KR101954918B1 - Manufacturing method of fuel additive and fuel using the same - Google Patents

Abstract

The present invention relates to a method for producing a water-soluble organic solvent, which comprises mixing at least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous solution, and an aqueous sodium salt solution, and an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / At a temperature of from 40 캜 to 150 캜.

Description

FIELD OF THE INVENTION The present invention relates to a method for producing a fuel additive,

The present invention relates to a process for producing a fuel additive for a hydrocarbon-based fuel and a fuel to which the fuel additive obtained from the process is applied.

Worldwide efforts are being made to prevent disasters that occur sporadically in various parts of the world due to global warming. In 2015, 195 countries around the world, including the United States and China, promised to cut greenhouse gas emissions by signing the Paris Climate Change Convention, and around the world are making various efforts to reduce greenhouse gas emissions. In the current situation where a low-carbon eco-friendly society is to be realized, research on hydrogen fuel that is pollution-free energy which does not discharge carbon dioxide at all is also active. Hydrogen fuel cell cars are eco-friendly vehicles, but the price per unit is too high to activate. In addition, electric vehicles are being actively studied as eco-friendly vehicles. Hydrogen-fueled cars and electric vehicles have no particulate matter emitted by combustion, and there are no gaseous substances associated with global warming.

However, since fossil fuels are an indispensable source of energy for electric power generation as well as transportation means such as automobiles, trains, ships and airplanes, countries around the world are striving to improve energy efficiency, especially energy efficiency of fossil fuels .

Increased use of fossil fuels accelerates the global warming phenomenon due to increased carbon dioxide emissions, deteriorates the global ecosystem and affects the living environment of the people. Especially, the increase of the fine dust (PM) Threatening the life expectancy and shortening the average life span.

In particular, in the petroleum industry, the problem of air pollution caused by NOx and PM (fine dust) emitted from automobiles and other vehicles is serious. Therefore, in order to reduce the emission of air pollutants, the quality of various fuels such as smokeless gasoline or diesel oil is improved I am trying to.

In Korean Patent No. 10-1210037, as a fuel additive for an internal combustion engine, fuel paraffin is heated to mix paraffin wax, fuel additive in which methylolate, liquid calcium sulfonate and synthetic fatty oil are mixed with each other is used, fuel efficiency of the vehicle is improved At the same time, it is suggested that hazardous emissions are greatly reduced.

Korean Patent 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 alkaline compound.

Korean Patent No. 10-1161638 discloses an emulsified nano-micro fuel additive and a method for producing the emulsified nano-micro fuel additive. The emulsified nano-micro fuel additive and the method for producing the emulsified nano micro fuel additive are disclosed in Korean Patent No. 10-1161638. It is described that the effect is excellent.

WO 02/059236 and WO 2003/078552 disclose a method for preparing an ethanol-diesel fuel composition by adding a surfactant to ethanol or propanol.

In the above-mentioned filed / registered patent, the fuel additive obtained by mixing the liquid hydrocarbon solvent and water has the effect of improving the fuel consumption and reducing the exhaust gas and fine particulate matter (PM) which are particulate matter. However, , The use of a surfactant is concerned with the generation of sludge due to the combustion of the surfactant, and it is not believed that the colloidal phase dispersed in the nanomicroparticles is stably dispersed in the hydrocarbon for a long period of time.

MTBE, a fuel additive still used by many countries, has a research report that MTBE from a gas station storage tank seeps into the ground and pollutes groundwater. MTBE is suspected to be a carcinogen. Is prohibited.

Thus, the use of bioethanol is increasing, instead of reducing the use of MTBE worldwide at present. However, bioethanol has a disadvantage in that the cost of constructing infrastructures such as new storage tanks and oil tanks is too high to limit the use of existing pipelines and to minimize water contamination during distribution due to the hydrophilic nature of bioethanol.

In addition, as the regulation of ship's greenhouse gas emission of IMO has become a reality, shipbuilding industry is studying to improve energy efficiency by reducing hull resistance, improving propulsion efficiency, improving operational efficiency, and improving engine efficiency. A study of ships using LNG fuel as fuel has been conducted to reduce carbon dioxide emissions and particulate matter (PM).

Marine fuels include marine diesel oil and residues, which are usually determined by the viscosity according to the mixing ratio of Bunker-C and marine gas oil. This is referred to as heavy oil (IFO), which is the best way to reduce carbon dioxide and fine dust while reducing costs for ship owners and operators. The International Maritime Organization (IMO) strongly condemns carbon dioxide emissions and is expected to suspend ship operations if it does not comply with regulations.

As of January 1, 2015, fuel oil sulfur limitations applicable to the Emission Control Area (ECA) are expected to heighten interest in the basic quality of marine fuel oil, while improving marine fuel energy efficiency and emissions of carbon dioxide (CO2) And the development of a fuel additive in which fine dust (PM) is reduced is urgently required.

Therefore, as a fuel additive, it is possible to stably disperse in a liquid hydrocarbon fuel without dispersing water with a homogenizer, without using a surfactant at all, to facilitate long-term dilution, to improve combustion efficiency, It is required to develop a technique capable of reducing exhaust gas and particulate matter (PM).

