Biodiesel production device and method for producing hydrocarbon-based biodiesel from animal and vegetable fats and oils

Abstract

A biodiesel manufacturing apparatus and method for producing hydrocarbon biodiesel from animal and vegetable oils are disclosed. The present invention provides a hydrocarbon biodiesel manufacturing apparatus (10) comprising: an oil supply unit (100) for supplying oil to a reactor (310); a solvent supply unit (200) for supplying a solvent to a reactor (310); a reaction unit (300) comprising a reactor (310) that receives a raw material mixture containing oil and solvent through an inlet (311), deoxygenates the mixture through a hydrothermal reaction, and supplies a product containing hydrocarbon biodiesel to a cooler (400) through an outlet (312); and a cooler (400) for cooling the product. The present invention has the effect of converting animal and vegetable oils into hydrocarbons by removing oxygen within ester bonds through a hydrothermal reaction by mixing and introducing animal and vegetable oils and water in a certain ratio and changing the conditions to high temperature and high pressure to induce a hydrothermal reaction.

Description

Technology Field

[0001] The present invention relates to a biodiesel manufacturing apparatus and method for producing hydrocarbon-based biodiesel from animal and vegetable oils. Background Technology

[0002] Biodiesel is a biofuel synthesized from animal and vegetable oils and has properties similar to diesel fuel, so it can be used to completely replace diesel fuel in existing diesel engines or mixed with diesel fuel in a certain ratio. Generally, biodiesel consists mainly of fatty acid methyl esters produced by the transesteification reaction of methanol with triglycerides, which are the main components of oils and fats, and glycerol is produced as a byproduct in this process.

[0003] Currently, most industrially produced biodiesel is manufactured using processes that utilize alkaline catalysts such as sodium hydroxide and potassium hydroxide. These catalysts participate in the reaction in the form of homogeneous catalysts dissolved in methanol, and after the reaction, they are separated along with glycerol through a washing process. Since a certain amount of water remains in the biodiesel even after separation, an evaporation process is also required to remove it.

[0004] Currently used ester-based biodiesel has the disadvantage of having properties such as oxidation stability and low-temperature fluidity inferior to diesel fuel, so additives are used to compensate for this. Recently, there has also been increasing interest in hydrocarbon-based biodiesel, in which ester functional groups are removed through hydrogenation reactions to overcome these shortcomings. Although hydrocarbon-based biodiesel possesses superior fuel properties compared to conventional biodiesel due to its structure and physical characteristics being nearly identical to diesel fuel, it has not yet been commercialized because it lacks competitiveness in terms of production costs, such as the requirement for expensive catalysts and high-temperature operating conditions. The problem to be solved

[0005] The objective of the present invention is to solve the aforementioned problems by providing a reaction method and apparatus for converting animal and vegetable oils into hydrocarbon-based biodiesel by reacting them with a high-temperature, high-pressure solvent to remove oxygen contained in the ester groups, and to provide a hydrothermal reaction method and apparatus in which the input of raw materials and the production of biodiesel can be carried out continuously in a continuous reaction manner. means of solving the problem

[0006] According to one aspect of the present invention, a hydrocarbon biodiesel manufacturing apparatus (10) is provided, comprising: a fat supply unit (100) for supplying fat to a reactor (310); a solvent supply unit (200) for supplying a solvent to a reactor (310); a reaction unit (300) comprising a reactor (310) that receives a raw material mixture containing fat and solvent through an inlet (311), deoxygenates the mixture through a hydrothermal reaction, and supplies a product containing hydrocarbon biodiesel to a cooler (400) through an outlet (312); and a cooler (400) for cooling the product.

[0007] In addition, the above biodiesel production device may be continuous.

[0008] Additionally, the above-mentioned maintenance supply unit (100) may include one or more selected from the group consisting of a maintenance pump (110) and a maintenance preheater (120), and the above-mentioned solvent supply unit (200) may include one or more selected from the group consisting of a solvent pump (210) and a solvent preheater (220).

