KR101670936B1 - Method for manufacturing bio fuel using animal and vegetable fats of high acid value - Google Patents

Abstract

More particularly, the present invention relates to a method for manufacturing a biofuel using a high acidity animal, and more particularly, to a method for manufacturing a biofuel using a high acidity animal / vegetable oil and a low alcohol in an alcohol- , The hydrophilic low alcohol is pulled up by the organic catalyst having the hydroxycarboxylic radical mixed with the hydrophilic radical so that the ester reaction between the glycerin and the lower alcohol is carried out to produce the monoalcohol glycerin and the dialcohol glycerin. In order to accelerate the reaction time, alcohol decomposition reaction is carried out in the same phase such as liquid-liquid phase and gas-gas phase at a high temperature, and the water produced in the reaction process is immediately evaporated at a high temperature to remove glycerin and by- The present invention relates to a method for producing heavy fuel oil.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a biofuel using high-

More particularly, the present invention relates to a method for manufacturing a biofuel using a high acidity animal, and more particularly, to a method for manufacturing a biofuel using a high acidity animal / vegetable oil and a low alcohol in an alcohol- , The hydrophilic low alcohol is pulled up by the organic catalyst having the hydroxycarboxylic radical mixed with the hydrophilic radical so that the ester reaction between the glycerin and the lower alcohol is carried out to produce the monoalcohol glycerin and the dialcohol glycerin. In order to accelerate the reaction time, alcohol decomposition reaction is carried out in the same phase such as liquid-liquid phase and gas-gas phase at a high temperature, and the water produced in the reaction process is immediately evaporated at a high temperature to remove glycerin and by- The present invention relates to a method for producing heavy fuel oil.

Biodiesel and biofuel produced from bio-oils isolated from animal and plant resources are renewable green fuels and are attracting attention as one of important future energy sources. At present, it has advantages in terms of production cost compared to petroleum-based diesel, but biodegradability, non-toxicity, and emission of fine dust and sulfur in burning are greatly reduced.

In addition, since carbon dioxide generated during combustion can be absorbed through the cultivation of raw crops, it can be said to be a clean fuel capable of coping with global warming in that the emission of carbon dioxide can be greatly reduced. As a result, bio-diesel is being produced from bio-oil and methanol at commercial level, and the development of innovative technologies to improve productivity, economy, and product performance is continuously being attempted.

Refined bio-oil, which is used as a common raw material in the biodiesel industry, has a high raw material price due to its refining cost. Therefore, if high-grade bio-oil having a relatively low refining level or an acid value of 5 or more such as waste oil can be used as a raw material, It is expected that the production cost will be lowered, and besides vegetable oil such as waste cooking oil and palm oil, a low-grade oil such as tallow, lard, animal oil such as clay and duck oil can be used as raw material for biodiesel.

Therefore, there is a growing interest in the technical field of converting high-acid bio-oils such as crude biodegradable oils such as crude biodegradable oils and waste edible oils into biodiesel, but effective techniques at a commercial level are not being presented.

The first method to convert high acidity bio-oil into biodiesel is to pretreat the fatty acids contained in the bio-oil before the biodiesel production reaction (ester exchange reaction) After separating the water generated in the pretreatment step, the conventional technique of manufacturing biodiesel is applied. The second method is to apply a metal oxide catalyst, which is relatively stable to water or acidic components and relatively low catalytic activity, and to introduce an excess amount of methanol at a high temperature and a high pressure of 250 ° C or more in order to increase the reaction activity, Time.

However, the first method for preparing biodiesel after performing the pretreatment process and the water separation process includes a preprocessing process and a moisture separation process, thereby increasing the manufacturing process and producing a low production cost due to a low production amount. The second method of producing biodiesel using a metal oxide catalyst at a high temperature for a long period of time also provides a high temperature of 250 ° C or higher and a long reaction time, which results in a large energy consumption and relatively low acceptance rate. And the safety problem that explosion can occur due to the production under high pressure conditions is inherent in both methods.

Korean Patent Laid-Open Publication No. 10-2012-0011060 (published on Apr. 21, 2014, hereinafter referred to as "Prior Art 1"), a biodiesel manufacturing apparatus has a short reaction time structure to produce biodiesel, which is not an animal, plant, animal, Biodiesel is produced from common vegetable raw materials. By circulating the remaining 120 ° C in the drying process of the reaction tank and supplying it to the raw material heating tank, the temperature of the raw material heating tank is maintained at 60 to 80 ° C to shorten the reaction time Device. However, the prior art document 1 does not suggest a method of improving productivity by using high-value animal or vegetable oil to rapidly produce biodiesel using a low-priced vegetable raw material which is generally refined.

In the apparatus and method for producing biodiesel using the waste cooking oil of Korean Patent No. 10-0929030 (registered on November 20, 2009, hereinafter referred to as 'Prior Art 2'), the reaction of excessively mixing methanol mixed with waste cooking oil and caustic soda A tank, a heater, and a stirrer to perform a reaction at a high temperature, and the heated methanol gas is supplied to a condenser, condensed in a liquid phase, and collected into a methanol recovery tank; The first step is to extract glycerin from the biodiesel production process by mixing methane mixed with waste cooking oil and caustic soda, and add the reaction mixture in which methanol and caustic soda are mixed with the residual liquid from which glycerin is extracted The remaining methanol is removed by vaporization, and glycerin is further removed to produce biodiesel.

