining as much white oil (such as gasoline fuel and light oil fuel base materials) as possible in demand in society. This catalytic cracking apparatus can mainly produce gasoline and middle distillate from vacuum gas oil and residual oil as raw materials. Of the products produced by this method, a fraction having a boiling point higher than that of gasoline is so-called cracked light oil. , Called LCO).

  LCO has low-temperature fluidity required for light oil fuel for automobiles, but has a low cetane number and poor hue, so that a process such as hydrorefining is required to make it a base material for light oil fuel for automobiles. . Moreover, since the ultra low sulfur is progressing in consideration of an environmental problem, it is the fact that it is hardly used as the base material of the light oil fuel for motor vehicles. Therefore, at present, most of LCO is used as a base material for A heavy oil. However, even when it is used as a base material for A heavy oil, the blending is restricted due to problems such as storage stability. Therefore, attempts have been made to solve the problems related to these properties and to mix as much LCO as possible. For example, in JP-A-10-298586 (Patent Document 1), storage is performed while using a large amount of LCO as a base material. formulations for obtaining excellent stability a fuel oil composition is disclosed. And according to this blending, by mixing more than a certain ratio of direct degassing light oil (light oil obtained from direct heavy oil desulfurization equipment), storage stability and hue stability while mixing 40-60% by volume using LCO as a base material. , it is possible to obtain a a heavy oil composition excellent in passing oil.

On the other hand, recently, environmental problems have been regarded as important, and various improvements to fuel oil have been attempted in order to improve exhaust gas properties from internal combustion engines such as automobile engines or reduce greenhouse gas emissions. An attempt has also been made to satisfy the exhaust gas characteristics (referring to the performance of improving exhaust gas properties, which is the same hereinafter) required by society for A heavy oil. For example, Japanese Patent Application Laid-Open No. 2007-231119. No. (Patent Document 2) discloses an A heavy oil composition capable of reducing unburned substances and particulate matter (PM) in exhaust gas, and Japanese Patent Application Laid-Open No. 2007-231120 (Patent Document 3) A heavy oil composition capable of reducing soot concentration in exhaust gas is disclosed.
JP-A-10-298666 JP 2007-231119 A JP 2007-231120 A

  However, the properties of the A heavy oil composition are based on the relationship between the base materials. When attention is paid to only one property, even if sufficient properties can be obtained for that property, other properties are necessary. May not meet the properties. In fact, the formulation disclosed in Patent Document 1 has a problem that the exhaust gas characteristics required by society cannot be sufficiently satisfied. On the other hand, the heavy oil composition disclosed in Patent Document 2 has a problem of A heavy oil. It is unclear whether the required low-temperature characteristics and storage stability are satisfied, and how much LCO can be used. In addition, the heavy oil composition disclosed in Patent Document 3 is further required for use in diesel engines. there is also a problem that can not meet the cetane number.

  Therefore, the present invention is an A heavy oil composition that is excellent in exhaust gas characteristics and greenhouse gas emission (carbon dioxide emission) reduction effects while using LCO as a base material as much as possible, and satisfies the properties required for A heavy oil. The purpose is to provide.

The A heavy oil composition according to the present invention does not contain a residual coal modifier, contains light cycle oil (LCO), biomass fuel, and Fischer-Tropsch synthetic oil, and the blending ratio of the light cycle oil is 20 to 45% by volume. The blending ratio of the biomass fuel is 30 to 45% by volume, and the blending ratio of the Fischer-Tropsch synthetic oil is 25 to 50% by volume .

In the present invention, the biomass fuel is a biomass-derived fuel, and bioethanol, biomethanol, biobutanol, esterified oil of vegetable oil, vegetable oil hydrotreated oil, and the like correspond to this. In addition, there is no restriction | limiting in the animals and plants used as a raw material, What is necessary is just to select suitably.
Plants, which are raw materials for biomass fuel, grow by taking in carbon dioxide, so theoretically, the concept of “carbon neutral” can be applied in which the total amount of carbon dioxide on the earth does not increase even when burned as fuel. Therefore, when biomass fuel is used, carbon dioxide emission during combustion, that is, greenhouse gas emission can be reduced as fuel.

  The esterified oil of vegetable oil is made from vegetable oil such as rapeseed oil, soybean oil, palm oil, sunflower oil, cottonseed oil, castor oil, corn oil, alkyl alcohol such as methanol, and a known method, that is, an alkaline catalyst such as sodium hydroxide. it can be obtained by reacting by a method using such. For example, rapeseed oil methyl ester (RME) is obtained by an ester reaction of rapeseed oil and methanol. Rapeseed oil methyl ester, soybean oil methyl ester (SME), palm oil methyl ester (PME), sunflower oil methyl ester, cottonseed oil methyl ester, castor oil methyl ester, corn oil methyl obtained by esterification reaction of vegetable oil and alkyl alcohol Fatty acid alkyl esters such as esters may be used alone or in combination.