[0009] In addition, the solvent may include one or more selected from the group consisting of water, ethanol, methanol, propanol, butanol, and mixtures thereof.

[0010] Additionally, in the reactor (310), the outlet (312) may be positioned higher than the inlet (311).

[0011] Additionally, in the reactor (310), the outlet (312) may be located at the same height as the inlet (311).

[0012] In addition, in the reactor (310), the raw material mixture can be deoxygenated and biodiesel produced as it moves upward or horizontally.

[0013] Additionally, in the cooler (400), the cooler inlet (410) into which the product is introduced may be located above the cooler outlet (420) into which the cooled product is discharged.

[0014] Additionally, in the cooler (400), the cooler inlet (410) into which the product is introduced may be located at the same height as the cooler outlet (420) into which the cooled product is discharged.

[0015] Additionally, in the cooler (400), the product can be cooled while moving in a horizontal or downward direction.

[0016] In addition, the above deoxygenation reaction can be carried out without using a catalyst.

[0017] Additionally, a rear pressure regulator (500) may be additionally included at the rear of the cooler (400) to regulate the pressure of the reactor (310).

[0018] Additionally, a filter (600) for removing solids contained in the product may be further included between the cooler (400) and the rear pressure regulator (500).

[0019] In addition, the above oil may include one or more selected from the group consisting of animal oil and vegetable oil.

[0020] In addition, the above oil may contain triglycerides.

[0021] In addition, the above hydrocarbon-based biodiesel may include hydrocarbons of C6 to C24.

[0022] According to another aspect of the present invention, a method for producing biodiesel is provided, comprising: (a) a step in which a fat supply unit (100) supplies fat to a reactor (310); (b) a step in which a water supply unit (200) supplies water to a reactor (310); (c) a step in which a reaction unit (300) receives a raw material mixture containing fat and water through an inlet (311), deoxygenates the mixture through a hydrothermal reaction, and supplies a product containing biodiesel to a cooler (400) through an outlet (312); and (d) a step in which the cooler (400) cools the product.

[0023] In addition, the operating temperature of the reactor (310) may be 300 to 550°C.

[0024] In addition, the operating pressure of the reactor (310) may be 1 to 30 MPa.

[0025] In addition, the residence time of the above raw material mixture in the reactor (310) may be 1 to 60 minutes. Effects of the invention

[0026] The present invention allows for the conversion into hydrocarbons by removing oxygen within ester bonds through the introduction of a mixture of animal and vegetable oils and water in a certain ratio and the induction of a hydrothermal reaction by changing the conditions to high temperature and high pressure.

[0027] In addition, by introducing a bottom-up reaction device capable of continuous reaction, the deoxygenation reaction can be performed efficiently.

[0028] In addition, it is possible to produce hydrocarbon-based biodiesel from animal and vegetable glass without using a catalyst, and productivity can be increased by implementing this in a continuous manner.

[0029] In addition, since the generated biodiesel and water do not mix, they can be easily separated through oil-water separation. Brief explanation of the drawing

[0030] These drawings are for reference to explain exemplary embodiments of the present invention, and therefore, the technical concept of the present invention should not be interpreted as being limited to the attached drawings. Figure 1 shows a schematic diagram of a device in which a hydrothermal reaction of animal and vegetable oils of the present invention is performed. FIG. 2 shows a schematic diagram of a downward continuous water supply device used in Examples 5 to 7. Figure 3 shows the GC analysis results of biodiesel obtained through the hydrothermal reaction of the alkane standard material, Example 2 and Example 7 of the present invention. Specific details for implementing the invention

[0031] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

[0032] However, the following description is not intended to limit the present invention to specific embodiments, and detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions could obscure the essence of the present invention.

[0033] The terms used herein are merely for describing specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as "comprising" or "having" are intended to indicate the presence of the features, numbers, steps, actions, components, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, or combinations thereof.

[0034] Additionally, terms including ordinal numbers, such as "first," "second," etc., used below may be used to describe various components, but said components are not limited by said terms. These terms are used solely for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be named the second component, and similarly, the second component may be named the first component.