The above prior art document 2 provides an apparatus and a method for producing biodiesel using waste cooking oil having a high acid value but a process of producing glycerin as a by-product in the process of producing biodiesel and extracting and removing glycerin generated during the production process The process time is prolonged, and the yield of biodiesel production is lowered, thereby lowering the productivity. In addition, since the temperature of the reactor is set to 65 ° C, which is lower than the methanol vaporization temperature, so that the methanol decomposition reaction can be performed by mixing the methanol with the waste cooking oil in a liquid state, the reaction time is long.

This prior art document 2 proposes an apparatus and a method for producing biodiesel using waste cooking oil having a high acid value. However, since a large amount of glycerin is generated due to moisture during the reaction process, the yield of the biofuel is lowered and the reaction time The problem of low productivity was not solved.

In the non-catalytic process for producing biodiesel fuel which does not produce a byproduct of Korean Patent No. 10-0693199 (hereinafter referred to as "Prior Art 3"), the animal or vegetable oil is mixed with methanol, and 370 And the methanolysis reaction is carried out by the reaction temperature of -500 ° C and the reaction pressure of 20-60 MPa. However, in the prior art 3, since the reaction is performed under supercritical conditions of high temperature and high pressure, there is a risk of explosion due to high pressure, and the installation equipment must be designed to withstand high pressure. Therefore, safety and equipment cost are excessively required. Not suitable for use.

Accordingly, the present invention provides a method for manufacturing a biofuel using high-

The biofuel is produced by carrying out the alcohol decomposition reaction without the pretreatment process of the high-acidity animal or vegetable matter, and the by-product glycerin produced in the reaction is synthesized with the monoalcohol glycerin or the dialcohol glycerin by performing the ester reaction by the organic catalyst And a production method capable of increasing the production yield of the biofuel.

Particularly, even when the reaction is performed at a temperature of 100 ° C or higher, a simultaneous reaction such as a liquid-liquid reaction and a vapor-gas phase reaction is performed at a high temperature to increase the reaction area, thereby shortening the reaction time and removing moisture, thereby maximizing the yield of the biofuel And to provide a manufacturing method that can be used.

In order to solve the above-described problems, the present invention provides a biofuel producing method using high-

A reaction column having a lower partition plate reaction chamber in which a plurality of horizontal partition plates are installed to increase the passage length, an upper pipe temperature control chamber in which a plurality of pipes are vertically piped and heat exchange is performed by a cooling fluid to control the temperature, A method for preparing a biofuel from a high acidity animal and vegetable matter by using a reactor equipped with a column and a condenser provided in communication with the reaction column, the method comprising the steps of: preparing a mixture of high-value animal and vegetable oil, low alcohol, alkali catalyst and organic catalyst And preheating the mixture; A second step of adding the preheated mixture to the reactor and heating the mixture to a temperature of 110 to 130 캜; A third step in which the lower alcohol vaporized by the heating in the second step is phase-changed into a liquid phase as it passes through the reaction column or is condensed by a condenser, and is directly or recycled into a high-temperature reactor; A fourth step in which the liquid triglyceride, which is an animal or vegetable oil retaining component, and a liquid alcohol in liquid form are mixed in a liquid-liquid phase under an alkaline catalyst to initiate an alcoholysis reaction at a high temperature of 110 to 130 DEG C; A fifth step of producing FAME (fatty acid methyl ester) and glycerin by an alcoholysis reaction; A sixth step of synthesizing a monoalcohol glycerin or a dialcohol glycerin by reacting the resulting glycerin with an organic carboxylic acid having a hydrophobic and hydroxyl radical and drawing a hydrophilic lower alcohol to react under an alkaline catalyst; A seventh step of evaporating and discharging the water and the lower alcohol produced in the synthesis step of the sixth step; An eighth step of removing water from the reactor by water separation by distillation of water and a lower alcohol, and storing the lower alcohol in which water is removed into a storage tank; During the reaction of the fourth and sixth steps, the alcohol stored in the storage tank is continuously supplied to the reactor, and when the reaction is completed, the supply of alcohol is stopped to collect the lower alcohol.

In the third step, the cooling fluid flow rate in the upper multitubular temperature control chamber may be adjusted so that the temperature of the gas discharged to the discharge side of the reaction column has a temperature of 70 to 90 ° C.

In the fourth step, a mixture of triglyceride, a lower alcohol and an alkali catalyst is sprayed into a high-temperature chamber space to increase the surface area of the lower alcohol and triglyceride, which is an animal or vegetable oil, by vaporization and nano size, Wherein the step of contacting the lower alcohol with the triglyceride and initiating the alcoholysis reaction by syngas in the vapor-gas phase is performed in parallel.

In the sixth step, the vaporized lower alcohol and the monoalcohol glycerin flow into the reaction column and are contacted in a gas-liquid phase, a liquid-liquid phase, and a gas-liquid phase while moving along the flow path of the reaction column to synthesize a dialcohol glycerin .

In the sixth step, a mixture of glycerin, a lower alcohol and an organic catalyst is sprayed into a high-temperature chamber space to vaporize the lower alcohol and glycerin and to granulate the glycerin into nano-sized particles to increase the surface area, The step of bringing the lower alcohol into contact with the glycerin by the organic catalyst to cause the synthesis reaction to occur on the same phase in the vapor-gas phase may be performed in parallel.

