KR20230094543A - Manufacturing and Desulfurizing Biodiesel using animal Animal Lipids - Google Patents

Abstract

One embodiment of the present invention, performing an esterification reaction by mixing animal lipids, a solvent, and a catalyst in a reactor, producing crude biodiesel; removing the solvent from the crude biodiesel through primary vacuum distillation; Removing glycerol from the crude biodiesel through layer separation; removing the catalyst from the crude biodiesel by washing with water; and removing sulfur components from the crude biodiesel from which the solvent, the glycerol, and the catalyst have been removed through secondary vacuum distillation and producing high-purity biodiesel. .

Description

Method for manufacturing and desulfurizing biodiesel using animal lipids {Manufacturing and Desulfurizing Biodiesel using animal Animal Lipids}

One embodiment of the present invention relates to a biodiesel production and desulfurization method using animal lipids, and more specifically, to a method for producing high-purity biodiesel by removing sulfur components contained in crude biodiesel through a vacuum distillation method. will be.

Along with the depletion of fossil fuels such as petroleum and coal, biodiesel is attracting attention as a next-generation energy source as a solution to environmental pollution. ” obliges transportation fuel suppliers to mix biodiesel with existing fossil fuels in a certain ratio.

Biodiesel is divided into first-generation biodiesel using edible crops such as corn, sugar cane, and soybean, second-generation biodiesel using waste wood as a raw material, and third-generation biodiesel using seaweed as a raw material. Among raw materials, both plant lipids and animal lipids are used as raw materials for biodiesel.

As most of the raw materials of biodiesel supplied in Korea are vegetable lipids such as waste cooking oil, palm oil, and palm by-products, it is necessary to develop a biodiesel manufacturing method that satisfies the raw material ingredients and quality standards based on animal lipids from the perspective of energy security. There is a need.

When insect lipids are adopted as raw materials for the production of biodiesel, differences occur in the characteristics and sulfur content of conventional biodiesel using animal and vegetable lipids as raw materials.

In particular, when insects that consume food waste are used as raw materials for biodiesel, the characteristics of organic matter consumed by insects are reflected in the produced biodiesel. In order to satisfy the quality standards specified in the "Notice", it is necessary to properly prepare a separate purification process such as desulfurization, decolorization, and deodorization.

Against this background, the purpose of this embodiment is, in one aspect, the quality of biodiesel produced from animal lipids as a raw material is the Korean biodiesel quality standard, FAME content (wt%) of 96.5 or more, and sulfur component (mg / kg) of 10 It is to provide a biodiesel production and desulfurization method for producing biodiesel to satisfy the following.

For the purpose of this embodiment, in one aspect, a biodiesel production method capable of maintaining a high yield while performing purification processes such as decolorization, deodorization, and desulfurization through vacuum distillation on crude biodiesel produced from insect lipids. is to provide

In order to achieve the above object, one embodiment of the present invention, performing an esterification reaction by mixing animal lipids, solvents, and catalysts in a reactor, producing crude biodiesel; removing the solvent from the crude biodiesel through primary vacuum distillation; Removing glycerol from the crude biodiesel through layer separation; removing the catalyst from the crude biodiesel by washing with water; and removing sulfur components from the crude biodiesel from which the solvent, the glycerol, and the catalyst have been removed through secondary vacuum distillation and producing high-purity biodiesel. .

In the biodiesel production method, the animal lipid is an insect lipid, and the insect lipid may include at least one of black soldier flies, king geese, and brown geese.

In the biodiesel production method, the solvent may include methanol or alcohol, and the catalyst may include at least one of sulfuric acid, hydrochloric acid, sodium hydroxide, and potassium hydroxide.

FAME 이하의 지방산 메틸 에스터(FAME)를 포함하도록 끓는점을 조절할 수 있다.In the biodiesel production method, the secondary vacuum distillation is

The boiling point can be adjusted to include fatty acid methyl esters (FAMEs) below FAME.

In the biodiesel production method, the secondary vacuum distillation may be performed under conditions of 10 mmHg and 150-180 ° C.

In the biodiesel production method, the high-purity biodiesel may have a sulfur component content of 10 mg/kg or less and a fatty acid methyl ester (FAME) content of 96.5% by weight or more.

