KR20040054318A - Production method of Biodiesel using a heterogeneous super base catalyst and Biodiesel by the same production method - Google Patents

Abstract

PURPOSE: Provided are a method for preparing a bio-diesel oil by using a heterogeneous catalyst and a bio-diesel oil prepared thereby. CONSTITUTION: The method comprises a step of esterifying an oil and fat and an alcohol in the presence of a heterogeneous catalyst, wherein the oil and fat is selected from the group consisting of soybean oil, corn oil, canola oil, linseed oil, poppy oil, walnut oil, peanut oil, cottonseed oil, bran oil, camellia oil, castor oil, beef tallow, lard, sheep fat, fish oil and whale oil, the heterogeneous catalyst is Na/NaOH/γ-Al2O3 or CsxO/γ-Al2O3 (x is 0.1-2) and the alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol and combinations thereof.

Description

Production method of Biodiesel using a heterogeneous super base catalyst and Biodiesel by the same production method}

The present invention relates to a method for producing biodiesel oil using a heterogeneous catalyst and to biodiesel oil prepared by the same method.

As the industry develops, the production of industrial machinery including diesel engines and vehicles is increasing worldwide, and the consumption of diesel oil used as their raw materials is also increasing. Diesel oil has an advantage in terms of cost because it is inexpensive among various fuels obtained from crude oil, but there is a problem in that air pollution is more generated after combustion than other fuels.

In order to solve this problem, various studies have been conducted on alternative fuels that have similar properties to diesel oil, are excellent in terms of economic cost, and can prevent air pollution. As a result of these studies, many studies have been made on biodiesel oils that have similar properties to diesel oils and can significantly reduce air pollution.

Biodiesel oils are esterified oils produced by reacting fats or oils such as vegetable oils or animal fats with waste foods with alcohols in the presence of acid or alkali catalysts.

Biodiesel oil has similar physical properties to diesel fuel used in vehicle fuel, and can be used in diesel engines by mixing and compressing diesel fuel or replacing diesel fuel.

Prior art for producing biodiesel oil is described in US Pat. Nos. 4,363,590, 4,608,202, etc., which produce soybean oil, rapeseed oil, corn oil, tallow, and the like as raw materials. See also Biodiesel Oil Production from Vegetable Oils (Bioresource Technology, 50, 153 (1994)), Biodiesel Oil Production and Properties from Vegetable Oils (JAOCS, 66, 1372 (1987)), transesterified The literature on the yield of fatty acid esters from vegetable oils (JAOCS, 61, 1638 (1984)) and the fuel properties of esters of tallow and vegetable oils (JAOCS, 67, 1557 (1997)) have been introduced. However, they all use basic catalysts such as NaOH and KOH as homogeneous reactions in producing biodiesel oil. If a homogeneous catalyst such as sodium hydroxide (NaOH) or potassium hydroxide (KOH) is used as a catalyst, an additional process is required to separate the catalyst because the catalyst is dissolved in the product. There is.

On the other hand, the technology for producing biodiesel oil using a heterogeneous catalyst is not actually established.

The present invention is to solve the above problems in the production of biodiesel oil using a conventional homogeneous catalyst as a heterogeneous catalyst as a solid Na / NaOH / γ-Al ₂ O ₃ or Cs _X O / γ-Al ₂ O ₃ An object of the present invention is to provide a method for producing biodiesel oil and a biodiesel oil prepared therefrom.

1 is a graph that can confirm the ester compound prepared in Example 1.

The method for producing the biodiesel oil of the present invention comprises the step of esterifying the fat or oil with an alcohol in the presence of a heterogeneous catalyst in the production of known biodiesel oil.

The fats and oils which are main ingredients in the biodiesel oil of this invention can use normal vegetable fats and oils and fats. As an example of such vegetable and animal fats and oils in the present invention, soybean oil, corn oil, rapeseed oil, linseed oil, sunflower oil, poppy oil, walnut oil, peanuts, cottonseed oil, rice bran oil, camellia oil, castor oil, olive oil, Uji (牛 脂), Pork (양), sunny (羊脂), fish oil (魚油), light oil (鯨 油) can be used any one selected.

Alcohol, which is an esterifying agent of fats and oils in the present invention, may be any one selected from methanol, ethanol, propanol, butanol, or a mixture of two or more thereof in a uniform ratio.

In the present invention, a heterogeneous catalyst may be used as Na / NaOH / γ-Al ₂ O ₃ or Cs _X O / γ-Al ₂ O ₃ to prepare biodiesel oil by reacting fats and oils with alcohol. x has a numerical value of 0.1 to 2.

In the present invention, the fats and oils during the production of biodiesel oil are esterified at a molar ratio of 1: 3 to 1: 9 at 60 to 80 ° C for 0.5 to 12 hours. According to the present invention, biodiesel oil was prepared at various reaction temperatures, reaction times, oil and alcohol molar ratios, and the reaction molar ratio of fats and oils was 1: 3 to 1: 9. Since the yield of biodiesel oil is good, the fats and oils in the present invention are preferably esterified at 60 to 80 ° C. for 0.5 to 12 hours at a molar ratio of 1: 3 to 1: 9.

