TWI648394B - Method for producing biodiesel and triacetin - Google Patents

Abstract

The acidic metal compound, the weakly acidic metal compound and the water are mixed in proportion, and are extruded and sintered at a high temperature to form a solid metal oxide catalyst, wherein the solid metal oxidation catalyst is filled in the tubular reactor for transesterification and exchange. The esterification reaction produces fatty acid methyl esters and triacetin. By virtue of the high activity and good stability of the solid metal oxidation catalyst, the fatty acid methyl ester and the triacetin can be continuously produced in one step and obtained higher. Conversion efficiency.

Description

Method for preparing biodiesel and triacetin

The present invention relates to a process for preparing biodiesel, and more particularly to a process which has a high conversion rate and which can continuously produce a mass of diesel fuel in one step and produce a high value of triacetin.

Petrochemical fuel is currently the most common source of power in the world, and it plays an important role in industrial development, transportation and agricultural development, and thus enhances the quality of human life and makes life more convenient. However, with the rapidly increasing population of the world, the use of fossil fuels has begun to increase substantially, but its limited production is a long-standing concern. Moreover, the long-standing problems of fossil fuels, such as the inability to reuse, air pollution, mining, and price instability, are difficult to solve.

In contrast, biodiesel in biomass has similar properties to fossil diesel, and this fuel has reduced pollutant emissions and health effects, biodegradability, non-toxic, sulfur-free, and post-combustion. The low gas pollution and safe storage are considered to be one of the economical and potential energy alternatives.

The production methods of biodiesel are mainly divided into chemical catalysis and biocatalysis. Among them, chemical base catalysis is a widely used technology due to its high transesterification rate and short reaction time. The catalyst used for chemical base catalysis includes liquids and solids. Among them, solid base catalysts are popular in the industry because of their easy separation and recyclability. At present, solid base catalysts commonly used in the manufacture of biodiesel have calcium oxide, lithium carbonate, etc. However, calcium oxide has poor air stability, easily absorbs moisture in the air and carbon dioxide, and has a larger surface area of calcium oxide particles. Small, the overall transesterification rate is low. The basic strength of lithium carbonate is weak, so the transesterification effect is not good.

In view of this, how to develop a new type of catalyst, and the catalyst has high activity and good stability, and under the proper operating conditions, the diesel fuel can be continuously produced in one step and the high-valued triacetin can be obtained. And the high conversion rate can be obtained, which is a problem that needs to be solved urgently.

In view of the fact that in the past, the transesterification reaction of the basic catalyst was used to produce the quality diesel, but the by-products accompanying the production were mostly low-valued. Therefore, the object of the present invention is to provide a novel solid acid catalyst. The catalyst has high activity and good stability. Under appropriate operating conditions, the diesel fuel can be continuously produced in one step and the high-valued triacetin can be produced, and a higher conversion rate can be obtained.

In order to achieve the above object, the present invention provides a method for preparing biodiesel and triacetin by mixing an acidic metal compound, a weakly acidic metal compound and water in a ratio, and forming a solid metal oxide by extrusion molding and high temperature sintering. A catalyst in which a solid metal oxidation catalyst is filled in a tubular reactor for transesterification and exchange esterification to produce fatty acid methyl esters and triacetin.

The method for preparing biodiesel and triacetin, wherein the reactant of the transesterification and the exchange esterification reaction comprises a carboxylic acid ester and a fat or oil.

The method for preparing biodiesel and triacetin, wherein the carboxylic acid esters are acetates.

The method for preparing biodiesel and triacetin, wherein the oil is soybean oil, jatropha seed oil, castor oil, tung oil, palm oil, coconut oil, oleic acid, pig Any one or a mixture of oil, butter, algae oil, waste cooking oil or spent acid oil.

The method for preparing biodiesel and triacetin, wherein the carboxylic acid ester is methyl acetate.

The method for preparing biodiesel and triacetin, wherein the carboxylic acid esters and the oils and fats are respectively reacted into the tubular reactor in an up-flow manner via a high pressure pump system.

The method for preparing biodiesel and triacetin, wherein the reaction temperature is between 170 ° C and 300 ° C.

The method for preparing biodiesel and triacetin, wherein the reaction pressure is between 40 bar and 80 bar.

The method for preparing biodiesel and triacetin, wherein the ratio of the ratio of the carboxylate to the oil is between 1 and 3.

