KR101508042B1 - Method of improving low temperature property of biodiesel from vegetable oils and animal fats with a high content of saturated fatty acids - Google Patents

Abstract

The present invention relates to a method for improving the low-temperature fluidity of an animal and vegetable oil-retained biodiesel having a high saturated fatty acid content, and more particularly, to a method for reducing saturated fatty acid methyl ester content by adding urea and methanol to biodiesel having a high saturated fatty acid methyl ester content (CFPP) by mixing the additives (CFPP-depressant additives) to the biodiesel with reduced saturated fatty acid methyl ester content, and a method of improving the low temperature filter clogging point Thereby greatly improving the low temperature fluidity of the biodiesel by maximizing its efficiency. According to the present invention, it is possible to obtain a biodiesel which can be applied to a fuel flow channel more favorable in domestic environmental conditions by improving the low temperature filter clogging point of biodiesel having a high saturated fatty acid methyl ester content.

Description

TECHNICAL FIELD The present invention relates to a method for improving the low temperature fluidity of biodiesel derived from vegetable and animal fats and oils having a high content of saturated fatty acids,

The present invention relates to a method for improving the low-temperature filter clogging point of a plant / plant biodiesel by reducing a saturated fatty acid methyl ester by using a fractionation method in animal and vegetable biodiesel, The present invention relates to a method for improving the low-temperature filter clogging point (CFPP), which comprises mixing a low-temperature filter clogging point (CFPP) Temperature filter clogging point of the diesel.

Biodiesel is one of the biomass energy sources that can replace petroleum. Biodiesel is produced by transesterification, in which glycerol is separated from triglycerides in which glycerol is bonded to trivalent fatty acids using methanol, and then fatty acid esters are produced. In other words, biodiesel is a mixture of fatty acid methyl ester (FAME), which has similar physical properties to petroleum-derived diesel, but also has a significantly lower emission of aromatic compounds as environmental pollutants, and above all, it has the advantage of being a renewable energy source. However, since biodiesel has poor low-temperature fluidity, coagulation is easy under low temperature conditions, which causes a problem that the fuel filter is clogged when applied to automotive fuel.

The low and low temperature fluidity of biodiesel is related to the content of saturated fatty acid methyl esters and unsaturated fatty acid methyl esters. That is, biodiesel having a high content of saturated fatty acid methyl esters and a low content of unsaturated fatty acid methyl esters has a low cold filter plug point (CFPP), which is poor in low temperature fluidity. In particular, palm oil-derived biodiesel has a high content of saturated fatty acid methyl esters and thus a high CFPP due to the proportion of saturated fatty acids contained in animal fats. In general, the proportion of saturated fatty acids in lard and woji is 36% and 50%, respectively. Therefore, in order to apply biodiesel, especially animal biodiesel, as fuel for automobiles, it is important to lower the content of saturated fatty acid methyl esters.

As a prior art, a mixture of an oil-soluble polar nitrogen compound and an oil-soluble aliphatic compound for lowering the cloud point in a middle distillate fuel is disclosed in Korean Patent Publication No. 2012-0011034.

As a result of studies to improve the low temperature fluidity of animal and vegetable biodiesel having high saturated fatty acid content, it has been found that when saturated fatty acid methyl ester is removed in the form of a precipitate by adding urea to biodiesel, (CFPP-depressant additives) to the biodiesel with reduced saturated fatty acid methyl ester content, it was found that the low temperature filter clogging of the biodiesel could be prevented by adding the additive (CFPP-depressant additives) It has been found that the point can be largely lowered and the efficiency can be maximized, thus completing the present invention.

The present invention relates to a method for the production of biodiesel, comprising: a) adding an urea to an animal and vegetable oil-derived biodiesel having a high saturated fatty acid content; b) the saturated fatty acid methyl ester and urea contained in the biodiesel are aggregated to form an inclusion compound; c) removing the inclusion compound; And d) mixing the additive in the biodiesel with the inclusion compound removed; The present invention provides a method for improving low-temperature fluidity of biodiesel derived from vegetable or vegetable oils, which has a high saturated fatty acid methyl ester content applicable to a fuel flow path.