In the biodiesel production method, the high-purity biodiesel may include FAMEs having 10 to 20 carbon atoms.

In the biodiesel manufacturing method, the high-purity biodiesel may include a compound having a GC-MS retention time of 10 to 47 minutes.

In the biodiesel production method, the mixing ratio of the animal lipid and the solvent may be 1:1 to 8 by weight.

In the biodiesel production method, the esterification reaction may be performed at a temperature of 40-100 ° C.

In the biodiesel production method, the first vacuum distillation is performed at 10 mmHg and 40 ° C. to remove the solvent by distillation under reduced pressure for 1 hour, and the layer separation can separate the mixture maintained for 12 hours by the difference in density.

In the biodiesel manufacturing method, the catalyst may be removed by repeating the process of mixing the mixture and water at a ratio of 1:1, stirring for 10 minutes, and maintaining for 6 hours five times.

In the biodiesel production method, the high-purity biodiesel may be characterized in that the yield of fatty acid methyl ester (FAME) is 90% or more based on the weight of the animal lipid.

As described above, according to one embodiment of the present invention, the quality of biodiesel produced from animal lipids as a raw material is FAME content (wt%) of 96.5 or more, and sulfur content (mg / kg), which is the Korean biodiesel quality standard. 10 or less biodiesel can be produced.

According to one embodiment of the present invention, crude biodiesel produced from insect lipids is subjected to purification processes such as decolorization, deodorization, and desulfurization through vacuum distillation to satisfy quality standards and produce products with high yield. .

1 is a flow chart of a biodiesel manufacturing method according to this embodiment.
2 is a flow chart of a biodiesel production method including a desulfurization process according to the present embodiment.
3 is an exemplary diagram of an experimental apparatus for a vacuum distillation process according to this embodiment.
4 is a graph showing the GC-MS results of biodiesel according to this example.
5 is a graph showing comparison of GC-MS results of biodiesel produced using insect lipids according to this example as a raw material.
6 is a diagram showing a comparison of properties of biodiesel before and after vacuum distillation according to the present embodiment.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same components have the same numerals as much as possible even if they are displayed on different drawings. In addition, in describing the present invention, a detailed description of a related known configuration or function, which is determined to obscure the gist of the present invention, will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, a, and b may be used. These terms are only used to distinguish the component from other components, and the nature, sequence, or order of the corresponding component is not limited by the term. When an element is described as being “connected,” “coupled to,” or “connected” to another element, that element is directly connected or connectable to the other element, but there is another element between the elements. It will be understood that elements may be “connected”, “coupled” or “connected”.

1 is a flow chart of a biodiesel manufacturing method according to this embodiment.

Referring to FIG. 1, the biodiesel production method 100 includes obtaining animal lipids (S101), synthesizing biodiesel through an esterification reaction (S102), and removing a solvent from crude biodiesel (S102). S103), removing glycerol from crude biodiesel (S104), removing catalyst from crude biodiesel (S105), purifying crude biodiesel (S106), producing high-purity biodiesel (S107) and the like.

Obtaining animal lipids (S101) is a step of extracting lipids from animals in a physical or chemical manner.

Animal lipids used in the synthesis process of biodiesel may be insect lipids, wherein the insects may be blackbird, kingfish, brown geese, etc., but are not limited thereto. Insects grow by ingesting food waste, and can be used as a raw material for biodiesel through separation, drying, and lipid extraction.

The step of synthesizing biodiesel through esterification (S102) is a step of synthesizing biodiesel through esterification by mixing animal lipids with a catalyst and a solvent in a reactor.

Various catalysts such as sulfuric acid, hydrochloric acid, sodium hydroxide, and potassium hydroxide may be used as catalysts in the biodiesel synthesis process. In addition, catalysts such as solid catalysts and organic catalysts may be used in consideration of the characteristics of raw materials. Acidic catalysts, basic catalysts, amphoteric catalysts, etc. may be used as needed.

Alcohols such as methanol and ethanol may be used as solvents in the biodiesel synthesis process.