The method for preparing biodiesel and triacetin, wherein the space velocity WHSV (Weight Hourly Space Velocity) is between 0.1 and 1.0 (hr-1), and the reaction residence time is estimated to be 6 minutes. ~60 minutes between.

The invention provides a method for preparing biodiesel and triacetin, which comprises mixing an acidic metal compound, a weakly acidic metal compound and water in proportion, and extruding and sintering at a high temperature to form a solid metal oxide catalyst, wherein the solid is solid. The metal oxide catalyst is filled in a tubular reactor, and is subjected to transesterification and exchange esterification to produce fatty acid methyl ester and triacetin. The solid metal oxidation catalyst has high activity and good stability, and can be one step. Continuous production of fatty acid methyl esters and production of high value triacetin and high conversion efficiency.

Specific embodiments of the present invention will now be described in more detail in conjunction with the drawings. The advantages and features of the present invention will become more apparent from the following description and claims. It should be noted that the drawings are in a very simplified form and all use non-precise proportions. Therefore, the proportions and configuration relationships of the attached drawings should not be interpreted or limited, and the scope of the invention is actually applied. The purpose of the embodiments of the present invention will be described in a convenient and clear manner.

Please refer to FIG. 1 , which is a schematic view showing the preparation of the raw diesel fuel device of the present invention. The carboxylic acid esters 1 and the oil and fats 2 are controlled to flow through the high pressure pump 3 from bottom to top, and enter the tubular reactor 5 . The tubular reactor 5 is provided with a plurality of temperature controllers 6 and is coupled with a thermocouple 7, and the reaction is maintained under high temperature and high pressure. The system pressure is controlled by the back pressure valve 8. If the pressure exceeds the system safety setting value, the safety valve 4 is performed. The pressure relief discharge operation, finally cooling the heat exchanger 9 to collect the liquid product in the product collection tank 10, comprising biodiesel and triacetin.

The method for preparing biodiesel and triacetin according to the present invention is described in more detail, wherein in the transesterification and exchange esterification reaction, a solid metal oxidation catalyst is filled in the middle of the tubular reactor 5, and the tubular reactor 5 The upper and lower sections are filled with glass beads. The diameter of the glass beads is preferably 1 mm, but this is not limited. The solid metal oxide catalyst is composed of an acidic metal compound, a weakly acidic metal compound or a basic metal compound. And water is mixed according to a certain ratio, and formed into a solid metal oxidation catalyst after extrusion molding and high temperature sintering, wherein the acidic metal compound may be ammonium metatungstate, and the weakly acidic metal compound may be zirconium hydroxide, hydrated oxidation. Aluminum, and the basic metal compound may be manganese dioxide. Thereafter, the carboxylic acid esters 1 and the fats and oils 2 are respectively reacted into the tubular reactor 5 via the high pressure pump 3 in an up-flow manner to react with the solid metal oxidation catalyst, and the reacted product is subjected to heat. The exchanger 9 is cooled and collected into the product collection tank 10.

The method for preparing biodiesel and triacetin according to the present invention will be described in more detail, wherein in the transesterification and exchange esterification reaction, the reactants comprise carboxylate esters and fats and oils. And the carboxylic acid esters may be acetates, including methyl acetate, ethyl acetate and butyl acetate, preferably methyl acetate, but not limited thereto; and the oils and fats may be soybean oil. a mixture of one or more of jatropha seed oil, castor oil, tung oil, palm oil, coconut oil, oleic acid, lard, tallow, algae oil, waste cooking oil or spent acid oil, But it is not a limitation.

The method for preparing biodiesel and triacetin according to the present invention will be described in more detail. When the reaction is carried out in the tubular reactor 5, the reaction temperature is between 170 ° C and 300 ° C. The preferred temperature range is Celsius. Between 200 ° C ~ 300 ° C, but not as a limit on the actual reaction temperature.

The method for preparing biodiesel and triacetin according to the present invention will be described in more detail. When the reaction is carried out in the tubular reactor 5, the reaction pressure is between 40 bar and 80 bar, and the reaction pressure is preferably 50. Between bar ~ 70 bar, the better reaction pressure is 68 bar, but this is not the limit of the actual reaction pressure.

The method for preparing biodiesel and triacetin according to the present invention is described in more detail. When the reaction is carried out in the tubular reactor 5, the ratio of the ratio of the carboxylate to the oil is between 1 and 3. But it is not a limitation.