The method of improving the low-temperature fluidity of the biodiesel according to the present invention significantly reduces the low-temperature filter clogging point by mixing the additives (CFPP-depressant additives) after reducing the saturated fatty acid methyl ester contained in the biodiesel (palm oil biodiesel: 12 ° C → -42 ° C; Uji Biodiesel: 10 ° C → -32 ° C) to improve low-temperature fluidity.

FIG. 1 is a flowchart showing steps of improving the low-temperature fluidity of biodiesel according to the present invention.
FIG. 2 is a photograph of the front side of the low temperature progress test in a -15 ° C freezing room after improving the low temperature fluidity by treating additives such as Flozol 515 or Infineum R408 after reducing the degree of saturation to palm oil and woji derived biodiesel.
FIG. 3 is a photograph of the top side of a low-temperature progress test in a -15 ° C freezer after treatment with additives (Flozol® 515 or Infineum R408) after lowering the degree of saturation to palm oil and woji-derived biodiesel.

The present invention provides a method for improving the low-temperature fluidity of biodiesel having a high saturated fatty acid methyl ester content so as to be applicable to a fuel flow path under domestic environmental conditions.

The present invention relates to a process for the preparation of a food product comprising the steps of: a) adding urea and methanol to an animal and vegetable oil-derived biodiesel having a high saturated fatty acid methyl ester content; b) the saturated fatty acid methyl ester and urea contained in the biodiesel are aggregated to form an inclusion compound; c) removing the inclusion compound; And d) mixing the additive in the biodiesel with the inclusion compound removed; Temperature fluidity improvement of biodiesel comprising the steps of:

The term " biodiesel "of the present invention includes those commonly used as vegetable oil-derived biodiesel containing animal fat and saturated fatty acid methyl esters.

The weight ratio of the biodiesel to the urea of the present invention may be 1 to 2: 1 to 3, preferably 1: 3.

"Inclusion compound" of the present invention means a substance in which another atom or molecule enters into a gap formed in the three-dimensional structure of the molecule without forming a chemical bond and forms a crystal structure of almost constant composition.

"Additives" of the present invention CFPP-depressant additives characterized by comprising copolymers of ethylene and vinyl acetate or other olefin-ester copolymers, including Flozol 515 (The Lubrizol Corporation, Wickliffe, OH), Infineum R408 (Infineum International Ltd., Abingdon, United Kingdom), Bioflow 875 (Octel Sterron, Newark, DE), MCC P205 (Midcontinental chemical, Overland Park, KS), and Arctic Express 0.25% , TX).

The additive may be mixed with 1,000 to 5,000 ppm, preferably about 3,000 ppm, especially 3,000 ppm.

In one embodiment of the present invention, biodiesel derived from palm oil is prepared and fractionated under different conditions, and a urea / methanol solution is added. Thereafter, the mixture of biodiesel and urea / methanol solution is centrifuged at 1,500 to 2,500 rpm for 3 to 7 minutes to separate the liquid phase and the solid phase. Preferably, centrifugation is carried out at 2,000 rpm for 5 minutes. Such a process can be repeatedly performed at a room temperature and a fractionation temperature of -2 to 2 캜 for a third continuous fraction to lower the saturated fatty acid content. Saturated fatty acid content is calculated by extracting the fatty acid methyl ester of the liquid phase. After the saturated fatty acid methyl ester content is reduced, further moisture and impurities can be removed, and an anhydrous sodium sulfate column can be used as an example.

The present invention provides a biodiesel produced by the above method.

Hereinafter, the present invention will be described in detail.

However, the following examples are intended to illustrate the contents of the present invention, but the scope of the present invention is not limited by the following examples.

< Example  1> Biodiesel production from palm oil

Palm oil having an acid value of 0.4 and a peroxide value of 2.5 ± 0.6, manufactured by Ottogi Co, Ltd., was used for biodiesel synthesis.

