JP2011063780A - Gas oil composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a gas oil composition which is effective for reduction of exhaust gas (especially particulate matter), with which particular enhancement of moisture control in a flow system is not necessary, and which prevents lowering of flash point observed in ethanol-mixed gas oil and does not deteriorate combustion efficiency. <P>SOLUTION: The gas oil composition has density at 15°C of 0.810-0.900 g/cm<SP>3</SP>, a sulfur content of 10 mass ppm or less, a cetane number of 42-65, a moisture content of equal to or more than 1 vol.% and less than 10 vol.%, and an ethanol content of 1-20 vol.%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a diesel oil composition for a diesel engine and a method for producing the diesel oil composition, and more particularly to a diesel oil composition containing an emulsion of an aqueous ethanol solution and a diesel oil base.

Improving the air environment is an urgent and extremely important global issue, and automobiles are strongly required to “simultaneously reduce CO ₂ and harmful emissions”. The automotive industry is responding to this social demand by improving engines and exhaust gas purification catalysts, remodeling the body (lightening, etc.), and introducing hybrid vehicles. In the petroleum industry, CO ₂ and harmful emissions are reduced by improving fuel quality (for example, reducing sulfur content in fuel) and introducing biofuel. In particular, biofuel derived from vegetable oil, which is carbon neutral, is recognized as important from the viewpoint of energy security through the introduction of non-petroleum fuel in addition to the improvement of the atmospheric environment.

Therefore, as gasoline, ethanol-mixed gasoline obtained by directly mixing biomass-derived absolute ethanol, and ETBE-mixed gasoline produced by producing ethyl tertiary butyl ether (ETBE) from ethanol and mixing the ETBE are put into practical use. On the other hand, as a light oil, a FAME mixed light oil obtained by producing a fatty acid methyl ester (FAME) from a vegetable oil and mixed with the light oil has been put into practical use. Further, commercialization of paraffinic light oil produced from vegetable oil by FT synthesis or hydrocracking is also planned. Furthermore, in addition to expanding the use of ethanol, in order to reduce particulate matter (PM), which is a drawback of diesel engines, mixing ethanol with light oil has attracted attention. However, mixing ethanol with light oil is effective in terms of improving the air environment and diversifying fuels, but has the following drawbacks. ing.
(1) Ethanol does not dissolve in light oil.
(2) The flash point of the mixture decreases.
(3) The fuel consumption deteriorates.
(4) The cetane number decreases.

  In particular, the above solution (1) is important for practical use. Therefore, a compatibilizer is used, but as a compatibilizer, the use of FAME has been proposed from the viewpoint of biofuel introduction, that is, a mixture of light oil / ethanol / FAME is reported to be effective. Has been made. However, even if FAME is used, phase separation occurs with a slight water content, for example, 0.1 wt% water (Non-Patent Document 1). Therefore, the ethanol to be used requires a product with a very low water content, and at the same time, requires strict water management in the distribution system of the mixture, which is a big obstacle from the viewpoint of practicality and economy.

On the other hand, dehydration of ethanol is a problem from the viewpoint of CO ₂ reduction related to bioethanol production. According to one estimate, distillation for bioethanol purification consumes 23% of total CO ₂ emissions from ethanol production and 14% for dehydration. There is also a study of putting hydrous ethanol directly into a premixed compression ignition (HCCI) engine (Non-patent Document 2). However, the HCCI engine is a future engine having excellent characteristics, but has not yet been put into practical use. In addition, from the viewpoint of CO ₂ reduction, in the present situation where it is desired to spread and expand a diesel engine having better fuel efficiency characteristics than a gasoline engine, water-containing ethanol (that is, CO ₂ reduction during production, If it is possible to use ethanol that can avoid phase separation due to water contamination, it is extremely beneficial from the viewpoint of energy security in addition to the improvement of the atmospheric environment. Furthermore, since the flash point of ethanol-mixed light oil is lowered to room temperature or lower, which is a concern from the viewpoint of safety associated with handling of the composition, it is a problem to be solved practically.

  On the other hand, diesel oil and water emulsions have the effect of improving fuel economy in addition to reducing emissions, and in urban areas in Europe, they are supplied to diesel vehicles such as buses as clean diesel oil to reduce PM. It is used for practical use. However, despite the development of emulsion manufacturing methods and surfactants and technical advances, the emulsion PM reduction effect is relatively small, from the viewpoint of cost-effectiveness focusing on PM reduction, etc. Light oil and water emulsions have not been put into practical use at present (Non-patent Document 3).

