JP2008024822A - Additive for alcohol-containing fuel oil, fuel oil containing the additive for alcohol-containing fuel oil, and method for producing fuel oil containing the additive for alcohol-containing fuel oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for an alcohol-containing fuel oil effective for increasing the affinity of alcohols to gasoline, etc., to enable the production of an excellent alcohol-containing fuel oil, a fuel oil containing the fuel oil additive and a method for producing the fuel oil containing the additive for an alcohol-containing fuel oil. <P>SOLUTION: The additive for an alcohol-containing fuel oil contains a lower alcohol isomer coupling agent, a coupling activation agent, an enriched fuel assistant, an ignition accelerator and a corrosion inhibitor. The invention further provides a fuel oil containing the additive for an alcohol-containing fuel oil, and a method for producing a fuel oil by adding the additive. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an alcohol-containing fuel oil additive. More specifically, the present invention relates to an alcohol-containing fuel oil additive such as methanol and / or ethanol, a fuel oil containing the alcohol-containing fuel oil additive, and the alcohol-containing fuel oil additive. The present invention relates to a method for producing a fuel oil containing an agent.

  Gasoline fuels used in powered vehicles such as automobiles are all refined from mineral resources petroleum, and their consumption has increased remarkably with the rapid increase in the number of vehicles due to rapid economic development. Petroleum resources buried underground are limited to the ever-increasing consumption of gasoline fuel.

  On the other hand, since petroleum contains harmful substances such as nitrogen and sulfur, harmful substances such as CO, HC and NOx are contained in the exhaust gas of the vehicle. These harmful substances pollute the air environment and seriously threaten the living environment of mankind. Accordingly, attention has been focused on alcohol-containing fuel oils, particularly alcohol-containing gasoline.

  Alcohols added to gasoline include ethanol, which is a flammable liquid whose basic chemical elements are carbon (C), hydrogen (H), and oxygen (O). Ethanol can increase the octane number of gasoline, increase the oxygen content of gasoline, increase the efficiency of gasoline combustion, and further reduce the content of CO, HC, etc. in the exhaust gas to pollute the atmospheric environment. Decrease. Therefore, by using ethanol / gasoline fuel made from ethanol and gasoline, gasoline resources can be saved and pollution of exhaust gas can be reduced.

  At present, ethanol gasoline E-10 containing 10% ethanol is being put to practical use in the United States, Brazil, China, and the like. However, at the current market price, ethanol is more expensive than gasoline, and such economic causes are considered to be an obstacle to the widespread use of ethanol and gasoline.

  Methanol is also a flammable liquid, and the basic chemical elements are carbon (C), hydrogen (H), and oxygen (O). In addition, methanol is known as a good smokeless fuel because of its good combustion performance, high octane number, high anti-knock properties, high combustion speed, high calorific value and thermal efficiency.

  Therefore, it is an effective method for saving gasoline resources and reducing exhaust gas pollution by using methanol / gasoline fuel in which methanol and gasoline are mixed. Moreover, the raw materials of methanol are very abundant, and the methanol production and production technology is sufficiently matured, so that it is convenient to store and transport. Furthermore, the current market price of methanol is one-half that of gasoline, for example, in China, gasoline is 4400 yuan / ton and methanol is 2200 yuan / ton). Methanol / gasoline fuel is attracting attention as an alternative to gasoline. ing.

  The methanol / gasoline fuel has been attracting attention since the 1970s and has been researched and developed. For example, in the United States and Italy, methanol / gasoline fuel containing 3% to 5% methanol was developed in 1977, and in west Germany, in 1979, methanol and gasoline fuel began to be studied in China and Brazil. However, in spite of its long-term research, many technical problems are still unsolved and have not been put into practical use. Currently, ethanol and gasoline are only in practical use in the United States, Brazil, and China.

