KR20110113955A - Alcohol mixed fuel emulsifier and method for preparing alcohol mixed fuel - Google Patents

Abstract

The present invention does not have a phase separation problem between alcohols such as methanol and ethanol and gasoline even when water is introduced, and thus can be safely used as a fuel, and in order to completely overcome the phase separation problem at low temperatures even in winter, alcohol such as methanol or ethanol The present invention relates to an emulsifier and an alcohol-containing gasoline that finely granulates the oil so that the gasoline is wrapped around it. Fatty acid such as oleic acid, lauryl acid, stearic acid or palmitic acid having a lipophilic group is esterified with one or more hydroxyl groups in one or more hydroxyl groups in the molecule in polyglycerol and oleic acid which is a lipophilic group At least one compound selected from fatty acids such as lauryl acid, stearic acid and palmitic acid and esterified with one or more hydroxyl groups in a sorbitol molecule with polyoxyethylene, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether Compound (B) has an emulsifier composition characterized in that it is used in combination, and the emulsifier is prepared by ultrasonic or mechanical emulsification to produce an emulsified alcohol mixture fuel, the fine particles of alcohol in the gasoline during combustion in the engine is fine By exploding it close to complete combustion Is a major contributor to the improvement of the atmospheric environment by reducing carbon monoxide and hydrocarbons.

Description

 Alcohol mixed fuel emulsifier and method for preparing alcohol mixed fuel {ALCOHOL MIXED FUEL EMULSIFIER AND METHOD FOR PREPARING ALCOHOL MIXED FUEL}

The present invention, when using a mixture of methanol and gasoline, ethanol and gasoline, or a mixture of methanol and ethanol and gasoline, alcohol fuel emulsified by mixing with an emulsifier using mechanical or ultrasonic to prevent phase separation occurs by mixing water Low temperature start-up is good, and to improve the atmosphere by reducing the carbon monoxide and hydrocarbons, which are air pollutants during combustion, and also to reduce energy consumption by reducing the amount of gasoline as a mixture of alcohol.

Unlike diesel engines that use gasoline, spark ignition engines have a relatively low air / fuel ratio, which generates large amounts of unburned hydrocarbons, SOF (Soluble Organic Fraction) and carbon monoxide from the exhaust gas. In particular, due to the characteristics of the metropolitan areas of Korea, the population is crowded, the traffic jam time is long, the distance between the road and the residential area is short, and the operation of private vehicles is frequent. The situation is serious enough to occupy%, and the degree of pollution felt by citizens is even higher, so countermeasures are urgently needed. On the other hand, attempts to use alternative fuels are actively underway due to depletion of oil resources and rising gasoline prices. In particular, attempts to extract alcohol from biomass or produce alcohol from natural biomaterials such as sugar cane, sweet potatoes, and potatoes, and mix it with gasoline at a certain rate to reduce greenhouse gas and replace expensive gasoline. It's going on.

As a method of reducing air pollution and suppressing phase separation between alcohol and gasoline, Korean Patent No. 553,532, Korean Patent No. 525363, Korean Patent No. 655101, Korean Patent No. 707133, and Korean Patent Publication No. 10-2009 As in -0003146, there is a method of adding isopropanol or isobutanol, or using ethyl cellosolve or butyl cellosolve, rosin derivative and rosin acid as in Korean Patent No. 741641. In addition, as in Korean Patent No. 740486, sorbitan monooleate, sorbitan laurate, and sorbitan-based surfactants such as sorbitan palmitate were simply added to prevent phase separation.

However, the mixed use of alcohols according to the above method is inadequate for use as fuel for internal combustion engines because it contains problems that arise due to the fundamental properties of alcohols such as methanol and ethanol. For this reason, alcohol's strong solvent properties dissolve gums and varnishes in fuel tanks or fuel supply systems, blocking fuel filters or injectors and causing failures.Inner cylinders, cranks, shafts, bearings It corrodes metal materials, and lubrication performance deteriorates, causing wear. In addition, swelling or deterioration of rubber materials such as gaskets, O-rings, and hoses due to simple mixing of alcohols with gasoline, and vaporization of methanol or ethanol causes vaporization, which causes problems in fuel supply, thereby degrading operability. The biggest problem is that the engine stops due to phase separation of methanol or ethanol and gasoline even with very little water inflow. Especially, in winter or in cold weather due to the rapid phase separation without the inflow of water at low temperature below 15 ℃. You can't use it as fuel.