In the ninth step, when the temperature of the reactor is increased to 130 ° C or higher, the supply amount of the lower alcohol supplied to the reactor is increased to adjust the temperature to maintain the reactor temperature at 110-130 ° C.

The biofuel is produced by mixing 50 to 100 parts by weight of a lower alcohol, 0.1 to 1 part by weight of an alkali catalyst and 0.2 to 2 parts by weight of an organic catalyst with respect to 100 parts by weight of the animal or vegetable oil.

The biofuels produced by the process of maintaining the plants and animals of high altitude and the low temperature alcohols in combination with the alkaline catalysts and the organic catalysts at 110 ~ 130 ℃ and atmospheric pressure in the liquid phase, Fatty Acid Methyl Ester (fatty acid methyl ester), and monoalcohol glycerin and dialcohol glycerin as main components.

The method for producing a biofuel using the above-mentioned solving means of the present invention,

It is possible to produce biofuel by utilizing various low-level flora and fauna maintenance regardless of moisture content and acid value. Especially, in the vaporization process, the gas low-alcohol having increased surface area is contacted with the gas oil component to activate the reaction. Condensing the alcohol and mixing it in a liquid phase in a reactor at 100 ° C or higher, so that the lower alcohol and the animal or vegetable oil are homogeneously mixed in the liquid phase at a high temperature of 100 ° C or higher to perform the alcoholysis reaction under the catalyst, By making the reaction proceed in parallel, the contact time can be improved and the reaction time can be shortened even under unpressurized conditions.

In addition, the spraying process can lower the reaction time by lowering the alcohol and maintaining the flora and fauna by nano-size granulation, and by lowering the contact area of the lower alcohol and the animal / vegetable holding by the gas phase.

In addition, the synthesis of monoalcohol glycerol or dialcohol glycerin by combining glycerin with a lower alcohol through an organic catalyst having a low water content and a hydroxyl radical to produce biofuel, The generated water is evaporated and removed, which makes it possible to produce biofuels with little generation of water or glycerin-containing byproducts without pretreatment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram of a method for producing a biofuel according to the present invention;
BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a biofuel.
3 is a schematic view of a reaction column according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the appended drawings illustrate only the contents and scope of technology of the present invention, and the technical scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

FIG. 1 is a process diagram of a method for producing a biofuel according to the present invention. FIG. 2 is a view illustrating a manufacturing apparatus according to an embodiment of the method for producing a biofuel of the present invention. .

As shown in FIG. 2, the manufacturing apparatus 10 used in the method of manufacturing a biofuel of the present invention includes a fuel supply tank 20 in which an animal and vegetable oil, a mixture of a lower alcohol, an alkali catalyst and an organic catalyst are stored, A reactor 30 in which a mixture of tanks is supplied and a stirrer is installed; and a reactor 30 which is integrally coupled to the upper part of the reactor, and a vaporized lower alcohol is contacted and reacted with an oil component, A condenser 50 for condensing the gas passed through the reaction column, a condensation circulation pipe 60 for supplying the liquid material of the condenser to the reactor or the storage tank 70, A reaction circulation pipe 80 for partially circulating the mixture of the reactors, and a spray chamber 90 provided on the reaction circulation flow path for gasification into nano-size by spraying It is open configuration.

The reaction column 40 includes a lower partition plate reaction chamber 41 provided with a plurality of horizontal partition plates 411 at a lower portion thereof to form zigzag flow paths and a plurality of pipes formed at an upper portion of the lower partition plate reaction chamber And the upper multitubular temperature control chamber 42 for moving the gas upward into the tube and lowering the temperature of the moving gas by moving the cooling fluid to the outside of the tube. The lower partition plate reaction chamber 41 may be liquefied by gas coagulation as the gas component moves, or may cause a reaction between the gasified lower oil component and the gaseous lower alcohol, and the liquefied lower alcohol or oil component may be gas So that the liquid-liquid reaction can perform both the gas-phase reaction. In addition, the upper multitubular temperature control chamber 42 controls the temperature of the passing gas to lower the condensation burden of the condenser. The temperature of the upper multitubular temperature control chamber 42 is controlled by the sensing value of the temperature sensor T provided on the discharge side of the reaction column. The cooling degree of the cooling water in the chamber 42 is interrupted to set the degree of cooling. Preferably, the temperature is maintained at a higher temperature than the vaporization temperature of the lower alcohol and a little lower than the vaporization temperature of water and discharged to the condenser, Is set to be in the range of 70 to 90 ° C.

The fuel supply tank 20 is provided with a fuel supply heating jacket on its outer surface to heat the mixture, and an agitator is provided to stir the mixture.

A fuel inlet is formed at one side of the reactor 30 to supply the mixture. An agitator 32 is installed in the inside of the reactor 30 to stir the mixed mixture. A heating jacket 33 is installed on the outer surface of the stirrer 32, And a discharge port 34 for discharging the reactant is formed on the bottom surface.