Ludivine Pidol, “Ethanol as a Diesel Base Fuel: Managing the Flash Point Issue-Consequences on Engine Behavior”, SAE Paper 2009-01-1807 (2009) Daniel L. Flowers, “Improving Ethanol Life Cycle Energy Efficiency by Direct Utilization of Wet Ethanol in HCCI Engines”, SAE Paper 2009-01-1867 (2009) E. Tzirakis, “Diesel-water Emulsion Emission and Performance Evaluation in Public Buses in Attica Basin”, SAE Paper 2006-01-3398 (2006)

As described above, the light oil and water emulsion is not practically used at present, but the emulsion has the following characteristics.
1) Exhaust gas (especially PM) is reduced.
2) The flash point becomes high.
3) Fuel economy is improved.
4) Strict moisture management is not required.

Based on the characteristics of the emulsion, the present inventors have conceived that the emulsion is combined with ethanol-mixed light oil to complement the shortcomings of ethanol-mixed light oil, and a combination of both technologies for improving the air environment and energy security. Then, I studied diligently to solve it. That is, an object of the present invention is to achieve improvement of the air environment and energy security by “light oil emulsion using hydrous ethanol”, and more specifically, “wet water to reduce CO ₂ during ethanol production”. “Effective in reducing exhaust gas (especially PM)”, “No need to specially strengthen water management in distribution system”, “Ethanol mixing” It is to develop a light oil composition that can prevent the reduction in flash point seen in light oil and that does not deteriorate combustion efficiency, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have found an ethanol aqueous solution in which water is added to water-containing ethanol (ethanol containing 5% by volume or more of water at the time of production) to make the water content 20-80% by volume. , It is necessary to specially strengthen the water management in the distribution system by supplying the diesel fuel to the diesel engine vehicle by mixing it with commercially available diesel oil in which 0.5 to 3 mass% surfactant is dissolved In addition, the inventors have found that exhaust gas (particularly PM) can be reduced without deteriorating combustion efficiency, and that the reduction in flash point seen in ethanol-mixed light oil can be prevented, thereby completing the present invention.

That is, the light oil composition of the present invention has a density of 0.810 to 0.900 g / cm ³ at 15 ° C., a sulfur content of 10 mass ppm or less, a cetane number of 44 to 65, and a water content of 1% by volume or more and 10 volumes. %, And the ethanol content is 1 to 20% by volume.

  Moreover, the manufacturing method of the light oil composition of this invention is 0.3-surfactant on the light oil base material whose initial boiling point is 130-200 degreeC, an end point is 330-400 degreeC, and a total aromatic content is 40 volume% or less. ~ 5% by mass, 75 to 97% by volume of the mixture of the light oil base and the surfactant, 1 to 20% by volume of ethanol, and 1 to less than 10% by volume of water to make an emulsion Features.

  The light oil composition of the present invention contributes to energy security and prevention of global warming, and has the effect of reducing particulate matter (PM) in the exhaust gas. Furthermore, water management in the distribution system is specially strengthened. In addition, it is possible to suppress a decrease in flash point seen in ethanol-mixed light oil, and in addition, there is a special effect that combustion efficiency is good.

  Details of the present invention will be described below. The light oil composition of the present invention is a light oil composition obtained by mixing ethanol, water, and a light oil base material into an emulsion, and is a fuel for a diesel engine having the following properties.

<Density>
The light oil composition of the present invention has a density at 15 ° C. of 0.810 to 0.900 g / cm ³ . When the density of the light oil composition exceeds 0.900 g / cm ³ , the effect of reducing particulate matter (PM) due to the emulsion is reduced and cannot contribute to the improvement of the atmospheric environment. Therefore, the density is 0.900 g / cm ³ or less, Preferably it is 0.880 g / cm < ³ > or less, More preferably, it is 0.860 g / cm < ³ > or less. On the other hand, if the density is less than 0.810 g / cm ³ , the calorific value based on the capacity is lowered and the fuel consumption and output are significantly reduced. Therefore, the density is 0.810 g / cm ³ or more, preferably 0.820 g / cm ^{3. 3} or more, more preferably 0.830 g / cm ³ or more.