[0035] Furthermore, when it is stated that a component is "formed" or "laminated" on another component, it should be understood that while it may be formed or laminated by being directly attached to the entire surface or one surface of the other component, there may also be other components present in between.

[0036] Hereinafter, a biodiesel manufacturing apparatus and method for producing hydrocarbon-based biodiesel from animal and vegetable oils will be described in detail. However, this is presented as an example and is not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0037] The present invention relates to a reaction method and apparatus for converting animal and vegetable oils into hydrocarbon-based biodiesel by reacting them with high-temperature and high-pressure water to remove oxygen contained in the ester groups, characterized in that the input of raw materials and the production of biodiesel can be carried out continuously in a continuous reaction manner.

[0038] More specifically, animal and vegetable oils and water are mixed and fed in a specific ratio, and a hydrothermal reaction is induced by changing the conditions to high temperature and high pressure to remove oxygen within the ester bonds and convert them into hydrocarbons. To achieve this, a bottom-up reaction device capable of continuous operation is introduced to efficiently carry out the deoxygenation reaction.

[0039] Figure 1 shows a schematic diagram of a device in which a hydrothermal reaction of animal and vegetable oils of the present invention is performed.

[0040] Referring to FIG. 1, the present invention provides a hydrocarbon biodiesel manufacturing apparatus (10) comprising: a fat supply unit (100) for supplying fat to a reactor (310); a solvent supply unit (200) for supplying a solvent to a reactor (310); a reaction unit (300) comprising a reactor (310) that receives a raw material mixture containing fat and solvent through an inlet (311), deoxygenates the mixture through a hydrothermal reaction, and supplies a product containing hydrocarbon biodiesel to a cooler (400) through an outlet (312); and a cooler (400) for cooling the product.

[0041] In addition, the above biodiesel production device may be continuous.

[0042] Additionally, the above-mentioned maintenance supply unit (100) may include one or more selected from the group consisting of a maintenance pump (110) and a maintenance preheater (120), and the above-mentioned solvent supply unit (200) may include one or more selected from the group consisting of a solvent pump (210) and a solvent preheater (220).

[0043] In detail, the oil and water, which are the raw materials of this reaction, are injected by the oil pump (110) and the solvent pump (210), respectively, and each raw material is preheated by the oil preheater (120) and the solvent preheater (220) before mixing so that it can reach the target temperature within a short time after mixing.

[0044] Additionally, after the reaction is finished, the product is cooled to room temperature in a cooler (8) and can be discharged after removing solids generated as by-reactions through a filter (9).

[0045] In addition, the solvent may include one or more selected from the group consisting of water, ethanol, methanol, propanol, butanol, and mixtures thereof.

[0046] Additionally, in the reactor (310), the outlet (312) may be positioned higher than the inlet (311).

[0047] Additionally, in the reactor (310), the outlet (312) may be located at the same height as the inlet (311).

[0048] In addition, in the reactor (310), the raw material mixture can be deoxygenated and biodiesel produced as it moves upward or horizontally.

[0049] Additionally, in the cooler (400), the cooler inlet (410) into which the product is introduced may be located above the cooler outlet (420) into which the cooled product is discharged.

[0050] Additionally, in the cooler (400), the cooler inlet (410) into which the product is introduced may be located at the same height as the cooler outlet (420) into which the cooled product is discharged.

[0051] Additionally, in the cooler (400), the product can be cooled while moving in a horizontal or downward direction.

[0052] In addition, the flow direction of the reactor (310) can be installed horizontally or upwardly.

[0053] Additionally, the flow direction of the cooler (400) can be installed in a downward direction. To ensure the smooth removal of byproduct gas generated during the deoxygenation reaction, the flow direction of the reactor must be installed horizontally or upwardly. At this time, it is desirable to install the flow direction of the cooler in a downward direction to prevent backflow and heat loss caused by reflux.

[0054] In addition, the above deoxygenation reaction can be carried out without using a catalyst.

[0055] Additionally, a rear pressure regulator (500) may be additionally included at the rear of the cooler (400) to regulate the pressure of the reactor (310).

