WO2018190533A1

WO2018190533A1 - Method for preparing fuel additive and fuel using same

Info

Publication number: WO2018190533A1
Application number: PCT/KR2018/003498
Authority: WO
Inventors: 김덕섭
Original assignee: 김덕섭
Priority date: 2017-04-10
Filing date: 2018-03-26
Publication date: 2018-10-18
Also published as: CN110730815B; CN110730815A

Abstract

The present invention relates to a method for preparing a fuel additive, the method comprising a step for reacting at least one aqueous reaction liquid, which is selected from the group consisting of water, a polar organic compound aqueous solution, and a sodium salt aqueous solution, with an alkylene glycol monoalkyl ether-based solvent, which has a weight average molecular weight of 50-250g/mol at a temperature of 40-150°C.

Description

[Explanation of invention]

[Name of invention]

Manufacturing method of fuel additive and fuel using same

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-201 No. 0046062 dated April 10, 2017 and Korean Patent Application No. 10-2018-0033910 dated March 23, 2018. All content disclosed in the literature is incorporated as part of this specification.

The present invention relates to a method for producing a fuel additive of a hydrocarbon fuel and a fuel to which the fuel additive obtained therefrom is applied.

[Technique to become background of invention]

Due to global warming, efforts are being made by countries around the world to prevent sporadic disasters occurring in various parts of the world. In 2015, 195 countries around the world, including the United States and China, signed a Paris climate change pact and pledged to reduce greenhouse gas emissions. Various countries are making various efforts to reduce greenhouse gas emissions. In the present situation of implementing a low-carbon eco-friendly society, some researches are also being conducted on hydrogen fuel, a pollution-free energy source that emits no carbon dioxide. Hydrogen fuel cell vehicles are eco-friendly vehicles, but the price per unit is so high that it takes a long time to be activated. Electric vehicles are also being actively researched as eco-friendly vehicles. Hydrogen fueled vehicles and electric vehicles have no particulate matter emitted by combustion, and no gaseous substances associated with global warming. However, since fossil fuels are an indispensable energy source not only in automobiles, trains, ships and airplanes, but also in thermal power plants for electricity production, countries around the world are trying to improve energy efficiency, especially fossil fuels.

Increasing fossil fuel usage is accelerating global warming due to higher carbon dioxide emissions. Have a very bad effect on the destruction of the global ecosystem In particular, the increase in the emission of fine dust (PM) is a serious harm, such as threatening the health of dense urban population, shortening the life expectancy.

In particular, in the petroleum industry, due to the serious air pollution problem caused by NOx and PM (fine dust) emitted from vehicles such as automobiles, the quality improvement of various fuels such as gasoline-free and low-sulfurization to reduce emissions of air pollutants. Working on.

Korean Patent Registration No. 10-1210037 for an internal combustion engine. Fuel paraffin wax is mixed by heating liquid paraffin as fuel additive, and the fuel additive of methyl oleate, liquid calsulsulfonate and synthetic fatty oil is mixed with each other to improve the fuel efficiency of the vehicle and at the same time, significantly reduce harmful emissions. It is shown to decrease.

Korean Patent Registration No. 10-0339859 discloses a fuel additive for combustion promotion comprising a hydrocarbon solvent, a nonionic surfactant, an alcohol, a molybdenum oxide compound, and an alkali compound.

Korean Patent No. 10-1161638 discloses an emulsified nano-microfuel additive and a method for manufacturing the same, wherein water-in-oil molecules dispersed as nanoparticles do not emulsify even when added to a fuel, and thermodynamically stabilizes the system to consume fuel during combustion. It is said to be excellent for reduction.

WO 02/059236 and WO 2003/078552 provide methods for preparing ethane-diesel fuel compositions by adding surfactants to ethanol or propanol.

In the above-mentioned application / registered patent, the fuel additive which mixes liquid hydrocarbon solvent and water improves fuel efficiency and reduces the exhaust gas and particulate matter (PM), but stabilizes water and hydrocarbon solvents. The use of surfactants for mixing is also concerned with the generation of sludge due to the combustion of the surfactants, and it does not appear that the colloidal phase dispersed in the nano-micro particles is stably dispersed in the hydrocarbon for a long time.

And MTBE, a fuel additive still in use in many countries, causes MTBE from the gas station storage tanks to penetrate the ground and contaminate groundwater. There are studies that suspect MTBE to be a carcinogenic component ^. The state is already banned.

As a result, the use of bioethanol is increasing instead of enjoying MTBE worldwide. However, the addition of bioethanol has the disadvantage of costly infrastructure construction due to the hydrophilic nature of bioethanol, such as the restriction of use of existing oil pipelines and the installation of new low oil and oil fuel hanks to minimize water ingress during distribution.

In addition, with the recent implementation of the International Maritime Organization (IM0) regulations on ship emission greenhouse gases, the shipbuilding and shipping industry is conducting research to improve energy efficiency such as reducing hull resistance, improving propulsion efficiency, operating efficiency, improving engine efficiency, etc. The research on ships using LNG fuel as an alternative fuel is to reduce carbon dioxide emissions and fine dust (PM).

Marine fuels include marine diesel and residues, usually determined numerically by the viscosity of the Bunker—C and Mare gas O.I l (ship diesel). This is called heavy oil (IF0), which is the best way for ship owners and operators to reduce carbon dioxide and fine dust while reducing costs. The International Maritime Organization (IM0) strongly regulates carbon dioxide emissions and punishes ships for suspension if they do not comply. Increasing interest in the basic quality of heavy oil for ships is expected due to the restriction of fuel sulfur content applied in the emission control area (ECA) after January 1, 2015. The development of fuel additives that reduce the amount of dust and reduce fine dust (PM) is urgently needed. .