In the prior art, it is difficult to supply fuel due to an increase in the vapor pressure of alcohols such as methanol or ethanol, or problems such as corrosion of fuel tanks, fuel supply systems, and phase separation between alcohol and gasoline.

The present invention solves the problem of phase separation of alcohol and gasoline, such as methanol and ethanol, solves the problem of corrosion of fuel tank and fuel supply system, and prevents difficulty in fuel supply by increasing the vapor pressure of alcohol such as methanol or ethanol. To this end, an emulsifier is added to emulsify the alcohol and gasoline, such as methanol or ethanol, by mechanical mixing or ultrasonic wave. Its purpose is to provide a way to make it.

In order to achieve the above and other objects, the present invention adds a predetermined emulsifier to a hydrocarbon of a gasoline or gasoline-like component to which methanol, ethanol or a mixture of methanol and ethanol is added and emulsified by mechanical mixing or ultrasonic wave. There is provided a process for producing an alcohol mixed fuel by making methanol, ethanol or a mixture of methanol and ethanol into small particles and surrounding them with gasoline or gasoline like components.

The emulsifier is selected from compounds made by esterifying a fatty acid such as oleic acid, lauryl acid, stearic acid or palmitic acid having a lipophilic group to a polyglycerol having several hydrophilic groups, depending on the degree of polymerization, by at least one hydroxyl group. At least one compound (" Compound A ") and a hydrophilic group, sorbitol having 6 hydroxyl groups, a fatty acid such as oleic acid, lauryl acid, stearic acid, and palmitic acid as a lipophilic group, polyoxyethylene, polyoxyethylene alkyl ether or polyoxyethylene alkyl A mixture of one or more compounds (" Compound B ") selected from compounds in which aryl ether is esterified with one or more hydroxyl groups in a weight ratio of 1: 100 to 100: 1 (A: B) is used.

When compound A, compound B, or both compounds are 2 or more types, it mixes so that the weight ratio of the sum of compound A and the sum of compound B may be 1: 100-100: 1. The polyglycerol has a repeating unit of 1 to 10, and the polyoxyethylene, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether has a repeating unit of 1 to 30. The emulsifier thus prepared is added to methanol or ethanol or hydrocarbons that can be used as a substitute for gasoline or gasoline mixed with methanol and ethanol. It is characterized by being made by emulsifying the ethanol to the particle diameter of 0.1 ~ 20㎛ to wrap around the gasoline. If the amount of the added emulsifier is less than 0.01%, the emulsification is not good, and if the amount of the emulsifier is larger than 15%, the economic efficiency is lost and it affects the properties of gasoline. The mixing ratio of the alcohol such as methanol or ethanol mixed with the hydrocarbon of the gasoline or gasoline like component is 5 to 95% by weight. When using ultrasonic waves, the amplitude is 5 to 200 μm, and when the amplitude is smaller than 5 μm, emulsification does not occur. When it is larger than 200 μm, too strong energy is injected to cause vaporization, which hinders emulsification.

In addition, at least one substance of methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), isopropyl alcohol (IPA), and isobutyl alcohol (IBA) was prepared in the alcohol mixed emulsion fuel prepared by the above method. If the mixture is prepared to 0.1 to 20% by weight can slightly enhance the above effect. However, if the amount of the added material is less than 0.1% by weight, the effect is almost insignificant. If the amount is more than 20% by weight, the octane number is affected.