  First, as an unsolved problem, there is a mutual compatibility between methanol and gasoline. Methanol and gasoline are two different types of compounds, and their densities are 0.79 kg / L (methanol) and 0.73 kg / L (gasoline), respectively. In addition, methanol contains a hydroxyl group in the molecule and is a strong polar compound that is easily soluble in water, whereas gasoline is a hydrocarbon and a nonpolar compound, so it cannot be dissolved in polar compounds. In addition, due to the difference in density, when methanol and gasoline are mixed, they are naturally separated, and the upper layer becomes gasoline and the lower layer becomes alcohols.

  Next, there is a problem of water resistance. Methanol and ethanol are both strong polar compounds and can be mixed with water at an arbitrary ratio, so both methanol and ethanol have high water absorption. For this reason, free water may be absorbed during the process of production, transportation, and use of alcoholic gasoline. Furthermore, methanol or ethanol contains a small amount of water due to poor purity in the product. The presence of the water molecules prevents methanol or ethanol and gasoline from dissolving each other. Therefore, in order to put methanol / gasoline (or ethanol / gasoline) into practical use, a certain level of water resistance must be imparted.

  Next, there is a problem that the engine or the like is difficult to start at a low temperature. Since the heat of vaporization of methanol is greater than that of gasoline and the low-temperature vapor pressure is low, the evaporability of alcohols is poor at low temperatures. Therefore, when the engine is at a temperature lower than the environmental temperature, the amount of evaporation of the fuel hardly reaches the minimum combustible amount. Therefore, for example, when methanol / gasoline (or ethanol / gasoline) is used when the environmental temperature is lower than 5 ° C., it is difficult to start the engine of the car.

  Further, the alcohol fuel has a problem that it is clogged with gas. Since some hydrocarbons in methanol / gasoline have a low boiling point, the vapor pressure of methanol / gasoline becomes higher than that of gasoline, and low-boiling components increase. Fuel pipes are easily clogged with gas. Ethanol and gasoline have similar problems.

  Finally, the alcohol fuels have corrosion problems. Methanol is a highly polar organic solvent, can dissolve products such as rubber and plastic, and has some degree of corrosiveness against colored metals. Without solving such problems related to corrosion, methanol and gasoline are difficult to spread. In addition, ethanol and gasoline have corrosive problems to some extent.

  An object of the present invention is to provide an additive for fuel oil that enhances the affinity between alcohols and gasoline or the like and enables the production of an excellent alcohol-containing fuel oil. Furthermore, an object of the present invention is to provide an alcohol-containing fuel oil containing the fuel oil additive and a method for producing the alcohol-added fuel oil.

In order to achieve the object of the present invention, the present invention provides an alcohol-containing fuel oil addition comprising a low alcohol isomer coupling agent, a coupling activator, a fortified fuel auxiliary agent, an ignition accelerator and a corrosion inhibitor. Provide the agent.
Furthermore, the present invention provides an alcohol-containing fuel oil containing the fuel oil additive.
Furthermore, the present invention includes a step of adding and mixing the fuel oil additive to alcohols such as methanol, ethanol or a mixture of these alcohols, and the alcohol and fuel oil obtained in the above step to a fuel oil such as gasoline. A method for producing an alcohol-containing fuel oil comprising the step of mixing a mixture with an additive for use.

  The alcohol-containing fuel oil additive of the present invention has characteristics relating to alcohols, particularly methanol, problems of being immiscible with gasoline, problems of water resistance, problems of difficulty in maneuvering of the engine under low temperature conditions, and bubbles of fuel vapors. The problem of clogging and corrosiveness can be solved, and the practical use of alcohol-containing fuel oils, particularly methanol gasoline, as an alternative fuel for gasoline can be promoted.

  According to the earnest research results of the present inventors, a hydroxyl group (OH) that is a polar group in methanol and a hydrocarbon group that is a non-polar group in a fuel such as gasoline have a three-dimensional molecular structure. Found "mediator". The present inventor has found that alcohols and fuel oils having different properties can be intimately mixed through the chain action of the “mediator”. The “mediator” is a low alcohol isomer coupling agent used in the additive of the present invention.