Therefore, as a fuel additive, no surfactant is used and no homogenizer is used to disperse the water, and it is stably dispersed in the liquid hydrocarbon fuel to facilitate long-term dilution, improve combustion efficiency and discharge after combustion. There is a demand for a technology that can reduce exhaust gas and fine dust (PM).

Prior Art Documents

[Patent literature] (Patent Document 1) Republic of Korea Registered Patent KR10-1210037

(Patent Document 2) Korean Patent Registration No. KR10-0339859

(Patent Document 3) Korean Patent Registration No. KR10-1161638

(Patent Document 4) International Publication W02002 / 059236

(Patent Document 5) International Publication W02003 / 078552

[Contents of the invention] ^'

Problem to be solved

The present invention does not use any surfactants and does not disperse water with a homogenizer, and is prepared through a method of combining water with -0-, -0H through a chemical reaction and liquid hydrocarbon fuel. As it is dispersed through chemical bonding, it is not only easy to dilute stably for a long time but also improves fuel consumption rate when used in addition to gasoline and diesel oil, and it is a fuel additive which can enjoy PM5 and PM2.5, which are emitted gas and particulate matter. It is to provide.

In addition, the present invention is to provide a fuel to which the fuel additive is added. [Measures of problem]

In the present specification, at least one aqueous reaction mixture selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous sodium salt solution, and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol Provided is a fuel additive manufacturing method comprising the step of reacting at a temperature of 40 ^° C to 150 ^° C. ^'

In the present specification, there is also provided a fuel comprising a fuel additive and a hydrocarbon-based fuel obtained by the fuel additive manufacturing method.

Hereinafter, a method of preparing a fuel additive and a fuel using the same according to specific embodiments of the present invention will be described in detail. According to one embodiment of the invention, at least one aqueous reaction solution selected from the group consisting of water, aqueous solution of polar organic compounds, aqueous solution of sodium salt, and alkylene having a weight average molecular weight of 50 g / mol to 250 g / mol Glycol Monoalkyl Ether A method of preparing a fuel additive, comprising reacting a solvent at a temperature of 40 ^° C. to 150 ^° C., may be provided.

The inventors of the present invention use the above-described method for preparing a specific fuel additive, and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mo l to 250 g / mo l, water, an aqueous solution of a polar organic compound, and sodium salt Through the chemical reaction of at least one aqueous reaction mixture selected from the group consisting of an aqueous solution, the final prepared fuel additive by inducing the bonding of the ether functional group or hydroxy period present in the alkylene glycol monoalkyl ether solvent or the aqueous reaction solution Experiment confirmed that the hydrophobicity of can be increased and completed the invention.

Particularly, the alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mo l to 250 g / mo l is at least one aqueous reaction selected from the group consisting of water, an aqueous polar organic compound solution, and an aqueous sodium salt solution. The reaction properties with the liquid are high, and it is easy to prepare a stably dispersed fuel additive without adding a separate surfactant, and it may be possible to solve the problem of sludge generation during combustion due to the addition of a conventional surfactant.

In addition, hydrophobicity is enhanced. When added to hydrocarbon fuels such as gasoline or diesel fuel through fuel additives, it can be easily diluted for a long time through stable dispersion, thereby improving the combustion efficiency of fuel added fuel additives, exhaust gas or fine dust Reduction was confirmed through experiments.

Specifically, the fuel additive manufacturing method of the embodiment is water, a polar organic compound aqueous solution, and sodium salt aqueous solution selected from the group consisting of aqueous solution of sodium salt, and the weight average molecular weight of 50 g / mo l to 250 g / mo It may comprise the step of reacting the alkylene glycol monoalkyl ether solvent of l at a temperature of 40 ^° C to 150.

First, the aqueous reaction solution is characterized by including water as pure water or an aqueous solution containing the same. Specifically, the aqueous reaction solution may include one or more selected from the group consisting of water, an aqueous polar organic compound solution, and an aqueous sodium salt solution. That is, the aqueous reaction mixture may include water, an aqueous polar organic compound solution, an aqueous sodium salt solution, or a mixture of two or more thereof. Preferably, water is used as the aqueous reaction solution, or a mixture of water and an aqueous solution of a polar organic compound, or a mixture of water and an aqueous sodium salt solution.

The polar organic compound solution refers to a solution in which the polar organic compound is dissolved in water, and the polar organic compound has a property of being very soluble in water-soluble solvents such as water, alcohols, ketones, ethers, esters, acetal peroxides, and epoxides. It may include one or more selected from the group consisting of the side.

The alcohol may include methanol, ethanol, propanol, n-butyl alcohol, sec-butyl alcohol, I SO-butyl alcohol, Tert-butyl alcohol, nucleic acid, or a combination of two or more thereof. Examples of the concentration of the alcohol is not particularly limited, for example, may be 90% or more, or 90% to 99.9%, or 9¾ to 99.9%.

The ketone may include diisobutyl ketone, ethyl amyl ketone, carbon (carvone), menton (Menthone or a combination of two or more thereof).

The ethers include monoethers such as dibutyl ether, tertiary-butyl isobutyl ether, ethylbutyl ether, diisoamyl ether, dinuxyl ether and diisooctyl ether; Or diethers thereof; Or dialkylcycloether having 4 to 10 carbon atoms; Or two or more combinations thereof. The ester includes organic acid esters such as ethyl formic acid ester, methyl acetate, octyl acetate, isoamyl poropionic acid ester, methyl butyric acid ester, ethyl oleic acid ester, and ethyl caprylic acid ester; Or inorganic acid esters such as cyclonuclear nitrate, isopropyl nitrate, n-amyl nitrate, 2-ethyl nucleosil nitrate, and iso-amyl nitrate; Or two or more combinations thereof. The acetal may include dimethyl acetal, formaldehyde diethyl acetal, acetaldehyde diethyl acetal, acetaldehyde dibutyl acetal, or a combination of two or more thereof.

