KR101395795B1 - Direct non-catalytic biodiesel production without oil extraction - Google Patents

Abstract

The present invention relates to a method for converting biomass into biodiesel (FAMEs: Fatty Acid Methyl Esters) through transesterification, and more particularly to a biomass containing biomass containing the same vegetable oil and a biomass having 1 to 12 carbon atoms And a step of transesterifying aliphatic alcohols to produce fatty acid alkyl esters and glycerol.
According to the present invention, high-purity fatty acid alkyl esters and glycerol can be produced directly using the biomass containing the vegetable oil without milking and extracting processes, and there is no need for wastewater treatment due to the use of an acid catalyst and a basic catalyst, The overall time and cost of the manufacturing process can be reduced and renewable fuels can be produced in a more environmentally friendly process.

Description

[0001] The present invention relates to an integrated non-catalytic continuous biodiesel conversion process for omitting the milking /

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for converting biomass containing vegetable oil into transesterification to convert biodiesel (FAMEs) into fatty acid methyl esters And directly reacting with aliphatic alcohols to produce fatty acid alkyl esters and glycerol.

Biodiesel generation is classified as follows for convenience. FAME derived from edible vegetable oil is called first generation biodiesel. When the same vegetable oil is used but the non-edible oil is used for FAME conversion, it is generally called second generation biodiesel. FAME derived from microalgae oil is called 3rd generation biodiesel for convenience. There is no distinction between generations, but it can be called first generation biodiesel.

For 1-2 generation biodiesel production, physical extraction by compression and chemical extraction using solvent extraction are common. Thus, a significant amount of oil residue is present in the milking byproduct. It also helps to squeeze oil by applying heat during squeezing. However, unlike the physical milking method of the first and second generation biomass, a chemical extraction method using solvent is generally used for the third generation biomass. In order to facilitate solvent extraction from the third generation biomass, physical pretreatment of pulverization, acid treatment, and heat treatment of biomass may be performed in parallel. This extraction process is an energy consuming process and is a large part of biodiesel production costs due to the recovery and consumption of solvents. Currently, companies such as Origin Oil and SRC in the US are extracting oil from microalgae at a pilot level (Pilot grade), but only about 80% of the total oil content is available.

Thus, conventional production of FAMEs (Fatty Acid Methyl Esters: FAMEs) can be carried out by transesterification of milk obtained from the vegetable oil (edible / non-edible vegetable oil, animal oil, microalgae oil) Was produced. In the case of non-edible / edible vegetable oil, milking by press method involves a considerable amount of oil in milking byproducts. In addition, milking of microalgae oil is a problem in that energy and cost are increased because solvent extraction is not performed by squeezing.

In the process of converting biodiesel to FAMEs through the transesterification process, only transesterification reaction processes in the biodiesel production process are currently commercialized. In the process of converting biodiesel into FAMEs, a triglyceride ) All edible / non-edible vegetable fats are the raw materials (reaction substrate) capable of producing FAMEs. However, until now, most of the transesterification biodiesel conversion process through transesterification has been carried out by pretreatment with acid catalyst (H ₂ SO ₄ ) according to the amount of free fatty acids (FFAs) isolated from triglyceride (KOH, NaOH). ≪ / RTI >

Particularly, the pretreatment and the present treatment each require a reaction time of at least 30 hours or more than 2 hours, respectively, and the pretreatment and the present treatment process are batch reactions, which are difficult to apply to mass production of FAMEs . In addition, the acid catalyst and the base catalyst used in the pretreatment and the present treatment essentially include a removal process through a washing process using hot water. However, such a water washing process not only causes a problem of generating a large amount of wastewater, but also causes a loss of the vegetable oil as a reaction substrate, which leads to a disadvantage that the overall process yield is significantly lowered.

On the other hand, as described above, the use of homogeneous catalyst in the commercialized biodiesel reaction process causes a lot of time and wastewater in the mass production of biodiesel due to washing and decantation processes. In the case of a natural state without a centrifuge, it takes at least one hour and usually two hours or more. However, the loss of the biodiesel substrate washed out in water can not be excluded at all. In order to solve such disadvantages, a supercritical transesterification process in which fatty acid alkyl esters (FAMEs) are obtained by reacting methanol or ethanol and a fat component under a high pressure condition of 120 to 250 ° C and 50 to 200 bar It is known. However, in the supercritical transesterification process, the produced fatty acid alkyl esters can be recovered. However, a large amount of alcohols such as methanol or ethanol and the oil are used in a ratio of about 20: 1 to 40: 1, It is only to do. As a result, the supercritical transesterification process is only a research R & D level technology until now, and the commercialization process for diesel production is not yet available because of the disadvantage that energy is inefficient because excess ethanol is added.