[0056] In addition, the pressure of the entire device can be controlled by a rear pressure regulator (500) installed at the rear end.

[0057] Additionally, a filter (600) for removing solids contained in the product may be further included between the cooler (400) and the rear pressure regulator (500).

[0058] Additionally, the reaction unit (300) may further include a heater (320) for controlling the temperature of the reactor (310), and the heater (320) may surround part or all of the area around the reactor (310).

[0059] In addition, the heater (320) may include an electric furnace.

[0060] Additionally, oil and water are mixed in the mixing section and then introduced into the reactor (310), and the temperature of the reactor can be controlled by an external heater (320). At this time, structures such as a static stirrer or a packing material can be introduced into the reactor to ensure smooth mixing between the reactants.

[0061] In addition, the above oil may include one or more selected from the group consisting of animal oil and vegetable oil.

[0062] In addition, the above oil may contain triglycerides.

[0063] In addition, the hydrocarbon-based biodiesel may include C6 to C24 hydrocarbons, preferably C10 to C20 hydrocarbons.

[0064] According to another aspect of the present invention, a method for producing biodiesel is provided, comprising: (a) a step in which a fat supply unit (100) supplies fat to a reactor (310); (b) a step in which a water supply unit (200) supplies water to a reactor (310); (c) a step in which a reaction unit (300) receives a raw material mixture containing fat and water through an inlet (311), deoxygenates the mixture through a hydrothermal reaction, and supplies a product containing biodiesel to a cooler (400) through an outlet (312); and (d) a step in which the cooler (400) cools the product.

[0065] In addition, the operating temperature of the reactor (310) may be 300 to 550°C, preferably 400 to 500°C. If the operating temperature of the reactor (301) is less than 300°C, it is not desirable because the deoxygenation reaction after hydrolysis does not proceed sufficiently, and if it exceeds 550°C, it is not desirable because the cost to increase the heat resistance of the reactor increases rapidly.

[0066] In addition, oxygen of the ester can be removed by the above hydrothermal reaction.

[0067] In addition, the operating pressure of the reactor (310) may be 1 to 30 MPa, preferably 5 to 15 MPa. If the operating pressure is less than 1 MPa, it is undesirable because the density of water is too low and the solubility with oil decreases, and if it exceeds 30 MPa, it is undesirable because the deoxygenation reaction efficiency decreases and the cost to ensure the pressure resistance of the reaction device increases.

[0068] In addition, the residence time of the raw material mixture in the reactor (310) may be 1 to 60 minutes, preferably 5 to 30 minutes. If the residence time is less than 1 minute, it is undesirable because the reaction product does not stay sufficiently under reaction conditions, resulting in a lower conversion rate, and if it exceeds 60 minutes, it is undesirable because excessive decomposition of the oil occurs, resulting in a lower yield.

[0069] [Example]

[0070] [Use of bottom-up continuous flow device]

[0071] Example 1: Temperature of reactor (310) 380°C, pressure 20 MPa, residence time 30 minutes

[0072] FIG. 1 is a schematic diagram of a device in which a hydrothermal reaction of animal and vegetable oils of the present invention is performed. Referring to FIG. 1, a deoxygenation reaction of soybean oil was carried out using an upward continuous hydrothermal device under conditions of a reactor (310) temperature of 380°C, a pressure of 20 MPa, and a residence time of 30 minutes.

[0073] Example 2: Temperature of reactor (310) 440°C, pressure 20 MPa, residence time 30 minutes

[0074] The deoxygenation reaction of soybean oil was carried out in the same manner as in Example 1, except that it was carried out under a temperature of 440°C instead of a temperature of 380°C.

[0075] Example 3: Temperature of reactor (310) 440°C, pressure 10 MPa, residence time 30 minutes

[0076] The deoxygenation reaction of soybean oil was carried out in the same manner as in Example 1, except that it was carried out under conditions of temperature 440°C and pressure 10 MPa instead of conditions of temperature 380°C and pressure 20 MPa.