Korea Patent No. KR10-1210037 Korea Patent No. KR10-0339859 Korea Patent No. KR10-1161638 WO2002 / 059236 WO2003 / 078552

The present invention relates to a process for producing a liquid hydrocarbon fuel, which comprises preparing a liquid hydrocarbon fuel by a method in which water is not bonded to a homogenizer at all and a surfactant is not used and only water is bound to a -O- or -OH through a chemical reaction with a liquid hydrocarbon solvent, And it is easy to dilute for a long period of time because it is dispersed through a chemical bond to the fuel. In addition, the fuel consumption rate is improved when it is added to gasoline and diesel oil, and the fuel additive capable of significantly reducing PM5 and PM2.5, .

Further, the present invention is to provide a fuel to which the fuel additive is added.

In the present specification, at least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous solution and an aqueous sodium salt solution is mixed with an alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / At a temperature of from 40 캜 to 150 캜.

Also provided herein is a fuel comprising a fuel additive and a hydrocarbon-based fuel obtained by the method for manufacturing the fuel additive.

Hereinafter, a method of manufacturing a fuel additive according to a specific embodiment of the present invention and a fuel using the fuel additive will be described in detail.

According to one embodiment of the present invention, there is provided a method for producing an aqueous solution, comprising reacting at least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous solution, and an aqueous sodium salt solution and an alkylene glycol mono Reacting an alkyl ether-based solvent at a temperature of 40 ° C to 150 ° C.

The present inventors have found that, by using the above-described specific fuel additive manufacturing method, it is possible to produce an alkylene glycol monoalkyl ether-based solvent having a weight average molecular weight of 50 g / mol to 250 g / mol and an aqueous solution of a polar organic compound and a sodium salt Or a hydroxyl group present in the aqueous reaction liquid through the chemical reaction of at least one aqueous reaction liquid selected from the group consisting of the alkylene glycol monoalkyl ether solvent and the aqueous reaction liquid, , And the invention was completed through experiments.

In particular, the alkylene glycol monoalkyl ether solvent having a weight average molecular weight of 50 g / mol to 250 g / mol may be prepared by mixing at least one aqueous reaction solution selected from the group consisting of water, a polar organic compound aqueous solution, and a sodium salt aqueous solution, It is possible to easily produce a fuel additive stably dispersed without addition of a surfactant. Thus, it is possible to solve the problem of generation of sludge during combustion according to the addition of a conventional surfactant.

Further, when added to a hydrocarbon-based fuel such as gasoline or light oil through a fuel additive having improved hydrophobicity, it is possible to facilitate long-term dilution through stable dispersion, thereby improving the combustion efficiency of the fuel to which the fuel additive is added, Experiments have confirmed the reduction of snow and dust.

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

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

The polar organic compound aqueous solution means a solution in which the polar organic compound is dissolved in water. The polar organic compound has a property of dissolving very well in a water-soluble solvent such as water, and has an alcohol, ketone, ether, ester, acetal, Epoxides, and the like.

The alcohol may include methanol, ethanol, propanol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, Tert-butyl alcohol, hexanol, or a mixture of two or more thereof. An example of the concentration of the alcohol is not particularly limited, but may be, for example, 90% or more, or 90% to 99.9%, or 95% to 99.9%.

The ketone may include diisobutyl ketone, ethyl amyl ketone, carvone, Menthone, or a mixture of two or more thereof.

Examples of the ether include monoethers such as dibutyl ether, tert-butyl isobutyl ether, ethyl butyl ether, diisobutyl ether, dihexyl ether and diisooctyl ether; Or diethers thereof; Or a dialkyl cyclo ether having 4 to 10 carbon atoms; Or a mixture of two or more thereof.

The ester may be an organic acid ester such as ethyl formate ester, methyl acetate, octyl acetate, isoamylporphionic acid ester, methyl butyric acid ester, ethyl oleate ester or ethyl caprylate ester; Or inorganic acid esters such as cyclohexyl nitrate, isopropyl nitrate, n-amyl nitrate, 2-ethylhexyl nitrate and iso-amyl nitrate; Or a mixture of two or more thereof.

The acetal may include dimethylacetal, formaldehyde diethyl acetal, acetaldehyde diethyl acetal, acetaldehyde dibutyl acetal, or a mixture of two or more thereof.

The peroxide may include 3-butyl hydroperoxide, tert-butyl peroxide acetate, secondary-tertiary butyl peroxide, or a mixture of two or more thereof.

The epoxide may include 1,2-epoxy-4-epoxyethylcyclohexane, epoxidized methyl ester, ethylhexyl glycidyl, or a mixture of two or more thereof.

The sodium salt aqueous solution means a solution in which a salt containing sodium (Na) as a cation is dissolved in water. Specific examples thereof include an aqueous solution of NaOH or an aqueous solution of sodium silicate (Na ₂ O-nSiO ₂ -xH ₂ O) can do.

Meanwhile, the alkylene glycol monoalkyl ether solvent may have a weight average molecular weight of 50 g / mol to 250 g / mol. The weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a detector such as a known analyzer and a refractive index detector, and an analyzing column can be used. Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30 DEG C, a chloroform solvent (Chloroform), and a 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, and there is a limit that sludge is generated in combustion after being applied to fuel.