Therefore, it is possible not only to produce high purity biodiesel by using the entire substrate material containing the vegetable oil in the transesterification reaction without milking and extracting the biomass, but also by using the continuous type method It is necessary to study the development of a biodiesel manufacturing process that can achieve environmentally friendly and remarkable energy saving effects.

The present invention can be effectively applied to a mass production process in a continuous manner rather than a batch type, and the biomass is environmentally friendly, without separate milking and extraction processes, And to provide a method for producing biodiesel.

The present invention includes a step of transesterifying a biomass containing the vegetable oil and an aliphatic alcohol having 1 to 12 carbon atoms to produce a fatty acid alkyl ester and glycerol. The biomass is subjected to a heat treatment process at a temperature of 200 < Wherein the biodiesel is converted into a substance.

Hereinafter, according to a specific embodiment of the present invention, a biomass which is converted into a porous material by applying heat to the biomass containing the vegetable oil is directly converted into a fatty acid alkyl ester through an ester exchange reaction without using milking and extraction processes, Will be described in more detail. It will be apparent to those skilled in the art, however, that this is not intended to limit the scope of the invention, which is set forth as an example of the invention, and that various modifications may be made to the embodiments within the scope of the invention.

In addition, throughout this specification, "comprising" or "containing ", unless specifically stated, refers to including any and all components (or components) Can not be interpreted as excluding.

The present inventors have repeatedly conducted studies on the production of biodiesel using biomass, and in the course of repeated research on the production of biomass, when the biomass containing the vegetable oil which is converted into a porous material is used, the entire substrate is subjected to transesterification It has been confirmed that a high purity fatty acid alkyl ester and glycerol can be produced in a continuous system instead of a batch system, thereby completing the present invention.

Particularly, the present invention is characterized in that a biomass raw material containing the vegetable oil fat is used as a porous material under a certain temperature condition, for example, at 200 ° C or higher or at 200 to 550 ° C. In addition, the present invention is advantageous in terms of environmental, engineering, and economical aspects by directly using the entire vegetable oil-containing biomass substrate without separate milking and extraction processes. Further, the present invention does not require an acid catalyst and a base catalyst, which are applied to the conventional transesterification reaction, and thus does not involve wastewater treatment due to the washing process of the catalyst, And the production of regenerated fuel is possible with a more environmentally friendly process.

According to one embodiment of the present invention, the biomass containing the vegetable oil is converted into a porous biomass by heating and then directly subjected to an ester exchange reaction without a separate milking and extraction process. A manufacturing method is provided. The method of producing biodiesel may include a step of transesterifying a biomass containing the vegetable oil and an aliphatic alcohol having 1 to 12 carbon atoms to produce a fatty acid alkyl ester and glycerol, Or may be converted to a porous material through the above-described heat treatment process. Here, the "heat treatment process" in which the biomass is converted into a porous material means that it is converted into a porous material during biodiesel conversion.

In particular, the present invention induces an ester exchange reaction by a thermochemical conversion method. That is, unlike the transesterification reaction using the existing catalyst, the present invention induces transesterification reaction by increasing the energy level of the reactor material by supplying a heat source. Therefore, the present invention does not use a catalyst, and the reactor is characterized by using only biomass containing the same vegetable oil together with alcohols (MeOH, EtOH, etc.).

As shown in FIG. 1, the present invention can produce biodiesel from the vegetable oil-containing biomass without a separate milking and extraction process through a non-catalytic continuous ester exchange reaction. In particular, in the case of a first generation biomass, an animal oil, or a dried third generation biomass, which contains a large amount of oil, biodiesel (FAME) is produced continuously in the same manner as Case I in FIG. 1 . However, micro-algae and waste water sludge, which are substrates of 3rd generation biodiesel, have high water content (80% moisture of dry weight biomass), unlike 1-2 generation biomass. Because of the high specific heat of water, it can be difficult to maintain the reaction temperature of the transesterified, transesterification process when biomass containing excess water is used. Thus, Case II of FIG. 1 is characterized in that the moisture is lowered through the dryer before the introduction of the substrate. In case of Case III in FIG. 1, it means that the dried biomass is used to evaporate oil components at a high temperature and then combined with the remaining processes including the transesterification reaction of the present invention.