The condenser 50 may be used alone without the reaction column 40 in operation. For example, when the reaction is initiated or completed, the operation of the reaction column is stopped, and only the condenser is operated, so that the lower alcohol or the excess lower alcohol containing a large amount of water can be condensed in the condenser 50 and recovered into the storage tank 70, The purity of the biofuel can be improved.

A heating means is provided on the outer surfaces of the reaction circulation pipe 80 and the spraying chamber 90 to prevent the temperature from dropping during circulation by heating the circulated mixture.

A method for manufacturing a biofuel using the production apparatus,

First, a first step is carried out in which a mixture of high-value animal and animal matter, low alcohol, alkali catalyst and organic catalyst is prepared and preheated to 50 to 60 ° C.

The alcohols having a high acidity can be used not only in acid esters of 5 to 20, but also in acids having an acid value of 50. The lower alcohols are alcohols having 5 or less carbon atoms, and animal and vegetable oils are typically used.

As the lower alcohol, there may be used one or more selected from methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol and ally alcohol.

As the alkali catalyst, one or more of NaOH, KOH, Ca (OH) ₂ , and Ba (OH) ₂ .8H ₂ O may be selected and used.

The organic catalyst may be one or more selected from the group consisting of fluorine-based, amine-based, and quaternary ammonium-based compounds. Typically, the organic catalyst is a fluorine-based catalyst such as trifluoromethyl; Amine catalysts such as diethanolamine, triethanolamine, ethylenediamine, triethylenetetramine, methyleneorthochloraniline, 4,4-diphenylmethanediamine, 2,6-dichloro-4,4-diphenylmethanediamine, 4-toluenediamine, or 2,6-toluenediamine; Quaternary ammonium-based catalysts such as Choline, Carnitine, Benzalkonium chloride, Denatonium, Cetrimonium bromide, Diallyldimethyl ammonium chloride, , 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC), 3-chloro-2-hydroxypropyltrimethylammonium chloride, a copolymer of acrylamide and tetramethylammonium ethyl methacrylate (Copolymer of acrylamide and quaternized dimethylammonium methyl methacrylate) Poly (diallyldimethylammonium chloride), a copolymer of acrylamide and diallyldimethylammonium chloride, quaternized hydroxyethylcellulose, vinylpyrrolidone, Copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate quaternized with para (Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride), Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride (Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride), Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride (Copolymer of Acrylic Acid and Diallyldimethylammonium Chloride) , Copolymers of vinylpyrrolidone and methacrylamidopropyl trimethylammonium, poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride) (poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride)), Acrylic acid and acrylamide, and diallyldimethylammonium chloride (Terpolymer of Acrylamide and Diallyldimethylammonium Chloride), vinylcaprolactam and vinylpyrrolidone, and tertiary vinylimidazole trimer (Terpolymer of vinylcaprolactam, vinylpyrrolidone , and quaternized vinylimidazole), and acrylic acid and methacrylamide (Terpolymer of acrylic acid, methacrylamidopropyl trimethyl ammonium chloride, and methyl acrylate).

The mixture is mixed at a ratio of 50 to 100 parts by weight of a lower alcohol, 0.1 to 1 part by weight of an alkali catalyst and 0.2 to 2 parts by weight of an organic catalyst per 100 parts by weight of a high-value animal or vegetable oil.

When the lower alcohol is mixed in an amount of less than 50 parts by weight, the fatty acid decomposition of the triglyceride of animal or vegetable oil is not easily performed. If the lower alcohol is mixed in an amount of 100 parts by weight or more, excess alcohol is added, It is preferable to mix them in the above range.

When the mixing ratio of the alkaline catalyst and the organic catalyst is less than the above ratio, the reaction rate of the alcoholysis reaction and the glycerin synthesis reaction is lowered, and when the mixing ratio is more than the above ratio, the reaction rate increase effect is insufficient, .

Further, the mixture is preheated. The animal or vegetable oil is kept at a temperature of at least 25 ° C in order to increase the fluidity, because it has a solidification point of about 10 ° C, and must be preheated to a temperature lower than the vaporization temperature of the lower alcohol. For example, methanol, which is a typical example of a lower alcohol, should be preheated to a temperature of 25 to 65 ° C due to the occurrence of vaporization at 65 ° C. Preferably, methanol should be preheated to improve fluidity of the animal and vegetable oil retention, Lt; RTI ID = 0.0 > C. ≪ / RTI >

In addition, the preheating temperature can be provided to about 100 캜, which is close to the reaction temperature of the reactor, for rapid reaction. This is because the lower alcohol is supplied to the reactor in the vapor phase, and the reaction temperature can be set quickly by condensing and dropping gaseous methanol by a vertical condensation column integrally installed in the reactor, which is a production apparatus applied to the present invention. However, And the internal pressure design of the fuel supply tank must be accompanied. As described above, the preheating of the mixture according to the present invention may be performed at a temperature in the range of 50 to 110 ° C, inclusive of 50 ° C to 60 ° C or 100 ° C depending on the required environment.

In the second step, the mixture preheated in the first step is charged into the reactor and heated to a temperature of 110 to 130 ° C. In this step, the temperature is heated to promote the reaction. The temperature is maintained above 100 ° C, which is higher than the vaporization temperature of water, and is formed at 110 ° C or higher so that the mixture is contained as impurities or water generated in the reaction is vaporized to be removed from the reaction will be. In addition, when heated to 130 ° C or higher, the degree of improvement of flowability of animal and plant oil is insufficient and energy consumption consumed in maintaining the temperature is increased, so that the energy consumption can be minimized by securing fluidity and water vaporization desirable.

