JP2004285346A - Low pollution fuel composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low pollution fuel composition comprising ethanol as principle component, usable as it is, for vehicles having conventionally used engine which uses gasoline. <P>SOLUTION: The low pollution fuel composition comprises (a) ethanol, and (b) at least two compounds selected from the group consisting of diisopropyl ether, methyl-t-butyl ether, ethyl-t-butyl ether, dipropyl ether, t-butanol, dibutyl ether and diethyl ether. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to low-pollution fuel compositions. More specifically, the present invention relates to a low-pollution fuel composition containing ethanol as a main component and applicable to engines that use conventionally used gasoline or the like as a fuel.

  Conventionally, petroleum, which is a fossil fuel, has been mainly used as industrial, automobile and other fuels. However, due to the recent massive consumption of petroleum-based fuels, oil reserves are beginning to see their limits.

Also, from an environmental point of view, global warming caused by mass consumption of petroleum fuels has become a major social problem. In particular, in Japan, CO ₂ emitted from the use of petroleum fuel (gasoline) for automobiles accounts for 2.8% of the total CO ₂ emission in Japan, which contributes to global warming. I have.

  Exhaust gas emitted by consumption of petroleum fuel contains unburned hydrocarbons, nitrogen oxides, sulfur oxides, and the like, and is a major factor in air pollution. In addition, Japan relies on imports of petroleum fuel for nearly 98%, and that petroleum fuel accounts for about 80% of Japan's total energy. When this happens, the impact on the Japanese economy is immense.

  As described above, in view of depletion of petroleum resources, deterioration of the global environment due to consumption of petroleum fuel, and energy security, development of a fuel composition as an alternative to petroleum fuel has been an issue.

  In recent years, corn, soybeans, kenaf, natural wood, and ethanol that can be produced in large quantities and at low cost from various raw materials or industrial wastes have attracted attention as fuels for automobiles, and are being studied in various countries around the world. Ethanol is excellent in that it generates a very small amount of toxic oxides during combustion as compared with gasoline and is a so-called clean fuel having a high octane value. However, ethanol has a small calorific value compared to gasoline, a small air-fuel ratio (lean state), a large amount of vaporization heat, making it difficult to start in cold weather, or corroding metals such as current automobile components in Japan, There are drawbacks such as oxidation.

  Until now, an ethanol-mixed gasoline fuel (referred to as E10 or E25 depending on the blending ratio of ethanol) in which ethanol having a water content of 0.3% or less is mixed with gasoline at 5 to 24% has been developed. It is officially used as a vehicle fuel in some countries (for example, see Patent Document 1). However, these ethanol-mixed gasoline fuels have problems in that the amount of ethanol added is small and the value as a petroleum alternative fuel is low, or water is absorbed and gasoline and ethanol are easily separated. Furthermore, in the case of ethanol-mixed gasoline fuel, the higher the ethanol content, the higher the heat of vaporization.Therefore, in order to use a fuel with a high ethanol content, it is necessary to heat the vaporizer or change to an injection type. It required additional equipment and engine modification.

Until now, fuels containing ethanol as a main component and containing substantially no gasoline (hydrocarbons) that can be used in existing engines without the need for heating the carburetor or changing to an injection system It has not been developed yet.
JP 05-202373 A

  Therefore, an object of the present invention is to solve the above conventional problems and to provide a low-pollution fuel composition. Specifically, an object of the present invention is to provide a low-pollution fuel composition which contains ethanol as a main component and can be used as it is in a conventionally used engine which operates on gasoline as fuel.

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and found that ethanol is a main component, and at least one selected from the group consisting of methyl t-butyl ether, ethyl t-butyl ether, dipropyl ether, dibutyl ether and diethyl ether It has been found that a fuel composition containing two compounds has low emission of harmful substances even when burned, has low pollution, and can be used as it is in an engine that operates on gasoline as fuel. The present invention has been completed based on such findings and further studies.