The alkylene glycol monoalkyl ether solvents include alkylene glycol monoalkyl ethers or derivative compounds thereof. Specifically, the alkylene glycol monoalkyl ether solvents include alkylene glycol monoalkyl ethers, di An alkylene glycol monoalkyl ether, a trialkylene glycol monoalkyl ether, and an ester thereof. That is, the alkylene glycol monoalkyl ether solvent may be an alkylene glycol monoalkyl ether, a dialkylene glycol monoalkyl ether, a trialkylene glycol monoalkyl ether, an alkylene glycol monoalkyl ether ester, a dialkylene glycol monoalkyl ether Esters, trialkylene glycol monoalkyl ether esters, or a mixture 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 (EGEEA), ethylene glycol monobutyl ether acetate (EGBEA), ethylene glycol monopropyl ether (EGPE), ethylene glycol monophenyl ether (EGPhE), ethylene glycol monohexyl ether (EGHE), ethylene glycol mono 2 -Ethylhexyl ether, and the like.

Examples of the above-mentioned 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), and diethylene glycol monohexyl ether (DGHE).

Examples of the trialkylene glycol monoalkyl ether or trialkylene glycol monoalkyl ether ester include triethylene glycol monomethyl ether (TGME), 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 reaction solution 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. The volume ratio of the non-polar 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 the reaction is carried out under the above-mentioned specific reactant input conditions, it is possible to suppress the side reaction while minimizing the loss of the reactants, thereby realizing a high reaction efficiency.

Meanwhile, at least one aqueous reaction solution selected from the group consisting of water, a polar organic compound aqueous 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 / The step of reacting at a temperature of from 40 캜 to 150 캜 may be carried out at a temperature of from 40 캜 to 150 캜, or from 45 캜 to 130 캜, or from 50 캜 to 120 캜, or from 50 캜 to 90 캜, or from 60 캜 to 90 캜, Lt; 0 > C. When the reaction is carried out under the above-mentioned specific temperature conditions, it is possible to suppress the side reaction while minimizing the loss of the reactants, thereby realizing high reaction efficiency.

At least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous 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 aqueous reaction liquid and the alkylene glycol monoalkyl ether solvent are mixed with each other to form a mixed solution only through physical mixing, and chemically react with alkyl A substitution reaction in which a bond such as -O-, -OH-, -OOH-, or the like is formed in a phenol-based solvent is difficult to proceed.

Also, it is preferable to use at least one aqueous reaction solution selected from the group consisting of water, a polar organic compound aqueous 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 / When the reaction is carried out at a high temperature of more than 150 ° C., the amount of the aqueous reaction solution or the alkylene glycol monoalkyl ether solvent to be reacted is lost due to vaporization, and the reaction efficiency may be reduced.

At least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous 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, To 150 캜 may be carried out in at least one gas atmosphere selected from the group consisting of oxygen, carbon dioxide, and carbon monoxide, if necessary. When the reaction is carried out under the above-described gas conditions, an oxidation reaction condition is formed and a high reaction efficiency can be realized.

The at least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous 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 / In the step of reacting at a temperature of < RTI ID = 0.0 > 150 C < / RTI >, phase separation may occur due to the chemical reaction between the aqueous reaction solution and the alkylene glycol monoalkyl ether solvent. At this time, if necessary, it may further include separating the upper layer liquid in the reaction product and the upper layer liquid in the lower layer liquid. An example of a method of separating the upper layer liquid and the lower layer liquid in the separation step is a separating funnel.

Here, the upper layer and the lower layer represent two different liquids which are separated by the interface due to phase separation in the reaction product. The lower layer and the lower layer have a larger density, The liquid located on the upper side with respect to the boundary surface can be classified into the supernatant.

More specifically, in the upper layer liquid, a substance in which an aqueous reaction liquid is chemically bonded to an alkylene glycol monoalkyl ether solvent is present, and the lower layer liquid is a substance in which some components of an alkylene glycol monoalkyl ether solvent are combined with an aqueous reaction solution It seems to exist in the state.

Meanwhile, at least one aqueous reaction solution selected from the group consisting of water, a polar organic compound aqueous 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 / And then adding the nonpolar organic solvent to the reaction product after the reaction at a temperature of 40 ° C to 150 ° C.

The non-polar organic solvent may be used after the reaction between the aqueous reaction solution and the alkylene glycol monoalkyl ether-based solvent to precipitate an excess aqueous reaction solution remaining in the reaction product.

The nonpolar organic solvent has a property of being insoluble in a water-soluble solvent such as water. Examples of the nonpolar organic solvent include hydrocarbon solvents having 5 to 20 carbon atoms, such as toluene, xylene, hexane, tetradecane, octadecene , And toluene can be preferably used. The toluene may be toluene having a purity of 99% or more or commercially available industrial toluene (industrial toluene containing 25% of benzene) without limitation.

When the nonpolar organic solvent is added to the reaction product as described above, the step of adding the nonpolar organic solvent to the reaction product results in separation of the upper organic solvent and the upper organic solvent from the lower organic solvent. . An example of a method of separating the upper layer liquid and the lower layer liquid in the separation step is a separating funnel.

Here, the upper layer and the lower layer represent two different liquids which are separated by the interface due to phase separation in the reaction product. The lower layer and the lower layer have a larger density, The liquid located on the upper side with respect to the boundary surface can be classified into the supernatant.

If necessary, the step of separating the supernatant in the reaction product and the supernatant in the supernatant may further include cooling the reaction product to room temperature (20 ° C). Through the step of cooling the reaction product to room temperature (20 ° C), phase separation can proceed in the reaction product as a supernatant and a supernatant.

