KR20140019615A - Solid acid catalyst and method for preparing biodiesel using the catalyst - Google Patents

Abstract

The present invention relates to a solid acid catalyst and a method for preparing biodiesel using the same. The method for preparing biodiesel includes a step of preparing biochar and a step of adding acid to the prepared biochar and sintering at 250-600 deg. C for 1-5 seconds. [Reference numerals] (AA) Dunalliella skim cell; (BB) Dunalliella bio-charcoal; (CC) Acid solid catalyst

Description

Technical Field [0001] The present invention relates to a solid acid catalyst and a method for preparing the same,

The present invention relates to a novel solid catalyst useful for producing biodiesel, a method for preparing the same, and a method for preparing biodiesel using the same.

Biodiesel, a sustainable renewable energy, is a clean energy that can solve the problem of eliminating environmental pollution and energy depletion caused by the use of fossil fuel. Biodiesel is an alkyl ester of fatty acids, and has similar kinematic viscosity to petroleum diesel, making it a liquid fuel with excellent applicability to existing diesel engines. Typically triglyceride (triglyceride) itself when used in a diesel engine deposits residues in the engine to reduce the engine performance. Accordingly, biodiesel made of triglycerides made of lower alcohols, especially inexpensive methanol and methyl esters of fatty acids substituted with glycerides, has been widely used as clean energy.

Catalyst is required for transesterification of biodiesel and alkaline catalyst and acid catalyst are widely used. Currently, alkaline catalysts such as sodium hydroxide, potassium hydroxide, sodium methoxide and acid catalysts such as sulfuric acid are widely used. However, all of the above catalysts are homogeneous catalysts which dissolve in methanol and react with a substrate as a reaction liquid. As a result, the homogeneous catalyst remains dissolved in the reaction solution even after completion of the reaction. It also has strong alkali or strong acidity, so it needs to be neutralized and disposed of, and the large amount of inorganic salts produced during neutralization also adversely affects the environment. In addition, since the reaction catalyst is used for one company and disposed of, the production cost of the catalyst and the cost of the neutralizing agent are generated, and thus, it is necessary to develop a catalyst for biodiesel production that can be repeatedly reused for economic production of biodiesel. On the other hand, when a heterogeneous catalyst which does not dissolve in the reaction liquid, that is, a solid catalyst, is used in the production of biodiesel, a catalyst which can be easily separated from the reaction liquid and catalyst and functions as an impurity, It is easy to purify the biodiesel because it is easily removed, and the cost of the catalyst is reduced, thereby reducing the manufacturing cost.

So far, edible oils such as soybean oil, palm oil and rapeseed oil are mainly used as raw materials for biodiesel production, but may cause food famine. Therefore, there is much interest in developing a resource that does not compete with food resources and can produce more oil. In order to produce biodiesel from microalgae economically, microalgae, which are microorganisms that are photosynthetic microorganisms, have excellent lipid productivity and are being developed as lipid production sources for biodiesel production. In order to economically produce biodiesel from microalgae, The economic utilization of avian cell pellets is also a major challenge.

(Toda M., et al., Nature , 438 (7065): 178, 2005) carbonized glucose or sugar and used sulfuric acid (Amir Mehdi Dehkhoda, et al., Applied Catalysis A : General, 382 (2): 197-204, 2010) was used to produce a solid catalyst for use in the production of biodiesel , Solid wood charcoal was sulfated with the raw material to prepare a solid catalyst. However, in the sense that glucose and sugar are important food resources, hardwood char is a raw material for use as a catalyst raw material in that it is a major fuel resource. Dora E. Lopez et al., Journal of Catalysis , 245 (2): 381-391, 2007) used Nafion, an ion exchange resin, as a catalyst, and Anton A Kiss, et al., Advanced Synthesis & Catalysis , 348 (1-2): 75-81, 2006) used sulfurized zirconia as a catalyst for biodiesel production.

However, since it is difficult to produce a solid catalyst and it is produced using an expensive raw material, there is a problem that the catalyst is very expensive and the activity of the solid catalyst disappears during the reaction. Therefore, in order to make the biodiesel economical and economical, The development of a catalyst is required.

DISCLOSURE Technical Problem The present invention is intended to solve various problems including the above problems, and it is an object of the present invention to provide a solid acid catalyst which is economical, has excellent catalytic activity and is stable, and a method for producing the same. However, these problems are exemplary and do not limit the scope of the present invention.

According to an aspect of the present invention, an acid is added to a biochar derived from degreasing microalgae and calcined to provide a solid acid catalyst for producing biodiesel.