The peroxide may include 3-butyl peroxide, tert-butyl acetate, secondary-tertiary butyl peroxide, or a combination of two or more thereof. The epoxide may include 1, 2-epoxy-4-epoxy ethylcyclonucleic acid, epoxidized methyl ester, ethylnuxyl glycidyl, or a combination of two or more thereof.

In addition, the aqueous sodium salt solution refers to a solution in which a salt containing sodium (Na) as a cation is dissolved in water, and specific examples thereof may include an aqueous NaOH solution or an aqueous sodium silicate (Na ₂ 0—nSi -xH ₂ 0) solution. Can be.

Meanwhile, the alkylene glycol monoalkyl ether solvent may have a weight average molecular weight of 50 g / mo l to 250 g / mo l. The said weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method. In the process of measuring the weight average molecular weight of polystyrene conversion measured by the GPC method, it is possible to use a detector and an analysis column, such as a conventionally known analysis device and a differential refractive index detector, and the like. Silver conditions, solvents, flow rate can be applied. Specific examples of the measurement conditions include silver ^at 30 ^° C., chloroform solvent (Chl oroform) and flow rate of 1 mL / min.

If the weight average molecular weight of the alkylene glycol monoalkyl ether solvent is excessively increased to more than 250 g / mol, it acts as a surfactant in the fuel additive, there is a limit that the sludge is generated during combustion after being applied to the fuel . The alkylene glycol monoalkyl ether solvents include alkylene glycol mono ^alkyl, ether or were used in the sense to include all of the derivatives thereof a compound, and specifically, the alkylene glycol monoalkyl ether solvents are alkylene glycol monoalkyl ether, It may include one or more selected from the group consisting of dialkylene glycol monoalkyl ether, trialkylene glycol monoalkyl ether and esters thereof. That is, the alkylene glycol monoalkyl ether solvent is alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, trialkylene glycol monoalkyl ether, alkylene glycol monoalkyl ether ester, dialkylene glycol monoalkyl ether Esters, trialkylene glycol monoalkyl ether esters, or combinations of two or more thereof.

More specifically, examples of the alkylene glycol monoalkyl ether or alkylene glycol monoalkyl ether ester include ethylene glycol monoethyl ether (EGEE), Ethylene glycol monomethyl ether (EGME), ethylene glycol monobutyl ether (EGBE), ethylene glycol monoethyl ether acetate (EGEEA), ethylene glycol monobutyl ether acetate (EGBEA) _. Ethylene glycol monopropyl ether (EGPE), ethylene glycol monophenyl ether (EGPhE), ethylene glycol mononuclear ether (EGHE), ethylene glycol mono 2-Ethyl nucleosil ether, etc. are mentioned.

In addition, examples of the dialkylene glycol monoalkyl ether or dialkylene glycol monoalkyl ether ester include diethylene glycol monomethyl ether (DGME), diethylene glycol monoethyl ether (DGEE), diethylene glycol monoethyl ether acetate ( DGEEA), diethylene glycol monobutyl ether (DGBE), diethylene glycol monobutyl ether acetate (DGBEA), diethylene glycol monopropyl ether (DGPE), diethylene glycol mononuclear ether (DGHE), etc. are mentioned.

In addition, examples of the trialkylene glycol monoalkyl ether or trialkylene glycol monoalkyl ether ester include triethylene glycol monomethyl ether (TGME) and triethylene glycol. Monoethyl ether (TGEE), triethylene glycol monobutyl ether (TGBE), triethylene glycol monopropyl ether (TGPE) and the like.

In this case, the volume ratio of the aqueous semicoagulant to the alkylene glycol monoalkyl ether solvent may be 0.1 to 1.5, or 0.2 to 1.3, or 0.24 to 1.12. In addition, the volume ratio of the nonpolar organic solvent to the alkylene glycol monoalkyl ether solvent may be 0.5 to 1, or 0.6 to 1. The volume ratio of the aqueous reaction solution to the alkylene glycol monoalkyl ether solvent means a value obtained by dividing the volume of the aqueous reaction solution by the volume of the alkylene glycol monoalkyl ether solvent. When reacting under the specific reactant input conditions described above, high reaction efficiency can be realized by suppressing side reactions while minimizing loss of reactants.

On the other hand, at least one aqueous reaction mixture selected from the group consisting of water, an aqueous polar organic compound solution, and an aqueous sodium salt solution and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol is used. ^° C to 150 ^° C The step of reacting at a temperature is 40 ^° C to 150 ^° C, or 45 ^' C to 130 ^° C, or 50 ^° C to 120 ^° C, or 50 ^° C to 90 ^° C, or 60 ^° C to 90 ^° C, Or at 80 ^° C. to 90 ^° C. temperature conditions. When the reaction is carried out under the specific silver conditions described above, it is possible to implement high reaction efficiency by suppressing side reactions while minimizing the loss of reactants.

40 ^{° of at} least one aqueous reaction mixture selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous sodium salt solution and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol When left at a temperature of less than C, specifically room temperature of 20 ^° C to 30 ^° C, for example, with the aqueous reaction solution. Alkylene glycol monoalkyl ether solvents simply form a mixed solution through physical mixing, and chemically form a substitution reaction of — 0-, -0H-, -00H- in the alkylene glycol monoalkyl ether solvent. This is hard to proceed.

In addition, at least one aqueous reaction mixture selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous sodium salt solution, and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol When the reaction is carried out at a high temperature of more than 150 ^° C, the amount of loss caused by evaporation of the aqueous side reaction liquid or alkylene glycol monoalkyl ether solvent, which is a side product, may be excessively large, thereby reducing the reaction efficiency.