Further, the stirring step may be further included so that the mixing of the temperature and the mixture is as uniform as possible. In the stirring method, stirring may be performed in the reactor by a stirring blade, or the stirring of the upper and lower parts may be further increased by a screw method, And the mixture of the lower layer can be made as uniform as possible.

In addition, the second step includes discharging the initially vaporized gas component. That is, the reactor maintains a high temperature condition of 110 to 130 ° C, and the mixture to be supplied to the reactor is not subjected to a pretreatment process, so that a large amount of moisture may be contained. Therefore, since the mixture introduced into the reactor is heated to the set temperature of the reactor, the vaporization of moisture occurs, so that the vaporized gas is initially discharged for a predetermined time, for example, 1 to 15 minutes to remove moisture contained in the mixture to minimize impurities can do.

In the third step, the vaporized lower alcohol is condensed or condensed by heating to directly or circulate the lower alcohol in the liquid phase and re-introduced into the high temperature reactor.

The liquid low alcohol is passed through the channel in the reaction column and is phase-changed to be directly introduced into the reactor or passed through the reaction column, condensed in the condenser, circulated along the condensation circulation tube and re- Supply alcohol.

As described above, the reactor used in the method for producing biofuel of the present invention is operated at a high temperature of 110 to 130 ° C, so that the lower alcohol having a vaporization temperature lower than the reactor temperature is vaporized in the reactor and collected in the upper part of the reactor, The vaporized lower alcohol is moved to the upper layer through a reaction column integrally installed at the upper part of the reactor, and a part of the vaporized liquid is condensed and falls to the reactor. Most of the vapor lower alcohol passes through the upper temperature- Is lowered to 70 ~ 90 < 0 > C, introduced into a condenser, condensed in a liquid phase in a condenser and directly fed to a reactor through a condensation circulation tube or stored in a storage tank. Then, pure liquid low alcohol separated from water is introduced into a reactor, To be mixed with each other.

Here, the upper multitubular temperature control chamber of the reaction column can regulate the degree of heat exchange in the upper multitubular temperature control chamber by controlling the flow rate of the cooling fluid by the sensing value of the temperature sensor installed on the discharge side of the reaction column. The upper multi-tube temperature control chamber formed by the reaction chamber upper chamber functions to lower the temperature of the passing gas partly, and functions differently from the condenser that condenses the gas into the liquid.

In the fourth step, the liquid phase triglyceride, which is an animal or vegetable oil retaining component, and the condensed liquid low alcohol are homogeneously mixed in a liquid-liquid phase under an alkaline catalyst to initiate an alcoholysis reaction at a high temperature of 110 to 130 ° C.

In this step, since the condensed liquid lower alcohol and triglyceride are mixed in the same way, the contact area is increased more than the mixing method of the gas-phase lower alcohol and the liquid triglyceride at the existing high temperature, And it is possible to prevent a large amount of impurities from being generated in the mixing of the liquid low alcohol and the liquid triglyceride at a low temperature below the conventional lower alcohol vaporization temperature.

That is, at the high temperature of 110 ~ 130 ℃ above the vaporization temperature of lower alcohol, animal / vegetable oil and lower alcohol are mixed in the same liquid phase and liquid phase to increase the contact area, so that alcohol decomposition under alkaline catalyst, So that the transesterification reaction in which the bonds are formed is initiated.

Here, the form in which the animal or vegetable oil and the lower alcohol are mixed with each other to increase the contact area can be further mixed with the vapor-gas phase method in addition to the liquid-liquid phase method described above.

For example, a mixture of a liquid lower alcohol and triglyceride, which is an animal or vegetable oil, is sprayed into a high-temperature chamber space so that the lower alcohol absorbs ambient heat and is vaporized. The triglyceride, which is an animal or vegetable oil, have. The gaseous vaporized lower alcohols and triglycerides vaporized by spraying may have an increased surface area of several hundred to several thousand times that of the liquid phase, thereby increasing the contact area of the two substances and improving the reaction rate.

Therefore, the fourth step may include the step of initiating alcohol decomposition reaction by vapor-gas phase syngas mixture, and the reaction of animal and vegetable matter retention with lower alcohol by the spraying is performed after 50-60% To accelerate the production of FAME.

Step 5 is a step of producing FAME (fatty acid methyl ester) and glycerin by an alcoholysis reaction.

In this step, animal and vegetable oil triglycerides react with lower alcohols under alkali catalyst to produce FAME (Fatty Acid Methyl Ester) and glycerin. The fatty acid is separated from the triglyceride and the fatty acid is esterified by transesterification reaction with a lower alcohol under alkaline catalyst to produce FAME (Fatty Acid Methyl Ester).

In the sixth step, the produced glycerine is hydrophilic, and a hydrophilic lower alcohol is drawn by an organic catalyst having a hydroxy radical, and the reaction is carried out under an alkaline catalyst to synthesize a hydrophobic oil component of a monoalcohol glycerin or a dialcohol glycerin.