  In the present invention, the residual coal modifier refers to an agent added to give 10% residual carbon necessary for the A heavy oil composition to be handled as tax heavy oil. It is added to almost all commercial A heavy oils, and includes atmospheric residual oil, vacuum residual oil, desulfurized residual oil, slurry oil, and extract.

A fuel oil composition according to the present invention, the Fischer-Tropsch synthetic oil (hereinafter, referred to as FT synthetic oil) you further contain.

  In the present invention, FT synthetic oil is a fuel obtained by synthesizing raw materials such as natural gas, coal, and biomass by Fischer-Tropsch synthesis. This FT synthetic oil is often called according to the raw material. For example, natural gas is used as GTL, coal is used as CTL, and biomass is used as BTL. There are many cases. On the other hand, the term GTL is sometimes used as a generic term for fuels obtained by Fischer-Tropsch synthesis. In the present invention, the term FT synthetic oil is used as a generic term for fuels obtained by Fischer-Tropsch synthesis. GTL, CTL, BTL, etc. shall be included in the FT synthetic oil. In addition, since BTL uses biomass as a raw material, there is a concept that it is included in the biomass fuel. However, in the present invention, BTL is included in FT synthetic oil.

Further, Blend ratio when having containing an FT synthetic oil, LCO 20 to 45 volume%, FT synthetic oil is 25 to 50 volume% and more preferably 25 to 45 volume%, with 30 to 45 volume% biomass fuel is there.

  According to the A heavy oil composition according to the present invention, the LCO blending ratio can be increased by using biomass fuel as a base material together with LCO in a predetermined blending ratio or more, and LCO can be effectively utilized. Moreover, it has the characteristics of low sulfur content, excellent exhaust gas characteristics and storage stability, and the ability to reduce carbon dioxide emissions. Other properties such as low-temperature fluidity, oxidation stability, and 10% residual carbon content are existing A Since it is equivalent to heavy oil and has the cetane number necessary for diesel engine applications, it can be used without problems as A heavy oil fuel. Note that the reduction of carbon dioxide emission here means reduction of the entire global environment (reduction of greenhouse gases) as well as reduction of the amount of carbon dioxide contained in the exhaust gas. As already mentioned, plants that are raw materials for biomass fuels grow by taking in carbon dioxide, so using biomass fuel instead of mineral oil that releases carbon buried in the ground as carbon dioxide to the atmosphere, It leads to a reduction of carbon dioxide in global environment. Therefore, according to the first and second A heavy oil compositions according to the present invention, carbon dioxide emissions (greenhouse gas emissions) can be reduced by using biomass fuel as a base material.

  Further, by using FT synthetic oil as a base material in addition to biomass fuel in combination with LCO, the blending ratio of LCO can be increased depending on the type of biomass fuel.

  However, the lower limit of the blending ratio of LCO is 20% by volume. When the blending ratio is lowered, low-temperature properties such as pour point and cloud point are deteriorated. On the other hand, the upper limit is 45% by volume, and if the blending ratio is high, the cetane number (usually 40 or more) required for the A heavy oil composition may not be obtained. The cause of the decrease in cetane number is a decrease in the blending ratio of biomass fuel that is also used as a base material. In addition, the cetane number of biomass fuel is usually higher than LCO, for example, about 55 to 65 for FAME (vegetable oil methyl ester) which is an esterified oil of vegetable oil, and about 100 for vegetable oil hydrotreated oil.

Furthermore, if containing FT synthetic oil, the upper limit of the mixing ratio of the FT synthetic oil shall be the 50% by volume considering the cold flow properties. On the other hand, it is preferable that the biomass fuel has a blending ratio as high as possible. The higher the blending ratio, the lower the carbon dioxide emission. However, considering the cetane number, the lower limit of the total of the biomass fuel and the FT synthetic oil is preferably 50% by volume, and considering the balance of properties such as low-temperature fluidity, the lower limit of the FT synthetic oil is 25 volume%, the lower limit value of the biomass fuel shall be the 30% by volume.

  LCO is excellent in low temperature characteristics and oxidation stability, but inferior in cetane number, esterified oil of vegetable oil is inferior in low temperature characteristics and oxidation stability, and FT synthetic oil is inferior in low temperature characteristics. has a property to deteriorate the properties required for the a heavy oil composition. However, according to the blending ratio of the present invention, it is possible to moderately suppress deterioration of properties as the A heavy oil composition caused by each base material, and satisfy the properties necessary for actual use as A heavy oil.

  The A heavy oil composition according to the present invention has the same properties as existing A heavy oil, as described above. However, if even better properties are required due to circumstances such as the use situation or use area, low temperature fluidity improver, antioxidant, cetane improver, rust inhibitor, metal deactivator, corrosion prevention as required various additives such as one or more agents may each be added in an appropriate amount.