In the biodiesel synthesis process, the reaction temperature may be 40-100 ° C, and the mixing ratio of the insect lipid and the solvent may be 1: 1 to 8 by weight, but is not limited thereto.

The step of removing the solvent from the crude biodiesel (S103) is a step of removing the solvent from the crude biodiesel produced through the esterification reaction. When the solvent is alcohol, vacuum distillation may be used to remove the alcohol from the mixture. The temperature and pressure of vacuum distillation may be defined in various ways depending on the solvent component of the mixture.

The step of removing glycerol from crude biodiesel (S104) is a step of separating glycerol from the mixture from which the solvent is removed through reduced pressure distillation using the difference in density.

For example, if the component of animal lipid is triglyceride, glycerol and fatty acid methyl ester (FAME) are produced by performing an esterification reaction with methanol as the solvent and sodium hydroxide as the catalyst. do.

Since glycerol has a higher density than fatty acid methyl ester (FAME) as a side reactant, it sinks in the lower layer, and fatty acid methyl ester (FAME) is located in the upper layer, so that glycerol can be selectively removed by layer separation for a certain period of time. Layer separation may be performed after maintaining the mixture for 12 hours, but is not limited thereto.

The step of removing the catalyst from the crude biodiesel (S105) is a step of removing the catalyst from the mixture.

Water washing may be a method of removing the catalyst by mixing and stirring the mixture and water, and maintaining the mixture for a certain time, but is not limited thereto.

The crude biodiesel purifying step (S106) is a step of purifying the mixture from which the solvent, glycerol, and catalyst are removed.

Depending on the characteristics of the animal lipid, it may contain other impurities in addition to the solvent, glycerol, and catalyst - for example, sulfur, phosphorus, etc. -, so it is necessary to remove the impurities by performing an appropriate purification process. If necessary, impurities may be included in various raw materials such as microalgae, and in this case, a purification process described later may be performed. In this case, conditions for vacuum distillation may be appropriately changed according to the number of carbons, yield, and the like.

Through the purification process, the mixture can be decolorized, deodorized, desulfurized, etc., and the purification process can remove impurities or reduce the concentration using vacuum distillation.

If the temperature of the vacuum distillation conditions is too low, there is a problem in that the yield of fatty acid methyl ester (FAME) is lowered, and if the temperature is too high, there is a problem in that the sulfur content does not satisfy domestic quality standards.

The step of producing high-purity biodiesel (S107) is a step of removing impurities through a purification process such as vacuum distillation and producing the obtained high-purity biodiesel.

The terms 'crude biodiesel' and 'high purity biodiesel' used in FIG. 1 may be defined to distinguish biodiesel before and after a purification process. In addition, in FIG. 1, removing the solvent from crude biodiesel (S103), removing glycerol from crude biodiesel (S104), removing catalyst from crude biodiesel (S105), crude biodiesel In the step of refining diesel (S106), the mixture to be processed may be collectively referred to as 'crude biodiesel'.

1 is an illustration to explain a biodiesel production method, and the technical spirit of the present invention can be applied to animal lipids and insect lipids, and some of the steps illustrated in FIG. 1 are omitted or the sequence is can be changed.

2 is a flow chart of a biodiesel production method including a desulfurization process according to the present embodiment.

Referring to FIG. 2, the biodiesel production method 200 including the desulfurization process according to the present embodiment includes an esterification reaction step (S201), a first vacuum distillation step (S202), a layer separation step (S203), and a water washing step. (S204), a second vacuum distillation step (S205), and the like.

The esterification reaction step (S201) is a step of performing an esterification reaction by mixing insect lipid with methanol and a catalyst. Insect lipids, methanol, and catalysts can be esterified to obtain crude biodiesel and glycerol.

The first vacuum distillation step (S202) is a step of removing methanol through reduced pressure distillation. Methanol may be removed by setting a boiling point in order to remove methanol, which is a solvent.

Here, 'primary vacuum distillation' may be defined to be distinguished from the step of distilling the mixture under reduced pressure for desulfurization (S205).

The layer separation step (S203) is a step of separating and removing glycerol by the density difference of each component of the methanol-removed mixture.

The water washing step (S204) is a step of separating and removing the catalyst from the mixture from which glycerol is removed.