Also, the fuel additive manufacturing method according to one embodiment of the present invention is a method for producing a fuel additive, which comprises reacting at least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous solution and an aqueous sodium salt solution and having a weight average molecular weight of 50 g / Treating the reaction product with an alkylene glycol monoalkyl ether solvent at a temperature of 40 ° C to 150 ° C to remove low boiling point impurities.

-O-, -OH-, or -OOH- bonds contained in the reaction product may be broken through heat treatment of the reaction product, and the atomic group including the -O-, -OH-, or -OOH- bond may be removed by evaporation as an impurity.

That is, the low boiling point impurity means a compound containing -O-, -OH-, or -OOH- bond, and the boiling point of the low boiling point impurity is low at less than 60 캜, have.

For this purpose, the heat treatment of the separated supernatant may be carried out at a temperature of 60 ° C to 150 ° C for 10 seconds to 30 hours.

If necessary, the step of removing the low boiling point impurities by heat treatment of the separated supernatant may further include adding a liquid hydrocarbon compound in an amount of 0.1% by volume to 30% by volume based on the total fuel additive volume have.

Examples of the liquid hydrocarbon compound include a liquid paraffin compound, a liquid naphthalene compound, a liquid olefin compound, and a liquid aromatic compound. As a more specific example, the liquid aromatic compound may include xylene.

On the other hand, according to another embodiment of the present invention, a fuel including the fuel additive and the hydrocarbon-based fuel obtained by the fuel additive manufacturing method of this embodiment can be provided. The fuel additive obtained from the fuel additive manufacturing method of one embodiment can reduce exhaust gas and particulate matter when added to gasoline fuel, diesel fuel, marine oil, and aviation oil, thereby improving fuel efficiency.

Also, since the fuel additive obtained from the fuel additive manufacturing method of the embodiment has a hydrophobic property, the added fuel has little phase separation depending on the moisture content, and the phase separation phenomenon is very small, .

The content of the fuel additive manufacturing method includes all of the above-mentioned contents in the embodiment.

The fuel additive may be included in an amount of 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 at least one selected from the group consisting of coal liquefied fuel, orimal fuel, gasoline, light oil, kerosene, heavy oil (bunk oil), aviation gasoline, and jet fuel. That is, the hydrocarbon-based fuel may include coal liquefied fuel, orimal fuel, gasoline, light oil, kerosene, heavy oil (bunk oil), aviation gasoline, jet fuel, or a mixture of two or more thereof.

The fuel may further include at least one additive selected from the group consisting of an anti-freezing agent, an antistatic agent, a corrosion inhibitor, an antioxidant, a lubricant, an octane number improver, a cetane number improver, a flow improver, a diffusing agent and a heat stabilizer. That is, the additives may include an anti-freezing agent, an antistatic agent, a corrosion inhibitor, an antioxidant, a lubricant, an octane number improver, a cetane number improver, a flow improver, a diffusing agent, a heat stabilizer or a mixture of two or more thereof.

INDUSTRIAL APPLICABILITY According to the present invention, since no surfactant is used and no water is dispersed in a homogenizer, it is stably dispersed in a liquid hydrocarbon fuel to facilitate long-term dilution, A method for producing a fuel additive capable of reducing gas and particulate matter (PM) and a fuel using the fuel additive obtained therefrom can be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Preparation Example: Preparation of fuel additive >

Production Example 1

100 ml of butyl cellosolve (BC) and 40 ml of 95% ethyl alcohol were added to a 300 ml beaker. A home oxygen generator (Model NO: EYVENZ3M, manufactured by Mitsubishi Heavy Industries, Ltd.) for separating oxygen and nitrogen while raising the beaker on a magnetic hot plate and stirring the mixture at 400 rpm using a magnetic bar while maintaining the temperature of the mixture at 75 to 85 ° C for 30 minutes ) Was used to supply only oxygen to the liquid of the beaker being reacted with the hose for 20 minutes and reacted with oxygen, and the remaining liquid was used as a fuel additive.

Production Example 2

1. Add 500 ml of ethylene glycol mono butyl ether (BC) at 70 ° C to a 1-liter beaker and add 120 ml of water at 85 ° C (at this time, the temperature of the whole liquid is 74 ° C) Using a home oxygen generator (Model NO: EYVENZ3M) that separates oxygen and nitrogen while stirring the beaker with a magnetic bar at 400 rpm for 5 minutes, only oxygen is supplied to the liquid of the beaker being reacted with the hose for 20 minutes, And the reaction was allowed to proceed for 1 hour. At this time, the whole liquid was transparent without phase separation.

2. Ethylene glycol mono butyl ether (BC), water, and oxygen were reacted with the reaction solution through a first reaction step. The reaction solution was heated on a hot plate at 400 rpm using a magnetic bar. (Toluene) was added to the reaction mixture, and the temperature of the reaction liquid during the heating reaction was cloudy at 62 ° C. In this state, the second reaction step of turning off and leaving the hot plate was performed.

3. The hot plate was turned off and left. At around 20 ℃, the liquid was transparent and separated into the supernatant and the supernatant by phase separation. The amount of the submerged solution was about 40 ml. The supernatant was evaporated to about 760 ml. A first separation step of separating the supernatant and the lower layer was carried out.