In particular, as illustrated in FIG. 2, the present invention is characterized by the use of porous materials formed from biomass. Also, as shown in FIG. 3, the vaporized MeOH existing in the pores or the bulk phase increases kinetic energy due to the high temperature. Therefore, transesterification reaction occurs due to collision with the triglyceride of the vegetable oil which is adsorbed on the pore. The reaction products, FAMEs and glycerine, are mostly out of the reactor due to the reaction temperature. High concentration of FAMEs and glycerin can be obtained simply by condensation.

Porous biomass in the present invention is a thermochemical conversion method of a biomass containing the same vegetable oil as a porous biomass. In the transesterification reaction of a high temperature, porosity, pore, pore, air gap (void, pore, air gap, opening, cavity, hole, hollow), and the like. Particularly, the porous biomass of the present invention can be produced by using a microporous (pore diameter: 2 nm or less), a mesopore (pore diameter: 2 to 50 nm) and a macroporous body Macropore, pore diameter: 50 mm or more). The shape of pores is not constant but many mesopores and macropores are generated. Because it has a random distribution, it is difficult to specify it. However, there are not many micropores. Therefore, since the generated porous body becomes porous, it does not require an acid catalyst and a base catalyst applied to the conventional transesterification reaction, and merely raises the energy level of the reactor to increase the transesterification reaction. High-purity fatty acid alkyl ester and glycerol can be produced. In addition, the present invention is capable of performing a sufficiently effective transesterification reaction even at normal pressure, and shows a clear difference from the conventional supercritical (250 to 400 ° C, 200 Bar) biodiesel conversion reaction.

In addition, the porous biomass may have a pore or bulk phase which can effectively increase the energy level of the same vegetable oil and alcohol contained in the biomass in the transesterification reaction at a high temperature according to the present invention May be any porous material formed. Especially, the vaporized alcohols increase in kinetic energy due to high temperature, and transesterification reaction occurs due to collision with the vegetable oil retaining component which is provided from biomass and adsorbed on the pore. You can proceed. Accordingly, the porous biomass of the present invention can form various pore sizes and pore distributions to the extent that the pore forms pores capable of vaporization and adsorption of the reactor material in the transesterification reaction.

For example, the porous biomass may be a micropore (pore diameter: 2 nm or less), a mesopore (pore diameter: 2 to 50 nm), or a macropore (pore diameter: ) May be used. However, in terms of optimizing the reactor size and improving the process efficiency, the porous biomass has pores having an average diameter of 1 nm or more or 1 nm or more and 500 占 퐉 or less, preferably 1.5 nm or more, more preferably 2 nm or more May be included.

As shown in FIG. 4, since the biomass containing the vegetable oil is composed of a membrane, existing pores may be destroyed or pores may be generated. Accordingly, in the present invention, biomass containing all the vegetable oils known so far can be used. Examples of such biomass include Charcoal, Almond, Sesame Seed, Perilla Seed, Sunflower Seed, Coffee Bean, Rape Seed, Diatoms At least one selected from the group consisting of diatom, microalgae, and sewage sludge.

In addition, the same vegetable oil contained in the biomass includes all non-edible oils and even micro-algae oil. The term vegetable oil refers to all oils, including triglycerides, including their free fatty acids (FFAs). In particular, the vegetable oil may include a triglyceride represented by the following formula (1).

[Chemical Formula 1]

Wherein,

R ¹ , R ² and R ³ are the same or different and each is an aliphatic hydrocarbon group having 4 to 38 carbon atoms, preferably an aliphatic hydrocarbon group having 4 to 24 carbon atoms, more preferably 12 to 20 carbon atoms . The carbon number of the fatty acid substituent of the above-mentioned triglyceride can be optimized to a level similar to that of ordinary diesel, diesel.

Physical and chemical properties of the animal or vegetable oil (viscosity, molecular weight, boiling point, etc.) are triglycerides that are present fatty acids: such kind of (Fatty Acids FAs), i.e., the substituents in the formula ^{1 R 1, R 2, R} 3 of the It depends on the kind.

As specific examples of the vegetable oil, there may be mentioned those containing triglyceride represented by the following formula (2).