The second vacuum distillation step (S205) is a step of removing impurities such as sulfur and unreacted lipids from the mixture from which the solvent, glycerol, and catalyst are removed.

The boiling point of secondary vacuum distillation can be appropriately adjusted according to the composition of target high purity biodiesel (FAME).

Referring to FIG. 2, the first step of synthesizing biodiesel through the esterification of insect lipids and methanol under a catalyst, the second step of removing methanol after the esterification reaction, the third step of removing glycerol as a by-product, and the catalyst It is possible to obtain high-purity biodiesel (FAME) by sequentially performing a fourth step of removing impurities and a fifth step of removing impurities such as decolorization, deodorization, and desulfurization.

3 is an exemplary diagram of an experimental apparatus for a vacuum distillation process according to this embodiment.

Referring to FIG. 3 , the vacuum distillation process according to this embodiment may be performed by controlling the boiling point of the mixture under a pressure lower than atmospheric pressure, but is not limited thereto.

Through the vacuum distillation process, the target material can be extracted using the relative boiling point difference in the mixture and impurities can be removed.

Since crude biodiesel contains impurities such as sulfur and phosphorus in addition to FAME, impurities can be removed through a distillation process. In particular, an appropriate boiling point and extraction standard may be set in consideration of the physical properties and yield of impurities.

4 is a graph showing the GC-MS results of biodiesel according to this example.

Referring to FIG. 4, biodiesel can be graphed through gas chromatography-mass spectrometry (GC-MS).

Biodiesel obtained through insect lipids may include FAMEs having 10 to 20 carbon atoms, and more specifically, C10 to C18 FAMEs may account for 90% by weight or more, and C20 or more FAMEs may be less than 5% by weight. can

Based on the distillation point, C20, components below C20 may be 89.4%, and components above C20 may be 10.6%.

In addition, in gas chromatography (GC), the higher the carbon number, the higher the temperature is separated and appears as a peak. Since the peak of the sulfur compound contained in the biodiesel is confirmed after the C20 FAME peak, a high yield of 90% by weight or more can be obtained by distillation up to the C20 FAME point, and a product containing no sulfur compound can be obtained.

If necessary, in the process of refining biodiesel, vacuum distillation can be performed up to the point of C10 FAME, C12 FAME, C14 FAME, C14 FAME, C18 FAME, C20 FAME, but to remove sulfur compounds, C18 FAME or C20 FAME is the reference point for purification. It is preferable to leave it as

In addition, the biodiesel purification process can control the boiling point or operating time including compounds having a retention time of 10 minutes to 47 minutes in GC-MS. For example, the purification process may selectively purify materials with a residence time of less than 45 or 47 minutes. However, the above-mentioned residence time may be defined in various ways according to the setting conditions of GC-MS, and the technical spirit of the present invention is not limited thereto.

FAME 이하의 지방산 메틸 에스터(FAME)를 포함하도록 끓는점을 조절할 수 있고, 10mmHg 및 150-180℃ 조건에서 수행될 수 있다.The vacuum distillation process is

The boiling point can be adjusted to include fatty acid methyl ester (FAME) below FAME, and can be performed at 10 mmHg and 150-180 ° C.

The high-purity biodiesel obtained through the vacuum distillation process may have a sulfur component content of 10 mg/kg or less and a fatty acid methyl ester (FAME) content of 96.5% by weight or more.

5 is a graph showing comparison of GC-MS results of biodiesel produced using insect lipids according to this example as a raw material.

Referring to FIG. 5, GC-MS results of biodiesel produced using insect lipids as raw materials can be compared and shown.

When comparing FAME distributions in the case of producing biodiesel by extracting insect lipids from blackfly, king geese, and brown geese, the distribution as shown in FIG. 5 may be shown in 10 to 20 carbon atoms.

The distillation point of biodiesel may be adjusted according to the characteristics of the insect lipids used, but in common, high FAME content may be exhibited at C18:0, C18:1, and C18:2.

Therefore, the yield can be improved by extracting components of C18 or lower or extracting components of C20 or lower. Even in this case, since the sulfur component can be found in components exceeding C20, the distillation reference point can be set to C18 or C20 in comprehensive consideration of the FAME yield and the purpose of sulfur removal.