In preparing the biodiesel oil of the present invention, a cosolvent may be added to further increase the contact between the fats and oils and the heterogeneous catalyst. This co-solvent acts as a kind of emulsifier, increasing the contact of fats, alcohols and heterogeneous catalysts, thereby improving the yield of biodiesel oil. In the present invention, such a cosolvent may be used as long as it has good fats, oils and solubility. As an example of such a co-solvent, hexane, tetrahydrofuran, 1,4-dioxane or methylester may be added in an amount of 15 to 30% more preferably based on the weight of the fat or oil. have.

In the present invention, when the esterification reaction between the fats and oils and the alcohol is completed, a heterogeneous catalyst is recovered by using a centrifuge. After recovering the catalyst, the glycerin and ester compound produced by the esterification reaction are divided around a constant boundary layer after standing for a predetermined time. At this time, the glycerin and the ester compound are separated. After separating the glycerin and the ester compound, the ester compound may be distilled to remove any alcohol which may be included, thereby obtaining a high purity ester compound.

The present invention includes biodiesel oil prepared by the above-mentioned method.

The present invention includes a method for producing a heterogeneous catalyst used in the production of biodiesel oil.

In the heterogeneous catalyst used in the present invention, Cs _X O / γ-Al ₂ O ₃ (x has a value of 0.1 to 2) represents 80 to 88% by weight of γ-Al ₂ O _{3 at} 550 to 600 ° C. Stirring for 1 to 2 hours, adjusting the temperature to 400 to 500 ° C., and then adding 12 to 20 wt% of Cs _X O to stir for 1 to 3 hours, and in a vacuum at 750 to 800 ° C. The heterogeneous catalyst may be prepared by calcination for 12 hours to remove acetate and then cooling to room temperature.

In the heterogeneous catalyst used in the present invention, Na / NaOH / γ-Al ₂ O ₃ is a step of stirring 80 to 88% by weight of γ-Al ₂ O _{3 at} 550 to 600 ° C. for 1 to 2 hours, and The temperature was lowered to the melting point, followed by stirring for 2 to 4 hours by adding 8-10 wt% of NaOH, stirring with addition of NaOH, and then stirring for 1-2 hours with the addition of 4-10 wt% of Na. After the cooling to room temperature it can be prepared a heterogeneous catalyst.

All heterogeneous catalysts are produced under a nitrogen atmosphere.

Hereinafter, the present invention will be described by the following examples and test examples. However, these are only examples of the present invention, and the scope of the present invention is not limited thereto.

<Example 1>

54.4 ml (0.05 mol) of soybean oil (obtained from CheilJedang), 12.2 ml (0.3 mol) of methanol, and 0.02 to 0.1% of Na / NaOH / γ-Al ₂ O ₃ as a heterogeneous catalyst at 60 ° C The reaction was carried out at a stirring speed of 100 rpm for 12 hours as shown in the following reaction formula.

R ₁ to R ₄ in the above scheme are alkyl groups.

After completion of the reaction, the product was centrifuged to recover the heterogeneous catalyst, and then allowed to stand until a boundary layer was formed in the product. When a boundary layer of glycerin and methyl ester was formed, glycerin was separated from the product.

Glycerin was isolated and the methyl ester was distilled at a temperature above the methanol boiling point to remove the methanol contained in the methyl ester to obtain a methyl ester, which is shown in FIG. 1. On the other hand, the yield of methyl ester was determined by gas chromatography to determine the standard substance of methyl ester obtained from the five main components of soybean oil through absolute quantification from the calibration curve. The methyl ester was distilled off and a 75% yield of methyl ester was obtained.

The heterogeneous catalyst in the above is a nitrogen atmosphere

85 wt% of γ-Al ₂ O ₃ was stirred at 550 ° C. for 1 to 2 hours, the temperature was lowered to the melting point of NaOH, and 9 wt% of NaOH was added thereto, followed by stirring for 2 hours. Then, 6% by weight of Na was added and stirred for 1 hour, followed by cooling to room temperature.

<Example 2>

Methanol 12.2ml (0.3mol), soybean oil 54.4ml (0.05mol) and the heterogeneous catalyst prepared in Example 1 (Na / NaOH / γ-Al ₂ O ₃ ) by adding 0.02 ~ 0.1% to the weight of soybean oil 60 The reaction was carried out at a stirring speed of 100 rpm for 0.5 hour, 1 hour, 2 hours, 4 hours, and 12 hours, respectively.

The subsequent process was carried out in the same manner as in Example 1 to obtain a methyl ester, the yield of the methyl ester according to the stirring time is shown in Table 1 below.

Table 1. Yield of methyl esters with stirring time

Stirring time (hours) Methyl ester yield (%) 0.5 72 One 75 2 75 4 75 12 75

<Example 3>

Methanol 12.2 ml (0.3 mol), soybean oil 54.4 ml (0.05 mol), the heterogeneous catalyst prepared in Example 1 (0.02 to 0.1% by weight of soybean oil) and auxiliary to facilitate contact between methanol, soybean oil and catalyst 10 ml of hexane was added as a solvent and reacted at 60 ° C. for 2 hours at a stirring speed of 300 rpm.