In the biodiesel for preparing the solid acid catalyst, wherein the microalgae are two throwing away Ella (Dunalliella), Chlamydomonas (Chlamydomonas), theta nede mousse (Scenedesmus), Chlorella (Chlorella), euglena (Euglena), tetra-cell Miss (Tetraselmis ) Selected from the group consisting of Botryococcus , Nannochloropsis , Coccomyxa , Phaeodactylum , Schizochytrium and Arthrospira . May be one or more of the microalgae belonging to the genus.

The microalgae may be selected from the group consisting of D. acidophila , D. bardawil , D. bioculata , D. lateralis , < RTI ID = 0.0 > D. maritima , D. minuta , D. parva , D. peircei , Dnaliella polyomorpha ( D) polymorpha , D. primolecta , D. pseudosalina , D. quartolecta , D. salina teodor . ), It may be D. tertiolecta , D. salina , or D. viridis . ≪ RTI ID = 0.0 >

The acid may be sulfuric acid.

The solid acid catalyst for the production of biodiesel can be reused and re-used from 1 to 200 times.

The solid acidic catalyst for producing biodiesel according to an embodiment of the present invention is economical since the degreasing microalgal cell foil, which is a by-product of the extraction of lipids, is used as a raw material, and thus, the solid catalyst can be repeatedly used and used. Industrial availability is very good.

According to another aspect of the invention, (a) calcining the degreasing microalgae, to produce a biochar (biochar); And (b) adding an acid to the prepared microalgae-derived biochar and firing the acid, thereby providing a solid acid catalyst for preparing biodiesel.

In the above production method, the calcination of step (a) means to heat the microalgae, to perform a pyrolysis reaction, it may be performed for 1 second to 5 hours at 250 ~ 600 ℃.

The acid of step (b) may be added in an amount of 1 to 50 parts by weight based on 1 part by weight of biochar, and the acid may be sulfuric acid.

The firing of step (b) may be performed at 50 to 300 ° C. for 0.5 to 3 hours.

According to another aspect of the present invention, in the presence of the above-mentioned solid acidic catalyst for producing biodiesel, the fatty acid derived from fat or oil, or a mixture thereof is transesterified or esterified with alcohol. There can be provided a method for producing biodiesel comprising the step of making.

The fats and oils include soybean oil, rapeseed oil, corn oil, rapeseed oil, sunflower oil, castor oil, palm oil, linseed oil, poppy oil, walnut oil, peanut oil, cottonseed oil, rice bran oil, camellia oil, olive oil, tallow oil, pork ), Sunny, fish oil, light oil, microalgae oil and fatty acids derived from them.

According to one embodiment of the present invention made as described above, it is economical and excellent in the activity of the catalyst can be implemented, it is possible to implement a solid acid catalyst for biodiesel production. Of course, the scope of the present invention is not limited by these effects.

1 is a denaliella degreasing cells of the degreasing microalgae of the raw material of the solid acid catalyst for producing biodiesel according to an embodiment of the present invention, the biochar prepared by firing it, and calcined by adding acid to the biochar Fig. 1 shows the prepared solid acid catalyst (microalgae solid catalyst).
FIG. 2 is a graph showing the conversion of biodiesel of a solid acid catalyst for biodiesel production according to an embodiment of the present invention.
3 is a graph illustrating conversion of biodiesel at the time of reusing a solid acid catalyst for biodiesel production according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. It should be understood, however, that the invention is not limited to the disclosed embodiments and examples, but may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, It is provided to fully inform the owner of the scope of the invention.

Example 1: Preparation of bio-charcoal using defatted microalgae cell foil

Lipids were extracted from 640 g of wet cells of microalgae Dunaliela tertiolecta using a mixed solvent of chloroform-methanol mixture ratio of 1: 2, and the remaining cells were dried to prepare a degreasing dwarf el / g, and the defatted dried cells were crushed finely with a mortar. Thereafter, 30 g of the above degreased and dried cells was placed in a round bottom flask and heated under reflux at 400 ° C for 2.5 hours while flowing a nitrogen gas. Thereafter, the remaining carbide was washed with methanol, and dried overnight at 40 ° C to obtain 15.6 g of biochar from black defatted microalgae cells (see FIG. 1).

Example 2: Preparation of microalgae acidic solid catalyst

30 ml of 98% concentrated sulfuric acid was added to 5 g of the biochar char derived from the degreased microalgae cell membrane obtained in Example 1, and the mixture was heated to reflux and reacted at 150 ° C for 1.5 hours. Washed with methanol, washed and dried until the washings had no acidity, yielding 3.86 g of a defatted microalgae cellulosic sulfuric acid acidic solid catalyst (see FIG. 1). Elemental analysis showed that carbon was 54.8%, hydrogen 3.1%, nitrogen 7.7%, oxygen 14.7% and sulfur 2.9%.