[0077] Example 4: Temperature of reactor (310) 440°C, pressure 10 MPa, residence time 15 minutes

[0078] The deoxygenation reaction of soybean oil was carried out in the same manner as in Example 1, except that instead of the conditions of temperature 380℃, pressure 20MPa, and residence time 30 min, it was carried out under the conditions of temperature 440℃, pressure 10MPa, and residence time 15 min.

[0079] [Use of Downward Continuous Sequence Device]

[0080] Example 5: Temperature of reactor (310) 420°C, pressure 20 MPa, residence time 20 min, oil / water ratio (w / w): 2

[0081] FIG. 2 shows a schematic diagram of a downward continuous water-heat device used in Examples 5 to 7. Referring to FIG. 2, a downward continuous water-heat device was used to perform a deoxygenation reaction of soybean oil under conditions where the temperature of the reactor (310) was 420°C, the pressure was 20 MPa, the residence time was 20 minutes, and the oil / water ratio (w / w) was 2.

[0082] Example 6: Temperature of reactor (310) 460°C, pressure 20 MPa, residence time 20 min, oil / water ratio (w / w): 5

[0083] The deoxygenation reaction of soybean oil was carried out in the same manner as in Example 5, except that instead of the condition of a temperature of 420°C and an oil / water ratio (w / w) of 2, it was carried out under the condition of a temperature of 460°C and an oil / water ratio (w / w) of 5.

[0084] Example 7: Temperature of reactor (310) 460°C, pressure 20 MPa, residence time 30 minutes, oil / water ratio (w / w): 5

[0085] The deoxygenation reaction of soybean oil was carried out in the same manner as in Example 5, except that instead of the conditions of a temperature of 420°C, a residence time of 20 minutes, and an oil / water ratio (w / w) of 2, it was carried out under conditions of a temperature of 460°C, a residence time of 30 minutes, and an oil / water ratio (w / w) of 5.

[0086] [Test Example]

[0087] Test Example 1: Confirmation of GC Analysis Results

[0088] FIG. 1 is a schematic diagram of a device in which the hydrothermal reaction of animal and vegetable oils of the present invention is performed, FIG. 2 is a schematic diagram of a downward continuous hydrothermal device used in Examples 5 to 7, and FIG. 3 is a GC analysis result of biodiesel obtained through the hydrothermal reaction of an alkane standard substance, Example 2 and Example 7 of the present invention.

[0089] Equation 1 below is a formula for calculating the yield of hydrocarbon-based biodiesel.

[0090] [Equation 1]

[0091] Hydrocarbon biodiesel yield =

[0092] Table 1 summarizes the conditions and GC analysis results of Examples 1 to 7 of the present invention.

[0093] division Temperature (°C) Pressure (MPa) Time of stay (minutes) Oil / Water Ratio (w / w) Acid value (mgKOH / g) transference number(%) Example 1 380 20 30 10 167 22 Example 2 440 20 30 10 78 41 Example 3 440 10 30 10 129 55 Example 4 440 10 15 10 181 38 Example 5 420 20 20 2 177 0 Example 6 460 20 20 5 165 0 Example 7 460 20 30 5 169 0

[0094] Referring to FIGS. 1 to 3 and Table 1 above, in the case of Examples 1 to 4 of the present invention, in which the deoxygenation reaction of soybean oil was carried out using an upward continuous hydrothermal device, it was confirmed that the acid value was acidic and hydrocarbons were detected, and the deoxygenation reaction proceeded with a maximum yield of 55%. In the case of Examples 5 to 7, in which the deoxygenation reaction of soybean oil was carried out using a downward continuous hydrothermal device, the acid value increased to 160~170 mgKOH / g, but no hydrocarbons were detected at all, confirming that the reaction did not proceed further at the stage where the hydrolysis of triglycerides took place.