(2)

The fatty acid present in the triglyceride in the vegetable oil is separated from the triglyceride by external stimulation (heat, sunlight, oxidation, etc.) and is called free fatty acids (FFAs). The free fatty acids (FFAs) contain a carboxyl group in a molecular structure and exhibit acidity. Accordingly, in the conventional transesterification reaction, an acid catalyst and a base catalyst were used depending on the content of the free fatty acid contained in the vegetable oil, that is, the acid value derived therefrom. However, in the present invention, the fatty acid alkyl ester can be produced by directly transesterifying the biomass containing the vegetable oil regardless of the content of the free fatty acid. Therefore, even when the amount of FFA is large among the vegetable oil retaining ingredients supplied from the biomass, the biodiesel can be effectively produced with excellent process efficiency. In particular, the biomass can be directly used without the milking and extraction process, It has the advantage of solving the restrictions on the diesel conversion substrate.

In the present invention, the biomass may contain other small amounts of impurities, water, or the like in addition to the vegetable oil, such as triglyceride, represented by the formula (1). Particularly, in the present invention, even when water is contained in the reactor, the transesterification reaction can be effectively performed. For example, microalgae and sewage sludge may contain large amounts of water, or even 10% of the dry weight of water may be present after drying. At this time, the water content applicable to the present invention may be 80 wt% or less, preferably 40 wt% or less, more preferably 10 wt% or less, based on the total amount of biomass.

Meanwhile, in the present invention, a waste water sludge as a raw material component of the biomass corresponds to a sediment collected from a sewage treatment plant through a precipitation process or the like, taking in domestic wastewater or industrial treatment water. The sewage sludge may be a kind of bacterial grouping, and when dehydrated, the water content may be about 80 wt%, and in case of oil content, about 15 wt% to 25 wt% . At this time, the oil is similar to the same vegetable oil based on triglyceride.

Accordingly, the present invention may further include a step of drying the biomass under a temperature condition of 250 DEG C or less (corresponding to CASE II). This drying step can be applied to all biomass containing more than 20% by weight of water based on the total amount of biomass. This drying step can significantly reduce water content and prevent pyrolysis of the oil component present in the biomass. Through this drying step, the moisture content of the biomass can be lowered to 45 wt% or less, preferably 40 wt% or less, more preferably 10 wt% or less, based on the total amount of biomass.

 Further, the biomass may further include a step of evaporating the oil component at a temperature of 480 DEG C (corresponding to CASE III). Such an oil component evaporation step can be applied to biomass used as a substrate for the production of oil-containing biodiesel. Such an oil component evaporation step can separate biomass and oil. In addition, moisture is also present, but moisture and oil can be easily separated by the specific gravity difference. Through this oil component evaporation step, the oil content contained in the biomass can be lowered to 45 wt% or less, preferably 40 wt% or less, more preferably 10 wt% or less, based on the total amount of biomass.

Examples of the vegetable oil include soybean oil, palm oil, corn oil, rapeseed oil, sunflower oil, safflower oil, cottonseed oil, sesame oil, rice bran oil, palm kernel oil, camellia oil, castor oil, olive oil, palm oil, Oil, tuna oil, and waste oils thereof. However, in the case of animal oil, since it is mostly composed of oil, it is preferable to mix it with another porous material such as activated alumina, or mix it with other biomass usable in the present invention.

Meanwhile, in the present invention, the alcohols used as the reactor material together with the vegetable-containing biomass include aliphatic alcohols having 1 to 12 carbon atoms. In particular, the alcohols may be at least one selected from the group consisting of methanol, ethanol, propanol, butanol, and pentanol. Of these, methanol and ethanol can be preferred in terms of price, and methanol is more suitable than ethanol in consideration of reactivity. In the case of methanol (MeOH), reactivity can be improved by reactivity and compound steric factors. Also, it is possible to increase the carbon number of Fatty Acid Methyl Esters (FAME) produced by using a carbon-rich alcohol. For example, in the case of light oil, although there are up to 31 carbon atoms, the number of carbon atoms is usually within 24, so that a change in physical properties can be imparted to this degree. Especially, by using various kinds of alcohols, it is possible to try various property changes to the FAME produced.

