KR20110095662A - Preparation methods of sugar from sea algae by plasma treatment and preparation methods of bio-fuel using thereof - Google Patents

Abstract

PURPOSE: A method for manufacturing a saccharide material using marine algae is provided to manufacture bio-fuel. CONSTITUTION: A method for manufacturing a saccharide material comprises: a step of performing a plasma treatment of marine algae; a step of placing marine algae in a plasma reactor; a step of reducing pressure of the plasma reactor using a vacuum pump; a step of removing vapor remaining in the plasma reactor; a step of injecting electric discharge gas to the plasma reactor; a step of discharging plasma by applying 10-500 W to the plasma reactor; and a step of performing acid treatment.

Description

Preparation Methods of Sugar From Sea Algae by Plasma Treatment and Preparation Methods of Bio-fuel Using Thereof}

The present invention relates to a method for preparing a saccharide material from seaweed and a method for producing a biofuel using the same, and more particularly, to prepare monosaccharides and / or disaccharides of reducing sugars by sequentially performing algae treatment with plasma and acid. It relates to a method for producing a saccharide material from seaweeds fermenting reducing sugars by a microorganism to produce a biofuel, and a method for producing a biofuel using the same.

With high oil prices, energy security, and stricter greenhouse gas regulations, the development of alternative energy has been a hot topic, and biofuels are rapidly spreading as a next generation fuel worldwide.

The biofuel refers to energy obtained by using biomass as a raw material, and is obtained through direct combustion, alcohol fermentation, methane fermentation, and the like.

Biomass, a raw material of biofuel, is divided into sugar-based (sugar cane, sugar beet, etc.), starch-based (corn, potato, sweet potato, etc.), and wood-based (wood, rice straw, waste paper, etc.). In this case, it is possible to convert raw materials into biofuels immediately through a relatively simple pretreatment followed by a fermentation process.However, in the case of starch and wood based biofuels, the fermentation process using a saccharified solution that has undergone proper pretreatment and saccharification process is used. It can manufacture.

On the other hand, the algae growth is fast, depending on the depth of the sea green algae in the upper layer, brown algae in the middle layer, red algae grow in the lower layer because it can have a higher productivity than the land biomass through the complex culture. In addition, algae have the advantage of being easy to decompose because there is no hardly degradable lignin in woody biomass.

However, seaweed has a high water content of more than 80%, the salt concentration occupies 20-30% of the dry weight, and has a high content of proteins (10-15%) and fat (1-5%). In addition, the carbohydrate composition, which occupies 25-50% of the dry weight, is also significantly different from that of land plants. Therefore, studies on pretreatment methods, saccharification methods, and fermentation methods suitable for each seaweed are necessary.

In particular, in order to produce biofuels, three steps of glycosylation, fermentation and distillation of raw materials are largely performed. In the saccharification step, chemical treatment, heat treatment, and pretreatment with enzymes are used.

However, these pretreatments have a problem in that the yield of the saccharide material produced is low.

The present invention provides a method for preparing a sugar substance in high yield using seaweed.

The present invention also provides a method for producing biofuel using the prepared saccharide material.

The present invention

A plasma processing step of plasma treating seaweed; And

It provides a method for producing a saccharide material comprising an acid treatment step of acid treatment of the seaweeds, the plasma treatment step is completed with an extraction solvent made of an acidic drug.

In addition,

It provides a method for producing a biofuel comprising fermenting a sugar material prepared by the method for producing a sugar material by a microorganism.

The present invention has the effect of producing a saccharide material in a high yield from seaweed through sequential plasma treatment and acid treatment, using the biofuel by using the same.

1 is a flow chart showing a method of manufacturing a biofuel according to the present invention.

In one aspect, the present invention is a plasma processing step of plasma processing seaweed; And an acid treatment step of acid-treating the algae in which the plasma treatment step is completed with an extraction solvent made of an acidic drug.

In another aspect, the present invention provides a method for producing a biofuel comprising fermenting a saccharide substance by a microorganism.

Herein, the saccharide material is preferably a reducing sugar, and the reducing sugar refers to a monosaccharide, a disaccharide, or both.