The method for preparing biodiesel and triacetin according to the present invention is described in more detail, wherein the space flow velocity WHSV (Weight Hourly Space Velocity) is between 0.1 and 1.0 (hr-1) when the reaction is carried out in the tubular reactor 5. Between, and can be derived from the reaction retention time between 6 minutes and 60 minutes, but not as a limit.

Several examples are given below to illustrate the preparation of different solid metal oxidation catalysts and the comparison of different solid metal oxidation catalysts for transesterification and exchange esterification to produce quality diesel.

The first to fourth embodiments illustrate the preparation of different catalysts A to D, and the fifth to eighth embodiments illustrate the reaction of different catalysts A to D in a tubular reactor.

Example 1 Preparation of Catalyst A: 9.6 g of ammonium metatungstate [(NH4)6H2W12O40·xH2O] was uniformly mixed with 21 g of hydrated alumina (pseudo-boehmite), and an appropriate amount of water was added to mix and stir to form an extrusion molding machine. (extruder) was made into a cylindrical shape, dried at room temperature for 24 hours, and then calcined in a high temperature furnace at a temperature of 800 ° C, a constant temperature of 4 hours, and then lowered to room temperature. Finally, a catalyst A having a diameter of 1 to 2 mm and a length of 3 to 5 mm can be obtained.

Example 2 Preparation of Catalyst B: 9.6 g of ammonium metatungstate [(NH4)6H2W12O40·xH2O] was uniformly mixed with 27.1 g of zirconium hydroxide, and an appropriate amount of water was added and mixed with stirring to prepare an extruder. It was made into a disk shape, dried at room temperature for 24 hours, and then calcined in a high temperature furnace at a temperature of 800 ° C for 4 hours and then lowered to room temperature. After pulverization and sieving, 3~5mm irregular granular catalyst B is obtained.

Example 3, Preparation of Catalyst C: 3 g of manganese dioxide and 27 g of hydrated alumina were uniformly mixed, mixed with an appropriate amount of water, stirred, and extruded into an extruder by an extruder, and dried at room temperature for 24 hours. Then, it is calcined in a high temperature furnace at a temperature of 550 ° C, a constant temperature of 4 hours, and then lowered to room temperature. Finally, a catalyst C having a diameter of 1 to 2 mm and a length of 3 to 5 mm can be obtained.

Example 4, Preparation of Catalyst D: 9.6 g of ammonium metatungstate, 3 g of manganese dioxide and 21 g of hydrated alumina were uniformly mixed, mixed with an appropriate amount of water, and stirred to form a cylindrical shape by an extruder. After drying at room temperature for 24 hours, it was calcined in a high temperature furnace at a temperature of 550 ° C for 4 hours and then lowered to room temperature. Finally, a catalyst D having a diameter of 1 to 2 mm and a length of 3 to 5 mm can be obtained.

In the fifth embodiment, the reaction was carried out by charging the catalyst A into the tubular reactor 5: 16.8 g of the catalyst A was filled in the middle of the tubular reactor 5, and the upper and lower sections of the tubular reactor 5 were filled with glass beads having a diameter of 1 mm. Methyl acetate and soybean oil enter the tubular reactor 5 via a high pressure pump 3 in an up-flow manner, operating at a temperature of 240 ° C, a pressure of 68 bar, methyl acetate and soybean oil. The volume ratio is 2. The space velocity WHSV (Weight Hourly Space Velocity) is 0.33 (hr-1). After the product was cooled by the heat exchanger 9, it was collected and analyzed by GC-FID (gas chromatography-flame ionization detector), and the conversion rate was 99.6%, and the product (fatty acid methyl ester + triacetin) was collected. The rate was 92.2%.

In the sixth embodiment, the catalyst B is filled into the tubular reactor 5 for reaction: 16.8 g of the catalyst B is filled in the middle of the tubular reactor 5 under the conditions of a temperature of 240 ° C, a pressure of 68 bar, a methyl acetate and a large The volume ratio of soybean oil is 2. The space velocity WHSV (Weight Hourly Space Velocity) is 0.33 (hr-1). The product analysis showed a conversion of 66.7% and a yield of the product (fatty acid methyl ester + triacetin) of 53.2%.

In the seventh embodiment, the reaction is carried out by charging the catalyst C into the tubular reactor 5: 16.8 g of the catalyst C is filled in the middle of the tubular reactor 5 under the conditions of a temperature of 286 ° C, a pressure of 68 bar, methyl acetate and large The volume ratio of soybean oil is 2. The space velocity WHSV (Weight Hourly Space Velocity) is 0.33 (hr-1). The product analysis showed a conversion of 79.4% and a yield of the product (fatty acid methyl ester + triacetin) of 55.1%.