6 is a diagram showing a comparison of properties of biodiesel before and after vacuum distillation according to the present embodiment.

Referring to FIG. 6, high-purity biodiesel and residue after vacuum distillation can be obtained from crude biodiesel before vacuum distillation through vacuum distillation according to the present embodiment.

By simultaneously performing decolorization, deodorization, and desulfurization of biodiesel through vacuum distillation, crude biodiesel having a pale yellow color can be purified in a transparent state, and it satisfies quality standards enough to be used as commercial fuel. Here, the test methods of KS M 2413 and EN 14103 can be applied to the FAME quality standards, and the test methods of KS M 2027 can be applied to the sulfur quality standards.

1. Manufacturing process of biodiesel

1-1. Biodiesel synthesis through esterification reaction

[Example 1]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 1-1 in camaraderie 5 0.05 40 80 3 13.15 Example 1-2 in camaraderie 5 0.1 40 80 3 33.22 Example 1-3 in camaraderie 5 0.25 40 80 3 66.48 Example 1-4 in camaraderie 5 0.35 40 80 3 78.74 Example 1-5 in camaraderie 5 0.5 40 80 3 94.65 Example 1-6 in camaraderie 5 0.75 40 80 3 94.53 Examples 1-7 in camaraderie 5 1.0 40 80 3 95.16

In Example 1, the FAME content ratio was obtained by adjusting the mixing ratio of the insect lipid and the catalyst. The FAME content was measured while changing the catalyst amount to 0.05 g, 0.1 g, 0.25 g, 0.35 g, 0.5 g, 0.75 g, and 1.0 g based on 5 g of lipid.

Through Example 1, it was confirmed that the FAME content increased as the mixing ratio of the catalyst amount increased.

[Example 2-1]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 2-1-1 in camaraderie 5 0.5 30 80 3 94.76 Example 2-1-2 in camaraderie 5 0.5 40 80 3 94.65 Example 2-1-2 in camaraderie 5 0.5 50 80 3 94.95

In Example 2-1, the FAME content ratio was obtained by adjusting the amount of methanol. At a reaction temperature of 80 ° C., the FAME content was measured while changing the amount of methanol to 30 g, 40 g, and 50 g based on 5 g of lipid and 0.5 g of catalytic amount.

Although it was not possible to confirm a significant change in the FAME content according to the change in the amount of methanol through Example 2-1, a FAME content of 90% or more was measured in Example 2-1.

[Example 2-2]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 2-2-1 in camaraderie 5 0.35 30 80 3 70.55 Example 2-2-2 in camaraderie 5 0.35 40 80 3 78.74 Example 2-2-3 in camaraderie 5 0.35 50 80 3 78.44

In Example 2-2, the FAME content ratio was obtained by adjusting the amount of methanol. The FAME content was measured while changing the amount of methanol to 30 g, 40 g, and 50 g based on 5 g of lipid and 0.35 g of catalyst at a reaction temperature of 80 ° C.

Through Example 2-2, the FAME content change according to the amount of methanol was confirmed between 30 g and 40 g of methanol amount, and no significant change was observed between 40 g and 50 g of methanol amount. In Example 2-2, FAME content of 70% to 80% was measured.

[Example 2-3]

Example insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 2-3-1 in camaraderie 5 0.25 30 80 3 63.97 Example 2-3-2 in camaraderie 5 0.25 40 80 3 66.48 Example 2-3-3 in camaraderie 5 0.25 50 80 3 68.16

In Example 2-3, the FAME content ratio was obtained by adjusting the amount of methanol. At a reaction temperature of 80 ° C., the FAME content was measured while changing the amount of methanol to 30 g, 40 g, and 50 g based on 5 g of lipid and 0.25 g of catalytic amount.

Although it was not possible to confirm a significant change in the FAME content according to the change in the amount of methanol through Example 2-3, in Example 2-3, the FAME content of 60% to 70% was measured.