4 C C to 1 C aqueous solution of the at least one aqueous reaction solution selected from the group consisting of water, an aqueous polar organic compound solution and an aqueous sodium salt solution and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol The reaction at 150 t temperature may be performed in one or more gas atmospheres selected from the group consisting of oxygen, carbon dioxide, and carbon monoxide, if necessary. When the reaction proceeds under the above-described gas conditions, an oxidation reaction condition may be formed to implement high reaction efficiency.

As described above, at least one aqueous reaction solution selected from the group consisting of water, an aqueous polar organic compound solution, and an aqueous sodium salt solution and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol are used. ^In the step of reacting at a temperature of ^° C to 150 ^° C, the aqueous reaction solution and alkylene glycol Phase separation may occur due to chemical reaction between the monoalkyl ether solvents. In this case, if necessary, the method may further include separating the supernatant in the supernatant and the lower layer in the reaction product. An example of a separation method of the supernatant and the lower layer liquid in the separation step is a separatory funnel.

Herein, the supernatant and the lower layer liquid are two different kinds of liquids separated by the boundary due to the phase separation occurring in the reaction product, and the lower liquid based on the interface has a lower density and a lower density. The upper liquid can be divided into the upper liquid based on the boundary surface.

More specifically, the supernatant is an alkylene glycol monoalkyl ether solvent having a substance in which an aqueous reaction solution is chemically bonded, the lower layer is an aqueous semi-aqueous solution in which some components of the alkylene glycol monoalkyl ether solvent are bonded It seems to exist in a state.

Meanwhile, at least one aqueous reaction solution selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous sodium salt solution, and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol After the step of reacting at a temperature of 40 ^° C to 150 t, adding a non-polar organic solvent to the reaction product; may further include.

The nonpolar organic solvent may be used to precipitate the excess aqueous reaction liquid remaining in the reaction product after the reaction between the aqueous reaction mixture and the alkylene glycol monoalkyl ether solvent.

The nonpolar organic solvent has a property of being very insoluble in water-soluble solvents such as water, and examples of the nonpolar organic solvent include hydrocarbon solvents having 5 to 20 carbon atoms, specifically, toluene, xylene, nucleic acid, tetradecane, and octa. Decene and the like, and preferably, luluene can be used. The toluene can be used without limitation the commercially available toluene of 99% purity or commercial toluene (industrial toluene contains 25% Benzene).

As described above, when the non-polar organic solvent is added to the reaction product, after adding the non-polar organic solvent to the reaction product, the supernatant and the supernatant in the non-polar organic solvent mixture are separated. It may further comprise a step. An example of a separation method of the supernatant and the lower layer liquid in the separation step is a separatory funnel.

Herein, the supernatant and the lower layer liquid are two different kinds of liquids separated by the boundary due to the phase separation occurring in the reaction product. The lower liquid has a greater density and the lower layer liquid has a lower density. The upper liquid can be divided into the upper liquid based on the boundary surface.

If necessary, the step of reacting the reaction product at room temperature (2crc) before the step of separating the supernatant in the reaction solution and the supernatant in the reaction product may further include. Through the step of reacting the reaction product at room temperature (20 ^° C.), phase separation may proceed to the upper and lower liquids in the reaction product.

In addition, the fuel additive manufacturing method of the embodiment, the water, a polar organic compound aqueous solution, and sodium salt aqueous solution selected from the group consisting of aqueous solution of sodium salt, and a weight average molecular weight of 50 g / mo l to 250 g / mo After the step of reacting the alkylene glycol monoalkyl ether solvent of l at 4 (rc to 150 ^° C.), the reaction product may be further heat-treated to remove low boiling point impurities.

The reaction product was included in the reaction product through heat treatment. -0-, -0H-, or — 00H- breaks the bond. Atomic groups containing these can be removed by evaporation as impurities.

That is, the low-boiling impurities are -0-, -0H-, or means, a compound containing a -00H- bond, and the low boiling point impurities having a boiling point of fire is reduced to less than 60 ^° C, to remove vaporized in heat treatment conditions above 60 ^° C Can be.

To this end, the heat treatment of the separated supernatant may be performed for 10 seconds to 30 hours at a temperature of 60 ^° C to 150 ^° C.

On the other hand, if necessary, after the step of heat-treating the separated supernatant to remove low-boiling impurities, further comprising the step of adding a liquid hydrocarbon compound in the volume of 0.1% to 30% by volume based on the total fuel additive volume Can be. Examples of the liquid hydrocarbon compounds include liquid paraffinic compounds, liquid naphthalene compounds, liquid olefin compounds, liquid aromatic compounds, and the like. Can be. As a more specific example, xylene may be used as the liquid aromatic compound. On the other hand, according to another embodiment of the invention, a fuel, including a fuel additive and a hydrocarbon-based fuel obtained by the fuel additive manufacturing method of the embodiment can be provided. When the fuel additive is obtained from the fuel additive manufacturing method of the embodiment of the present invention is added to the gasoline fuel ᅳ diesel fuel, marine oil, aviation oil to reduce the exhaust gas and particulate matter, it is possible to improve the efficiency of fuel economy. The fuel additive obtained from the above one embodiment the fuel additive production process is because of the nature of the hydrophobic, the fuel is little or a phase separation according to a moisture content not cause phase separation very small addition of them, ^■ transport of the fuel through the pipeline It is believed that this will be possible.

Information on the fuel additive manufacturing method includes all of the above-described information in the embodiment.

The fuel additive may be included in 0.05% by volume to 50% by volume, or 0.1% by volume to 30% by volume, based on the total fuel volume.