In the reaction of the vegetable oil-containing biomass with the alcohols, the alcohol may be used in an amount of 5 parts by weight or more, 10 parts by weight or more, or 10 parts by weight to 30 parts by weight, or 50 parts by weight or more with respect to 100 parts by weight of the biomass Can be used. The alcohols are preferably at least 5 parts by weight of the oil which is biomass-dependent in terms of stoichiometry and can be reacted in a large amount, but the reaction with the vegetable oil can be performed by minimizing the amount of energy consumption. When a conventional method using an acid catalyst or an alkali catalyst or a superchemic ester exchange method is used, when 20 to 40 parts by weight of alcohol is reacted with 100 parts by weight of the vegetable oil, no conversion reaction for generating biodiesel occurs at all or at least A reaction time of 2 hours or more was required. However, the present invention exhibits a conversion of at least 90%, preferably at least 95%, more preferably at least 98% in a short time of 10 minutes or less even when a small amount of alcohol as described above is applied, This feature is characterized by the use of a significantly smaller amount of alcohol compared to the diesel conversion process.

The transesterification reaction according to the present invention can be carried out by a non-catalytic reaction, but can also be carried out by mixing catalysts such as Na ₂ CO ₃ , platinum, copper, and zirconium. In the case of using the catalyst together, the amount of carbonated water, aromatic compound, etc. of 12 to 20 carbon atoms in the diesel range can be increased because cracking of the vegetable oil supplied from the biomass occurs in a large amount .

On the other hand, the transesterification reaction according to the present invention is characterized in that thermal cracking of the vegetable oil of the biomass as the reactor is hardly occurred and only the heat is applied only to the extent of raising the energy level by heat. In this respect, the transesterification reaction of the present invention can be carried out at a reaction temperature of 250 to 550 ° C, preferably 300 to 500 ° C, preferably 350 to 450 ° C, and a reaction pressure of 10 mmHg to 10 atm, 0.5 to 7 atm, and more preferably 1 to 5 atm. As described above, the reaction can be carried out at 250 ° C or higher so that the FAMEs can be effectively converted from the same vegetable oil of the biomass through the non-catalytic continuous transesterification reaction of the present invention. In addition, it may be carried out at 550 DEG C or less in terms of preventing the generation of aromatic compounds by thermal cracking. In particular, the transesterification reaction of the present invention can be carried out at atmospheric pressure but also at high pressure.

The transesterification reaction can be carried out under the temperature and pressure conditions as described above at a retention time of 0.1 to 10 minutes, preferably 0.2 to 5 minutes, more preferably 0.2 to 3 minutes. This reaction time is remarkably improved compared with the case of using the existing acid catalyst and base catalyst for at least 2 hours in the pretreatment and the present treatment step, and the reaction time of 5 to 20 minutes And exhibits excellent process efficiency as compared with the reaction time.

The transesterification reaction of the present invention can be carried out by a heterogeneous reaction between a liquid animal fat and a gaseous aliphatic alcohol. This has advantages in terms of energy saving and maximization of reaction yield.

Meanwhile, the noncatalytic continuous reaction of the present invention can produce FAMEs without purge gas, but it is also possible to use purge gas for controlling the retention time of the reaction. The purge gas may include at least one selected from the group consisting of nitrogen, argon, and carbon dioxide. However, when the transesterification reaction is carried out in a gas atmosphere containing carbon dioxide, thermal decomposition can be minimized. In the present invention, conversion of fatty acid alkyl esters (FAMEs) Can be significantly improved.

In the method for producing biodiesel according to the present invention, the transesterification reaction can be carried out in a continuous process.

In the meantime, since biodiesel is produced by reacting only the aliphatic alcohol with the vegetable oil, without using an acid catalyst and a base catalyst, the present invention minimizes impurities and has high purity. At this time, the conversion rate can also be obtained to the extent that it significantly improves the existing process.

The fatty acid alkyl ester produced through the transesterification reaction of the present invention may contain an aliphatic moiety having 10 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and more preferably 14 to 20 carbon atoms.

Meanwhile, in the transesterification reaction according to the present invention, the same vegetable oil and aliphatic alcohols contained in the biomass in the presence of the porous material produced from the biomass are as shown in the following reaction formula (1).

[Reaction Scheme 1]

Wherein,

R ¹ , R ² , R ³ , R ^{1 '} , R ^2' and R ^{3 '} are the same or different and each is an aliphatic hydrocarbon group having 4 to 38 carbon atoms, preferably 4 to 24 carbon atoms, May be an aliphatic hydrocarbon group having 12 to 20 carbon atoms.