That is, the present invention is a low-pollution fuel composition listed below:
Item 1. A low-pollution fuel composition containing the following components (a) and (b):
(A) ethanol, and (b) at least one selected from the group consisting of t-butanol, di-n-butyl ether, di-t-butyl ether, ethyl t-butyl ether, diisopropyl ether, diethyl ether, dipropyl ether and methyl t-butyl ether. Two compounds.
Item 2. Component (b) is
(B1) at least one selected from the group consisting of t-butanol, di-n-butyl ether, di-t-butyl ether and ethyl t-butyl ether; and (b2) diisopropyl ether, diethyl ether, dipropyl ether and methyl t-butyl ether Item 2. The low-pollution fuel composition according to Item 1, which is at least one mixture selected from the group consisting of:
Item 3. Item 3. The low-pollution fuel composition according to Item 1 or 2, wherein the component (b) is a mixture of t-butanol, diisopropyl ether, diethyl ether and methyl t-butyl ether.
Item 4. Item 4. The low-pollution fuel composition according to any one of Items 1 to 3, wherein the composition contains the component (a) in an amount of 25 to 85 parts by weight per 100 parts by weight of the total amount of the components (a) and (b).
Item 5. Item 5. The low-pollution fuel composition according to any one of Items 2 to 4, wherein the component (b2) is contained in an amount of 30 to 600 parts by weight based on 100 parts by weight of the component (b1).

  Hereinafter, the present invention will be described in detail. The low-pollution fuel composition of the present invention comprises (a) ethanol and (b) t-butanol, di-n-butyl ether, di-t-butyl ether, ethyl t-butyl ether, diisopropyl ether, diethyl ether, dipropyl ether and methyl t-butyl ether. It is characterized by containing at least two compounds selected from the group consisting of butyl ether.

Component (a)
The low-pollution fuel composition of the present invention contains ethanol as a main component as the component (a). Ethanol used in the present invention is not limited in its origin and production method. From the viewpoint of effective utilization of biomass, ethanol produced by fermenting sugar derived from cereals or other biomass (so-called biomass ethanol) is preferred. Further, the ethanol used in the present invention does not necessarily have to have a purity of 100%, and may contain other components such as moisture as long as the effects of the present invention are not impaired. . For example, ethanol used in the present invention has a purity of 87% or more, preferably 99% or more.

Component (b)
In addition, the low-pollution fuel composition of the present invention comprises, as component (b), t-butanol, di-n-butyl ether, di-t-butyl ether, ethyl t-butyl ether, diisopropyl ether, diethyl ether, dipropyl ether and methyl t-butyl ether. Contains at least two compounds selected from the group consisting of butyl ethers. By blending the component (b), the air-fuel ratio and distillation properties are improved, and the fuel composition can have the same calorific value, output, and operating performance as conventional gasoline.

  The combination is not particularly limited as long as two or more of the above compounds are used as the component (b). Examples of a preferred combination include t-butanol, di-n-butyl ether, di-t-butyl ether and ethyl. at least one member selected from the group consisting of t-butyl ether (hereinafter, referred to as component (b1)) and at least one member selected from the group consisting of diisopropyl ether, diethyl ether, dipropyl ether, and methyl t-butyl ether ( Hereinafter, it is referred to as component (b2).) The component (b1) mainly contributes to the improvement of the heat of combustion and the distillation properties, while the component (b2) mainly contributes to the improvement of the flash point and the air-fuel ratio. Therefore, the components (b1) and (b2) are combined. Thereby, a fuel composition having more excellent characteristics can be obtained. Particularly preferred components (b) include those containing t-butanol as component (b1) and those containing diisopropyl ether, diethyl ether and methyl t-butyl ether as component (b2). Further, preferred examples of the component (b) include those containing t-butanol, diisopropyl ether, diethyl ether and methyl t-butyl ether.

  When the component (b1) and the component (b2) are mixed as the component (b), the mixing ratio of the component (b1) and the component (b2) is not particularly limited, but as an example, the component (b1) The ratio is such that the total amount of (b2) is 30 to 600 parts by weight, preferably 40 to 400 parts by weight, and more preferably 50 to 200 parts by weight, based on 100 parts by weight of the total amount of the components.