[0095] The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention. Explanation of the symbols

[0096] 10: Hydrocarbon-based biodiesel production device 100: Maintenance supply unit 110: Maintenance pump 120: Maintenance preheater 200: Solvent supply unit 210: Solvent pump 220: Solvent preheater 300: Reaction part 310: Reactor 311: Inlet 312: Outlet 320: Heater 400: Cooler 410: Cooler inlet 420: Cooler outlet 500: Rear pressure regulator 600: Filter

Claims

Claim 1 A hydrocarbon biodiesel manufacturing apparatus (10) comprising: a fat supply unit (100) for supplying fat to a reactor (310); a solvent supply unit (200) for supplying a solvent to a reactor (310); a reaction unit (300) comprising a reactor (310) that receives a raw material mixture containing fat and solvent through an inlet (311), deoxygenates the mixture through a hydrothermal reaction, and supplies a product containing hydrocarbon biodiesel to a cooler (400) through an outlet (312); and a cooler (400) for cooling the product; wherein the hydrocarbon biodiesel manufacturing apparatus is continuous, and in the reactor (310), the outlet (312) is positioned higher than the inlet (311), and in the reactor (310), the raw material mixture moves upward and deoxygenates the mixture to produce biodiesel. Claim 2 delete Claim 3 A biodiesel manufacturing apparatus according to claim 1, characterized in that the maintenance supply unit (100) comprises one or more selected from the group consisting of a maintenance pump (110) and a maintenance preheater (120), and the solvent supply unit (200) comprises one or more selected from the group consisting of a solvent pump (210) and a solvent preheater (220). Claim 4 A biodiesel manufacturing apparatus according to claim 1, characterized in that the solvent comprises one or more selected from the group consisting of water, ethanol, methanol, propanol, butanol, and mixtures thereof. Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 A biodiesel manufacturing apparatus according to claim 1, characterized in that, in the cooler (400), the cooler inlet (410) into which the product is introduced is located above the cooler outlet (420) into which the cooled product is discharged. Claim 9 A biodiesel manufacturing apparatus according to claim 1, characterized in that, in the cooler (400), the cooler inlet (410) into which the product is introduced is located at the same height as the cooler outlet (420) into which the cooled product is discharged. Claim 10 A biodiesel manufacturing apparatus according to claim 1, characterized in that the product is cooled while moving in a horizontal or downward direction in the cooler (400). Claim 11 A biodiesel manufacturing apparatus according to claim 1, characterized in that the deoxygenation reaction is performed without using a catalyst. Claim 12 A biodiesel manufacturing apparatus according to claim 1, further comprising a rear pressure regulator (500) to regulate the pressure of the reactor (310) at the rear of the cooler (400). Claim 13 A biodiesel manufacturing apparatus according to claim 12, further comprising a filter (600) for removing solids contained in the product between the cooler (400) and the rear pressure regulator (500). Claim 14 A biodiesel manufacturing apparatus according to claim 1, characterized in that the oil comprises one or more types selected from the group consisting of animal oil and vegetable oil. Claim 15 A biodiesel manufacturing apparatus according to claim 1, characterized in that the above oil contains triglycerides. Claim 16 A biodiesel manufacturing apparatus according to claim 1, characterized in that the hydrocarbon-based biodiesel comprises C6 to C24 hydrocarbons. Claim 17 A method for producing biodiesel comprising: using a hydrocarbon-based biodiesel manufacturing apparatus (10) according to claim 1; (a) a step in which a fat supply unit (100) supplies fat to a reactor (310); (b) a step in which a water supply unit (200) supplies water to a reactor (310); (c) a step in which a reaction unit (300) receives a raw material mixture containing fat and water through an inlet (311), deoxygenates the mixture through a hydrothermal reaction, and supplies a product containing biodiesel to a cooler (400) through an outlet (312); and (d) a step in which the cooler (400) cools the product. Claim 18 A method for producing biodiesel according to claim 17, characterized in that the operating temperature of the reactor (310) is 300 to 550℃. Claim 19 A method for producing biodiesel according to claim 17, characterized in that the operating pressure of the reactor (310) is 1 to 30 MPa. Claim 20 A method for producing biodiesel according to claim 17, wherein the residence time of the raw material mixture in the reactor (310) is 1 to 60 minutes.

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