4. Into a 1-liter beaker, 760 ml of the supernatant separated in the first separation step was poured, the side of the beaker was wrapped with a plastic wrap, and the upper portion of the beaker was sealed with a little space so that the steam could escape. The resulting solution was heated to a temperature of 20 ° C. and heated to distill for 12 hours while maintaining the temperature at 70 ° C. The solution was used as a fuel additive.

Production Example 3

1. 100 ml of butyl cellosolve (BC: Ethylene Glycol Mono Butyl Ether) and 100 ml of water were added to a 300 ml beaker and mixed transparently without phase separation. A mixture of water and ethylene glycol mono butyl ether (BC) was placed on a hot plate and heated. There was no clear phase separation from room temperature to 40 ℃. As the liquid temperature exceeded 44 ° C, air bubbles started to be generated from the lower side. The bubble spreads around the liquid temperature of 50 ° C, and the whole liquid becomes cloudy. At a liquid temperature of 60 ° C, about 25 ml of water was deposited underneath, and the above solution was cloudy. I lowered it from the hot plate, and the sediment on the bottom of the beaker was increased to about 30 ml. The beaker was placed on the hot plate again and the temperature was raised, and about 50 ml of precipitate was deposited on the bottom at about 70 ° C. The supernatant poured at around the liquid temperature of 79 ° C became transparent, and the transparent precipitate at the lower layer was increased to about 50 ml. The upper layer of the transparent ethylene glycol mono butyl ether (BC) compound was about 150 ml.

2. A beaker phase-separated from the supernatant (150 ml) and the supernatant (50 ml) was placed on a hot plate, and 30 ml of toluene (toluene) was gradually added thereto at 65 ° C. The supernatant was immediately poured into a precipitate, The liquid has increased to 80 ml. 20 ml of toluene was added as a syringe and added in an amount of 50 ml. The lower layer liquid was transparent, the upper layer liquid became cloudy, and the temperature was raised to 70 占 폚 so that the supernatant liquid became transparent, To 85 ml. When 20 ml of toluene was added to the solution at 70 ° C, the supernatant immediately became cloudy. When the temperature reached 70 ° C again, the entire solution became transparent and the lower layer remained almost transparent Respectively. When 30 ml of toluene (toluene) was further added thereto at a total liquid temperature of 70 ° C, the lower layer liquid remained at 85 ml with almost no change.

3. The process of separating into supernatant and lower supernatant was performed with a separating funnel.

4. Transfer 215 ml of the supernatant into a 500 ml beaker, wrap the beaker in a plastic wrap to warm the side of the beaker, and place a 200 ml beaker in the center of the beaker to contain the evaporated and condensed liquid, and wrap the upper part of the 500 ml beaker in plastic wrap The bottle was warmed and placed on a hot plate. The glass was placed in a round glass flask with cold water at the top of the bottle. The vaporized gas inside the beaker contacted with the cold water, easily condensed, and collected in a 200 ml beaker. Thereafter, the hot plate was set at 120 ° C. for 6 hours, the 500 ml beaker on the hot plate was raised and left, and the solution contained in the 500 ml beaker was 195 ml. In the middle 200 ml beaker, about 15 ml condensate was collected . At this time, a solution contained in a 500 ml beaker was used as a fuel additive.

Production Example 4

1. 100 ml of ethylene glycol mono butyl ether (BC) and 100 ml of a 95% aqueous solution of bio-alcohol ('Prethanol A', manufactured by DUKSAN) were mixed at 15 ° C and kept warm with a vinyl wrap The beaker was sealed with a plastic wrap in the same manner as that in which a 200 ml beaker was placed in a 500 ml beaker in the middle of a 500 ml beaker. A beaker was placed on the hot plate and a round glass flask with cold water was placed on the top of the beaker. The gas was contacted with cold water, condensed easily, and collected in a 200 ml beaker inside. The hot plate was turned on and the temperature was set at 110 ° C for 6 hours. After 5 hours, the solution temperature was 70 DEG C, and 0.5 mL of condensate was accumulated.

2. 100 ml of toluene was added to a 500 ml beaker containing ethylene glycol mono-butyl ether (BC) and bio-alcohol, and the hot plate temperature was set at 125 ° C. for 8 hours. A 200 ml beaker in a 500 ml beaker contained 20 ml of condensate. At this time, 15 ml of the solution in a 500 ml beaker is poured into another beaker, and the cold water is dropped into the eyedropper to confirm the hydrophilicity. The cold water falls down to the bottom of the beaker, and some of the solution seems to be diluted. Again, the beaker was placed on a hot plate, turned on, set at 125 ° C for 8 hours, and left to heat-distill in the same manner. A 200 ml condensate beaker in the beaker contained 35 ml of condensate. In order to characterize 35 ml of condensate, 3 ml of condensate was added to 30 ml of light oil, and some of them were submerged in the bottom, and then diluted transparently in the solution.

3. About 265 ml of the reaction solution contained in a 500 ml beaker is poured into a PET bottle. The air is separated into oxygen and nitrogen, the hose is connected to an oxygen generator for supplying oxygen, and a glass tube is connected to the end. Oxygen was supplied for 30 minutes to react with oxygen, and 26 ml of liquid paraffin was added to prepare the fuel additive of the present invention.