Fuel Composition The proportion of the components (a) and (b) contained in the low-pollution fuel composition of the present invention is not particularly limited. For example, for example, per 100 parts by weight of the total amount of the components (a) and (b), The proportion of the component (a) is 25 to 85 parts by weight, preferably 25 to 60 parts by weight, more preferably 30 to 60 parts by weight, and particularly preferably 40 to 60 parts by weight. Further, as a blending ratio of the component (b), for example, the component (b) is 15 to 75 parts by weight, preferably 40 to 75 parts by weight, more preferably 100 parts by weight of the total amount of the components (a) and (b). The ratio may be 40 to 70 parts by weight, particularly preferably 40 to 60 parts by weight. The lower limit of the ratio of each compound constituting the component (b) to the total amount of the components (a) and (b) is, for example, (b) based on 100 parts by weight of the total amount of the components (a) and (b). 3), preferably 4 parts by weight, more preferably 5 parts by weight of each compound constituting the component. Within the above range, excellent performance can be provided in terms of heat generation, output, operation performance, storage stability, and the like.

  In the low-pollution fuel composition of the present invention, in addition to the components (a) and (b), additives known in the technical field may be appropriately added depending on the purpose, as long as the effects of the present invention are not impaired. It can also be contained. Specific examples of additives thus arbitrarily added include antioxidants such as 2,6-di-t-butylparacresol and phenyl-α-naphthylamine-dialkyldiphenylamine t-butylhydroxyanisole (BHA); Metal deactivators such as N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and dialkylselenium; and corrosion inhibitors such as benzotriazole and 4-nonylphenol. Examples can be given. In addition to these additives, the low-pollution fuel composition of the present invention may also contain a metal deactivator or a corrosion inhibitor suitably used in ethanol.

  When the above additive is blended in the low-pollution fuel composition of the present invention, the blending ratio of the additive varies depending on the type and use of the additive and cannot be uniformly defined. The amount of the additive is 0.02 to 3 parts by weight, preferably 0.03 to 1 part by weight, based on 100 parts by weight of the total amount of the component (b).

  When the water content of the low-pollution fuel composition of the present invention is too large, layer separation easily occurs. Therefore, it is desirable to keep the water content in the composition low. The water content of the low-pollution fuel composition of the present invention is desirably 5% by weight or less based on the total weight of the composition.

  The low-pollution fuel composition of the present invention can be prepared by mixing the above components according to a conventional method. Since t-butanol is solid at 15 ° C or lower, a low-pollution fuel composition containing t-butanol as a component of the component (b) is prepared, for example, under a temperature condition of 15 ° C or higher. The t-butanol / ethanol mixture is prepared by pre-mixing t-butanol and an appropriate amount of ethanol or dissolving solid t-butanol in ethanol. What is necessary is just to mix a liquid mixture with another compounding component.

  The low-pollution fuel composition of the present invention has an engine that uses a conventionally used gasoline as a fuel without the need for engine modification or additional equipment such as heating a carburetor or using an injection type. It can be suitably used as a fuel for automobiles.

  Further, the low-pollution fuel composition of the present invention can be used in addition to the above-mentioned automobiles, as well as conventional motorcycles using gasoline, motorcycles, motorcycles, light automobiles, jet skis, motor boats, go-karts, ships, various other industrial vehicles, or gasoline. Can also be used as fuel for various devices that use.

  In addition, the low-pollution fuel composition of the present invention can be used for an engine that uses a conventionally used gasoline as a fuel even if it does not substantially contain a hydrocarbon (gasoline) as long as it contains the above components. Although it can be used as a fuel, it may be mixed with conventional gasoline as long as the characteristic of low pollution is not impaired, and used as a gasoline-containing fuel in the above-mentioned vehicle or device.

  When the low-pollution fuel composition of the present invention is used by being mixed with gasoline, the mixing ratio with gasoline is not particularly limited, but, for example, based on 100 parts by weight of the total amount of components (a) and (b) Examples of the ratio include gasoline in a total amount of 0.1 to 100 parts by weight.