The glycerin has a CH ₂ OH-CH ₁ OH-CH ₂ OH structure, but a hydrophilic lower alcohol is drawn by an organic catalyst having a hydrophobic and hydroxyl radical, thereby inducing an ester reaction in which a hydrocarbon group is bonded. By such an ester reaction, glycerin sequentially synthesizes monoalcohol glycerin and dialcohol glycerin, and water is produced as a byproduct. For example, when the lower alcohol is methanol, synthesis of mono methyl ether glycerin and di methyl ether glycerin is performed, and water is produced as a byproduct. The generated water may participate in the reaction to cause a reversible reaction. However, in the production method of the present invention, it is possible to prevent the reversible reaction from occurring by vaporizing and removing the generated water at a high temperature.

In addition, the lower alcohol is vaporized in the reactor and transferred to the reaction column, where some of the oil components are vaporized and flowed into the reaction column so that the lower alcohol and oil components in the vapor phase are contacted while passing through the reaction column, do. That is, a reaction in which a lower alcohol and a monoalcohol glycerin react in a reaction column to synthesize a dialcohol glycerin can be achieved. In addition, in the reaction column, a gaseous lower alcohol or an oil component is deposited on the inner wall of the reaction column to perform liquefaction, and a gaseous lower alcohol or an oil component passing therethrough is contacted with a liquid lower alcohol or an oil component placed on the inner wall of the reaction column, And a gas phase-liquid phase reaction. In addition, the liquid-liquid synthesis reaction can be performed by bringing liquid phases into contact with each other in the course of lowering a liquefied lower alcohol and an oil component into a reactor by aggregating a large amount of gas components. Therefore, both the gas-phase synthesis reaction, the gas-liquid phase synthesis reaction, and the liquid-liquid phase synthesis reaction can be performed through the reaction column through the lower alcohol and the oil component.

As described above, the present invention improves the biofuel reception rate by minimizing the generation of by-products by synthesizing monoalcohol glycerin or diol glycol glycerin, which is one element of biofuel, from glycerin, .

In this step, a mixture containing glycerin, lower alcohols, an alkali catalyst and an organic catalyst is sprayed into a high-temperature chamber space to vaporize the lower alcohol and glycerin and to granulate the glycerin into nano-sized particles to increase the surface area. The synthesis reaction can be performed in the same phase to increase the reaction rate.

Further, a lower alcohol having a higher reactivity can be further mixed to facilitate the synthesis reaction from glycerin to any one of monoalcohol glycerin, dialcohol glycerin and trialcohol glycerin to complete the reaction. For example, if the reaction is carried out using methanol, glycerin is produced by reacting glycerin with propanol (propyl alcohol) or butanol (butyl alcohol) to synthesize monoalcohol glycerin, dialcohol glycerin and trialcohol glycerin To be completed. In this case, the lower alcohol may be added in an amount of 5 to 10 parts by weight based on 100 parts by weight of the animal or vegetable oil. That is, in this step, it may further include a step of adding 5 to 10 parts by weight of a lower alcohol at the point of time when glycerin is produced during the reaction process to terminate the reaction.

The seventh step is a step of evaporating and discharging the water and the lower alcohol produced in the synthesis step of the sixth step.

The water produced in the synthesis process is collected in the upper space of the reactor and the lower alcohol not participating in the reaction is also vaporized by the high temperature of the reactor and collected in the upper space of the reactor. The vaporized gas components are discharged through the reaction column and the condenser to remove water from the reactor.

In the eighth step, the water discharged from the reactor and the lower alcohol are removed by water separation, and the lower alcohol from which the water is removed is stored.

The gaseous components that are vaporized and discharged from the reactor are condensed while passing through the condenser and are phase-changed into liquid water and lower alcohol. The liquid water and the lower alcohol are not introduced into the reactor but stored in the storage tank and separated from the reactants in the reactor.

At this time, the liquid water and the lower alcohol may be stored only in the storage tank through which the water is removed by passing through the oil-water separator, or may include a water-oil separator in the storage tank so that only the lower alcohol from which the water is removed may be stored.

In the ninth step, the lower alcohol stored in the storage tank is continuously supplied to the reactor during the reactions of the fourth and sixth steps, and when the reaction is completed, the supply of the lower alcohol is stopped to collect the lower alcohol.

That is, during the reaction, the lower alcohol stored in the storage tank is continuously supplied to the reactor to induce the liquid-liquid reaction in the fourth and sixth steps, and the water generated in the reaction can be rapidly removed during the reaction, When the reaction is complete, the feed line from the reservoir to the reactor may be closed to block the supply of lower alcohols to reduce the by-product content in the final product.

In the ninth step, when the temperature of the reactor is raised to 130 ° C or higher, the low-alcohol having moisture removed is re-supplied to the reactor to adjust the temperature to maintain the reactor temperature at 110-130 ° C. That is, when the temperature of the reactor is raised to the set temperature or more by the temperature sensor of the reactor, the valve in the line connected to the storage tank is opened to regulate the supply flow rate of the liquid low alcohol fed into the reactor, So that the reaction can be performed at a constant temperature.

The biofuel produced by this method has a FAME of 50 to 70% by weight, a monoalcohol glycerin of 10 to 30% by weight, a dialcohol glycerin of 5 to 20% by weight, a trialcohol glycerin and a glycerin of less than 1% Lt; RTI ID = 0.0 > biofuel < / RTI >

Example

An apparatus having a reactor equipped with a reaction column as shown in Fig. 2 was used as a production apparatus.