5 g of KOH (1% w / w of palm oil) was added to the mixture of palm oil and methanol at a molar ratio of 1:15 (palm oil 50 g: methanol 28.95 g), followed by reaction at 65 ° C for 30 minutes to obtain biodiesel Respectively. The saturated fatty acid content of palm oil-derived biodiesel obtained at this time was 50.1%.

< Example  2 to 6>

The mixing weight ratio of biodiesel and urea obtained in Example 1 was as shown in Table 1 below.

Mixed weight ratio of biodiesel and urea derived from palm oil Palm oil BD ^* Element: MeOH Fraction condition Temperature (℃) Processing time (h) Example  2 2 g 6 g: 30 mL Room temperature 2 Example 3 2 g 6 g: 30 mL Room temperature 17 Example 4 2 g 6 g: 30 mL 0 2 Example  5 2 g 6 g: 30 mL 0 17 Example 6 2 g 2 g: 10 mL
1 g: 5 mL
1 g: 5 mL Room temperature 3 minutes each for 5 minutes
Continuous centrifugation

* BD: Biodiesel

In Examples 2 to 5, 10 g of methanol and 6 g of urea were added to 2 g of biodiesel derived from palm oil and dissolved in a constant temperature water bath (temperature: 65 ° C) at 80 ° C, and then subjected to different fractionation conditions (room temperature, , 17 hours). The liquid phase and the solid phase (precipitate) were separated using centrifugation, and the obtained liquid phase was transferred to a 50 mL vial. To extract the fatty acid methyl esters of the liquid phase, add 10 mL of hexane and 15 mL of distilled water, vortex and centrifuge to separate the upper layer (hexane) from the anhydrous sodium sulfate column To remove moisture and impurities. The lower layer was recovered, and 10 mL of hexane was added thereto, followed by extraction twice. After the solvent was completely removed by using nitrogen, the production yield (wt%) was calculated from the weight (g) of the obtained biodiesel / the weight (g) of the raw palm oil.

In Example 6, 10 mL of urea / methanol solution (20 g / 100 mL) was added to 2 g of palm oil-derived biodiesel and the mixture was centrifuged at 2000 rpm for 5 minutes to separate the liquid phase and the first solid phase. mL urea / methanol solution and centrifuged at 2000 rpm for 5 minutes to separate the liquid phase and the second solid phase. The liquid phase separated again into the liquid phase and the third solid phase by adding 5 mL urea / methanol solution to the separated liquid phase, The saturated fatty acid methyl ester content was lowered continuously. The extraction of the liquid phase in which the saturated fatty acid methyl ester content was reduced and the yield were calculated in the same manner as in Examples 2 to 5.

From the results of analysis by gas chromatography before adding urea to biodiesel derived from palm oil and by adding urea to biodiesel derived from palm oil and removing the precipitate, the liquid phase portion was purified and analyzed by gas chromatography. The results are shown in Table 2 Respectively.