The hydrocarbon-based fuel may include one or more selected from the group consisting of liquefied coal, oral, gasoline, diesel, kerosene, heavy oil (bunk oil), aviation gasoline, and jet fuel. That is, the hydrocarbon-based fuel may include coal liquefied fuel, oral emulsion, gasoline, diesel, kerosene heavy oil (bunk oil), aviation gasoline, jet fuel, or a combination of two or more thereof.

The fuel may further include one or more additives selected from the group consisting of an antifreeze agent, an antistatic agent, a corrosion inhibitor, an antioxidant, a lubricant, an octane number improver, a cetane number improver, a flow improver, a diffusion agent, and a heat stabilizer. That is, the additive may include an antifreeze agent, an antistatic agent, a corrosion inhibitor, an antioxidant, a lubricant, an octane number improver, a cetane number improver, a fluidity improver, a diffusion agent, a heat stabilizer, or a combination of two or more thereof.

【Effects of the Invention】

According to the present invention, no surfactant is used and no homogenizer is used to disperse water, and stably dispersed in a liquid hydrocarbon fuel. In addition to easy dilution for a long time, a method of preparing a fuel additive capable of improving combustion efficiency and reducing exhaust gas and fine dust (PM) discharged after combustion, and a fuel using the fuel additive obtained therefrom may be provided.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. ^{'<Preparation} Example: Preparation of a fuel additive>

Preparation Example 1

To a 300 ml beaker was added 100 ml of butyl cellosolve (BC; Ethylene Glycol Mono Butyl Ether) and 40 ml of 95% ethyl alcohol. Household oxygen generator that separates oxygen and nitrogen while placing the beaker on a magnet ic hot plate and stirring the mixture at 400rpm while maintaining the temperature of the mixture at 75 ^° C to 85 ^° C for 30 minutes with a magnetic ic bar. (Model NO: EYVENZ3M) the ^use, supplied in the use only of the beaker are reaction solution hose for 20 minutes and oxygen was used as the liquid remaining geochye the step of banung and oxygen as a fuel additive. Preparation Example 2

1.Pour 500 ml of 70 ^° C butyl cellosolve (BC; Ethyl ene Glycol Mono Butyl Ether) into a 1-liter beaker, add 120 ml of 85 ^° C water (the temperature of the entire liquid is 74 ^° C), Place the beaker on the magnet ic hot piate and stir the oxygen for 20 minutes using a domestic oxygen generator (Model NO: EYVENZ3M) that separates oxygen and nitrogen while stirring at 400 rpm for 5 minutes with a magnetic ic bar. The first reaction step was carried out to supply the beaker liquid and react with oxygen, and to stand for 1 hour. At this time, the whole liquid was transparent without phase separation.

2. Industrial reaction of the above butyl cellosolve (BC; Ethylene Glycol Mono Butyl Ether), water and oxygen, which has passed through the first reaction stage, with water and oxygen on a hot plate for 30 seconds in MIX at 400 rpm using a magnet ic bar. Toluene 300 ml were added and the reaction mixture became milky at 62 ^° C during heating. In this state, the second reaction step of turning off and leaving the hot pilate was performed.

3. When the hot plate was turned off and left, the liquid was transparent at 20 ^° C and separated into supernatant and lower layer by phase separation. The amount of substratum is about

40 ml. The supernatant was about 760 ml and the remaining amount was evaporated. A first separation step of separating the supernatant and the lower layer was performed.

4. Pour 760 ml of the supernatant from the first separation step into a 1-liter beaker, wrap the beaker side with a vinyl ram to keep warm, and seal the top of the beaker with a small amount of space to allow steam to escape. And ^{"oligonucleotide} heating the solution above the Hot pl ate, through a heated distillation step of leaving for 12 hours the solution temperature, while maintaining the 70 ^° C, it was left liquid that is about 500ml at 20 ^° C, which was used as a fuel additive . Preparation Example 3

1. 100 ml of butyl salosolve (BC; Ethyl ene Glycol Mono Butyl Ether) and 100 ml of water were added to a 300 ml beaker, and the mixture was mixed transparently without phase separation. Water-added butyl cellosolve (BC; Ethylene Glycol Mono Butyl Ether) mixture was heated on a hot liquid and heated. At room temperature up to 40 ^° C. there was no phase separation transparently. As the liquid temperature exceeded 44 ^° C., bubbles began to form at the bottom. Bubbles are spreading around the temperature of 50 ^° C, the whole liquid is cloudy. At the liquid temperature of 60 ^° C, about 25 ml of water is settled below, and the liquid is cloudy. When unloaded from the hot plates, the sediment increased to about 30 ml at the bottom of the beaker. When the beaker was put on the hot glass again and the temperature was raised, about 50 ml of precipitate was precipitated at the bottom near 70 ^° C. The supernatant liquid which became cloudy near the liquid temperature of 79 ^° C. became transparent, and in the lower layer, the transparent precipitate increased to about 50 ml. The supernatant was about 150 ml of a transparent butyl salosolve (BC; Ethylene Glycol Mono Butyl Ether) compound.

2. A beaker separated from the supernatant (150 ml) and the lower layer (50 ml) was placed on a hot glass, and 30 ml of toluene was slowly added to the dropper at 65 ^° C. As the supernatant became cloudy, a precipitate formed immediately, and the lower layer increased to 80 ml. Toluene 2 (l was added to the dropper to add up to 5 (l). The lower layer became clear and the upper layer became cloudy, and the temperature was raised to 70 ^° C. and a transparent lower layer liquid is increased to 85ml. solution temperature was made further added at 70 ^° C for toluene (Toluene) 20ml with dropper immediately, but the supernatant is cloudy, the fluid temperature When it was back to 70 ^° C, the entire transparent The lower layer solution remained transparent at about ₈₅ ml with little change, even though 30 ml of toluene was further added as a dropper at a total liquid temperature of 70 t, the lower layer solution was maintained at 85 ml # with little change.