[Example 2-4]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 2-4-1 in camaraderie 5 0.1 40 80 9 80.11 Example 2-4-2 in camaraderie 5 0.1 50 80 9 82.01 Example 2-4-3 in camaraderie 5 0.1 60 80 9 85.29

In Examples 2-4, the FAME content ratio was obtained by adjusting the amount of methanol. At a reaction temperature of 80 ° C., the amount of methanol was changed to 40 g, 50 g, and 60 g based on 5 g of lipid and 0.1 g of catalyst, and the FAME content was measured.

Although it was not possible to confirm a significant change in the FAME content according to the change in the amount of methanol through Example 2-4, in Example 2-4, the FAME content of 80% to 90% was measured.

[Example 2-5]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 2-5-1 in camaraderie 5 0.25 30 75 6 85.14 Example 2-5-2 in camaraderie 5 0.25 40 75 6 93.15 Example 2-5-3 in camaraderie 5 0.25 60 75 6 93.77

In Examples 2-5, the FAME content ratio was obtained by adjusting the amount of methanol. At a reaction temperature of 75 ° C., the FAME content was measured while changing the amount of methanol to 30 g, 40 g, and 60 g based on 5 g of lipid and 0.25 g of catalytic amount.

Through Examples 2-5, the change in FAME content according to the change in methanol amount was confirmed between 30 g and 40 g of methanol amount, and no significant change was observed between 40 g and 60 g of methanol amount. In Examples 2-5, FAME content of 80% to 95% was measured.

Considering Example 2-2 and Example 2-5, it can be interpreted that a significant FAME content change is observed between 1:6 and 1:8 mixing ratio of lipid and methanol regardless of the amount of catalyst.

[Example 3-1]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 3-1-1 in camaraderie 5 0.1 60 80 9 85.29 Example 3-1-2 in camaraderie 5 0.1 60 75 9 84.43 Example 3-1-3 in camaraderie 5 0.1 60 70 9 76.85

In Example 3-1, the FAME content ratio was obtained by adjusting the reaction temperature. The FAME content was measured while changing the reaction temperature to 80 ° C, 75 ° C, and 70 ° C based on 5 g of lipid, 0.1 g of catalyst and 60 g of methanol.

Through Example 3-1, it was confirmed that the FAME content decreased as the reaction temperature decreased, and in Example 3-1, a FAME content of 70% to 90% was measured.

[Example 3-2]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 3-2-1 in camaraderie 5 0.25 40 80 6 93.50 Example 3-2-2 in camaraderie 5 0.25 40 75 6 93.15 Example 3-2-3 in camaraderie 5 0.25 40 70 6 92.92

In Example 3-2, the FAME content ratio was obtained by adjusting the reaction temperature. Based on 5 g of lipid, 0.25 g of catalyst, and 40 g of methanol, the reaction temperature was changed to 80 ° C, 75 ° C, and 70 ° C, and the FAME content was measured.

Through Example 3-2, a significant change in FAME content could not be observed as the reaction temperature decreased. In Example 3-2, FAME content of 90% to 95% was measured.

[Example 4]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 4-1 in camaraderie 5 0.25 30 80 3 63.97 Example 4-2 in camaraderie 5 0.25 30 80 6 87.91 Example 4-3 in camaraderie 5 0.25 30 80 9 93.28

In Example 4, the FAME content ratio was obtained by adjusting the reaction time. At a reaction temperature of 80 ° C., the FAME content was measured while changing the reaction time to 3 hours, 6 hours, and 9 hours based on 5 g of lipid, 0.25 g of catalyst, and 30 g of methanol.

Through Example 4, it was confirmed that the FAME content increased as the reaction time increased. Content change was measured.

[Example 5-1]

division insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) Example 5-1-1 in camaraderie 5 0.25 40 75 3 84.57 Example 5-1-2 king meal 5 0.25 40 75 3 47.05 Example 5-1-3 brown mealworm 5 0.25 40 75 3 54.39

In Example 5-1, the FAME content ratio was obtained by changing the type of insect. Based on the reaction temperature of 75 ° C., 5 g of lipid, 0.25 g of catalyst, and 40 g of methanol, the type of insects was changed to black soldier flies, king crab, and brown caterpillar, and the FAME content was measured.

Through Example 5-1, it was confirmed that the FAME content of Dongae etc. was the highest at about 85%.