The present invention can be used because there is no problem of phase separation between alcohols such as methanol or ethanol and gasoline even if water is introduced, and can completely overcome the problem of phase separation at low temperature by water even in winter. In addition, since gasoline surrounds alcohols such as methanol and ethanol, there is no corrosion problem in the fuel tank and the fuel supply system, and there is no difficulty in supplying fuel due to an increase in the vapor pressure of alcohols such as methanol and ethanol. And when the combustion inside the engine, the finely granulated alcohol in the gasoline makes the micro-explosion close to the complete combustion, thereby reducing the carbon monoxide and hydrocarbons emitted, which greatly contributes to the improvement of the atmosphere and reduces the emission of carbon dioxide, a greenhouse gas as an alternative fuel. Contribute to.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples. However, the scope of the present invention is not limited by these embodiments, and those skilled in the art can variously modify the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. And can be changed.

To 200 ml of alcohol-containing gasoline prepared from Examples and Comparative Examples, water was added without addition, 0.1 to 1% by weight, shaken for 2 minutes, and allowed to stand at room temperature for 6 hours to investigate the degree of phase separation. Also, -15 ° C to -25 6 hours was put in a low temperature thermostat to ℃ ℃ to investigate the degree of phase separation at low temperature is shown in Table 1. In addition, the four-cylinder raceti 1.6 having a cylinder bore × stroke of 79 mm × 81.5 mm, maximum output of 109 Nm / 6,000 rpm, and maximum torque of 15.0 kg · m / 3,800 rpm using alcohol-containing gasoline prepared in the following examples and comparative examples. Table 2 shows the emissions of carbon monoxide and hydrocarbons using a DOHC vehicle. In order to accurately compare the emission gas with the base state, the three-way catalyst device, which is a device that oxidizes and removes carbon monoxide and hydrocarbons, was removed and measured, and the emission gas investigation was operated in CVS-75 mode to operate EXL-1628 exhaust analyzer from Firm Ware Technology. Used.

Example 1

Gasoline in which 30% by weight of methanol is mixed with an emulsifier in which 5 g of diglycerin distearate having a polyglycerol repeating unit of 2 is compound A and 5 g of polyoxyethylene sorbitol monostearate having 10 polyoxyethylene repeating units as a compound B Into a 10kg ultrasonic irradiation with a 20㎛ amplitude for 15 minutes, the average particle size of methanol was 1㎛ and the gasoline was emulsified by wrapping the outside.

Example 2

2.5 g of diglycerin distearate having a repeating unit of 2 polyglycerol as compound A, 2.5 g of triglycerine monostearate having 3 repeating units of polyglycerine, and polyoxyethylene having 10 repeating polyoxyethylene repeating units as B compound. An emulsifier containing 2.5 g of sorbitol monostearate and 2.5 g of polyoxyethylene sorbitol distearate having a polyoxyethylene repeating unit of 10 was placed in 10 kg of gasoline mixed with 30% by weight of methanol and irradiated with ultrasonic waves having a 20 μm amplitude for 15 minutes. In addition, the average particle diameter of methanol was 1 μm, and gasoline was emulsified with methanol.

Example 3

5 g of triglycerol monolaurate having 3 repeat units of polyglycerol as compound A and 5 g of sorbitol dilaurate as compound B were added to 10 kg of gasoline mixed with 30% by weight of ethanol. Investigation showed that the average particle diameter of methanol was 1 μm, and gasoline was emulsified outside the ethanol.

Example 4

2.5 g of triglycerine monolaurate having 3 repeating units of polyglycerol as compound A, 2.5 g of diglycerin monolaurate having 2 repeating units of polyglycerine, and polyoxyethylene having 10 repeating polyoxyethylene repeating units as B compound. An emulsifier containing 2.5 g of sorbitol monolaurate and 2.5 g of polyoxyethylene sorbitol dilaurate having a polyoxyethylene repeating unit of 10 was put in 10 kg of gasoline mixed with 30% by weight of ethanol and irradiated with ultrasonic waves having a 20 μm amplitude for 15 minutes. The average particle diameter of the ethanol was 1㎛, and the gasoline was emulsified by wrapping the outside of the ethanol.