The plasma treatment step according to the present invention is to decompose polysaccharides, for example, cellulose, contained in seaweed into monosaccharides and / or disaccharides, and is not particularly limited as long as it is a plasma treatment method for this purpose. It is preferable to use a plasma or solution plasma treatment method, and to recommend a vacuum plasma treatment method.

The plasma treatment, specifically vacuum plasma treatment, comprises: placing algae in a plasma reactor; Reducing the pressure of the plasma reactor using a vacuum pump; Removing residual gas present in the plasma reactor; Injecting a discharge gas into the plasma reactor; And applying a power of 10 to 500 W to the plasma reactor to perform plasma discharge.

In this case, the plasma treatment is preferably performed for 1 to 300 minutes.

The acid treatment step according to the present invention is to immerse the plasma treated algae in an extraction solvent made of an acidic drug, preferably for 1 to 600 minutes.

The acidic agent may be H ₂ SO ₄ , HCl, HBr, HNO ₃ , CH ₃ COOH, HCOOH, HClO ₄ (perchloric acid), H ₃ PO ₄ (phosphoric acid), para-toluene sulfonic acid (PTSA) or commercial solid acid Or a mixture thereof.

In this case, the acidic chemicals are dissolved in a solvent to form an extraction solvent, and the solvent is not particularly limited as long as it is a substance capable of dissolving the acidic chemicals, but preferably water is used.

The acid treatment is to decompose a partially formed disaccharide into monosaccharides or to decompose polysaccharides into monosaccharides and / or disaccharides.

The biofuel according to the present invention may be selected from the group consisting of C ₁ to C ₄ alcohols and C ₂ to C ₄ ketones, preferably methanol, ethanol, propanol, butanol or acetone, but not limited thereto. It doesn't happen.

On the other hand, in the step of fermenting a saccharide material, for example reducing sugars by a microorganism according to the present invention, the microorganism is not particularly limited as long as it can produce a biofuel by fermenting the reducing sugar, preferably Clostridium aceto Clostridium acetobutylicum, Clostridium beijerinckii, Clostridium aurantibutylicum or Clostridium tetanomorphum, but is not limited thereto. They are more preferred for butanol and acetone fermentation. In addition, Saccharomyces cerevisiae, Sarcina ventriculi, Kluyveromyces fragilis, Zygomomonas mobilis or Kluyberomyces maximans (Kluyveromyces marxianus) IMB3, Bretanomyces custersii and the like can be used, which are more preferred for ethanol fermentation.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. However, the following description is only for the purpose of specifically describing the present invention, and the scope of the present invention is not limited by the following description.

1 is a flow chart illustrating a method of manufacturing a biofuel according to the present invention.

As shown in FIG. 1, in the biofuel production method according to the present invention, a plasma treatment step of plasma treatment of seaweeds and an acid treatment of acidic treatment of acidic seaweeds with an extraction solvent composed of an acidic drug are completed. step; And fermenting the sugars produced through acid treatment by microorganisms.

The algae according to the present invention may be used without limitation for large algae or microalgae, the large algae include red algae, brown algae, green algae, and the like, chlorella, spirulina and the like.

The red algae include gamble, laver, kotoni, dog gambling, and gambling, gambling, round buckwheat, daikon radish, buckwheat, green grass, twine, jindubal, spiny radish, silk grass, vulgaris, stone starch, stone, jinari Etc. may be used, but the present invention is not limited thereto, and among them, gambling and / or loot may be used. The most diverse species of red algae are excellent in their growth ability, and on the basis of dry weight, about 15 to 25% of cellulose is composed of cellulose, and about 60 to 50% is made of galactan as a main ingredient. It is composed of less than% protein and less than 7% lipid.

As the brown algae, seaweed, kelp, barn horse, folk eggplant, shellfish, hooked seaweed, seaweed, Ecklonia cava, gompi, rhubarb, iron seaweed cousin, mabanban, hoesan mabanban, jichungyi, 톳 and the like may be used. It doesn't happen. Brown algae are multicellular bodies and are best differentiated among algae.