3. The separation funnel was separated into a supernatant and a lower layer.

4. Put 215 ml of the supernatant into a 500 ml beaker, wrap it in a plastic wrap to warm the sides of the beaker, and hang the 200 ml beaker in the center of the beaker to hold the evaporated condensed liquid. Wrapped and kept warm, and heated on a hot glass, the top of the vinyl was placed in a glass flask with cold water so that the gas evaporated inside the beaker was easily condensed in contact with the cold water and condensed inside the 200 ml beaker. Then, set the hot liquid at 120 ^° C for 6 hours, put the 500ml beaker with liquid on the hot liquid, and leave it, and the liquid in the 500ml beaker became 195ml, and about 15ml in the 200ml beaker suspended in the middle. It was an australia. At this time, the liquid contained in the 500 ml beaker was used as a fuel additive. Preparation Example 4

1.Insulate vinyl wrap by mixing 100 ml of butyl cellosolve (BC; Ethylene Glycol Mono Butyl Ether) and 100 ml of 95% bioalcohol ('Prethanol A', manufactured by Duksan Co., Ltd.) at 15 ^° C. Place in a 500 ml beaker, seal the top of the beaker with a plastic wrap in the same way with a 200 ml beaker in the middle of the 500 ml beaker, place the beaker on a hot plate, place an isometric glass flask with cold water on top of the beaker and evaporate inside the beaker Gas is contacted with cold water and is easily condensed to collect in a 200 ml beaker suspended inside It was. The hot plate was turned on and the temperature was set to llOT :, 6 hours and left. After 5 hours the liquid temperature was 70 ^° C., and 0.5 ml of the gasoline solution had accumulated.

2. 100 ml of toluene was added to a 500 ml beaker containing butyl cellosolve (BC; Ethylene Glycol Mono Butyl Ether) and bio alcohol, and the hot plate temperature was set at 125 ^° C. for 8 hours. 20 ml of condensate was collected in a 200 ml beaker in a 500 ml beaker. At this time, 15 ml of the liquid in the 500 ml beaker was poured into another beaker, and cold water was dropped into the dropper to confirm hydrophilicity. When the bumbled drops into the bottom of the beaker, some seem to be diluted in the liquid. Again, the beaker was placed on a hot plate, 0N was set at 125 ^° C and 8hr and left to heat distillation in the same manner, and 35 ml of condensate was collected in the 200 ml condenser beaker in the beaker. To characterize the 35 ml of condensate, 3 ml of condensate was added to 30 ml of diesel oil.

3. Pour about 265ml of the reaction solution in the 500ml beaker into the PET bottle, connect the hose to the oxygen generator that supplies oxygen by separating the air into oxygen and nitrogen, and connect the glass tube to the end. After supplying oxygen for 30 minutes and reacting with oxygen, 26 ml of liquid paraffin (LiQuid Paraffine) was added to prepare a fuel additive of the present invention. Preparation Example 5

1. Place a 5-liter beaker on a hot plate and place 1,200 ml of butyl cellosolve (BC; Ethylene Glycol Mono Butyl Ether) and 95% concentration of bioalcohol (Prethanol A, manufactured by DUKSAN). Add 1,000 ml of toluene and 100 ml of fire, set the temperature to 120 ^° C, time 60hr, seal the side with mixing by magnetic bar at 480rpm, hang the 500ml beaker to collect the liquid in the 5 liter beaker. The top was sealed with a plastic wrap, and a back-filled flask was placed on the sealed vinyl so that the gas evaporated inside the beaker was easily contacted with cold water and collected in a 500 ml beaker suspended inside. 2. Add 900 ml of 99.9% ethanol (EtOH) aqueous solution to 5 liter beaker to increase the content of ethanol in the reaction of butyl cellosolve (BC) with bio alcohol and toluene. The hot plate was turned on and set to a temperature of 120 ^° C and a time of 36hr, and left to mix with a magnetic bar at 150rpm.

3. 400 ml of 2-Methyl-2-Propanol was added to the 5 liter beaker to about 10 vol% of the reaction solution. The hot piate was turned on and the silver was set at 120 ^° C., 48 hours, and 250 rpm.

4. 300 ml of 2-Methyl-2-Propanol was further added to the reaction solution in 5 liters, and the hot piate was turned on, and the temperature was set at 120 ^° C, time 12hr, and 250rpm. After 13 hours, the liquid contained in a 5 liter beaker was used as a fuel additive in a hot plate off state. Preparation Example 6

1.Pour 3500 ml of butyl cellosolve (BC; Ethylene Glycol Mono Butyl Ether) in a 15-liter plastic container and 850 g of sodium silicate (water glass # 2; Na ₂ 0-nSi0 ₂ -xH ₂ 0) in 3500 ml of water ^at approximately 50 ^° C After dissolving the sodium silicate solution was added, the mixture was mixed for 4 hours using a 4,500rpm hand drill motor with an impeller for mixing, followed by a first reaction step of leaving the lid closed and sealed.

2. The transparent phase-separated supernatant reacted in the first reaction step was about 4,800 ml, and the lower layer was about 2,600 ml. Only about 4,800 ml of the supernatant was separated and collected in a 15 liter plastic container.

3. Into a 15-liter plastic container, 4.8 liters of the supernatant obtained in the first separation step, add 2.4 liters of toluene, immerse it in a 15-liter plastic container with a wide opening, and pour hot water. ^After heating up to ^° C and mixing with a 4,500 rpm hand drill with an impeller for 20 minutes to mix, two ¾ of a 15 liter plastic container was closed and left for 12 hours to proceed with the second reaction step.