  ADVANTAGE OF THE INVENTION According to the low-pollution fuel composition of this invention, the amount of harmful substances in the exhaust gas generated by use can be significantly reduced. Further, according to the low-pollution fuel composition of the present invention, it is possible to use a conventionally used gasoline-operated engine as a fuel without the need to modify the engine or equip additional equipment, and to produce a heat value comparable to that of gasoline. , Output and driving performance. In addition, the low-pollution fuel composition of the present invention has characteristics that it is difficult to separate layers even at low temperatures, and that it can withstand long-term storage and use in winter. Therefore, the low-pollution fuel composition of the present invention is useful as a low-pollution gasoline substitute fuel.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, the present invention is not limited at all by the examples and the like.

  In the examples, the density was measured using a density tester (vibration type density machine) (model DMA4, manufactured by Pioneer Anton Paar) according to JIS K 2249. The octane number (motor method) was measured according to JIS K2280 using an octane number tester (model CFR, manufactured by WAUKESHA MOTOR COMPANY). Reed vapor pressure was measured by a dry method. The flash point was measured by a closed tag method, and the ignition point was measured according to ASTM E659. Further, the distillation properties were tested using a distillation tester (model AD4, manufactured by Tanaka Kagaku Kikai Seisakusho) in accordance with JIS K 2254.

Example 1-15
A low-pollution fuel composition having the composition shown in Table 1 below was prepared according to a conventional method.

上記実施例１−１５の低公害燃料組成物を燃料として使用して、ガソリンエンジンを搭載する自動車（トヨタマークII、水冷直列６気筒DOHC24パルブ、総排気量1988cc、圧縮比9.6、内径（ボア）75mm、工程（ストローク）75mm、電子制御式噴射装置）を用いて走行試験を行った。その結果、いずれの燃料組成物でも上記自動車は走行可能であり、加速時及び定速時の走行状態はともに良好であった。

An automobile equipped with a gasoline engine (Toyota Mark II, water-cooled in-line 6-cylinder DOHC 24 valve, total displacement 1988 cc, compression ratio 9.6, inner diameter (bore)) using the low-pollution fuel composition of Example 1-15 as a fuel A running test was performed using a 75 mm process (stroke) 75 mm, electronically controlled injection device. As a result, the vehicle was able to run with any of the fuel compositions, and the running conditions at the time of acceleration and at the time of constant speed were both good.

  Table 2 shows the density, octane number (motor method), and distillation properties of the low-pollution fuel composition of Example 3.

該組成物中に銅片を50℃で3時間浸したところ、腐蝕は認められなかった。また、該組成物を360日間室温で外気を遮断した状態で保存したところ、層分離、組成変化等の性状変化は認められなかった。更に、該組成物の層分離温度は−29.5℃であり、冬季の使用にも耐えることが確認された。

When copper pieces were immersed in the composition at 50 ° C. for 3 hours, no corrosion was observed. In addition, when the composition was stored at room temperature for 360 days in a state where the outside air was blocked, no property change such as layer separation and composition change was observed. Further, the layer separation temperature of the composition was −29.5 ° C., and it was confirmed that the composition could withstand use in winter.

Test Example 1 Exhaust gas test Using the low-pollution fuel composition of Example 1, an exhaust gas test was performed by the following method. Using a gasoline vehicle (Toyota Mark II, water-cooled in-line 6-cylinder DOHC 24 valve, total displacement 1988cc, compression ratio 9.6, inner diameter (bore) 75mm, process (stroke) 75mm, electronically controlled injection device), according to the 10 mode method Carbon monoxide (CO) and unburned hydrocarbons (HC) in the exhaust gas were measured. The measurement of CO and HC was performed using a CO / HC analyzer (manufactured by HORIBA, Ltd., product number MEXA-324F). For comparison, an exhaust gas test was similarly performed using a commercially available regular gasoline (Comparative Example 1).

  Table 3 shows the obtained results. As is clear from Table 3, it was confirmed that the exhaust gas generated by using the low-pollution fuel composition of the present invention had very low CO and HC values. From these results, according to the low-pollution fuel composition of the present invention, it is possible to significantly reduce the amounts of CO and HC discharged during combustion and reduce the burden on the environment, as compared with conventional regular gasoline. Became clear.