The green algae may be Cheongtae, Hakkham, green, hearing, bead hearing, jade, salt juice, etc., but is not limited thereto. Green algae have chlorophyll and make starch by photosynthesis.

Looking at the components of the brown algae and green algae, brown algae contains 30-40% alginic acid, 5-6% fibrin, and green algae contains 40-50% starch, the main component of carbohydrate, and less than 5% fibrin. have.

Daikon is the main component of galactan composed of galactose polymer, and galactan can be converted into monosaccharides such as galactose and 3,6-anhydrogalactose through proper low molecular weighting process.

Fibrin is a substance composed of cellulose, and in the case of lodge, it accounts for 15 to 25% of the total component. The cellulose may be converted into glucose, a monosaccharide, through a saccharification process using an appropriate enzyme or an acid catalyst. The above-described galactose and glucose are used as precursors that can be converted into biofuels through the fermentation process.

Starch, also called starch, is a carbohydrate that is made and stored photosynthesically in the chloroplasts of green plants. It is a polysaccharide composed of glucose. The starch may be converted into glucose, a monosaccharide, through a saccharification process using an appropriate enzyme or an acid catalyst.

The plasma treatment step according to the present invention is to decompose polysaccharides, for example, cellulose, contained in seaweed into monosaccharides and / or disaccharides, and is not particularly limited as long as it is a plasma treatment method for this purpose. , Atmospheric pressure plasma treatment or solution plasma treatment.

The plasma treatment, particularly vacuum plasma treatment, comprises the steps of placing algae in a plasma reactor; Reducing the pressure of the plasma reactor using a vacuum pump; Removing residual gas present in the plasma reactor; Injecting a discharge gas into the plasma reactor; And applying a power of 10 to 500 W to the plasma reactor to perform plasma discharge.

In reducing the pressure of the plasma reactor, the pressure may be reduced to a base pressure, for example, a pressure of 0.001 millibar (mb). Here, it is preferable to use an ion gauge for the pressure measurement of the plasma reactor.

In addition, the step of removing the residual gas present in the plasma reactor is to maintain the pressure-reduced plasma reactor for 1 to 60 minutes, preferably about 20 minutes.

On the other hand, the plasma treatment step according to the present invention may use not only a vacuum plasma treatment but also an atmospheric pressure plasma treatment method. The atmospheric pressure plasma treatment method is performed in the same manner as the vacuum plasma treatment method, but since the plasma discharge proceeds under atmospheric pressure, Depressurizing the internal pressure of the reactor may be omitted.

Therefore, when the plasma processing step according to the present invention uses an atmospheric plasma processing method, the atmospheric plasma processing method includes the steps of placing the algae in the plasma reactor; Injecting a discharge gas into the plasma reactor; And performing a plasma discharge by applying an output of 10 to 500 W to the plasma reactor.

The discharge gas injected into the plasma reactor may be a conventional gas in the art for plasma reaction, for example argon, nitrogen, xenon, neon, helium or mixtures thereof.

In the step of discharging the plasma, the discharge method is not particularly limited, but it is preferable to use the ICP method, and it is preferable to discharge the plasma by using a matching box and a plasma generator.

If necessary, the plasma treatment method according to the present invention may use a solution plasma treatment method.

At this time, the solution plasma treatment method includes supporting the cathode in the algae and solvent mixture, and installing the anode to be spaced apart from the mixture and applying a current of 1 to 100mA to each electrode.

At this time, the solvent constituting the algae and the solvent mixture may be used as long as the algae can be supported, but preferably water or a nonvolatile organic solvent such as DMSO (dimethylsulfoxide) or decane may be used. , The mixing ratio of the algae and the solvent is preferably 1:99 to 50:50.

In addition, the separation distance of the algae and the solvent mixture is not particularly limited, but is preferably 0.1 to 3 cm, more preferably about 0.5 cm.

Plasma treatment according to the invention, for example vacuum plasma, atmospheric plasma or solution plasma treatment is preferably carried out for 1 to 300 minutes.