4. A second separation step was carried out in which two liters of the supernatant in the liquid separated in the supernatant and the lower layer reacted in the second reaction step were collected in a three liter beaker. 5. Raise the reaction solution containing 2 liters obtained in the second separation step on the hot plate, insulate the side of the beaker with a plastic wrap, let the steam escape with the top of the beaker open, and mix the magnetic bar on the bottom of the beaker. Put a mercury thermometer so that the temperature of the liquid, the hot piate was turned on, set to 120 ^° C, 12hr, left to stand off, the reaction solution was about 1,500ml.

6. On the hot plate, add 150 ml of Xylene and 150 ml of liquid paraffine to the mix bar with magnetic bar while heating the reaction solution. The mixture was finished when the liquid temperature reached 50 ^° C. ^'

7. After turning off the hot PIate and allowing it to cool, the remaining liquid in the beaker was used as a fuel additive.

Example Manufacture of Fuel

Example 1

A fuel was prepared by mixing the fuel additive obtained in Preparation Example 1 with gasoline to be about 25 vol. Of the total fuel. Example 2

A fuel was prepared by mixing the fuel additive obtained in Preparation Example 2 with gasoline such that about 0.5 vol ¾ of the total fuel was used. Example 3

Fuel was prepared by mixing with light oil so as to be about 0.8% by volume of the total fuel additive obtained in Preparation Example 2. Example 4

A fuel was prepared by mixing with diesel to be about 0.4% by volume of the fuel additive fuel obtained in Preparation Example 1. Comparative Example Manufacture of Fuel Comparative Example 1

In the above preparation. The gasoline to which the obtained fuel additive was not added was used as a fuel. Comparative Example 2

The diesel oil which did not add the fuel additive obtained by the said preparation example was used as fuel.

Experimental Example

1. Fuel economy actual vehicle test

A vehicle equipped with a 1,999 cc gasoline engine (Hyundai Motor Model 2016; SONATA CWL) was prepared, the fuel of Example 2 and Comparative Example 1 was filled, and a fuel consumption actual vehicle test was performed.

In the specific fuel consumption test, the vehicle traveled at a constant speed of 80 km (25 km) on the 25th national highway from Gumi to Sangjubo, and measured the fuel economy of ascending (Gumi → Sangjubo) and descending (Sangjubo → Gumi). On a sunny day, the vehicle was filled with full fuel and traveled more than 100 km, and the next day it was measured with a section fuel economy meter installed on the dashboard of the car.

Table 1

As shown in Table 1, the reciprocating fuel economy of Comparative Example 1 which was run without the addition of the fuel additive was 18.5km / L, and the reciprocating average fuel economy of Example 2 which was run by adding 0.5vol% of the fuel additive of Preparation Example 2 Was 20.85km / L, and the fuel additive was added as in Example 2, showing a 12.7% fuel efficiency improvement. 2. Exhaust Gas / Fuel Efficiency Test (1) For the fuel of Example 1 and the fuel of Comparative Example 1, the exhaust gas measurement test using the automobile inspection equipment (JASTEC.CO., LTD.CGA-4700) was carried out at the automobile inspection station in Gumi, Gyeongsangbuk-do. It is shown in Table 2 below.

The test vehicle is a vehicle equipped with a gasoline engine (HYUNDAI, SONATA, CWL, 2.0 gasoline, 2015 model).

Table 2

As shown in Table 2, the fuel of Example 1 to which the fuel additive obtained in Preparation Example 1 was added to the gasoline to be 0.25VOL, the amount of HC and CO relative to the fuel of Comparative Example 1 without the fuel additive added in the exhaust gas test This came out less ..

(2) For the fuel of Example 3, the fuel of Example 4 and the fuel of Comparative Example 2, October 2016 at EMHA SION LABORATORY, Inha Technical College, Incheon, Korea. The results of conducting the exhaust gas and fuel consumption test on the day are shown in Table 3 below.

The test vehicle, HYUNDAI MOTORS 1.6L Diesel AT, is a 2012 model with a total mileage of 107,000 km. The test mode was CVS-75 MODE, and hot running and modal analysis were performed.

Table 3

_<qs A _p s _d £ -4.3% 2.5% -36.4% 4.8%

Comparative Example 2 0.022 1 .792 0 .90 14. 18

Example 4 0.017 0.919 0.43 15.23

7.23 As shown in the test results, when the fuel of Example 3 is used, HC and soot emissions are improved by about 3 to 40% compared to the fuel of Comparative Example 2. The fuel efficiency is improved by about 4.8%. In the case of using the fuel of Example 4, compared with the fuel of Comparative Example 2, HC, ΝΟχ, soot emission showed a tendency to be improved by about 25-50%, and the fuel economy was improved to about 7%. The following is a detailed analysis of the test results for each phase. After analyzing the dat a in the phase 1, phase 2, and phase 3 sections of the compact vehicle test mode (domestic CVS-75 mode), it is analyzed. The CVS-75 mode in Korea is the same as the FTP-75 mode used in the United States.It is a mode created by simulating the actual driving pattern by evenly combining the morning rush hour, the congestion section in the city, and the high-speed section out of the office. to be.

l

500 厘 »15∞ 2 幡 2500

Time (sec)

Mode total time is 1877 seconds, total distance is 17.8km, average speed is 34km / h, speed is 92km / h. For the fuel of Example 3, the fuel of Example 4 and the fuel of Comparative Example 2 for each of the following phasel, phase2, and phase3 sections: · Inha Technical College exhaust gas test laboratory (EMISSION LABORATORY) in Incheon, Korea In the results of the exhaust gas and fuel economy test on October 18, 2016 is shown in Tables 4 to 6.