Accordingly, the present invention provides an alcohol-containing fuel oil addition characterized by comprising a low alcohol isomer coupling agent, a coupling activator, a fortified fuel adjuvant, an ignition accelerator, and a corrosion inhibitor. .
In the present invention, the low alcohol isomer coupling agent is 60 wt% to 90 wt%, the coupling activator is 4.9 wt% to 20 wt%, and the enhanced fuel adjuvant is 2.5 wt% to 15 wt%. An alcohol-containing fuel oil additive containing 1 wt%, 2.5 wt% to 4.5 wt% of the ignition accelerator, and 0.1 wt% to 0.5 wt% of the corrosion inhibitor is preferred.

Further, in the present invention, the low alcohol isomer coupling agent is 70% by weight to 85% by weight, the coupling activator is 8% by weight to 15% by weight, and the reinforcing fuel adjuvant is 2.5% by weight to 10% by weight. An alcohol-containing fuel oil additive containing 1 wt%, 2.5 wt% to 3.5 wt% of the ignition accelerator, and 0.1 wt% to 0.3 wt% of the corrosion inhibitor is preferred.
Further, in the present invention, the low alcohol isomer coupling agent is 80% by weight, the coupling activator is 14% by weight, the reinforcing fuel auxiliary agent is 2.9% by weight, and the ignition accelerator is 2.9% by weight. %, And an additive for alcohol-containing fuel oil containing 0.2% by weight of the corrosion inhibitor is particularly preferred.

  In the present invention, the low alcohol isomer coupling agent is preferably 60% by weight to 90% by weight, more preferably 70% by weight to 85% by weight, particularly 80% by weight based on the total amount of the additive. % Is most preferable. Examples of the low alcohol isomer coupling agent include isopropyl alcohol, isoptyl alcohol, trimethyl carbinol, and 3-methyl-pentanol, particularly trimethyl carbinol and 3-methyl-1-ptanol. Is preferred. These can be used alone or in combination.

  It is possible to mix alcohols such as methanol and fuel oils such as gasoline by simply using a highly effective coupling agent. Methanol and gasoline can be easily separated. Therefore, the coupling activation of the coupling agent can be strengthened by adding a coupling activator to the additive. That is, by adding a coupling activator, it is possible to increase the miscibility of methanol and gasoline and increase the water resistance.

The coupling activator used in the present invention is preferably 4.9 to 20% by weight, more preferably 8 to 15% by weight, particularly 14% by weight, based on the total amount of the additive. Most preferred. Examples of the coupling activator include MTBE, isopropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, dimethylisopropanolamine, and diethylisopropanolamine. Or in combination.
In the present invention, by adding the coupling activator, methanol gasoline becomes difficult to separate, and its water resistance is greatly increased from 0.3% to 1.0%. The same applies to ethanol and gasoline.

Further, in order to solve the problem of startability of the engine or the like at the low temperature, a reinforced fuel auxiliary agent is used in the present invention. The reinforcing fuel auxiliary is preferably 2.5% to 15% by weight, more preferably 2.5% to 10% by weight, and particularly 2.9% by weight, based on the total amount of the additive. Is most preferred.
Examples of the reinforcing fuel auxiliary agent include dimethyl ether, methyl-tert-butyl ether (MTBE), tertiary amyl methyl ether (TAME), ethylene glycol monomethyl ether, dimethyl carbonate (DMC), 1,1- There are dimethylhydrazine (UDMH) and isopropanol ether.

  In the present invention, in the alcohol-containing fuel oil, an ignition accelerator is used in order to solve the problem of clogging of fuel vapors at high temperatures. The ignition accelerator is preferably 2.5% to 4.5% by weight, more preferably 2.5% to 3.5% by weight, particularly 2.9%, based on the whole additive of the present invention. Most preferred is weight percent. Examples of the ignition accelerator include cyclohexyl nitrate, hexyl nitrate, ethylene glycol ether nitrate, and triethyllene glycol ether nitrate, which can be used alone or in combination.