The above-described process for producing biodiesel of the present invention overcomes the disadvantages of the transesterification process for the conventional biodiesel production and overcomes all of the disadvantages of the transesterification reaction which is currently under active R & D. In biodiesel conversion, the biodiesel conversion process has been improved on a continuous basis, not in a batch mode. The present invention can be effectively carried out regardless of the amount of the free fatty acid, unlike the conventional process in which the process and the operation are changed according to the free fatty acids (FFAs) present in the vegetable oil.

The present invention does not use the catalyst used in the transesterification process, so that the biodiesel conversion process can be newly constructed by combining the pretreatment and the present treatment. Through the integrated pretreatment / treatment process with catalyst, there is also an effect of blocking the existing wastewater generation and loss of biodiesel (FAMEs) originally. Also, unlike the ester exchange reaction process by the supercritical reaction at high temperature / high pressure in the current research and development (R & D) stage, the main characteristic of the present invention is to react at normal pressure. On the other hand, since carbon dioxide is used in the process, it shows a clear contrast with the conventional transesterification process and the transesterification process in the R & D stage. This is an effect of the present invention because it is an environmentally friendly process.

In addition, since the present invention can produce biodiesel faster than conventional commercial processes, it shows a remarkable effect in terms of energy saving. Particularly, since bamboo diesel (FAMEs) are produced only by using methanol and the same vegetable oil as the reaction materials, a considerable cost reduction in the distillation purification cost can be expected.

In addition, the present invention is characterized in that the first, second, and third generation biodiesel can share the same process and can obtain high purity FAMEs and glycerin.

According to the present invention, the conversion rate of the fatty acid alkyl ester resulting from the transesterification reaction using the biomass containing the vegetable oil fat can be 90% or more, preferably 95% or more, more preferably 98% or more.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

According to the present invention, the biomass is directly used without any separate milking and extraction process, and the transesterification reaction is carried out without using the existing acid catalyst or base catalyst, whereby the biodiesel It is possible to obtain an excellent effect of obtaining a high purity fatty acid alkyl ester and glycerol in an environmentally friendly and energy saving manner without a separate washing process.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram for producing biodiesel from a plant biomass containing vegetable oil according to an embodiment of the present invention without a separate milking and extraction process through a non-catalytic continuous ester exchange reaction.
2 is a schematic diagram schematically showing the mechanism of the transesterification reaction according to one embodiment of the present invention.
FIG. 3 is a diagram schematically showing the mechanism of transesterification reaction using MeOH according to one embodiment of the present invention.
4 is a photograph showing an example of the porous vegetable-containing porous biomass applicable to an ester exchange reaction according to an embodiment of the present invention.
FIG. 5 is a graph showing conversion of FAME by temperature control at 400 ° C. using perilla seed according to an embodiment of the present invention.
FIG. 6 is a graph showing conversion of FAME by controlling moisture content of a water weight ratio (0-100%) relative to oil by weight using charcoal according to an embodiment of the present invention.
7 is a mass spectrometry chromatogram of the product after transesterification using perilla according to Example 1 of the present invention.
8 is a mass spectrometry chromatogram of a product after transesterification using sewage sludge according to Example 15 of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example  One

The ester exchange reaction with an aliphatic alcohol having 1 to 12 carbon atoms was carried out in a continuous process using perilla as a biomass with a water content of about 10% by weight under the conditions shown in the following Table 1, and the resultant fatty acid alkyl ester Glycerol was recovered to prepare biodiesel.

The conversion of the resulting fatty acid methyl ester (FAME) was measured by the following method.

<FAME conversion rate>

FAME conversion rates are based on analytical values through GC / MS. ASTM D6751 or EN14214 standard specification for biodiesel analysis. In particular, the yield of FAME was determined using EN14103 (content of ester and linoleic acid methyl ester). In addition, EN14106 / ASTM D6584 was used to determine the content of glycerin, mono-, di- and triglycerides.

Example  2 to 9

The ester exchange reaction was carried out in the same manner as in Example 1 except for the conditions as shown in Table 1 below. The resulting fatty acid alkyl ester and glycerol were recovered to prepare biodiesel, and the resulting fatty acid methyl ester (FAME) were measured.