In the eighth embodiment, the reaction is carried out by charging the catalyst D into the tubular reactor 5: 16.8 g of the catalyst D is filled in the middle of the tubular reactor 5 under the conditions of a temperature of 254 ° C, a pressure of 68 bar, a methyl acetate and a large The volume ratio of soybean oil is 2. The space velocity WHSV (Weight Hourly Space Velocity) is 0.33 (hr-1). The product analysis showed a conversion of 97.8% and a yield of product (fatty acid methyl ester + triacetin) of 83.7%.

Table 1 lists product analysis data using different catalysts (catalyst A~D). It is preferred to show the conversion ratio of the catalyst A and the product yield. Table I  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Catalyst</td><td> Grease Source</td><td> Operating Time Hr </td><td> pressure bar </td><td> temperature °C </td><td> WHSV hr-1 </td><td> conversion rate (%) </td><td> product Yield (%) </td><td> Metal dissolution (ppm) </td></tr><tr><td> A </td><td> soybean oil</td><td> 36 < /td><td> 68 </td><td> 240 </td><td> 0.33 </td><td> 99.6 </td><td> 92.2 </td><td> W: ND Al : 1.3 </td></tr><tr><td> B </td><td> Soybean Oil</td><td> 36 </td><td> 68 </td><td> 240 </td><td> 0.33 </td><td> 66.7 </td><td> 53.2 </td><td> W: ND Zr: ND </td></tr><tr><td > C </td><td> Soybean Oil</td><td> 36 </td><td> 68 </td><td> 286 </td><td> 0.33 </td><td> 79.4 </td><td> 55.1 </td><td> Mn: 4.8 Al: 1.4 </td></tr><tr><td> D </td><td> Soybean Oil</td> <td> 36 </td><td> 68 </td><td> 254 </td><td> 0.33 </td><td> 97.8 </td><td> 83.7 </td><td > W: 35 Mn: 0.3 Al: 2.9 </td></tr></TBODY></TABLE>

Table 2 lists product analysis data using different catalysts and different operating times. It is preferred to show the conversion ratio of the catalyst A and the product yield. Table II  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Catalyst</td><td> Grease Source</td><td> Operating Time Hr </td><td> Pressure bar </td><td> Temperature °C </td><td> WHSV hr^-1</td><td> Conversion rate (%) < /td><td> Product yield (%) </td><td> Metal dissolution (ppm) </td></tr><tr><td> A </td><td> soybean oil</ Td><td> 24 </td><td> 68 </td><td> 220 </td><td> 0.33 </td><td> 88.9 </td><td> 67.5 </td> <td> W: 1.0 Al: 3.4 </td></tr><tr><td> </td><td> </td><td> 132 </td><td> 68 </td> <td> 220 </td><td> 0.33 </td><td> 83.2 </td><td> 61.0 </td><td> W: 1.4 Al: 1.7 </td></tr>< Tr><td> C </td><td> soybean oil</td><td> 36 </td><td> 68 </td><td> 284 </td><td> 0.33 </td ><td> 79.4 </td><td> 55.1 </td><td> Mn: 4.8 Al: 1.4 </td></tr><tr><td> </td><td> </td ><td> 156 </td><td> 68 </td><td> 284 </td><td> 0.33 </td><td> 63.3 </td><td> 40.7 </td>< Td> Mn: ND Al: 1.4 </td></tr><tr><td> D </td><td> soybean oil</td><td> 24 </td><td> 68 </ Td><td> 220 </td><td> 0.33 </td><td> 82.8 </td><td> 64.7 </td>< Td> W: 113 Mn: ND Al: 2.9 </td></tr><tr><td> </td><td> </td><td> 120 </td><td> 68 </ Td><td> 220 </td><td> 0.33 </td><td> 48.4 </td><td> 29.3 </td><td> W: 1.2 Mn: ND Al: 3.5 </td> </tr></TBODY></TABLE>