Example 3: Preparation of biodiesel using microalgae acidic solid catalyst

10 mg of a microalgae acidic solid catalyst (10 mg) was sealed in 1 ml of a solution of oleic acid dissolved in methanol at 10% (w / v) in methanol, sealed, and then stirred at 65 rpm with a 4 cm amplitude at 120 rpm, And the reaction rate over time was measured using gas chromatography. A methyl ester of a saturated fatty acid having 17 carbon atoms was used as an internal standard material to quantify the produced methyl oleate. The conversion rate was calculated by the following equation (1).

As a result, the reaction was carried out at a yield of 84.5% in the 12-hour reaction, and the reaction rate by time was as shown in FIG.

Example 4: Preparation of biodiesel at the time of reuse of a microalgae acidic solid catalyst

10 mg of a microalgae acidic solid catalyst was placed in a 2 ml cap tube and sealed at 1 ml of a solution prepared by dissolving oleic acid in 10% (w / v) methanol, followed by reaction at 65 ° C for 12 hours in the same manner as in Example 3, Respectively. At this time, the microcavity acidic solid catalyst was used as a once catalyst and centrifuged once to separate the solid catalyst, followed by washing with methanol, drying at 40 ° C overnight, and then reacting with 10% (w / v) oleic acid.

When the conversion rate was confirmed by repeating the steps of centrifugation, washing, drying, and oleic acid, the catalyst was found to have a conversion rate of about 67.8%, which is similar to the conversion rate at the time of reuse at the seventh reuse Reference). The conversion rate was slightly lower in the case of three times of reuse because the container sealing was insufficient during the reaction and the methanol leaked and the reaction was not normally performed.

recycle Conversion Rate (%) 1 time 86.0 Episode 2 81.6 3rd time 68.1 4 times 92.7 5 times 74.7 6 times 66.9 7 times 67.8

While the present invention has been described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (12)

Solid acid catalyst for biodiesel production, which is calcined by adding acid to biochar derived from skim microalgae. The method of claim 1,
Wherein the microalgae are two throwing away Ella (Dunalliella), Chlamydomonas (Chlamydomonas), theta nede mousse (Scenedesmus), Chlorella (Chlorella), euglena (Euglena), tetra-cell Miss (Tetraselmis), boat Rio Rhodococcus (Botryococcus), nanno claw drop system (Nannochloropsis), nose comic four (Coccomyxa), L ohdak tea room (Phaeodactylum), progenitor kit Solarium (Schizochytrium) and Ars as pyrazole (Arthrospira) at least one of the genus selected from the group consisting of biodiesel for preparing solid acidic catalyst . The method of claim 1,
The microalgae are Dunaliella asidophilia ( D. acidophila ), Dunaliella Bardawil ( D. bardawil ), Dunaliella Biocurata ( D. bioculata ), Dunaliella Lateralis ( D. lateralis ), two flying it Ella Thermotoga maritima (D. maritima), two flying it Ella minu other (D. minuta), two flying it Ella paba (D. parva), two flying it Ella pair assays (D. peircei), two flying it Ella mopa poly (D polymorpha , D. primolecta , D. prismolina , D. pseudosalina , D. quartolecta , D. salina Teodor. Solid acid catalyst for biodiesel production, which is Dunaliella teiolecta , Dunaliella salina , or Dunaliella viridis . The method of claim 1,
Wherein the acid is sulfuric acid. The method of claim 1,
The solid acid catalyst for the production of biodiesel is reusable. (a) calcining degreasing microalgae to produce biochar; And
(b) adding an acid to the prepared microalgae-derived biochar and firing the acid; The method according to claim 6,
Wherein the calcination of the step (a) is carried out at 250 to 600 ° C for 1 second to 5 hours. The method according to claim 6,
Wherein the acid of step (b) is added in an amount of 1 to 50 parts by weight based on 1 part by weight of biochar. The method according to claim 6,
Firing of the step (b) is carried out for 0.5 to 3 hours at 50 ~ 300 ℃, a method for producing a solid acid catalyst for biodiesel production. The method according to claim 6,
Wherein the acid of step (b) is sulfuric acid. In the presence of a solid acidic catalyst for producing biodiesel of claim 1,
Comprising the step of trans-esterifying or esterifying a fatty acid derived from a fatty acid, a fatty acid, a fatty acid, a fatty acid derived from a fatty acid, a fatty acid derived from a fatty acid, 12. The method of claim 11,
The fats and oils include soybean oil, rapeseed oil, corn oil, rapeseed oil, sunflower oil, castor oil, palm oil, linseed oil, poppy oil, walnut oil, peanut oil, cottonseed oil, rice bran oil, camellia oil, olive oil, tallow oil, pork ), Sun grease, fish oil, diesel oil, microalgal oil and at least one selected from the group consisting of fatty acids derived from them.

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