<Sulfur content>
The gas oil composition of the present invention has a sulfur content of 10 mass ppm or less, preferably 9 mass ppm or less, more preferably 7 mass ppm or less. Since the light oil composition of the present invention has a sulfur content of 10 ppm by mass or less, there are few sulfur oxides as combustion products, which can contribute to reduction of environmental burden. Further, since the sulfur content poisons a DPF (diesel particulate filter) catalyst that oxidizes and removes PM, reduction of the sulfur content is extremely important in order to maintain the PM purification rate. Furthermore, in a vehicle equipped with a NOx occlusion reduction catalyst, fuel is used for regeneration of sulfur poisoning of the catalyst. Therefore, reduction of the sulfur content also contributes to improvement of fuel consumption. And since these effects are so remarkable that a sulfur content is low, the sulfur content in the light oil composition of this invention becomes like this. Preferably it is 9 mass ppm or less, More preferably, it is 7 mass ppm or less.

<Distillation properties>
The distillation property of the light oil composition of the present invention is defined by the property of the base light oil (hereinafter referred to as a light oil base) used to produce the emulsion (distilling the emulsion destroys the emulsion and obtains an accurate distillation property. Can't). The light oil base used in the production of the light oil composition of the present invention has an initial boiling point (IBP) of 130 to 200 ° C, preferably 140 to 180 ° C, more preferably 160 to 180 ° C. When the initial boiling point is lower than 130 ° C., there is a concern that fuel vapor is generated in the fuel injection system under high temperature conditions, and a necessary fuel injection amount cannot be secured. In addition, if the initial boiling point is too low, the danger associated with handling in the fuel distribution system increases, so the initial boiling point must be 130 ° C. or higher. Further, when the initial boiling point exceeds 200 ° C., the atomization and vaporization characteristics of the light oil deteriorate, so there is a concern that the engine operability deteriorates under low temperature conditions. Furthermore, light oil having an excessively high initial boiling point is not preferable from the viewpoint of noble use of oil because the light fraction in the light oil base is not used as light oil.

  On the other hand, the end point (EP) of the light oil base is 330 to 400 ° C, preferably 350 to 370 ° C, more preferably 350 to 360 ° C. When the end point exceeds 400 ° C., the increase in particulate matter (PM) emission becomes significant, and the environmental load cannot be reduced sufficiently. Further, when the end point is lowered, the PM emission amount is reduced, but the heavy fraction in the light oil base material is not used, which is not preferable from the viewpoint of noble use of petroleum. Furthermore, if the end point is too low, the calorific value is remarkably lowered, and the end point is 330 ° C. or more because the capacity fuel consumption is deteriorated.

<Cetane number>
The light oil composition of the present invention has a cetane number of 42 to 65, preferably 44 to 60, and more preferably 45 to 50. If the cetane number is less than 42, the deterioration of ignitability under low temperature starting conditions of the diesel engine causes deterioration of exhaust gas and operability. Therefore, the cetane number is 42 or more, preferably 44 or more, more preferably 45. That's it. On the other hand, if the cetane number exceeds a certain value, the ignition delay accompanying the improvement of the cetane number cannot be shortened. Therefore, it is meaningless from the standpoint of engine performance to increase it higher than necessary. Further, in order to increase the cetane number, it is necessary to increase the cetane number of the light oil base material. Therefore, not only the CO ₂ emission amount during production increases but also the fuel production price increases. Therefore, since it is necessary to set the minimum cetane number required by the engine from the viewpoint of economy, the cetane number of the light oil composition of the present invention is 65 or less, preferably 60 or less, more preferably 50 or less. It is.

<Aromatic content>
The light oil base used in the production of the light oil composition of the present invention has a total aromatic content of 40% by volume or less, preferably 30% by volume or less, and more preferably 25% by volume or less. If the aromatic content in the light oil base increases too much, the amount of particulate matter (PM) discharged increases, so the PM reduction effect by the emulsion is offset, so the total aromatic content of the light oil base is 40% by volume or less. Although not particularly limited, since aromatics having two or more rings have a greater effect on PM emissions than single-ring aromatics, the content of aromatics having two or more rings in the light oil base is as follows: Preferably it is 5 volume% or less, More preferably, it is 2 volume% or less.