Example 5

15 wt% methanol and 15 wt% ethanol were emulsifiers in which compound A was mixed with 5 g of diglycerin monopalmitate having 2 repeat units of polyglycerol and 2.5 g of sorbitol dipalmitate and 2.5 g of octylphenyl sorbitol monopalmitate as compound B. Into the mixed gasoline 10kg was irradiated with ultrasonic waves of 20㎛ amplitude for 15 minutes, the average particle diameter of methanol and ethanol was 1㎛ and the gasoline was emulsified by wrapping the outside of methanol and ethanol.

Example 6

Gasoline in which 30% by weight of methanol is mixed with an emulsifier in which 5 g of diglycerin distearate having a polyglycerol repeating unit of 2 is compound A and 5 g of polyoxyethylene sorbitol monostearate having 10 polyoxyethylene repeating units as a compound B Into a 10kg ultrasonic irradiation with a 20㎛ amplitude for 15 minutes, the average particle size of methanol was 1㎛ and the gasoline was emulsified by wrapping the outside. And 5% by weight of isopropyl alcohol was added thereto and mixed.

Comparative Example 1

No compound B was used, and 10 g of diglycerin distearate having a repeating unit of polyglycerol of 2 as a compound A was put in 10 kg of gasoline mixed with 30% by weight of methanol and irradiated with ultrasonic waves having a 20 μm amplitude for 15 minutes.

Comparative Example 2

No compound A was used, and 10 g of polyoxyethylene sorbitol monostearate having 10 polyoxyethylene repeating units as a B compound was placed in 10 kg of gasoline mixed with 30% by weight of methanol and irradiated with ultrasonic waves having a 20 μm amplitude for 15 minutes. .

Comparative Example 3

Gasoline mixed with 30% by weight of methanol was irradiated with ultrasonic waves having a 20 μm amplitude for 15 minutes.

Comparative Example 4

Only gasoline mixed with 15 wt% methanol and 15 wt% ethanol was used.

Comparative Example 5

Only gasoline was used.

Phase separation degree of gasoline containing alcohol Example Amount of water added to alcohol-containing gasoline (% by weight) Low temperature phase separation degree (℃) No additives 0.1% 0.2% 0.5% 1.0% -15 ℃ -20 ° C -25 ℃ Example 1 stability stability stability stability stability stability stability stability Example 2 stability stability stability stability stability stability stability stability Example 3 stability stability stability stability stability stability stability stability Example 4 stability stability stability stability stability stability stability stability Example 5 stability stability stability stability stability stability stability stability Example 6 stability stability stability stability stability stability stability stability Comparative Example 1 stability Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation Comparative Example 2 stability Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation Comparative Example 3 stability Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation Comparative Example 4 stability Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation Phase separation

There is a lot of water present in the air in the low oil station, gas station storage facility for storing alcohol-containing gasoline, and fuel tank of the vehicle, and the water is mixed by one crossing. Therefore, in order to safely use alcohol-containing gasoline it is very important to maintain a stable state even in the mixing of water.

  As shown in Table 1, in Examples 1 to 5, in which A and B compounds were mixed and used as an emulsifier, emulsification was good and phase separation of alcohol and gasoline did not occur even if water was added to the alcohol-containing gasoline, and at low temperature. Phase separation does not occur even at, so it can be used safely.

Emissions analysis Example Carbon Monoxide Emission Concentration (ppm) Hydrocarbon Emission Concentration (ppm) Example 1 464 ppm 359 ppm Example 2 457 ppm 347 ppm Example 3 460 ppm 354 ppm Example 4 453ppm 341 ppm Example 5 459 ppm 351 ppm Example 6 457 ppm 348 ppm Comparative Example 1 1013 ppm 754 ppm Comparative Example 2 1017ppm 761 ppm Comparative Example 3 1102 ppm 803 ppm Comparative Example 4 1078 ppm 783 ppm Comparative Example 5 1286 ppm 921 ppm

As shown in Table 2, when the alcohol-containing gasoline is emulsified and used as in the embodiment of the present invention, the alcohol component, which has been finely granulated inside the gasoline, causes micro-explosion inside the engine, so that the gasoline particles are finely divided, thereby smoothly contacting with oxygen. It has been shown to reduce carbon monoxide and hydrocarbon emissions by more than 60% by inducing close to complete oxidation. Therefore, it is thought that it can contribute greatly to the improvement of the atmospheric environment by releasing less air pollutants, and by using alcohols such as methanol or ethanol obtained from bio materials, the effect of reducing carbon dioxide emission, which is a greenhouse gas, can be simultaneously obtained.