Production Example 5

1. Place a 5 liter beaker on a hot plate and add 1,200 ml of ethylene glycol mono butyl ether (BC), an aqueous solution of 95% concentration of bio-alcohol ('Prethanol A', available from DUKSAN) (Toluene) and 100 ml of water. The temperature was set at 120 ° C for 60 hours. The side surface was sealed with mixing at 480 rpm using a magnetic bar. A 500 ml beaker was hung in a 5-liter beaker to collect the condensate. Sealed with a lap, and placed in a sealed round plastic flask on a sealed plastic. The vaporized gas inside the beaker was contacted with cold water, easily condensed, and collected in a 500 ml beaker inside.

2. Add 900 ml of 99.9% ethanol (EtOH) aqueous solution to 5 liter beaker to increase the ethanol content in the reaction between ethylene glycol monobutyl ether (BC) and toluene, plate was turned on and the temperature was set to 120 ° C and the time was set to 36 hours. The mixture was allowed to mix with a magnetic bar at 150 rpm.

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

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

Production Example 6

1. A 15-liter plastic container was charged with 3500 ml of ethylene glycol mono-butyl ether (BC), 850 g of sodium silicate (water glass No. 2; Na ₂ O-nSiO ₂ -xH ₂ O) was added to 3500 ml of water at about 50 ° C, The mixture was stirred for 4 hours using a 4,500 rpm hand drill motor equipped with a mix impeller, and then the lid was closed, sealed, and left to perform a first reaction step.

2. The transparent phase-separated supernatant which was reacted in the first reaction step was about 4,800 ml, and the supernatant was about 2,600 ml. A first separation step of separating only about 4,800 ml of the supernatant into a 15 liter plastic container was carried out.

3. In a 15 liter plastic container, add 4.8 liters of the supernatant obtained in the first separation step, add 2.4 liters of toluene (toluene), immerse it in a 15-liter plastic container with a wide opening, pour hot water, , Mixed with a 4,500 rpm hand drill with a mix impeller for 20 minutes, and then the lid of the 15-liter plastic container was closed and allowed to stand for 12 hours to carry out the second reaction step.

4. A second separation step was carried out in which 2 liters of the supernatant liquid phase-separated into the supernatant and the lower layer reacted in the second reaction step were collected in a 3 liter beaker.

5. Place the reaction solution containing the 2 liters obtained in the second separation step on the hot plate, warm the side surface of the beaker with a plastic wrap, allow the steam to escape with the upper part of the beaker open, , And a mercury thermometer was inserted so that the temperature of the solution could be known. The hot plate was turned on, and the temperature was set at 120 ° C for 12 hours. When the solution was left standing, the reaction solution became 1,500 ml.

6. While hot plate was turned on, 150ml of xylene and 150ml of liquid paraffin were added to 1,500ml of reaction liquid in a mixer by magnetic bar and the mixture was completed when the temperature reached 50 ℃.

7. The hot plate was turned off, allowed to cool, and the liquid remaining in the beaker was used as a fuel additive.

≪ Example: Production of fuel >

Example 1

A fuel was prepared by mixing the fuel additive obtained in Preparation Example 1 with gasoline so as to be about 0.25% by volume of the total fuel.

Example 2

The fuel additive obtained in Preparation Example 2 was mixed with gasoline so as to be about 0.5% by volume of the total fuel to prepare a fuel.

Example 3

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

Example 4

A fuel was prepared by mixing the fuel additive obtained in Preparation Example 1 with light oil so as to be about 0.4% by volume of the total fuel.

≪ Comparative Example: Production of fuel >

Comparative Example 1

Gasoline without the addition of the fuel additive obtained in the above Production Example was used as fuel.

Comparative Example 2

Light oil not containing the fuel additive obtained in the above Production Example was used as fuel.

<Experimental Example>

1. Fuel Economy Vehicle Test

A vehicle equipped with a 1,999 cc gasoline engine (Hyundai Motor's 2016 model: SONATA CVVL) was prepared and filled with the fuel of Example 2 and Comparative Example 1, and fuel efficiency vehicle test was performed.

The specific fuel mileage test was carried out on the average speed of 80 KPH (33 km) on the 25th national road from Gumi to Sangjubo, and the fuel consumption of the uphill (Gumi → Sangjubo) and the downhill (Sangjubo → Gumi) was compared. On a clear, windy day, the fuel was filled in full and traveled more than 100 km, and the next day, it was measured by an interval fuel mileage meter installed on a car instrument panel.

division Uphill fuel consumption Downstream fuel consumption Average mileage Example 2 20.5km / L 21.2km / L 20.85km / L Comparative Example 1 18.2km / L 18.8km / L 18.5km / L

As shown in Table 1, the reciprocating fuel efficiency of Comparative Example 1 running without addition of the fuel additive was 18.5 km / L, and the reciprocating average fuel efficiency of Example 2, which was run by adding 0.5% by volume of the fuel additive of Production Example 2 Was 20.85 km / L, and the addition of the fuel additive as in Example 2 showed a fuel efficiency improvement of 12.7%.

2. Exhaust gas / fuel consumption test

(1) The results of the exhaust gas measurement test using the automobile inspection equipment (JASTEC.CO., LTD. CGA-4700) at the automobile inspection center in Gumi city, Gyeongsangbuk-do for the fuel of the embodiment 1 and the fuel of the comparative example 1 The results are shown in Table 2 below.