<Elemental analysis>
The gas oil composition of the present invention is not particularly limited, but the hydrogen / carbon molar ratio (H / C) is preferably 1.85 or more, more preferably 1.87 or more, and particularly preferably 1.89. That's it. When the H / C ratio of the light oil composition is reduced, the emission amount of particulate matter (PM) is increased, and in addition, the CO ₂ emission amount per unit calorific value of the fuel is increased, so that the CO ₂ emitted from the engine is increased. Will increase.

<Flash point>
The flash point is an important property that affects the safety of handling the light oil composition, and it is necessary to handle it with extreme caution when the flash point is below room temperature. Therefore, the flash point of the light oil composition of the present invention is preferably 20 ° C. or higher, more preferably 25 ° C., and particularly preferably 27 ° C. or higher.

<Moisture>
In order to produce a stable emulsion, the light oil composition of the present invention preferably contains 20 to 80% by volume of water in the total of ethanol and water (hereinafter referred to as an ethanol aqueous solution), more preferably 30 to 70%. It is volume%. In order to reduce the amount of CO ₂ emission during ethanol production, which is the object of the present invention, the water content of the aqueous ethanol solution is preferably 5% by volume or more. Further, in order to produce a stable emulsion over a long period of time. It is preferable that the water | moisture content in ethanol aqueous solution is 20-80 volume%. That is, when the water content exceeds this range, it is difficult to economically produce a stable emulsion even when a surfactant is used. “To maintain the emulsion, the stirrer for the light oil composition is on-site. Restrictions such as “wear on” or “use for a short time” occur. Furthermore, if the water content is too high (the ethanol content is too low), the amount of biofuel used becomes too small, so that the object of the present invention cannot be achieved and is not practical. 80% by volume is preferred.

Moreover, the water | moisture content of the light oil composition of this invention is 1 volume% or more and less than 10 volume%, Preferably it is 2 volume% or more and less than 10 volume%. In order to economically and practically produce a stable emulsion, the water content of the light oil composition needs to be less than 10% by volume. Further, in the water is less than one volume percent of the gas oil composition, or increase CO ₂ Emissions during ethanol production, is possible to produce stable emulsions over a long period of time becomes difficult.

<Ethanol>
The light oil composition of the present invention has an ethanol content of 1 to 20% by volume, preferably 3 to 20% by volume, and more preferably 3 to 15% by volume. If the content of ethanol is less than 1% by volume, the effect of the present invention due to the addition of ethanol cannot be obtained. On the other hand, if the content exceeds 20% by volume, the ignitability of the light oil composition is significantly deteriorated. The content of is 1 to 20% by volume. The ethanol used may be water-containing ethanol in which the dehydration step is omitted or dehydrated absolute ethanol. Moreover, it is preferable that the ethanol to be used is derived from biomass from the viewpoint of reducing CO ₂ generated when the light oil composition is burned by a diesel engine.

In the light oil composition of the present invention, the mixing amount of the aqueous ethanol solution is preferably 3 to 25% by volume, more preferably 3 to 20% by volume, particularly 5 to 20% by volume. When the mixing amount of the ethanol aqueous solution exceeds 25% by volume, water-containing ethanol has extremely low ignitability. Therefore, in order to secure the cetane number of 42 or more necessary for the light oil composition, the cetane number of the light oil base to be used is set. The use of a cetane number improver not only increases CO ₂ emissions during production, but is also inappropriate from the viewpoint of economy. On the other hand, in order to reduce CO ₂ , the light oil composition of the present invention preferably contains as much ethanol as possible. Also, in order to obtain a larger PM reduction effect by ethanol, since a large amount of ethanol is desired to be mixed, the ethanol content of the light oil composition of the present invention is 1% by volume or more, preferably 3% by volume or more. . From the viewpoint of simultaneously satisfying the suitable range of the ethanol content in the light oil composition and the water content in the aqueous ethanol solution, the mixed amount of the aqueous ethanol solution is preferably 3% by volume or more, and more preferably 5% by volume or more.

<Additives>
(Surfactant)
In the light oil composition of the present invention, use of a surfactant for ensuring storage stability is effective. As the surfactant, ethoxyamine, which is a nonionic surfactant, is effective. Moreover, 0.3-5 mass% is preferable with respect to the said light oil base material, and, as for the addition amount of this surfactant, More preferably, it is 0.5-3 mass%. If the addition amount of the surfactant is less than 0.3% by mass, it is difficult to ensure sufficient storage stability of the emulsion (light oil composition). On the other hand, if it exceeds 5% by mass, the effect of improving the storage stability is obtained. Further improvement is not achieved and the manufacturing cost increases.