Furthermore, in the present invention, a corrosion inhibitor is used as the additive of the present invention in order to solve the problem of corrosion of alcohol-containing fuel oils, particularly methanol gasoline and ethanol gasoline. The corrosion inhibitor is preferably 0.1% by weight to 0.5% by weight, more preferably 0.1% by weight to 0.3% by weight, particularly 0.2%, based on the total amount of the additive of the present invention. Most preferred is weight percent. Examples of the corrosion inhibitor include organic phosphorus compounds, amines, naphthenic acid esters, petroleum sulfonates, EYJ022, and the like, and these can be used alone or in combination.
The EYJ022 is a product manufactured by the China Petroleum and Chemical Institute of Science, containing an organic amine, an organic carboxylic acid, and a nitrogen heterocyclic compound.

The fuel oil additive prepared at the above ratio (% by weight) is mixed with alcohols at a ratio of 8% by weight to 16% by weight to prepare alcohols containing the fuel oil additive, followed by fuel oil. The mixture is mixed so that the ratio is 15 wt% to 50 wt%. Thereby, the alcohol-added fuel oil of the present invention can be produced.
Therefore, the ratio between the fuel oil additive of the present invention, the alcohol and the fuel oil is 1.5% to 5.0% by weight for the fuel oil additive and 13.5% by weight for the alcohol. 45% by weight, and 50 to 85% by weight of fuel oil.
The alcohol used in the present invention is not particularly limited, but methanol or ethanol is preferable, and fuel oil is not particularly limited, but gasoline is particularly preferable.

  In the alcohol-containing fuel oil containing the fuel oil additive of the present invention, the mixing ratio (% by weight) of the fuel additive, the fuel additive-containing alcohol (particularly methanol or ethanol) and gasoline is 2 to 3: 15: 82-83 (hereinafter referred to as “M15”), 2-3: 20: 77-78 (hereinafter referred to as “M20”), 3-4: 25: 70-72 (hereinafter referred to as “M25”), 4-5: 30: 65-66 (hereinafter “M30”) 4-5: 35: 60-61 (hereinafter “M35”) 4-5: 40: 55-56 (hereinafter “M40”) 4-5: 45: 50-51 (hereinafter referred to as “M45”), and 4-5: 48: 47-48 (hereinafter referred to as “M48”). Particularly preferred are M35, M40, and M48.

  Production of alcohol-containing fuel oils containing the fuel oil additive of the present invention can be carried out at refineries, specialized processing factories, gasoline stunts, and the like. The additive for fuel oil of the present invention is added to the alcohols (particularly methanol or ethanol) to obtain modified alcohols (modified methanol or modified fuel ethanol). Then, it is transported to a refinery, a specialized processing factory, or a gas station to produce methanol / gasoline (or ethanol / gasoline).

  The proportion of the fuel oil additive of the present invention added to the alcohol is 8 to 16% by weight, preferably 8 to 10% by weight. In the preparation, for example, the amount of additive for fuel oil can be increased in the severe cold season, and the amount of additive for fuel oil can be reduced in the warm season. Further, the amount of fuel oil additive can be increased during periods of high humidity, and the amount of fuel oil additive can be reduced during the dry season. Furthermore, if the purity of methanol is not high, it contains water (methanol, gasoline, and the total water content of methanol / gasoline including additives must be less than 1%), so increase the amount of additive for fuel oil, When the purity of methanol is high, the amount of additive for fuel oil can be reduced because the water content is very small.

  The fuel oil additive of the present invention is a uniform and transparent light green liquid. And by mixing and stirring, methanol and ethanol and automobile gasoline can be mixed very well at room temperature. Thus, an alcohol-containing fuel oil suitable for a gasoline engine vehicle can be provided. This fuel has the same performance as general gasoline fuel, can be used directly in various gasoline engine vehicles, and can be mixed with gasoline for ordinary vehicles at an arbitrary ratio. In addition, when using the fuel of this invention, it is not necessary to modify | repair the engine of a vehicle or the components of another power part.