Example  10-12

The same procedures as in Example 1 were carried out except that 10% by weight of soybean, 10% by weight of rapeseed, and 30% by weight of water content of cyanobacteria were used as the biomass under the conditions shown in the following Table 1 Ester exchange reaction was carried out, and the produced fatty acid alkyl ester and glycerol were recovered to prepare biodiesel, and the conversion of the resulting fatty acid methyl ester (FAME) was measured.

Example  13

10 weight% of lard was used as biomass and 10 weight parts of charcoal (average pore diameter: 45 nm) as 100 parts by weight of biomass was added as a refractory porous material under the conditions shown in Table 1 below. Ester exchange reaction was carried out in the same manner as in Example 1, except that the fatty acid alkyl ester and glycerol were recovered to prepare biodiesel and the conversion of the resulting fatty acid methyl ester (FAME) was measured .

Example  14-15

Chlorella Vulgaris and sewage sludge having a water content of 30% by weight corresponding to microalgae (Chlorella vugaris) were used as biomass under the conditions shown in the following Table 1, respectively. , The ester exchange reaction was carried out in the same manner as in Example 1, except that the water content of the biomass was reduced to 5% by weight or less, and then the ester exchange reaction was carried out. The resultant fatty acid alkyl ester and glycerol The biodiesel was recovered and the conversion of the resulting fatty acid methyl ester (FAME) was measured.

Example  16

Perilla dried at a moisture content of 10% by weight was used as the biomass under the conditions shown in the following Table 1, and the oil content of the biomass obtained by heating the oil component at 490 ° C at high temperature was reduced to 80% , The ester exchange reaction was carried out in the same manner as in Example 1 except that the ester exchange reaction was carried out, and the resulting fatty acid alkyl ester and glycerol were recovered to prepare biodiesel, and the resulting fatty acid methyl ester (FAME ) Was measured.

The process conditions of the transesterification reaction according to Examples 1 to 16 and the conversion rates of the resulting fatty acid methyl esters (FAME) are shown in Table 1 below.

division Bio
mass
ingredient Bio
mass
Moisture content
(wt%) Alcohol
ingredient Biomass:
Alcohol
Weight ratio charge
gas
ingredient reaction
Temperature
(° C) reaction
pressure
(mmHg) visit
time
(min) FAME
Conversion Rate
(%) Example 1 Perilla 5 MeOH 10: 1 CO ₂ 400 760 One 99 Example 2 Perilla 10 MeOH 10: 1.5 CO ₂ 300 760 0.7 82 Example 3 Perilla 10 MeOH 10: 1.5 CO ₂ 320 760 One 84 Example 4 Perilla 10 MeOH 10: 1.5 CO ₂ 400 1,500 One 98.5 Example 5 Perilla 10 MeOH 10: 0.8 CO ₂ 450 1,500 One 98.1 Example 6 Perilla 10 MeOH 10: 0.6 CO ₂ 400 760 One 98.41 Example 7 Perilla 15 MeOH 10: 4 CO ₂ 400 760 One 97.48 Example 8 Perilla 15 EtOH 10: 2 CO ₂ 400 760 One 98.5 Example 9 Perilla 20 MeOH 10: 0.8 N ₂ 400 760 One 97.95 Example 10 Big head 10 MeOH 10: 2 CO ₂ 400 760 One 97.12 Example 11 Rapeseed 10 MeOH 10: 1.5 CO ₂ 400 760 One 99.1 Example 12 Green algae 30 MeOH 10: 2 CO ₂ 400 760 One 98.74 Example 13 Lard 10 MeOH 10: 2 CO ₂ 400 760 One 98.6 Example 14 Chlorella 30 MeOH 10: 1 CO ₂ 400 760 One 98.8 Example 15 sewer
Sludge 30 MeOH 10: 1 CO ₂ 400 760 One 98.7 Example 16 Perilla 10 MeOH 10: 1 CO ₂ 400 760 One 97.7

Comparative Example  One

Biodiesel was prepared using soybean oil having a moisture content of 10% by weight by performing transesterification reaction for 2 hours at a reaction temperature of 60 占 폚 using NaOH as a base catalyst in a conventional manner. At this time, the weight ratio of soybean oil: methanol was 100: 20, and the conversion rate of the resulting fatty acid methyl ester (FAME) was 92%.

Comparative Example  2

Biodiesel was prepared using soybean oil having a moisture content of 20% by weight by performing transesterification reaction for 2 hours at a reaction temperature of 60 占 폚 using NaOH as a base catalyst in a conventional manner. At this time, the weight ratio of soybean oil to methanol was 100:20, and the conversion rate of the resulting fatty acid methyl ester (FAME) was 88%.