Table 4

[g / km] [g / km] liter]

Comparative Example 2 0.034 0.076 1.790 0.43 14.70 Example 3 0.026 0.007 1.698 0.13 15.40 Change -23.7% -90.2% -5.2% -69.6% 4.7% Comparative Example 2 0.034 0.076 1.790 0.43 14.70 Example 4 0.021 0.001 0.981 0.12 16.56 Change -38.5 % -98.4% -45.2% -71.3% 12.7% The test results for each driving pattern are analyzed below. For the fuel of Example 3, the fuel of Example 4, and the fuel of Comparative Example 2, the CVS 75 MODE is running. The data generated under acceleration, acceleration and deceleration, deceleration, and idling operation are classified and analyzed. First, the results in the acceleration operation conditions are shown in Table 7 below.

Table 7

As shown in Table 7, when the fuel of Example 4 is applied, the fuel consumption rate and fuel economy are improved to about 10%, especially high speed (60km / more) and low speed (30km / less) When accelerated from 13 to 15% improved fuel economy. HC showed a tendency to decrease at high speed, and NOx showed a tendency to decrease about 40% regardless of speed. The results under the weak acceleration and deceleration operation conditions are shown in Table 8.

Table 8

As shown in Table 8, under weak acceleration and deceleration operation conditions, the fuel consumption rate was improved by 2 to 9% as a whole. Particularly, the fuel consumption rate was improved by about 13% at low speed. Regardless of speed, it tended to decrease by 20-40%. .

The results in the idling conditions are shown in Table 9 below.

Table 9

As shown in Table 9, when the engine idle, the fuel consumption was improved by about 11%.

3. Phase change experiment by moisture.

For the fuel additives prepared in Preparation Example 5, the results of conducting a phase change test by water in gasoline and diesel are shown in Table 10 below. Table 10

As shown in Table 10, in Sample 1, when 0.5 ml of water was added to the gasoline 20i with 0.5 ml of water, 0.5 ml of precipitate was maintained even after 20 minutes, and the precipitate was 0.5 ml after 5 days without hydrophobicity. In Samples 2 and 3, 20 ml of gasoline was added to 6 ml and 9 ml of fuel additive. There was no phase change 20 minutes after the addition of 0.5 ml of water, but after 5 days it became transparent and a phase change occurred.

In samples 4, 5, and 6, 3 ml, 6 ml, and 9 ml of fuel additives were added to diesel, and 0.5 ml of water was added, respectively. After 5 days, the width of the phase change was increased, and a lot of phase changes occurred in 3ml, 6ml, and 8ml.

Through this, it was confirmed that bioalcohol maintains hydrophobicity for 5 days in gasoline and there is no phase change (sample 1). In this case, the bioalcohol is not diluted in diesel, but the fuel additive was confirmed to be transparently diluted in diesel.

Claims

[Claim]

[Claim 1]

40 ^° C of at least one aqueous reaction solution selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous sodium salt solution, and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol. Reacting at a temperature of from 150 to 150 ton, the fuel additive manufacturing method.

[Claim 2]

The method of claim 1,

A volume ratio of the aqueous semicoagulant to the alkylene glycol monoalkyl ether solvent is 0.01 to 1.5, the fuel additive manufacturing method.

[Claim 3]

The method of claim 1,

The polar organic compound aqueous solution,

A method for producing a fuel additive, comprising water, at least one polar organic compound selected from the group consisting of alcohols, ketones, ethers, esters, acetals, peroxides, and epoxides.

[Claim 4]

The method of claim 1,

The alkylene glycol monoalkyl ether solvent,

A method for producing a fuel additive, comprising at least one selected from the group consisting of alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, trialkylene glycol monoalkyl ethers and esters thereof. ^·

[Claim 5]

The method of claim 1,

In the step of removing the low boiling point impurities by heat-treating the separated supernatant, Heat treatment is characterized in that for 10 seconds to 30 hours at a temperature of 6 (C to 150 ^° C, fuel additive manufacturing method.

[Claim 6]

Tax in Clause 1

At least one aqueous reaction solution selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous sodium salt solution, an alkylene glycol monoalkyl ether solvent, and nonpolar. The step of reacting the organic solvent at a temperature condition of 40 ^° C to 150 ^° C, characterized in that the progress in one or more gas atmosphere selected from the group consisting of oxygen, carbon dioxide, and carbon monoxide, fuel additive manufacturing method.

[Claim 7]

The method of claim 1,

At least one aqueous reaction solution selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous sodium salt solution, and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mo l to 250 g / mo l After the step of reacting at a temperature of 40 ^° C to 150 ^° C,

And heat-treating the reaction product to remove low-boiling impurities.

[Claim 8]

The method of claim 7, wherein

After the step of heat-treating the reaction product to remove the low boiling impurities, further comprising the step of adding a liquid hydrocarbon compound from 0.1% to 30% by volume ¾ based on the total fuel additive volume, fuel additive manufacturing method.

[Claim 9]

The method of claim 1,

At least one aqueous reaction mixture selected from the group consisting of water, an aqueous solution of a polar organic compound, and an aqueous salt solution, and a weight average molecular weight of 50 g / mo l to 250 After the step of reacting the alkylene glycol monoalkyl ether solvent of g / mol at a temperature of 40 ^° C to 150 ^° C,

Adding a non-polar organic solvent to the reaction product further comprising; fuel additive manufacturing method.

[Claim 10]

The method of claim 9,

The volume ratio of the nonpolar organic solvent to the alkylene glycol monoalkyl ether solvent is 0.5 to 1, fuel additive manufacturing method.

[Claim 11]

A fuel comprising a fuel additive and a hydrocarbon-based fuel obtained by the fuel additive manufacturing method of claim 1. [Claim 12]

The method of claim 11,

The fuel additive comprises 0.05% by volume to 50% by volume based on the total fuel volume. [Claim 13]

The method of claim 11,

The hydrocarbon fuel includes at least one selected from the group consisting of liquefied coal fuel, oral emulsion, gasoline, diesel, kerosene, heavy oil, aviation gasoline, and jet fuel.