The subsequent step was carried out in the same manner as in Example 1 to obtain a methyl ester of 91% yield.

<Example 4>

54.4 ml (0.05 mol) of soybean oil, a heterogeneous catalyst prepared in Example 1 (0.02-0.1% by weight of soybean oil), 10 ml of hexane, 6.1 ml (0.15 mol) of methanol, 9.15 ml (0.225) mol), 12.2 ml (0.3 mol), 18.25 ml (0.45 mol), and 24.4 ml (0.6 mol) were added and reacted at a stirring speed of 300 rpm for 2 hours at 60 ° C.

The subsequent process was carried out in the same manner as in Example 1, to obtain a methyl ester, the yield of the methyl ester according to the molar ratio of methanol and soybean oil is shown in Table 2 below.

Table 2. Yields of methyl esters according to the molar ratio of methanol and soybean oil

Soybean Oil (Mall) Methanol (mol) yield(%) 0.05mol 0.15mol 60 0.05mol 0.225 mol 66 0.05mol 0.3mol 90 0.05mol 0.45mol 93 0.05mol 0.6mol 93

As shown in Table 2, when the molar ratio of soybean oil and methanol is 1: 6, 90% yield of methyl ester can be obtained, and when the molar ratio of soybean oil and methanol is 1: 9, 93% yield of methyl ester can be obtained.

Example 5

The heterogeneous catalyst (Na / NaOH / γ-Al ₂ O ₃ ) prepared in Example 1 was added to a reaction solution containing 18.25 ml (0.45 mol) of methanol, 54.4 ml (0.05 mol) of soybean oil, and 10 ml of hexane. 1%, 1.5%, 2%, 2.5%, and 3% by weight of soybean oil were added and reacted at a stirring speed of 300 rpm for 2 hours at 60 ° C.

Subsequent processes were carried out in the same manner as in Example 1 to obtain a methyl ester, and the yield of the methyl ester according to the addition of the heterogeneous catalyst is shown in Table 3 below.

Table 3. Yields of methyl esters with heterogeneous catalysts

Catalyst usage (based on soybean oil weight) Methyl ester yield (%) One % 86 1.5% 89 2.0% 93 2.5% 93 3.0% 93

The present invention can simplify the process compared to the prior art using a homogeneous catalyst by using a heterogeneous catalyst which is a kind of solid base catalyst in the production of biodiesel oil through esterification of fats and oils. In addition, since the heterogeneous catalyst used in the present invention is a solid, it can be easily used again during the manufacturing process of the biodiesel oil, and it can contribute to preventing environmental pollution by reducing the generation of waste water. Meanwhile, according to the present invention, high-purity glycerin can be obtained from fats and oils, and additional income can be expected.

Claims (10)

In the production of known biodiesel oil, A method for producing biodiesel oil using a heterogeneous catalyst, comprising the step of esterifying a fat or oil with an alcohol in the presence of a heterogeneous catalyst. The fat or oil of claim 1, wherein the fats and oils are soybean oil, corn oil, rapeseed oil, linseed oil, sunflower oil, poppy oil, walnut oil, peanuts, cottonseed oil, rice bran oil, camellia oil, castor oil, olive oil, tallow oil, and pork fat. ), A method for producing biodiesel oil using a homogeneous catalyst, characterized in that any one selected from sunny, fish oil, light oil. The method of claim 1, wherein the heterogeneous catalyst is Na / NaOH / γ-Al ₂ O ₃ or Cs _X O / γ-Al ₂ O ₃ . In the above, x has a value of 0.1 to 2. The method of claim 1, wherein the alcohol is any one selected from methanol, ethanol, propanol, butanol, or a mixture of two or more thereof. The method for producing biodiesel oil using a heterogeneous catalyst according to claim 1, wherein the oil and alcohol are esterified in a molar ratio of 1: 3 to 1: 9 in the presence of a heterogeneous catalyst. The method for producing biodiesel oil using a heterogeneous catalyst according to claim 1, wherein the fat and oil are esterified for 0.5 to 12 hours at 60 to 80 ° C in the presence of a heterogeneous catalyst. The method according to claim 1, wherein any one selected from hexane, tetrahydrofuran, 1,4-dioxane or methyl ester is included in an amount of 15 to 30% with respect to the amount of fat or oil added to improve the contact between the fat or oil and the alcohol and the catalyst. Method for producing biodiesel oil using a heterogeneous catalyst. Biodiesel oil prepared by the method of claim 1. Na / NaOH / γ-Al ₂ O ₃ in the heterogeneous catalyst of claim ₃ is a step of stirring 80 to 88% by weight of γ-Al ₂ O _{3 at} 550 to 600 ℃ for 1 to 2 hours, Lowering the temperature to the melting point of NaOH and adding 8-10% by weight of NaOH and stirring for 2-4 hours; Stirring by adding NaOH and then adding 4-10 wt% of Na and stirring for 1-2 hours, followed by cooling to room temperature. 10. The process for producing a heterogeneous catalyst according to claim 9, wherein the production of the heterogeneous catalyst is carried out under a nitrogen atmosphere.