[Example 5-2]

insect species lipids
(g) catalytic amount
(g) amount of methanol
(g) reaction temperature
(℃) reaction time
(h) FAME content
(%) in camaraderie 5 0.25 40 70 6 91.17 king meal 5 0.25 40 70 6 91.33 brown mealworm 5 0.25 40 70 6 91.23

In Example 5-2, the FAME content ratio was obtained by changing the type of insect. Based on the reaction temperature of 70 ° C., 5 g of lipid, 0.25 g of catalyst, and 40 g of methanol, the FAME content was measured by changing the type of insects to black soldier flies, king geese, and brown geese.

Through Example 5-2, the FAME content of Dongae, king geese, and brown geese was measured to be 90% or more, and no significant deviation was confirmed.

By comparing Examples 5-1 and 5-2, it was confirmed that the FAME content could be increased by decreasing the reaction temperature and increasing the reaction time.

1-2. Solvent, glycerol, catalyst removal

After completion of the esterification reaction, methanol was removed by distillation under reduced pressure at 10 mmHg and 40 °C for 1 hour.

After removal of methanol, the mixture was allowed to stand for 12 hours to remove glycerol by layer separation by density difference.

After removal of glycerol, the mixture of the product and water in a ratio of 1:1 was stirred for 10 minutes, allowed to stand for 6 hours, and the process of layer separation was repeated 5 times to remove the catalyst.

1-3. Removal of sulfur components through vacuum distillation

[Example 6]

division enter
(mm Hg) temperature
(℃) hour
(hr) sulfur content
(mg/kg) FAME content
(%) transference number
(%) Comparative Example 1
(before distillation) - - - 150.0 92.4 91.2 Example 6-1 10 140 5.5 98.7 65.6 Example 6-2 10 150 5.6 98.5 72.6 Example 6-3 10 160 5.6 97.2 90.0 Example 6-4 10 170 9.8 96.8 90.3 Example 6-5 10 180 132.2 92.8 90.8

In Example 6, an experiment was performed to remove the sulfur component through vacuum distillation while changing the vacuum distillation temperature conditions for the mixture subjected to the esterification reaction, solvent removal, glycerol removal, and catalyst removal.

In Example 6, the temperature conditions were changed to 140 °C, 150 °C, 160 °C, 170 °C, and 180 °C, and sulfur component (mg/kg), FAME content (%) and yield (%) were measured.

Through Example 6, the sulfur component content satisfies 10 mg/kg or less at less than 180 ° C., and rapid changes in properties were confirmed in Examples 6-4 and 6-5. Considering the experimental data of Comparative Example 1 and Examples 6-1 to 6-5, it is preferable to perform vacuum distillation at a temperature condition of 140 ° C. or more and less than 180 ° C. In addition, a sulfur content of 10 mg/kg may be obtained at a temperature condition of 140 °C to 170 °C, but a sulfur content of 6 mg/kg or less may be obtained at a temperature condition of 140 °C to 160 °C.

Through Example 6, the FAME content satisfied 95.6% or more at 140 ° C to 180 ° C, and no significant difference in FAME content according to temperature was confirmed. A difference in FAME content ratio of 4% was confirmed between Example 6-4 and Example 6-5.

Through Example 6, the yield satisfied 90% or more at 160 ° C to 180 ° C, and satisfied 70% or more at 150 ° C to 180 ° C. A difference in yield of about 18% was confirmed between Example 6-2 and Example 6-3. In addition, a yield of 90% or more can be obtained at a temperature condition of 160 ° C to 180 ° C, but a yield of less than 70% is obtained at a temperature condition of 140 ° C to 150 ° C.

Considering Example 6, the distillation conditions for reducing the sulfur component (mg/kg) and improving the FAME content (%) are preferably a pressure of 10 mmHg and a temperature of 140 ° C to 180 ° C, but a pressure of 10 mmHg and a temperature of 140 ° C to 170 ° C. °C may be more preferred.

In addition, in order to reduce the sulfur component while maintaining a yield of 90% or more, the distillation conditions are preferably a pressure of 10 mmHg and a temperature of 150 ° C to 180 ° C, but a pressure of 10 mmHg and a temperature of 150 ° C to 170 ° C are more preferable.