  Next, based on Examples, the fuel oil additive of the present invention, the alcohol-containing fuel oil containing the fuel oil additive, and the method for producing the alcohol-added fuel oil will be described. The technical scope is not limited to this description.

The fuel oil additive used in this example is 80% by weight of a low alcohol isomer coupling agent, 80% by weight of isoptyl alcohol, 14% by weight of methyl tert-butyl ether (MTBE), a reinforced fuel. It contains 2.9% by weight of ethylene glycol monomethyl ether as an auxiliary agent, 2.9% by weight of cyclohexyl nitrate as an ignition accelerator, and 0.2% by weight of a corrosion inhibitor (EYJ022).
In addition, this corrosion inhibitor (EYJ022) is a product manufactured by the China Petroleum and Chemical Institute of Science, containing an organic amine, an organic carboxylic acid, and a nitrogen heterocyclic compound.

(Example 1)
From July to August 2001, experiments were conducted in the Xian district of China under conditions of temperatures from 24 ° C to 38 ° C. Two tons of M35 methanol / gasoline was made at a ratio of 4% methanol / gasoline additive of the present invention, 35% methanol, and 61% gasoline for automobiles. Using two private cars and one large car, methanol and gasoline were put in each, and an actual operation experiment was conducted. After refueling methanol and gasoline to the three vehicles, the highway from Xi'an to Kengawa, National Highway 312 from Xi'an to Nanyang, National Highway 310 from Xi'an to Baoji, Xi'an to Ankang I ran a total of 11,200 kilometers on national highways such as the 210 National Highway. During the course of the experiment, all operations such as vehicle ignition start-up, speed-up, high-speed driving, power condition during climbing, and braking were normal.

  In this example, there was no particular difference from when ordinary gasoline was used. In addition, there was no methanol / gasoline separation phenomenon, neither ignition difficult nor gas clogging. In addition, methanol and gasoline were not allowed to corrode, melt or swell rubber and plastic products in the piping system. As a result of inspection by Xi'an Car Quality Audit Center, compared to using methanol / gasoline and using octane 90 # normal gasoline, carbon monoxide in exhaust gas is 69.6%, HC is 26. 7% decrease.

(Example 2)
From February to March 2002, experiments were conducted in the Northeast Daqing region of China under conditions of temperatures from -18 ° C to -24 ° C. An alcoholic gasoline additive of the present invention was mixed at a ratio of 5%, methanol 35%, and vehicle gasoline 60% to make M35 methanol gasoline. Using a total of six cars, two private cars, two trucks, one large bus, and one microbus, an experiment using methanol and gasoline was conducted in each car. As a result of road surface driving experiments on various roads, there was almost no difference between using methanol / gasoline and normal vehicle gasoline. Furthermore, separation of methanol and gasoline was not observed, and the combustion situation was excellent. In addition, the engine was in good starting condition, and there was no problem of cold start and no gas clogging problem. It was clear that methanol / gasoline power performance was not inferior to that of ordinary car gasoline on ordinary roads, mountain roads, and hills, and it was possible to completely replace ordinary gasoline.

(Example 3)
From April to May 2003, a methanol / gasoline operation experiment was conducted in the Sanming area of Southeast China along the temperature range of 15 ° C to 28 ° C. Methanol gasoline was produced using 99.5% pure methanol. The proportions were 4% for the alcoholic gasoline additive of the present invention, 40% for methanol, 56% for gasoline for cars, and M40 methanol / gasoline was made. As a result of driving and using cars such as minibuses, passenger cars, trucks, motorcycles, etc., the combustion situation of methanol / gasoline was very good, and there was no problem of ignition start-up or gas clogging problem. Furthermore, the power performance of the vehicle was the same as when using gasoline for ordinary vehicles, and no corrosion of the power system pipe system was observed.