In the ninth embodiment, the reaction is carried out by filling the tubular reactor 5 with the catalyst A. In the same manner as in the fifth embodiment, 24.9 g of the catalyst A is filled in the middle of the tubular reactor 5, and the upper and lower sections of the tubular reactor 5 are made of glass having a diameter of 1 mm. Bead filling. Methyl acetate and soybean oil enter the tubular reactor 5 through the high pressure pump 3 in an up-flow manner, respectively, under the operating conditions of a temperature of 260 ° C, a pressure of 68 bar, a volume ratio of methyl acetate to soybean oil. 1. The space velocity WHSV (Weight Hourly Space Velocity) is 0.67 (hr-1). After the product was cooled by the heat exchanger 9, it was collected and analyzed by GC-FID (gas chromatography-flame ionization detector), and the conversion rate was 99.6%, and the product (fatty acid methyl ester + triacetin) was collected. The rate is 97.3%. The collected product is subjected to removal of excess methyl acetate by a short-path evaporator to obtain fatty acid methyl ester, unreacted triglyceride, diglyceride, monoglyceride, and triacetin and its derivatives. (Reduced product of diacetin, monoacetin, etc.). The two-stage reactor operation replaces the oil source with the recovered product and reacts with excess methyl acetate. The product was collected by heat exchanger cooling and analyzed by GC-FID (gas chromatography-flame ionization detector) to obtain a conversion rate of 93-95%. The product (fatty acid methyl ester + triacetin) The yield was 80-86%. Table 3 lists product analysis data under long-term operating time and two-stage reactor operation. Table 3  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Catalyst</td><td> Grease Source</td><td> Operating Time Hr </td><td> pressure bar </td><td> temperature °C </td><td> WHSV hr-1 </td><td> conversion rate (%) </td><td> product Yield (%) </td><td> Metal dissolution (ppm) </td></tr><tr><td> A </td><td> soybean oil</td><td> 24 < /td><td> 68 </td><td> 260 </td><td> 0.67 </td><td> 99.6 </td><td> 97.3 </td><td> W: 0.1 Al : 1.6 </td></tr><tr><td> </td><td> </td><td> 96 </td><td> 68 </td><td> 260 </td ><td> 0.67 </td><td> 83.3 </td><td> 72.9 </td><td> W: 0.7 Al: 4.0 </td></tr><tr><td> </ Td><td> </td><td> 156 </td><td> 68 </td><td> 260 </td><td> 0.67 </td><td> 93.4 </td>< Td> 79.5 </td><td> W: ND Al: 6.1 </td></tr><tr><td> </td><td> </td><td> 192 </td>< Td> 68 </td><td> 260 </td><td> 0.67 </td><td> 91.4 </td><td> 75.7 </td><td> W: 1.9 Al: 2.5 </ Td></tr><tr><td> </td><td> 24-108 hr Recovered product</td><td> 216 </td><td> 68 </td><td> 260 < /td><td> 0.67 </td><td> 93.5 </td><td> 80.4 </td><td> W: ND Al: 5.1 </td></tr><tr><td> </td><td> </td><td> 288 </td><td> 68 </td><td> 260 < /td><td> 0.67 </td><td> 93.0 </td><td> 80.2 </td><td> W: ND Al: 5.7 </td></tr><tr><td> </td><td> 108-192 hr recovered product</td><td> 300 </td><td> 68 </td><td> 260 </td><td> 0.67 </td>< Td> 96.4 </td><td> 86.6 </td><td> W: ND Al: 6.0 </td></tr><tr><td> </td><td> </td>< Td> 360 </td><td> 68 </td><td> 260 </td><td> 0.67 </td><td> 94.8 </td><td> 86.2 </td><td> W: ND Al: 1.6 </td></tr></TBODY></TABLE>