(Cetane improver)
A cetane number improver may be added to the light oil composition of the present invention as necessary, and as the cetane number improver, an alkyl nitrate cetane number improver or an organic peroxide cetane number improve Agents. Here, as said alkyl nitrate type | system | group cetane number improver, a C6-C12 alkyl nitrate is preferable and 2-methylhexyl nitrate is especially preferable. Moreover, as said organic peroxide type | system | group cetane number improver, a C6-C12 dialkyl peroxide is preferable and di-t-butyl peroxide is especially preferable. And the addition amount of these cetane improvers is preferably 0.5% by mass or less, and more preferably 0.1% by mass or less. Increasing the amount of cetane number improver increases the cetane number, but the rate of increase becomes extremely small when the amount added exceeds 0.5% by mass. Therefore, the addition amount is preferably 0.5% by mass or less.

(Other additives)
Further, the light oil composition of the present invention optionally includes an antioxidant for ensuring the stability of the light oil composition, a low temperature fluidity improver for ensuring the low temperature fluidity of the light oil composition, and a light oil composition. It is possible to appropriately add a lubricity improver for ensuring the lubricity and a detergent for ensuring the cleanliness of the engine.

  Here, as the antioxidant, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,4-dimethyl-6-t-butylphenol, 2,4 , 6-tri-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2-t-butylphenol, and other phenolic antioxidants, N, N′-diisopropyl-p-phenylenediamine, N, Examples thereof include amine antioxidants such as N′-di-sec-butyl-p-phenylenediamine, and mixtures thereof. Here, the addition amount of these antioxidants is preferably in the range of 0.001 to 0.10% by mass. This is because the effect of addition of the antioxidant is great, so that practically sufficient effect can be obtained by adding 0.10% by mass.

  Examples of the low temperature fluidity improver include known ethylene copolymers, and vinyl esters of saturated fatty acids such as vinyl acetate, vinyl propionate and vinyl butyrate are particularly preferable. The addition amount of these low-temperature fluidity improvers is not particularly limited, and can be appropriately selected according to the purpose.

  Examples of the lubricity improver include long-chain (for example, having 12 to 24 carbon atoms) fatty acids or fatty acid esters thereof. And by adding 10 to 500 mass ppm, preferably 50 to 100 mass ppm of the lubricity improver to the light oil composition, the lubricity of the light oil composition is improved and the wear of the fuel injector is suppressed. Can do.

  Examples of the detergent include succinimide, polyalkylamine, and polyetheramine. The addition amount of these detergents is not particularly limited, and can be appropriately selected according to the purpose.

(Preparation of light oil base)
The light oil base material used in the present invention is, as a raw material oil, various gas oil fractions obtained from, for example, an atmospheric distillation apparatus, a catalytic cracking apparatus, a thermal cracking apparatus, etc., that is, a boiling point range from an initial boiling point to an end point (hereinafter, It is obtained by appropriately mixing and hydrodesulfurizing using a fraction distilled in a range of 140 to 400 ° C. (boiling point range), or by mixing appropriately after hydrodesulfurization, but is a raw material rich in aromatics When processing oil, it is effective to increase the reaction temperature and hydrogen partial pressure and to increase the hydrogen / oil ratio in order to keep the sulfur content and aromatics of the product within predetermined ranges. In addition, since the raw material oil containing a lot of aromatics contains a lot of difficult desulfurization components, it is necessary to use a catalyst that selectively removes sulfur in hydrodesulfurization.

The hydrodesulfurization uses a hydrogenation catalyst containing one or more of Co, Mo and Ni, and optionally carrying P, with a reaction temperature of 270 to 380 ° C., preferably 295 to 360 ° C., a reaction pressure of 2. Conditions of 5-8.5 MPa, preferably 2.7-7.0 MPa, LHSV 0.9-6.0 h ⁻¹ , preferably 0.9-5.4 h ⁻¹ , hydrogen / oil ratio 130-300 Nm ³ / kL It is good to select suitably from above so that the above-mentioned light oil base material may be obtained.

  In the present invention, the hydrodesulfurized gas oil fraction is a kerosene fraction, a by-product fraction when producing GTL, BTX, a by-product fraction when producing a lubricating oil, a normal paraffin compound, a normal paraffin series. Solvent, isoparaffin compound, isoparaffin solvent, aromatic compound, aromatic solvent, biomass-derived fuel substrate, naphthene compound, naphthenic solvent, etc. are appropriately blended to prepare a light oil substrate suitable for the above properties and quality. Can be prepared.