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

division additive Additive amount
(VOL%) rpm HC (ppm) CO (%) λ (excess air ratio) Comparative Example 1 - - 660 ~ 2,250 38 to 80 0.03 to 0.08 1.00 Example 1 Production Example 1 0.25 660 to 2,500 6 to 25 0.00 to 0.05 1.01

As shown in Table 2, the fuel of Example 1, in which the fuel additive obtained in Production Example 1 was added to gasoline in an amount of 0.25 VOL%, was compared with the fuel of Comparative Example 1 in which the fuel additive was not added in the exhaust gas test, Less quantities came out.

(2) The fuel of Example 3, the fuel of Example 4, and the fuel of Comparative Example 2 were obtained from the Inha Technical College Emission Laboratory of Incheon, Republic of Korea, October 18, 2016 The results of exhaust gas and fuel consumption tests are shown in Table 3 below.

The test vehicle is HYUNDAI MOTORS 1.6L Diesel AT, 2012 year, and the total mileage is 107,000km. The test mode is the CVS-75 MODE, and the hot run and modal analysis were performed.

HC [g / km] No _x [g / km] Smoke factor [% -liter] F / E [km / l] Comparative Example 2 0.022 1.792 0.90 14.18 Example 3 0.021 1.837 0.57 14.86 Increase / decrease rate -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 Increase / decrease rate -23.2 -48.7 -51.9 7.4

As shown in the test results, when the fuel of Example 3 is used, the exhaust amount of HC and soot tend to be improved by about 3 to 40% compared with the fuel of Comparative Example 2, and the fuel consumption of about 4.8% . In the case of using the fuel of Example 4, the exhaust amount of HC, NOx, and soot were improved by about 25 to 50% compared with the fuel of Comparative Example 2, and the fuel efficiency was improved to about 7%.

The following is an analysis of the detailed phase-by-phase test results. The analysis is performed after classifying the data that occurred in phase 1, phase 2, and phase 3 under the compact car test mode (domestic CVS-75 mode). The domestic CVS-75 mode 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 connecting the morning departure time, the stagnant part of the city, and the high- to be.

The total mode time is 1877 seconds, the total mileage is 17.8km, the average speed is 34km / h, and the maximum speed is 92km / h.

For the fuel of Example 3, the fuel of Example 4 and the fuel of Comparative Example 2 for each phase 1, phase 2, and phase 3 sections, an exhaust gas testing laboratory of Inha Technical College (Incheon, Korea) The results of exhaust gas and fuel consumption tests conducted on October 18, 2016 are shown in Tables 4 to 6 below.

Phase 1 HC [g / km] CO [g / km] No _x [g / km] Smoke factor [% -liter] F / E [km / l] Comparative Example 2 0.025 0.000 1.237 0.74 15.12 Example 3 0.029 0.009 1.694 0.78 15.48 Increase / decrease rate 14.4% - 36.9% 4.5% 2.3% Comparative Example 2 0.025 0.000 1.237 0.74 15.12 Example 4 0.023 0.033 0.701 0.36 15.89 Increase / decrease rate -7.7% - -43.3% -51.9% 5.1%

Phase 2 HC [g / km] CO [g / km] No _x [g / km] Smoke factor [% -liter] F / E [km / l] Comparative Example 2 0.015 0.007 2.016 1.21 13.58 Example 3 0.016 0.013 1.968 0.73 14.37 Increase / decrease rate 6.1% 70.7% -2.4% -40.2% 5.8% Comparative Example 2 0.015 0.007 2.016 1.21 13.58 Example 4 0.013 0.156 0.974 0.63 14.38 Increase / decrease rate -15.6% 2025.7% -51.7% -48.2% 5.9%

Phase 3 HC [g / km] CO [g / km] No _x [g / km] Smoke factor [% -liter] F / E [km / l] 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 Increase / decrease rate -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 Increase / decrease rate -38.5% -98.4% -45.2% -71.3% 12.7%

The following is an analysis of the test results according to the operation pattern. The results are shown in the following. The fuel of Example 3, the fuel of Example 4, and the fuel of Comparative Example 2 were subjected to the CVS 75 MODE running under the conditions of acceleration, deceleration, The data was classified and analyzed. The results under the accelerated operating conditions are shown in Table 7 below.

Acceleration operation condition Speed [km / h] Acc rate [m / s ² ] HC [g / km] CO [g / km] No _x [g / km] Smoke factor [% -liter] FC [cc] F / E [km / l] Comparative Example 2 72.5 0.55 0.02 0.03 1.75 0.43 1.7 11.5 39.7 0.71 0.03 0.02 2.12 0.82 1.1 10.8 16.5 1.02 0.04 0.02 2.76 1.38 0.7 6.7 Example 4 75.2 0.53 0.02 0.20 1.10 0.16 1.6 13.0 40.1 0.72 0.03 0.32 1.24 0.39 1.0 11.6 16.3 1.09 0.05 0.60 1.45 0.71 0.6 7.7

As shown in Table 7, when the fuel of Example 4 was applied, the fuel consumption rate and the fuel consumption ratio were improved to about 10%. Especially, the high speed (60 km / , The fuel economy is improved by 13 ~ 15%. HC showed a tendency to decrease at high speed, and NOx tended to decrease by 40% regardless of the speed.

Table 8 shows the results under the weak and decelerating operation conditions.