Example 4
From November to December 2004, an operation test using methanol / gasoline was carried out in the northern area of Shaanxi Province, China under the temperature range of -12 ° C to -18 ° C. Methanol and gasoline were produced using 99.8% pure methanol produced locally. The proportions were 4% for the alcoholic gasoline additive of the present invention, 48% for methanol, and 48% for automobile gasoline, and M48 methanol gasoline was made. As a result of experiments using vehicles such as microbuses, passenger cars, trucks, and large buses, the combustion of methanol and gasoline was very good, and there were no problems of difficulty in starting due to cold or gas clogging problems. Furthermore, the power performance of the vehicle was the same as when using ordinary gasoline. Furthermore, no corrosion phenomenon was observed in the pipe system of the vehicle power section. Therefore, it was clear that the methanol / gasoline could be completely replaced with gasoline.

Claims (13)

  An alcohol-containing fuel oil additive comprising a low alcohol isomer coupling agent, a coupling activator, a reinforcing fuel adjuvant, an ignition accelerator, and a corrosion inhibitor.   60% to 90% by weight of the low alcohol isomer coupling agent, 4.9% to 20% by weight of the coupling activator, 2.5% to 15% by weight of the enhanced fuel adjuvant, The fuel oil additive according to claim 1, comprising 2.5 wt% to 4.5 wt% of an ignition accelerator and 0.1 wt% to 0.5 wt% of the corrosion inhibitor.   70 wt.% To 85 wt.% Of the low alcohol isomer coupling agent, 8 wt.% To 15 wt.% Of the coupling activator, 2.5 wt.% To 10 wt. The additive for fuel oil according to claim 1, comprising 2.5 wt% to 3.5 wt% of an agent and 0.1 wt% to 0.3 wt% of the corrosion inhibitor.   80% by weight of the low-alcohol isomer coupling agent, 14% by weight of the coupling activator, 2.9% by weight of the enhanced fuel adjuvant, 2.9% by weight of the ignition accelerator, and corrosion inhibition The additive for fuel oil according to claim 1, comprising 0.2% by weight of the additive.   The low alcohol isomer coupling agent is at least one selected from the group consisting of isopropyl alcohol, isoptyl alcohol, trimethyl carbinol, and 3-methyl-butanol. The additive for fuel oil according to 1.   The coupling activator is selected from the group consisting of methyl tert-butyl ether (MTBE), isopropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, dimethylisopropanolamine, and diethylisopropanolamine; The additive for fuel oil according to any one of claims 1 to 5, which is at least one kind.   The enhanced fuel adjuvant is dimethyl ether, methyl tert-butyl ether (MTBE), tertiary amyl methyl ether (TAME), ethylene glycol monomethyl ether, glycol methyl ether, dimethyl carbonate (DMC), 1,1-dimethylhydrazine The additive for fuel oil according to any one of claims 1 to 6, which is at least one selected from the group consisting of (UDMH) and isopropanol ether.   8. The ignition accelerator according to claim 1, wherein the ignition accelerator is at least one selected from the group consisting of cyclohexyl nitrate, hexyl nitrate, ethylene glycol ether nitrate, and triethyllene glycol ether nitrate. Fuel oil additive.   The said corrosion inhibitor is at least 1 sort (s) chosen from the group which consists of an organophosphorus compound, amines, naphthenic acid ester, petroleum sulfonate, and EYJ022, The any one of Claims 1-8 characterized by the above-mentioned. The additive for fuel oil according to 1.   The additive for fuel oil according to any one of claims 1 to 8, wherein the alcohol-containing fuel oil is methanol, ethanol, or a gasoline containing a mixture thereof.   The fuel oil additive according to any one of claims 1 to 11, 1.5 wt% to 5.0 wt%, methanol, ethanol or a mixture thereof 13.5 wt% to 45 wt%, and An alcohol-containing fuel oil containing 50 to 85% by weight of fuel oil.   The alcohol-containing fuel oil according to claim 11, wherein the fuel oil is gasoline. Adding and mixing 8% to 16% by weight of the fuel oil additive according to any one of claims 1 to 10 to methanol, ethanol or a mixture thereof;
A method for producing an alcohol-containing fuel oil, comprising a step of mixing 15% by weight to 50% by weight of a mixture of the alcohol and the fuel oil additive obtained in the above step with gasoline.