  The following property test was carried out on the A heavy oil composition obtained by mixing LCO, biomass fuel and FT synthetic oil having the properties shown in Table 1 and produced in a normal production process. In addition, rapeseed oil methyl ester (hereinafter referred to as RME) was used as the biomass fuel, and a gas oil equivalent fraction (hereinafter referred to as GTL light oil) derived from natural gas was used as the FT synthetic oil.

<Density> Measured according to JIS K 2249 “Crude oil and petroleum products—Density test method and density / mass / volume conversion table”.
<Kinematic viscosity> Measured according to JIS K 2283 "Crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method".
<Distillation Properties> Measured according to JIS K 2254 “Petroleum Products—Distillation Test Method”.
<Sulfur content> Measured according to JIS K 2541-2 “Crude oil and petroleum products—Sulfur content test method Part 2: Micro-coulometric oxidation method”. In addition, about the Example, comparative example, and commercially available A heavy oil which are mentioned later, it measured by JISK2541-4 "Crude oil and petroleum products-Sulfur content test method Part 4: Radiation type excitation method".
<Cetane number> It was measured according to JIS K 2280 "Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method".
<Pour Point> Measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
<Cloud point> Measured according to JIS K 2269 “Pour point of crude oil and petroleum product and cloud point test method of petroleum product”.
<Clogging point> Measured according to JIS K 2288 "Petroleum products-light oil-clogging point test method".
<10% Residual Carbon Content> Measured according to JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
<Oxidation stability> It measured by EN14112 [Fat and oil derivatives-Fatty Acid Methyl Esters (FAME) -Determination of oxidation stability (accelerated oxidation test)]. If it is 15.0 hours or more, it is considered that there is no problem in the oxidation stability performance, and if it is less than 15.0 hours, the oxidation stability performance is regarded as poor.
<Storage Stability> The peroxide value of a sample after being stored at 43 ° C. for 4 weeks while being protected from light was measured using JPI-5S-46-96 “Testing Method for Peroxide Value of Kerosene”. When the peroxide value was 40 mg / kg or less, the storage stability performance was good, and when it was 40 mg / kg or more, the storage stability performance was poor.
<CO ₂ reduction effect>
Each greenhouse gas emission value of LCO, RME, and GTL diesel oil is “Well-to-Wheel evaluation of transportation fuel. Research on greenhouse gas emissions centering on transportation fuel production in Japan (Well-to-Tank)” Report November 2004 Toyota excerpts from Toyota Motor Corporation and Mizuho Information & Research Co., Ltd.
<PM emissions>
Using a diesel engine DY23 (produced by Fuji Heavy Industries Ltd.) with a displacement of 0.23 L, exhaust gas under operating conditions of 3000 rpm and 91% load was introduced into the dilution tunnel, and the PM weight and dilution collected by the filter The weight was calculated from the measured values of the exhaust gas flow rate and the sampling flow rate, and the PM emission amount (g / h) was obtained.
<THC emissions>
Using a diesel engine DY23 (made by Fuji Heavy Industries Ltd.) with a displacement of 0.23L, exhaust gas under operating conditions of 3000 rpm and 91% load was introduced into the dilution tunnel, detected by a FID detector, and exhaust gas From the dilution rate and the diluted exhaust gas flow rate, the THC emission value (g / h) was determined.

Table 2 shows the blending ratio of the A heavy oil composition obtained by mixing these base materials and the properties measured by the above test. For reference, the properties of commercially available A heavy oil composition samples are also shown.

As shown in Table 2, the actual Example 1, while containing a large amount of LCO, less sulfur content, exhaust emissions, excellent storage stability, has the characteristics of reducing carbon dioxide emissions, low temperature fluidity In addition, other properties such as oxidation stability were the same as existing heavy oil A, and it was confirmed that it had the cetane number necessary for diesel engine applications. That is, it was confirmed that the exhaust gas characteristics were excellent while satisfying the properties required for the heavy fuel oil composition A.
In addition, LCO is excellent in low temperature characteristics and oxidation stability, but inferior in cetane number, esterified oil of vegetable oil is inferior in low temperature characteristics and oxidation stability, and FT synthetic oil is inferior in low temperature characteristics. Although it has the property which deteriorates the property required for A heavy oil composition, the compounding ratio for giving the required property to A heavy oil composition using these base materials was able to be confirmed. With this blending ratio, it is possible to reduce the PM emission amount while containing a residual carbon component (measured with a 10% residual carbon amount) similar to that of the conventional A heavy oil. Therefore, it was also confirmed that this blending ratio is effective for improving the exhaust gas characteristics.
Further, it was found from Comparative Examples 1 and 2 that the pour point and cloud point deteriorate as the LCO blending ratio decreases.

Claims (1)

Does not contain residual coal modifier, contains light cycle oil, biomass fuel and Fischer-Tropsch synthetic oil, the blending ratio of the light cycle oil is 20 to 45 vol%, the blending ratio of the biomass fuel is 30 to 45 vol% A fuel oil composition , wherein the blending ratio of the Fischer-Tropsch synthetic oil is 25 to 50% by volume .