Methanol was used as the lower alcohol, KOH was used as the alkali catalyst, and trifluoromethyl (CF ₃ ) was used as the organic catalyst.

50 parts by weight of methanol, 0.2 parts by weight of KOH as an alkali catalyst, and 0.8 parts by weight of an organic catalyst, CF ₃ , were mixed with 100 parts by weight (100 L) of the same acid value of waste cooking oil to prepare a mixture.

Experimental Example 1)

The mixture was stored in the fuel supply tank of the production apparatus, preheated to 95 DEG C, and charged into the reactor.

The temperature of the reactor was set at 120 DEG C and operated without applying pressure.

During the initial 10 minutes, the condenser was driven to remove water through a reservoir or an oil separator. After 10 minutes, the reaction column was operated to adjust the temperature of the gas supplied to the condenser from the upper part of the reaction column to a constant value. Respectively.

The liquid methanol produced by the agglomeration of the gas in the reaction column is directly fed into the reactor and liquid methanol condensed by the condenser is circulated to the reactor so that the waste cooking oil, methanol, glycerin and methanol are mixed in a liquid phase Respectively.

100 ml of the sample of the reactor was sampled according to time, and the components were analyzed and shown in Table 1 below.

[Table 1]

Referring to Table 1, it can be seen that the production reaction of biofuel is completed in the reaction time of about 8 hours.

Experimental Example 2)

The device was driven under the same conditions as in Experiment 1.

In addition, some mixture of the reactor was allowed to circulate through the reaction circulation tube in an amount of 25 L per hour. The spray chamber was sprayed with circulation so that methanol, triglyceride or methanol and glycerin were mixed in the vapor phase to perform the reaction.

100 ml of a sample of the reactor was sampled according to time, and the components were analyzed and shown in Table 2 below.

[Table 2]

Referring to Table 2, it can be seen that the reaction was completed in about 3 hours.

Experimental Example 3)

The mixture having the same composition ratio as in Experimental Example 1 was stored in the fuel supply tank of the production apparatus, preheated to 40 캜, and charged into the reactor.

The temperature of the reactor was set at 60 占 폚 and the reactor was operated under no pressure.

100 ml of the sample of the reactor was sampled according to time, and the components were analyzed and shown in Table 3 below.

[Table 3]

As shown in Table 3, it can be seen that the reaction is not completed even after 20 hours, and the combined amounts of monomethyl ether glycerin and dimethyl ether glycerin are as low as 11% by weight and 6% by weight. Respectively.

When the biofuel is performed by the liquid-liquid phase reaction as in Experimental Example 1, the biofuel of 68% by weight of FAME, 17% by weight of monomethyl ether glycerin and 14% by weight of dimethyl ether glycerin is received at a reaction time of about 8 hours I could.

In Experiment 2 in which the gas-phase reaction was further performed, the reaction time was shortened to about 3 hours, and the biofuel of about 62% by weight of FAME, 21% by weight of monomethyl ether glycerin and about 16% by weight of dimethyl ether glycerin could be received there was.

However, in Experiment 3 in which only the liquid-liquid reaction was performed at a low temperature below the methanol vaporization temperature, the content ratio of FAME was low and the amount of monomethyl ether glycerin and dimethyl ether glycerin was extremely low even after 20 hours, A large amount of water and glycerin, by-products, were received.

Therefore, when the biofuel is produced by the hybrid production process of the present invention which performs both the liquid-liquid reaction and the gas-phase reaction while heating the reaction solution at a temperature higher than the water vaporization temperature, the reaction time can be greatly reduced, The biofuel, which is a biofuel having a composition ratio equal to that of the biofuel produced by the reaction, can be produced.

10: Biofuel production equipment
20: fuel supply tank
30: Reactor
31: fuel inlet 32: stirrer
33: heating jacket 34: outlet
40: condensation column
41: Lower partition plate reaction chamber
42: Upper tube temperature control chamber
411: Horizontal diaphragm
50: condenser
60: condensation circulation pipe
70: Storage tank
80: reaction circulation tube
90: Spray chamber
* US city code: 31

Claims (9)