Example 10, a step of continuous production of quality diesel oil and triacetin was carried out as shown in Example 5. After using Catalyst A and operating for 200 hours, the experiment was carried out by changing different oil sources. The operating conditions were 220 ° C, 68 bar, the volume ratio of methyl acetate to grease 2. Space velocity WHSV (Weight Hourly Space) Velocity) is 0.33 (hr-1), and product analysis data is listed in Table 4. Table 4  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Grease source </td><td> Pressure bar </td><td> Temperature °C </td><td> WHSV hr-1 </td><td> Conversion rate (%) </td><td> Product yield (%) </td><td> Metal dissolution (ppm) </ Td></tr><tr><td> soybean oil</td><td> 68 </td><td> 220 </td><td> 0.33 </td><td> 80.0 </td> <td> 55.9 </td><td> W: 0.5 Al: 3.4 </td></tr><tr><td> Castor oil</td><td> 68 </td><td> 220 < /td><td> 0.33 </td><td> 99.6 </td><td> 84.1 </td><td> W: 0.2 Al: 3.0 </td></tr><tr><td> Palm oil</td><td> 68 </td><td> 220 </td><td> 0.33 </td><td> 72.6 </td><td> 49.8 </td><td> W : 0.1 Al: 1.0 </td></tr><tr><td> Coconut Oil</td><td> 68 </td><td> 220 </td><td> 0.33 </td>< Td> 97.8 </td><td> 36.1 </td><td> W: 0.1 Al: 1.1 </td></tr><tr><td> Tung oil</td><td> 68 </td ><td> 220 </td><td> 0.33 </td><td> 95.6 </td><td> 59.3 </td><td> W: 0.7 Al: 3.9 </td></tr> <tr><td> Jatropha curcas oil</td><td> 68 </td><td> 220 </td><td> 0.33 </td><td> 74.2 </td><td> 51.5 </td><td> W: 0.6 Al: 1.5 </td></tr><tr><td> Edible oil</td><td> 68 </td><td> 220 </td><td> 0.33 </td><td> 73.5 </td><td> 50.1 </td><td> W : 0.9 Al: 1.2 </td></tr></TBODY></TABLE> Note: The free fatty acid content in Jatropha curcas oil is about 8.5 wt%, and the free fatty acid content in waste cooking oil is about 4.3 wt%.  

In summary, the present invention provides a method for preparing biodiesel and triacetin, and a novel solid acid catalyst is developed, which has high activity and good stability, and under appropriate operating conditions, One-step continuous production of quality diesel oil and high-valued triacetin production, and can obtain higher conversion rate and product yield, compared with the current one-step continuous solid-state catalyst to produce quality diesel and three The process technology of glycerol acetate must be completed in a small batch operation with supercritical technology (350 degrees Celsius and 200 bar high pressure), and it is not suitable for containing unsaturated oil as a source. Most bio-fat cannot be used. As a raw material for the reaction, it is still extremely difficult to implement in the industry. In addition, triacetin is a high-priced raw material, which can be used as a plasticizer, solvent, additive, etc., and has great economic value.

The above is only a preferred embodiment of the invention and is not intended to limit the invention. Any changes in the technical means and technical contents disclosed in the present invention may be made by those skilled in the art without departing from the technical means of the present invention. The content is still within the scope of protection of the present invention.

1‧‧‧Carboxylic esters

2‧‧‧ Grease

3‧‧‧High pressure pump

4‧‧‧Safety valve

5‧‧‧Tubular reactor

6‧‧‧ Temperature Controller

7‧‧‧Electrical couple

8‧‧‧Back pressure valve

9‧‧‧ heat exchanger

10‧‧‧Product collection tank

Figure 1 is a schematic view showing the apparatus for preparing biodiesel and triacetin of the present invention.

no

Claims (10)

A method for preparing biodiesel and triacetin, wherein at least one acidic metal compound and water are mixed in proportion, and after extrusion and high temperature sintering, a solid metal oxide catalyst is formed, wherein the solid metal is oxidized The medium is packed in a tubular reactor for one transesterification and exchange esterification to produce a fatty acid methyl ester and triacetin. The method for preparing biodiesel and triacetin according to claim 1, wherein the reactant of the transesterification and the exchange esterification reaction comprises a monocarboxylic acid ester and a fat or oil. The method for producing biodiesel and triacetin according to claim 2, wherein the carboxylic acid ester is an acetate. The method for preparing biodiesel and triacetin according to claim 2, wherein the oil is soybean oil, jatropha seed oil, castor oil, tung oil, palm oil, coconut oil, oil. a mixture of any one or more of oleic acid, lard, tallow, algae oil, waste cooking oil or spent acid oil. The method for producing biodiesel and triacetin according to claim 3, wherein the carboxylic acid ester is methyl acetate. The method for preparing biodiesel and triacetin according to claim 1, wherein the carboxylic acid ester and the oil and fat are respectively up-flowed via a high-pressure pump system. The reaction is carried out in the tubular reactor. The method for preparing biodiesel and triacetin according to claim 6, wherein the reaction temperature is between 170 ° C and 300 ° C. The method for preparing biodiesel and triacetin according to claim 6, wherein the reaction pressure is between 40 bar and 80 bar. The method for preparing biodiesel and triacetin according to claim 6, wherein the ratio of the volume ratio of the carboxylic acid ester to the oil or fat is between 1 and 3. The method for preparing biodiesel and triacetin according to claim 6, wherein the space velocity WHSV (Weight Hourly Space Velocity) is between 0.1 and 1.0 (hr-1).