The acid treatment step according to the present invention is to decompose partially formed disaccharides into monosaccharides or to decompose polysaccharides into monosaccharides and / or disaccharides through plasma treatment, as well as to extract polysaccharides contained in seaweeds. The acid treatment method commonly used in the industry is not particularly limited.

In one embodiment, the acid treatment according to the present invention is to immerse algae in an extraction solvent consisting of an acidic drug.

Here, the time and temperature to immerse the algae in the extraction solvent can be changed according to the user's choice, but it is recommended to immerse in the temperature range of 50 to 300 ℃ for 1 to 600 minutes.

The acidic agent may be H ₂ SO ₄ , HCl, HBr, HNO ₃ , CH ₃ COOH, HCOOH, HClO ₄ (perchloric acid), H ₃ PO ₄ (phosphoric acid), para-toluene sulfonic acid (PTSA) or commercial solid acid Or a mixture thereof, but is not limited thereto.

In this case, the acidic chemicals are dissolved in a solvent to form an extraction solvent, and the solvent is not particularly limited as long as it is a substance capable of dissolving the acidic chemicals, but preferably water is used.

Preferably, the sugar material according to the present invention is a reducing sugar, which refers to a monosaccharide, a disaccharide or a mixture thereof.

The monosaccharides are galactose, galactose derivatives, 3,6-anhydrogalactose, glucose, fucose, rhamnose, xylose, mannose or mixtures thereof.

In the step of fermenting the sugar material according to the present invention, that is, reducing sugar by the microorganism, the microorganism is not particularly limited as long as it can produce a biofuel by fermenting the reducing sugar, but preferably Clostridium acetobutylicum ( Clostridium acetobutylicum, Clostridium beijerinckii, Clostridium aurantibutylicum or Clostridium tetanomorphum, but are not limited to these butanols And in acetone fermentation. Also, Saccharomyces cerevisiae, Sarcina ventriculi, Kluyveromyces fragilis, Zygomomonas mobilis or Kluyveromyces maxia (Kluyveromyces marxianus) IMB3, Bretanomyces custersii and the like can be used, which are more preferred for ethanol fermentation.

In addition, the fermentation conditions for fermenting the sugar substance by the microorganism is not particularly limited as long as the fermentation conditions are conventional in the art, preferably fermentation for a temperature range of 20 to 50 ℃ and / or 12 to 50 hours.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention by these examples.

First, prior to explaining the embodiment of the present invention, a method for analyzing the sugar substance prepared according to the embodiment of the present invention, DNS analysis method will be described as follows.

The DNS method is a method of analyzing the reduction sugars converted from polysaccharides to monosaccharides through the reaction with DNS, and it is possible to know the production amount of the entire monosaccharides, not the specific monosaccharides.

The experimental procedure of the DNS method is as follows.

First, 1 ml of DNS solution was added to 1 ml of the sample treated through each pretreatment method, followed by heating in a bath at 90 ° C. for 10 minutes, and cooling at room temperature for 10 minutes. The results obtained by measuring the absorbance at 575 nm using UV spectrometer (Ultrospec 3000, Pharmacia Biotech) were compared to compare the effect on each treatment condition.

≪ Example 1 >

Two parts by weight of kelp were placed in a beaker and placed in a plasma reactor [EPPS2000, Plasmart Inc., South Korea].

Then, using a vacuum pump [SDP-400, Era Electronics, Korea] to reduce the pressure in the plasma reactor to 0.003 millibar (mb) and to maintain a reduced pressure for about 20 minutes to remove residual gas in the plasma reactor It was.

Then, 30 sccm of argon gas was injected into the plasma reactor.

Then, the plasma reactor injected with argon gas was left to stand for about 20 minutes so that argon gas was sufficiently dispersed in the plasma reactor.

Then, the output of the plasma reactor was fixed at 150 W, and plasma was discharged by using a matching box [AMN-100, Youngshin Engineering, South Korea] and a plasma generator [YSE-03F, Youngshin Engineering, South Korea] to discharge the plasma. Run for minutes.