Derived from palm oil Saturation on biodiesel Abatement  Subsequent fatty acids Methyl ester  Composition analysis result division Palm oil BD * Example 2 Example 3 Example 4 Example 5 Example 6 Fatty acid methyl ester composition C12: 0 0.4 ± 0.1 0.6 ± 0.2 0.5 ± 0.1 0.6 ± 0.3 0.2 ± 0.3 0.6 ± 0.1 C14: 0 1.2 ± 0 1.7 ± 0.6 1.4 ± 0.2 1.2 ± 0.2 0.4 ± 0.6 1.3 ± 0.3 C16: 0 43 ± 0 17 ± 1.8 11 ± 0 9.5 ± 3.6 5.9 ± 2.3 5 ± 1.8 C16: 1 0.4 ± 0.1 0.5 ± 0 0.7 ± 0.3 0.5 ± 0 0.3 ± 0.4 0.6 ± 0.1 C18: 0 5 ± 0.2 0.6 ± 0 0.1 ± 0.2 0.5 ± 0.1 0.2 ± 0.2 0 ± 0 C18: 1 38.1 ± 0.3 58.9 ± 1 63.5 ± 0 64.1 ± 1.5 63.6 ± 0.2 67.3 ± 0.7 C18: 2 10.9 ± 0 19.7 ± 0.1 21.8 ± 0.2 23.2 ± 1.4 29 ± 4.1 24.4 ± 0.6 C20: 0 0.4 ± 0.1 0 ± 0 0 ± 0 0 ± 0 0 ± 0 0 ± 0 C18: 3 0.3 ± 0.1 0.5 ± 0 0.5 ± 0.1 0 ± 0 0.2 ± 0.3 0.3 ± 0 C20: 1 0.3 ± 0 0.6 ± 0 0.6 ± 0.1 0.5 ± 0.2 0.2 ± 0.3 0.5 ± 0.1 Saturation (%) 50.1 19.9 13 11.7 6.7 6.9 Unsaturation (%) 49.9 80.1 87 88.3 93.3 93.1 회 Recovery rate of saturated fatty acids (%) - 43 41.5 37.5 35.5 9.5

* BD: Biodiesel

In Table 2, Example 2 and Example 3 were obtained by adding urea and then fractionating at room temperature for 2 hours and 17 hours. In Example 4 and Example 5, after adding urea, And Example 6 is a result of third continuous fractionation at room temperature with addition of urea.

As shown in Table 2, all three conditions such as time, temperature, and fraction recovery affected the reduction of saturated fatty acid methyl esters.

Palmitic acid (C16: 0) and stearic acid (C18: 0), saturated fatty acids, myristic acid (C14: 0) The lower the temperature, the better the degree of saturation. The third sequential fractionation takes less time and the saturation degree is also reduced, but the recovery rate is lower. On the other hand, when the urea-cooling temperature difference is large (0 ° C fraction), the crystallization time is short and the crystal is smooth. On the contrary, when the dissolution-cooling temperature difference is small (room temperature fraction) It was relatively large.

The palm oil-derived biodiesel contained 50.1% of saturated fatty acid methyl ester, while the recovery rate (%) and the fatty acid methyl ester content of the fraction, the third continuous fraction, and the fatty acid methyl ester content of biodiesel derived from palm oil were 50.1% The recovered fraction of the obtained fraction was 39.8 to 46.5%, and the content of the unsaturated methyl ester was 79.4 to 80.8%.

In Example 3, the recovered fraction of the obtained fractions was 41.3 to 41.8%, and the content of unsaturated methyl esters thereof was 87 to 87.1%.

In Example 4, the recovery rate of the obtained fractions was 35.7 to 34.6%, and the content of unsaturated methyl esters was 86.1 to 90.50%.

In Example 5, the recovered fraction of the obtained fraction was 34.8 to 36.5%, and the unsaturated methyl ester content thereof contained 91.9 to 95.7%.

In Example 6, the yield of the obtained fractions was 8.1 to 10.8%, and the content of unsaturated methyl esters was 92.1 to 94.1%.

Example 5 showing the optimum conditions in Examples 2 to 6 was similar to the saturated fatty acid content of biodiesel in liquid state at -17 ° C, and it was found that the addition of urea effectively reduced saturated fatty acid methyl ester.

< Example  8 to 9>

Example  2 and Example  5, before and after the additive mixture CFPP ( Low temperature filter clogging point ) analysis Biodiesel (Saturation) CFPP (° C) analysis Biodiesel (Saturation) + Additive (Flozol® 515, 3,000 ppm) CFPP (° C) analysis Palm Oil BD * (50.1%) 12 Palm Oil BD (50.1%) 9 Example 2 (19.9%) -2 Example 8 (19.9%) -9 Example 5 (6.7%) -7 Example 9 (6.7%) -42

* BD: Biodiesel

Table 3 shows the results of analysis of CFPP for biodiesel derived from palm oil, Example 2 (the sample having the lowest unsaturation degree but the highest recovery rate) and Example 5 (the sample having the highest unsaturation degree and the comparatively high recovery rate) Diesel, and CFPP after addition of additives (Flozol 515, 3,000 ppm) in Examples 2 and 5.