(Preparation of light oil composition)
The light oil composition of the present invention is obtained by forming an emulsion of an aqueous ethanol solution and the light oil base material. In the light oil composition of the present invention, a solution obtained by dissolving a predetermined amount of the above surfactant in the above light oil base and further mixing a predetermined amount of the above aqueous ethanol solution is stirred until an emulsion state is obtained. Can be obtained. What is necessary is just to stir for 3 to 10 minutes, for example using a vacuum stirrer. The emulsion state is visually confirmed that the solution after stirring is not phase-separated at normal temperature and pressure. In addition, if the emulsion state is stable, for example, phase separation is not recognized even if it is allowed to stand at room temperature and normal pressure for 1 week after stirring.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of light oil composition>
Light oil compositions (Fuel-1 to Fuel-7) prepared as follows were evaluated. Table 1 shows the analysis results of these fuels.

・ Fuel-1: Commercial JIS No. 2 diesel oil ・ Fuel-2: Ethanol-containing diesel oil in which 10% by volume of absolute ethanol is mixed with fuel-1 ・ Fuel-3: Five volumes of distilled water to fuel-1 with added surfactant Emulsified diesel oil / fuel-4%: Surfactant added to fuel-1 Emulsion-containing emulsion gas oil / fuel-5: Surfactant added with 5% by volume absolute ethanol and 5% by volume distilled water Ethanol-containing emulsion gas oil / fuel-6 with 10% by volume of absolute ethanol and 5% by volume of distilled water mixed with fuel-1: 20% by volume of absolute ethanol and 10 volumes of distilled water to fuel-1 with added surfactant % High-concentration ethanol-containing emulsion gas oil and fuel-7: absolute ethanol

<Preparation of emulsion>
The emulsion was produced by the following method.
Lubrizol 1002 (trade name) manufactured by Lubrizol, a surfactant, was added to the base light oil (light oil base material, fuel-1) in the preparation of fuel-3 to fuel-5, and 2% by weight in the preparation of fuel-6. Was added by 4% by mass and dissolved by stirring manually. This continuous phase is mixed with water-containing ethanol (ethanol aqueous solution) in which reagent-grade absolute ethanol and distilled water are mixed at a specified ratio, and an EME vacuum stirrer V-MINI 300 is rotated at a rotation speed of 600 rpm and a revolution speed of 300 rpm for 4 minutes. Stir to make an emulsion. Furthermore, it was confirmed that the emulsion did not phase separate even when allowed to stand at room temperature and normal pressure for 1 week.

<Fuel property analysis>
・ Density: JIS K2249 “Density test method for crude oil and petroleum products”
・ Distillation properties: JIS K2254 "Distillation test method"
・ Sulfur content: JIS K2541-6 “Sulfur content test method (ultraviolet fluorescence method)”
-Total aromatic content, aromatic content of 2 or more rings: Petroleum Society method JPI-5S-49-97 "Petroleum products-Hydrocarbon type test method-High performance liquid chromatographic method"
-Cetane number: JIS K2280 "Petroleum products-Fuel oil-Octane number and cetane number test method and cetane index calculation method"
-Flash point: JIS K2265-1 "How to find the flash point-Part 1: Tag sealing method"
-H component, C component, O component: Measured using an organic element analyzer (CHN-1000 type manufactured by LECO).

-Naphthene content: It measured using GC system which consists of GC-6 with the HP-6890N type FID detector by Agilent Technologies, and AccuTOF JMS-T100GC time-of-flight mass spectrometer made by JEOL. Detailed analysis conditions are as follows.
Primary column: Micropolar column (PTE-5 manufactured by Supelco, length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm), modulator hollow column: length 2 m, inner diameter 0.1 mm
Secondary column: High-polarity column (SpelcoWAX10 from Supelco, length 2 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Temperature rising condition: 10 ° C./min (from 50 ° C. (5 min hold) to 280 ° C. (27 min hold))
Inlet temperature: 280 ° C
Injection volume: 1.0 μl
Split ratio: 100: 1
Carrier gas: helium (He), 1.0 ml / min Modulator temperature: The following cold temperature and hot temperature are repeated.
Hot jet gas temperature: The temperature was raised from 150 ° C. (5 minutes hold) to 320 ° C. (33 minutes hold) at 10 ° C./min.
Cold jet gas temperature: about -140 ° C
Modulator frequency: 6 seconds for 0.3 seconds hot temperature, then 5.7 seconds for cold temperature.
Interface hollow column: 0.5m length, 0.25mm inner diameter
FID gas conditions: hydrogen (45 mL / min), air (450 mL / min), make-up helium (25 mL / min)
Here, the GC system can measure a compound having 7 to 44 carbon atoms, and the compound corresponding to each peak (yamagata) is identified from the elution time and mass spectrum of the measured peak (yamagata). To do. The sum of all identified peaks (yamagata) is defined as the total content (100 peak volume%), and the content of each corresponding compound is calculated as the peak volume% from each peak (yamagata). To do.