A reaction column having a lower partition plate reaction chamber in which a plurality of horizontal partition plates are installed to increase the passage length, an upper pipe temperature control chamber in which a plurality of pipes are vertically piped and heat exchange is performed by a cooling fluid to control the temperature, 1. A method for producing a biofuel by maintaining a high-yielding animal and plant matter by using a reactor having a column installed at an upper portion thereof and a condenser connected to the reaction column,
A first step of preparing a mixture of a high-value animal and vegetable oil, a low alcohol, an alkali catalyst and an organic catalyst, and preheating the mixture;
A second step of adding the preheated mixture to the reactor and heating the mixture to a temperature of 110 to 130 캜;
A third step in which the lower alcohol vaporized by the heating in the second step is phase-changed into a liquid phase as it passes through the reaction column or is condensed by a condenser, and is directly or recycled into a high-temperature reactor;
A fourth step in which the liquid triglyceride, which is an animal or vegetable oil retaining component, and a liquid alcohol in liquid form are mixed in a liquid-liquid phase under an alkaline catalyst to initiate an alcoholysis reaction at a high temperature of 110 to 130 DEG C;
A fifth step of producing FAME (fatty acid methyl ester) and glycerin by an alcoholysis reaction;
A sixth step of synthesizing a monoalcohol glycerin or a dialcohol glycerin by reacting the resulting glycerin with an organic carboxylic acid having a hydrophobic and hydroxyl radical and drawing a hydrophilic lower alcohol to react under an alkaline catalyst;
A seventh step of evaporating and discharging the water and the lower alcohol produced in the synthesis step of the sixth step;
An eighth step of removing water from the reactor by water separation by distillation of water and a lower alcohol, and storing the lower alcohol in which water is removed into a storage tank;
And a ninth step of continuously supplying the lower alcohol stored in the storage tank to the reactor during the reactions of the fourth and sixth steps and collecting the lower alcohol by shutting off the supply when the reaction is completed. Gt; The method according to claim 1,
Wherein in the third step, the flow rate of the cooling fluid in the upper multitubular temperature control chamber is adjusted so that the temperature of the gas discharged to the discharge side of the reaction column has a temperature of 70 to 90 占 폚. The method according to claim 1,
In the fourth step, a mixture of triglyceride, a lower alcohol and an alkali catalyst is sprayed into a high-temperature chamber space to increase the surface area of the lower alcohol and triglyceride, which is an animal or vegetable oil, by vaporization and nano size, Wherein the step of bringing the lower alcohol and the triglyceride into contact with each other is performed in parallel with the step of initiating the alcoholysis reaction by the syngas of the gas phase and the gas phase. The method according to claim 1,
In the sixth step, the vaporized lower alcohol and the monoalcohol glycerin flow into the reaction column and travel along the flow path of the reaction column while being contacted in a vapor-gas phase, a liquid-liquid phase, and a gas-liquid phase to synthesize a dialcohol glycerin Wherein the biofuel is produced by the method. The method according to claim 1,
In the sixth step, a mixture of glycerin, a lower alcohol and an organic catalyst is sprayed into a high-temperature chamber space to vaporize the lower alcohol and glycerin and to granulate the glycerin into nano-sized particles to increase the surface area. And bringing the lower alcohol into contact with glycerin to cause the synthesis reaction to take place on the same phase in the vapor-gas phase. The method according to claim 1,
The ninth step includes increasing the supply amount of the lower alcohol supplied to the reactor when the temperature of the reactor is increased to 130 ° C or more to adjust the temperature so that the reactor temperature is maintained at 110 to 130 ° C. Gt; The method according to claim 1,
The lower alcohol is an alcohol having 5 or less carbon atoms including ethanol methanol,
The alkali catalyst is selected from one or more of NaOH, KOH, Ca (OH) ₂ , and Ba (OH) ₂ .8H ₂ O;
The organic catalyst is selected from the group consisting of trifluoromethyl; Diethanolamine, triethanolamine, ethylenediamine, triethylenetetramine, methyleneorthochloraniline, 4,4-diphenylmethanediamine, 2,6-dichloro-4,4-diphenylmethanediamine, 2,4-toluenediamine , Or 2,6-toluenediamine; Quaternary ammonium compounds such as choline, carnitine, benzalkonium chloride, denatonium, cetrimonium bromide, diallyldimethyl ammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC), copolymer of acrylamide and quaternized dimethylammonium methyl methacrylate quaternized with quaternized dimethylammonium ethyl methacrylate, (Diallyldimethylammonium chloride), a copolymer of acrylamide and diallyldimethylammonium chloride, quaternized hydroxyethylcellulose, vinylpyrrolidone, and the like. And quaternized dimethylaminoethyl methacrylate (Copolymer of vinylpyrrolidone and Quaternized dimethylaminoethyl methacrylate, copolymers of vinylpyrrolidone and quaternized vinylimidazole quaternized with vinylpyrrolidone, copolymers of acrylic acid and diallyldimethylammonium chloride, Poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride) (poly (acrylamide 2-methacryloxyethyltrimethyl ammonium chloride)), acrylic acid and the like, a copolymer of polyvinyl pyrrolidone and methacrylamidopropyl trimethyl ammonium, Acrylamide and diallyldimethylammonium chloride of diallyldimethylammonium chloride, terpolymers of vinylcaprolactam, vinylpyrrolidone, and diallyldimethylammonium chloride, vinylcaprolactam and vinylpyrrolidone, and tertiary vinylideneimidazole trimer. quaternized vinylimidazole), and acrylic acid and methacrylamidop Wherein at least one selected from the group consisting of tetrapolymer of acylic acid, methacrylamidopropyl trimethyl ammonium chloride and methyl acrylate is selected and used. The method according to claim 1,
The method comprising: mixing 50 to 100 parts by weight of a lower alcohol, 0.1 to 1 part by weight of an alkali catalyst, and 0.2 to 2 parts by weight of an organic catalyst with respect to 100 parts by weight of the animal or vegetable oil. The method according to any one of claims 1 to 8, wherein high-value animal and plant fats and oils are mixed with an alkaline catalyst and an organic catalyst and subjected to simultaneous liquid-liquid and gas-liquid phase reactions at 110 to 130 ° C and normal pressure FAME (Fatty Acid Methyl Ester), a mono-alcohol glycerin and a di-alcohols glycerin.

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