As shown in Table 3, CFPP of biodiesel derived from palm oil was 12 ° C, and CFPP had no improvement effect at 9 ° C after addition of additives (Flozol® 515, 3,000 ppm).

On the other hand, as the saturated fatty acid methyl ester of palm oil derived biodiesel was reduced (Example 2, Example 5), CFPP improved to -2 캜 and -7 캜, respectively. Particularly, when the additive was mixed with the biodiesel in which the saturated fatty acid methyl ester was reduced (Examples 8 and 9), CFPP fell to -9 ° C and -42 ° C, respectively, and the effect of improving the low temperature fluidity was maximized.

Uji  Saturation of derived biodiesel Abatement  And before and after the addition of the additive CFPP ( Low temperature filter clogging point ) analysis Biodiesel (Saturation) CFPP (° C) analysis Biodiesel + Additive
(Infineum R408, 3,000 ppm) CFPP (° C) analysis Uji BD (50%) 10 Uji BD (50%) 9 Uji BD (6%) -26 Uji BD (6%) -32

Table 4 shows the results of analysis of CFPP after saturation reduction of biodiesel derived from Uji and analysis of CFPP after saturation reduction and addition of additives (Infineum R408, 3,000 ppm).

As shown in Table 4, the CFPP of the biodiesel derived from Uji was 10 ° C, and the addition of the additive (Infineum R408, 3,000 ppm) did not improve the CFPP at 9 ° C.

On the other hand, CFPP was improved to -26 ° C when the saturated fatty acid of biodiesel derived from Uji was reduced from 50% to 6%, and when the additive (Infineum R408, 3,000 ppm) was added after saturation reduction, CFPP fell to -32 ° C, The effect of improving low temperature fluidity was maximized.

After lowering the saturation of the palm oil and the woji-derived biodiesel, the additive was treated and the low temperature fluidity was tested in a -15 ° C freezer, and the results are shown in FIG. 2 and FIG.

As a result, low-temperature fluidity of bamboo-derived biodiesel (saturated 6%) and palm oil-derived biodiesel (saturated 6% and 7%) in which the saturated fatty acid methyl ester according to the above example was reduced was lower than that of conventional biodiesel derived from woji and biodiesel derived from palm oil Temperature fluidity of &lt; / RTI &gt; In Figs. 2 and 3, typical Uji-derived biodiesel and palm oil-derived biodiesel treated with additive after the saturated fatty acid methyl ester had been reduced while coagulating the normal Uji-derived biodiesel and palm oil-derived biodiesel at -15.6 deg. It was confirmed that it was not solidified.

Claims (8)

a) adding urea to biodiesel so that the weight ratio of biodiesel to urea is 1: 1 to 3, and further adding methanol thereto;
b) allowing the saturated fatty acid methyl ester and the urea contained in the biodiesel to aggregate to form an inclusion compound and leaving at a fractionation temperature of -2 to 2 캜;
c) removing the inclusion compound; And
d) mixing an additive comprising a copolymer of ethylene and vinyl acetate or another olefin-ester copolymer to the biodiesel wherein the inclusion compound is removed and the relatively unsaturated fatty acid methyl ester is integrated; Wherein the low temperature fluidity improving method of the biodiesel comprises:
The method according to claim 1,
Wherein the biodiesel is a vegetable oil-derived biodiesel containing an animal fat and saturated fatty acid methyl ester.
delete delete The method according to claim 1,
Wherein the additive is mixed at 3,000 ppm.
The method according to claim 1,
Wherein the inclusion compound is removed by centrifugation at 1,500 to 2,500 rpm for 3 to 7 minutes.
The method according to claim 1,
And after step c), further removing moisture and impurities.
A biodiesel produced by any one of claims 1 to 2 and 5 to 7.

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