Then, after the plasma treatment was completed, the plasma treated kelp was placed in an Erlenmeyer flask with 0.2M hydrochloric acid solution, which is an extraction solvent for acid treatment, and then a high temperature and high pressure sterilizer [VS-1221, Vision Scientific Co., LTD., Korea ] Was reacted at 120 ° C. for 10 minutes for acid treatment.

Subsequently, the acid-treated material was naturally cooled to room temperature and then centrifuged at 8,000 rpm for 10 minutes using a centrifuge [MICRO-12, HANIL, South Korea] to obtain only the supernatant.

Then, the obtained supernatant was subjected to a filtration process using a syringe filter [GD / X PVDF Filter, Whatman international LTD., UK].

As a result, the produced reducing sugar is shown in Table 1.

Comparative Example 1

0.2 M aqueous hydrochloric acid solution and 2 parts by weight kelp were placed in an Erlenmeyer flask, and then reacted at 120 ° C. for 10 minutes using a high temperature autoclave [VS-1221, Vision Scientific Co., LTD., South Korea].

Subsequently, the material after the reaction was naturally cooled to room temperature and then centrifuged at 8,000 rpm for 10 minutes using a centrifuge [MICRO-12, HANIL, South Korea] to obtain only the supernatant.

Then, the obtained supernatant was subjected to a filtration process using a syringe filter [GD / X PVDF Filter, Whatman international LTD., UK].

As a result, the produced reducing sugar is shown in Table 1.

As shown in Table 1, it was found that the amount of reducing sugar produced in Example 1, which was subjected to an acid treatment after plasma treatment, was higher than that of Comparative Example 1, in which only acid treatment was performed.

As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. Therefore, the scope of the present invention should be construed as being included in the scope of the present invention all changes or modifications derived from the meaning and scope of the claims to be described later rather than the detailed description and equivalent concepts thereof.

Claims (10)

A plasma processing step of plasma treating seaweed; And
And acid treatment step of acid treatment of the algae in which the plasma treatment step is completed with an extraction solvent made of an acidic drug. The method of claim 1,
The plasma treatment may include placing algae in a plasma reactor;
Reducing the pressure of the plasma reactor using a vacuum pump;
Removing residual gas present in the plasma reactor;
Injecting a discharge gas into the plasma reactor; And
Method of producing a saccharide material comprising the step of performing a plasma discharge by applying an output of 10 to 500W to the plasma reactor. The method of claim 1,
The plasma treatment may include placing algae in a plasma reactor;
Injecting a discharge gas into the plasma reactor; And
Method of producing a saccharide material comprising the step of performing a plasma discharge by applying an output of 10 to 500W to the plasma reactor. The method of claim 1,
In the plasma treatment, a cathode is supported on a seaweed and solvent mixture, and a cathode is installed to be spaced apart from the mixture, and a current of 1 to 100 mA is applied to each electrode. The method of claim 1,
The plasma treatment is a method for producing a saccharide material, characterized in that for 1 to 300 minutes. The method of claim 1,
The acid treatment step is a method for producing a saccharide material, characterized in that the plasma-treated seaweed is immersed for 1 to 600 minutes in the extraction solvent consisting of acidic chemicals. A method for producing a biofuel comprising fermenting a saccharide substance prepared according to the method for producing a saccharide substance according to any one of claims 1 to 6 with a microorganism. The method of claim 7, wherein
The fermentation microorganisms are Clostridium acetobutylicum, Clostridium Bayerky, Clostridium aurantibutyricum, Clostridium tetanomorphium, Saccharomyces cerevisiae, Sarcina ventriculum, Klui Veromaises Fragilis, Zaigomonas Mobilis, Cluj Veromaises Maxianus IMB3, Bretanomyces Custerssee, Clostridium Acetobutylicum, Clostridium Bayerki, Clostridium aurantibutyl Method for producing a biofuel, characterized in that selected from the group consisting of Qum and Clostridium tetanomorphium. The method of claim 7, wherein
Wherein said biofuel is selected from the group consisting of C ₁ to C ₄ alcohols and C ₂ to C ₄ ketones. 10. The method of claim 9,
Wherein said biofuel is selected from the group consisting of methanol, ethanol, propanol, butanol and acetone.

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