Claims (9)

At least one compound (A) selected from compounds in which at least one fatty acid is esterified in the hydroxyl group in the polyglycerol molecule and at least one fatty acid, polyoxyethylene, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl in the hydroxyl group in the sorbitol molecule Alcohol mixed fuel emulsifier, characterized in that the ether is made by mixing at least one compound (B) selected from esterified compounds in a weight ratio of 1: 100 to 100: 1. 2. The alcohol mixed fuel emulsifier of claim 1 wherein the fatty acid is oleic acid, lauryl acid, stearic acid or palmitic acid. The alcohol of claim 1, wherein the polyglycerol has a repeating unit of 1 to 10, and the polyoxyethylene, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether has a repeating unit of 1 to 30. Mixed fuel emulsifiers. The compound (A), the compound (B), or both compounds are two or more kinds, and the weight ratio of the sum of the compound (A) and the compound (B) is 1: 100 to 100: 1 Alcohol mixed fuel emulsifier, characterized in that the mixed. An alcohol mixed fuel prepared by mixing methanol, ethanol, or a mixture of methanol and ethanol to 5 to 95% by weight to a hydrocarbon of a gasoline or gasoline-like component and mixing the emulsifier of claim 1 with emulsifier. The method according to claim 5, wherein the emulsifier is added to the hydrocarbon of the gasoline or gasoline-like component added by mixing methanol or ethanol or methanol and ethanol in a weight ratio of 0.01% to 15% by emulsification using mechanical or ultrasonic, methanol, An alcohol mixed fuel, characterized in that the ethanol or a mixture of methanol and ethanol is cut into particles having a particle diameter of 0.1 to 20 µm and emulsified so as to surround gasoline. The method according to claim 5, wherein the emulsifier is added to the hydrocarbon of the gasoline or gasoline-like component added by mixing methanol or ethanol or methanol and ethanol in a weight ratio of 0.01% to 15% by emulsification using mechanical or ultrasonic, methanol, Ethanol or a mixture of methanol and ethanol is shredded to a particle size of 0.1 to 20 µm to emulsify the gasoline around it. Alcohol mixed fuel, characterized in that prepared by mixing to 0.1 to 20% by weight. The emulsifier of claim 1 is added to the hydrocarbon of a gasoline or gasoline-like component to which methanol, ethanol or a mixture of methanol and ethanol is added in a weight ratio of 0.01% to 15%, and emulsified mechanically or using ultrasonic waves having an amplitude of 5 to 200 µm. Methanol, ethanol or a mixture of methanol and ethanol in a particle size of 0.1 to 20㎛ finely prepared by emulsifying the surrounding gasoline or gasoline-like hydrocarbons to surround the emulsification. The emulsifier of claim 1 is added to the hydrocarbon of a gasoline or gasoline-like component to which methanol, ethanol or a mixture of methanol and ethanol is added in a weight ratio of 0.01% to 15%, and emulsified mechanically or using ultrasonic waves having an amplitude of 5 to 200 µm. Methanol, ethanol, or a mixture of methanol and ethanol is shredded to a particle size of 0.1 to 20 µm, and then emulsified to surround the hydrocarbons of gasoline or gasoline-like components, which are methyl tert-butyl ether, ethyl tert-butyl ether, Method for producing an alcohol mixed fuel, characterized in that the mixture is prepared by mixing at least one of isopropyl alcohol, isobutyl alcohol to 0.1 to 20% by weight.