Drug Decelerating Operation Condition Speed [km / h] Acc rate [m / s ² ] HC [g / km] CO [g / km] No _x [g / km] Smoke factor [% -liter] FC [cc] F / E [km / l] Comparative Example 2 86.6 0.00 0.03 0.03 1.30 0.40 1.4 17.2 76.9 0.03 0.02 0.03 1.45 0.39 1.3 17.3 47.9 0.02 0.02 0.02 1.44 0.63 0.7 18.9 34.2 0.02 0.01 0.02 1.49 0.95 0.6 18.3 8.7 0.05 0.03 0.00 3.11 2.24 0.3 8.5 Example 4 86.8 0.00 0.02 0.18 0.74 0.14 1.4 18.2 77.0 0.01 0.01 0.17 0.66 0.13 1.1 19.0 48.0 0.01 0.01 0.26 0.71 0.30 0.7 20.1 34.6 0.02 0.01 0.38 0.66 0.40 0.6 18.7 10.0 0.08 0.02 0.92 1.19 0.95 0.3 12.0

As shown in Table 8, the fuel consumption rate is improved by about 2 to 9% in the entire engine speed under the low acceleration / deceleration operation condition, and the fuel consumption rate is improved by about 13% Regardless of the speed.

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

Idling condition Fuel consumption (cc / sec) Comparative Example 2 0.299 Example 3 0.285 Example 4 0.266

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

3. Phase change experiment by moisture

The fuel additive prepared in Preparation Example 5 was subjected to a test for phase change by moisture in gasoline and light oil, and the results are shown in Table 10 below.

Sample Oil type Fuel additive
Addition amount Water addition / ml Change in sediment / ml Gasoline / ml Diesel / ml ml After 20 minutes After 5 days One 20 - 3 0.5 0.5 0.5 2 20 - 6 0.5 0.5 0.0 (transparent) 3 20 - 9 0.5 0.5 0.0 (transparent) 4 - 20 3 0.5 1.0 3.0 5 - 20 6 0.5 2.0 6.0 6 - 20 9 0.5 3.0 8.0

As shown in Table 10, in Sample 1, when 0.5 ml of water was added to 3 ml of fuel additive in 20 ml of gasoline, 0.5 ml of the precipitate was retained even after 20 minutes, and after 5 days, However, in Samples 2 and 3, 6 ml and 9 ml of fuel additives were added to 20 ml of gasoline, and 0.5 ml of water was added. After 20 minutes, there was no phase change, but after 5 days, the phase became transparent and a phase change occurred. In Samples 4, 5, and 6, the amount of the fuel additive added to the diesel fuel was 3 ml, 6 ml, and 9 ml, respectively. When 0.5 ml of water was added to each of the diesel fuel, the generation of the precipitate was changed to 1.0 ml, 2.0 ml, After 5 days, the phase change width increased to 3ml, 6ml and 8ml.

It was confirmed that there was a case in which the bio alcohol retains hydrophobicity for 5 days in the gasoline and the phase change does not occur (Sample 1). In the case of the light oil, the bio alcohol is not diluted in the light oil, It was confirmed that it was transparently diluted.

Claims (13)

At least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous 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, Lt; RTI ID = 0.0 &gt; 120 C, &lt; / RTI &
Wherein the polar organic compound aqueous solution comprises at least one polar organic compound selected from the group consisting of an alcohol, a ketone, an ether, an ester, an acetal, a peroxide, and an epoxide, and water.
The method according to claim 1,
Wherein the volume ratio of the aqueous reaction solution to the alkylene glycol monoalkyl ether solvent is 0.1 to 1.5.
delete The method according to claim 1,
The alkylene glycol monoalkyl ether-
Alkylene glycol monoalkyl ether, alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, trialkylene glycol monoalkyl ether, and an ester thereof.
delete The method according to claim 1,
The step of reacting at least one aqueous reaction solution, alkylene glycol monoalkyl ether solvent and nonpolar organic solvent selected from the group consisting of water, a polar organic compound aqueous solution and an aqueous sodium salt solution at a temperature of 50 ° C to 120 ° C,
Wherein the reaction is carried out in at least one gas atmosphere selected from the group consisting of oxygen, carbon dioxide, and carbon monoxide.
The method according to claim 1,
At least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous 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, To 120 &lt; 0 &gt; C,
And heat treating the reaction product to remove low boiling point impurities.
8. The method of claim 7,
After the reaction product is heat-treated to remove low boiling point impurities,
Further comprising the step of adding a liquid hydrocarbon compound in an amount of 0.1% by volume to 30% by volume based on the total fuel additive volume.
The method according to claim 1,
At least one aqueous reaction liquid selected from the group consisting of water, a polar organic compound aqueous 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, To 120 &lt; 0 &gt; C,
And adding a non-polar organic solvent to the reaction product.
10. The method of claim 9,
Wherein the volume ratio of the non-polar organic solvent to the alkylene glycol monoalkyl ether solvent is 0.5 to 1.
A fuel, comprising a fuel additive and a hydrocarbon-based fuel obtained by the method of manufacturing the fuel additive of claim 1.
12. The method of claim 11,
Wherein the fuel additive is comprised between 0.05% and 50% by volume based on the total fuel volume.
12. The method of claim 11,
Wherein the hydrocarbon-based fuel comprises at least one selected from the group consisting of coal liquefied fuel, orimal fume, gasoline, light oil, kerosene, heavy oil, air gasoline, and jet fuel.