In Examples 6-1 to 6-5, it was confirmed that Example 6-3 satisfied all of the low sulfur component (mg / kg), high FAME content (%) and yield (%).

In Table 12, the distillation time was continued until the time at which distillation was no longer under temperature and pressure conditions.

2. Comparison of decolorization, deodorization and desulfurization performance of vacuum distillation

method biodiesel
(g) menstruum
(g) temperature
hour
(hr) decolorization takeover sulfur content
(mg/kg) degumming 10 1g H2NO3 50 3 ○ - 150 deoxidation 10 1g NaOH 60 3 △ △ 65 hydrothermal treatment 10 50g H2O 100 One - - 85 absorbent 10 acid clay - One ○ - 150 vacuum distillation - - - - ○ ○ 5.6

Table 13 compares the performance of decolorization, deodorization, and desulfurization by performing treatments such as degumming, deoxidation, hydrothermal treatment, and adsorption in order to compare the purification efficiency of vacuum distillation according to this embodiment.

When biodiesel was degummed, the effect of decolorization was found, but the effect of reducing the sulfur component content was not found.

When biodiesel was deoxidized, no decolorization and deodorizing effects were found, but the sulfur content slightly decreased. However, even in this case, the content of the sulfur component exceeded 10 mg/kg.

When biodiesel was subjected to high-temperature hydrothermal treatment, the sulfur content slightly decreased, but the sulfur content exceeded 10 mg/kg.

When biodiesel was treated with acid clay, the effect of decolorization was confirmed, but the effect of reducing the sulfur component content was not found.

Decolorization, deodorization, and desulfurization could be implemented simultaneously through vacuum distillation according to this embodiment.

Claims (13)

Performing an esterification reaction by mixing animal lipids, a solvent, and a catalyst in a reactor, and producing crude biodiesel;
removing the solvent from the crude biodiesel through primary vacuum distillation;
Removing glycerol from the crude biodiesel through layer separation;
removing the catalyst from the crude biodiesel by washing with water; and
Biodiesel production method comprising the step of removing a sulfur component from the crude biodiesel from which the solvent, the glycerol, and the catalyst have been removed through secondary vacuum distillation and producing high-purity biodiesel. According to claim 1,
The animal lipid is an insect lipid,
The insect lipid is a biodiesel production method comprising at least one of black soldier flies, king geese, and brown geese. According to claim 1,
The solvent includes methanol or alcohol,
The catalyst comprises at least one of sulfuric acid, hydrochloric acid, sodium hydroxide, and potassium hydroxide, biodiesel production method. According to claim 1,
The second vacuum distillation is

Controlling the boiling point to include fatty acid methyl ester (FAME) below FAME, biodiesel production method. According to claim 1,
The secondary vacuum distillation is performed at 10 mmHg and 150-180 ° C conditions, biodiesel production method. According to claim 1,
The high-purity biodiesel has a sulfur component content of 10 mg / kg or less, and a fatty acid methyl ester (FAME) content of 96.5% by weight or more. According to claim 1,
The high-purity biodiesel is characterized in that it comprises FAME having 10 to 20 carbon atoms, biodiesel production method. According to claim 1,
The high-purity biodiesel comprises a compound having a retention time of 10 minutes to 47 minutes in GC-MS, biodiesel production method. According to claim 1,
Characterized in that the mixing ratio of the animal lipid and the solvent is 1: 1 to 8 in weight ratio, biodiesel production method. According to claim 1,
The esterification reaction is carried out at 40-100 ℃ temperature conditions, biodiesel production method. According to claim 1,
The primary vacuum distillation is to remove the solvent by vacuum distillation at 10 mmHg and 40 ° C for 1 hour,
The layer separation is a biodiesel production method in which the mixture maintained for 12 hours is separated by a density difference. According to claim 1,
The washing with water is a biodiesel production method in which the catalyst is removed by mixing the mixture and water at a ratio of 1: 1, stirring for 10 minutes, and maintaining for 6 hours five times. According to claim 6,
The high-purity biodiesel is characterized in that the yield of fatty acid methyl ester (FAME) relative to the weight of the animal lipid is 90% or more, biodiesel production method.

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