Comparative Example  3

Biodiesel was prepared using soybean oil having a moisture content of 10% by weight by performing transesterification reaction for 2 hours at a reaction temperature of 60 占 폚 using NaOH as a base catalyst in a conventional manner. At this time, the weight ratio of soybean oil to methanol was 100:40, and the conversion rate of the resulting fatty acid methyl ester (FAME) was 94%.

As shown in Table 1, according to the present invention, a biomass raw material itself containing vegetable fat and converted into a porous material through a heat treatment process at 200 ° C or higher without using an acid catalyst, a base catalyst, In Examples 1 and 4 to 16 in which the transesterification reaction was carried out without separate milking and extraction processes, the reaction time was all within about 1 minute and the conversion rate was more than 95% . On the other hand, in the case of Comparative Examples 1 to 3 using the base catalyst in the conventional manner, it was found that the conversion rate was only 88% to 94%, which is not good.

On the other hand, the chromatograms obtained by carrying out the transesterification reaction using perilla and sewage sludge according to Examples 1 and 15, respectively, were subjected to GC-MS (Gas Chromatography Mass Spectroscopy) 7 and Fig. As shown in FIGS. 7 and 8, the perilla seed and the sewage sludge per se can be subjected to an ester exchange reaction without separate milking and extraction processes without using any acid catalyst, base catalyst or the like according to the present invention 1 and Example 15, it was confirmed that the fatty acid corresponding to the initial component was not detected and the conversion to bacteriocin (Fatty Acid Methyl Esters: FAMEs) was effectively performed.

Claims (18)

Comprising the step of transesterifying a biomass containing the vegetable oil and an aliphatic alcohol having 1 to 12 carbon atoms to produce a fatty acid alkyl ester and glycerol,
Wherein the biomass is converted into a porous material through a heat treatment process at a temperature of 200 ° C or higher and the transesterification reaction is carried out at a temperature of 250 to 550 ° C, a pressure of 760 mmHg to 1,500 mmHg, and a retention time of 0.1 to 10 minutes. Method of manufacturing diesel. The method according to claim 1,
Wherein the temperature of the transesterification reaction is 300 to 500 占 폚. delete The method according to claim 1,
Wherein the residence time of the transesterification reaction is 0.2 to 5 minutes. The method according to claim 1,
The biomass may be selected from the group consisting of Charcoal, Almond, Sesame Seed, Perilla Seed, Sunflower Seed, Coffee Bean, Rape Seed, Diatom, , Sewage sludge (Sludge), and microalgae (Microalgae). The method according to claim 1,
Wherein the vegetable oil of the biomass comprises a triglyceride represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

Wherein,
R ¹ , R ² , and R ³ are the same or different and each is an aliphatic hydrocarbon group having 4 to 38 carbon atoms. The method according to claim 1,
The vegetable oil of the biomass may be selected from the group consisting of palm oil, soybean oil, rape oil, corn oil, rapeseed oil, sunflower oil, safflower oil, cottonseed oil, sesame oil, rice bran oil, palm kernel oil, camellia oil, castor oil, olive oil, palm oil, , Whale oil, tuna oil, and waste oils thereof. The method according to claim 1,
Wherein the water content of the biomass is 80 wt% or less. The method according to claim 1,
Wherein the alcohols are at least one selected from the group consisting of methanol, ethanol, propanol, butanol, and pentanol. The method according to claim 1,
Wherein the alcohols are reacted in an amount of 6 to 40 parts by weight based on 100 parts by weight of the biomass. The method according to claim 1,
Further comprising the step of drying the biomass at 250 DEG C or less. The method according to claim 1,
Further comprising the step of evaporating the oil component at 400 to 540 占 폚 in the biomass. The method according to claim 1,
Wherein the transesterification reaction is carried out by dissociation of an animal fat in liquid phase with aliphatic alcohols in gaseous phase. The method according to claim 1,
Wherein the transesterification reaction is carried out in at least one gas atmosphere selected from the group consisting of nitrogen, argon, and carbon dioxide. The method according to claim 1,
Wherein the transesterification reaction is carried out in a continuous process. The method according to claim 1,
Wherein the fatty acid alkyl ester comprises an aliphatic moiety having 4 to 38 carbon atoms. delete delete

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