<Test engine specifications and operating conditions>
Direct injection diesel engine Number of cylinders: 1
Displacement: 1007 (cm ³ )
Compression ratio: 20
Fuel injection system: common rail, high pressure injection

  The engine rotation speed was fixed at 1300 (rpm), and the exhaust gas and combustion efficiency were measured under 20 (%) and 80 (%) load conditions.

<Engine performance evaluation method>
Combustion analysis: The pressure in the combustion chamber was detected with a pressure sensor, and the combustion behavior such as the indicated mean effective pressure and combustion fluctuation was analyzed with a combustion device manufactured by Shikenken.
Exhaust gas: PM, NOx, HC, CO and CO ₂ in the exhaust gas were analyzed using an exhaust gas analyzer manufactured by Horiba.
Combustion efficiency: The fuel consumption rate (ml / min) was measured with a fuel flow meter manufactured by SHIKENKEN, and the efficiency was calculated from the indicated mean effective pressure (kg / cm ² ) obtained by the combustion analysis described above.

<Method for evaluating and judging engine performance>
Emissions from each fuel in engine tests are based on commercial diesel oil JIS No. 2 diesel oil (fuel-1) as a standard (x) for fuel with more exhaust gas, (△) for equivalent fuel, and fuel for less (○), markedly less fuel is represented by (◎). Similarly, the combustion efficiency was also relatively evaluated by comparison with fuel-1, and the fuel with poor combustion efficiency was represented as (x), the equivalent fuel (Δ), and the good fuel (◯). These results are shown in Table 1.

<Fuel evaluation results>
As shown in Table 1, the evaluation results of each fuel are as follows.
Fuel-2: Emissions of particulate matter (PM) were reduced by the oxygen-containing effect of ethanol, but there was no improvement in combustion efficiency, and the flash point was lowered to 13 ° C. Moreover, in order to dissolve ethanol in light oil, absolute ethanol is required.

Fuel -3: reduction of PM emissions emulsions effect was seen to improve the combustion efficiency, bioethanol contributes to CO ₂ reduction and energy security improvement is not utilized.

Fuel-4: An emulsion to which water-containing ethanol is added exhibits a remarkable reduction in PM emission and improvement in combustion efficiency, and achieves the object of the present invention. There is no problem in the storage stability of the emulsion.
Fuel-5: An emulsion to which water-containing ethanol has been added shows a remarkable reduction in PM emission and an improvement in combustion efficiency, thus achieving the object of the present invention. There is no problem in the storage stability of the emulsion.

  Fuel-6: High-concentration water-containing ethanol-added emulsion has a worsening of combustion fluctuations estimated to be due to a worsening of ignitability, a significant deterioration of exhaust gases (especially unburned hydrocarbons, carbon monoxide), and combustion efficiency is It was not possible to measure.

Claims (2)

The density at 15 ° C. is 0.810 to 0.900 g / cm ³ , the sulfur content is 10 mass ppm or less, the cetane number is 42 to 65, the water content is 1 volume% or more and less than 10 volume%, and the ethanol content is 1 to 1. A gas oil composition characterized by being 20% by volume. A surfactant is added to a light oil base having an initial boiling point of 130 to 200 ° C., an end point of 330 to 400 ° C., and a total aromatic content of 40% by volume or less, and 0.3 to 5% by mass of a surfactant.
2. The emulsion comprising 75 to 97% by volume of a mixture of the light oil base and a surfactant, 1 to 20% by volume of ethanol, and 1 to 10% by volume of water. A process for producing a diesel oil composition.