試験例２
実施例１５の低公害燃料組成物を用いて、下記方法で排ガス試験及び駆動輪出力試験を行った。ガソリン自動車（マツダロードスター、水冷４気筒、ＤＯＨＣバルブ、総排気量１５９７ｃｃ）を用いて、エンジンの回転数を２２５０から６０００ｒｐｍ程度に加速させることにより駆動した際に、各回転数毎の、排気ガス中の一酸化炭素（ＣＯ）、二酸化炭素（ＣＯ₂）及び未燃焼炭化水素（ＨＣ）の測定、及びエンジントルク（ｋｇ）と駆動輪出力（ＰＳ）の測定を行った。なお、ＣＯ、ＣＯ₂及びＨＣの測定は、排気ガス測定器（堀場製作所製、品番MEXA544.T）を用いて行った。また、エンジントルク及び駆動輪出力の測定は、過渡動力特性計測シャーシダイメーター（エイ・エム・エスフジイ社製）を用いて行った。

Test example 2
Using the low-pollution fuel composition of Example 15, an exhaust gas test and a driving wheel output test were performed by the following methods. When a gasoline vehicle (Mazda Roadster, water-cooled 4-cylinder, DOHC valve, total displacement 1597 cc) is driven by accelerating the engine speed from 2250 to 6000 rpm, the amount of exhaust gas at each speed is reduced. Of carbon monoxide (CO), carbon dioxide (CO ₂ ) and unburned hydrocarbons (HC), and the measurement of engine torque (kg) and drive wheel output (PS). The measurement of CO, CO ₂ and HC was carried out using an exhaust gas measuring instrument (manufactured by Horiba Seisakusho, product number MEXA544.T). The measurement of the engine torque and the output of the driving wheel was performed using a transient power characteristic measurement chassis dimeter (manufactured by AMSF Fujii).

  For comparison, an exhaust gas test was similarly performed using a commercially available regular gasoline (Comparative Example 2).

The obtained results are shown in FIGS. FIG. 1 shows the concentration of CO ₂ in the exhaust gas at each rotation speed. FIG. 2 shows the concentration of CO in the exhaust gas at each rotation speed. FIG. 3 shows the concentration of HC in the exhaust gas at each rotation speed. FIG. 4 shows the engine torque (kg) at each rotation speed. FIG. 5 shows the drive wheel output (PS) at each rotation speed. As is clear from FIGS. 1 to 3, it was confirmed that the exhaust gas generated by using the low-pollution fuel composition of the present invention had very low concentrations of CO, CO ₂ and HC. 4 and 5, it was confirmed that the low-pollution fuel composition of the present invention has the same or higher engine power characteristics as a conventional gasoline engine.

FIG. 9 is a diagram showing the concentration of CO ₂ in exhaust gas at each rotation speed in Test Example 2. FIG. 9 is a diagram showing the concentration of CO in exhaust gas at each rotation speed in Test Example 2. FIG. 9 is a view showing the concentration of HC in exhaust gas at each rotation speed in Test Example 2. FIG. 9 is a diagram showing engine torque (kg) at each rotation speed in Test Example 2. FIG. 9 is a diagram showing a drive wheel output (PS) at each rotation speed in Test Example 2.

Claims (5)

A low-pollution fuel composition containing the following components (a) and (b):
(A) ethanol, and (b) at least one selected from the group consisting of t-butanol, di-n-butyl ether, di-t-butyl ether, ethyl t-butyl ether, diisopropyl ether, diethyl ether, dipropyl ether and methyl t-butyl ether. Two compounds. Component (b) is
(B1) at least one selected from the group consisting of t-butanol, di-n-butyl ether, di-t-butyl ether and ethyl t-butyl ether; and (b2) diisopropyl ether, diethyl ether, dipropyl ether and methyl t-butyl ether The low-pollution fuel composition according to claim 1, which is at least one mixture selected from the group consisting of: The low-pollution fuel composition according to claim 1 or 2, wherein component (b) is a mixture of t-butanol, diisopropyl ether, diethyl ether and methyl t-butyl ether. The low-pollution fuel composition according to any one of claims 1 to 3, wherein the composition contains the component (a) in an amount of 25 to 85 parts by weight per 100 parts by weight of the total of the components (a) and (b). . The low-pollution fuel composition according to any one of claims 2 to 4, wherein the component (b2) is contained in an amount of 30 to 600 parts by weight based on 100 parts by weight of the component (b1).

Images