KR20100024665A - Method of producing hydrolysate from sea algae using acidic ionic liquid catalysts - Google Patents

Abstract

PURPOSE: A method for preparing sea algae-derived saccharification liquid using an ion liquid and a method for manufacturing bio fuel are provided to suppress or minimize the generation of 5-HMF(5-hydroxymethylfurfural) and to lower processing costs. CONSTITUTION: A saccharification liquid is prepared by treating acidic ion liquid to polysaccharide extracted from sea algae. The acidic ion liquid is imidzolium, phosphonium, ammonium, morpholinium, or choline. The polysaccharide is gelidium jelly, starch, carrageenan, alginic acid, or cellulose. The sea algae are large seaweed or microalgae. The monosaccharide is galactose, galactose derivative, 3,6-anhydro galactose, glucose, fucose, rhamnose, xylose, or mannose. A method for manufacturing biofuel comprises: a step of treating acidic ion liquid catalyst to polysaccharide extracted from sea algae to obtain monosaccharide; and a step of fermenting the monosaccharide using microorganisms. The biofuel is C1-C4 alcohol or C2-C4 ketone.

Description

Method of producing hydrolysate from sea algae using acidic ionic liquid as catalyst

The present invention relates to a method for preparing a seaweed-derived saccharified solution using an ionic liquid as an acid glycosylation catalyst, and more particularly, inhibits or minimizes the production of 5-HMF (5-hydroxymethylfurfural), which is a fermentation inhibiting substance when acid alkalizing is used as a raw material. The present invention relates to a method for preparing saccharified solution using an ionic liquid as a catalyst.

Biofuel is a generic term for 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 the case of raw materials, biofuel can be directly converted into biofuel through a fermentation process following a relatively simple pretreatment process. However, in the case of starch and wood, biofuel is manufactured through fermentation process using saccharified liquid after proper pretreatment and saccharification process. can do. Wood-based materials can use waste wood in the form of urban waste or forest by-products scattered throughout the forest as raw materials, and there is no useful value as food, so the stability of supply and demand of raw materials can be secured, but the lignin removal pretreatment process must be accompanied in the process. Due to the increase in the process cost, due to the crystalline structure consisting of hydrogen bonds, which is a characteristic of the wood-based cellulose substrate, there is a disadvantage that the economic efficiency is low due to low saccharification yield.

The successful commercialization of biofuels as an alternative fuel for transportation lies in securing the price competitiveness of biofuels such as bioethanol over gasoline. In general, the ratio of raw material costs and process costs among biofuel manufacturing costs varies widely depending on the type and process of biomass. For example, in case of sugar system using sugar cane or sugar beet, raw material cost: process cost is about 75: 25, while starch system of corn, potato, cassava, etc. is about 50: 50, and in case of wood system, about 25: 75 to be.

However, except for the wood-based biofuel production technology that is currently commercialized, it uses the sugar- or starch-based raw materials that humans can use as food. Supply-demand problems can occur, and economically, using grains is a problem in terms of raw material costs. In addition, corn cultivation requires a considerable amount of pesticides and nitrogen fertilizers, as well as environmental disadvantages such as severely corroding the soil or emissions of carbon dioxide compared to other crops.

Bioethanol is produced in 2006 at about 50.1 billion liters worldwide. The world production of biofuels using saccharides, in particular bioethanol, is about 17.7 billion liters (as of 2006), and the main producers are Brazil, India and Taiwan. (Global Bio Energy Partnership (GBEP), 2006). Brazil is actively producing bioethanol for transportation using sugarcane, which is an abundant resource, and various types of ethanol-mixed gasoline (gasohol) are being spread. In 2003, FFV (Flexible Fuel Vehicle), which can operate even if the ethanol and gasoline contents change, began to be sold, and as of May 2005, it accounted for about 50% of the total sales of passenger cars.

Global production of corn-based bioethanol is about 19.8 billion liters (as of 2006), with major producers in the United States, Europe and China, with the United States producing 18.5 billion liters (see Table 1). The United States enacted the Energy Tax Act in 1978, shortly after the oil shock, to expand the supply of gasoline containing less than 10% ethanol to a federal tax cut of $ 4 per gallon. As such, the United States is actively producing biofuels for transportation based on corn, which is a large cropland and abundant resources, and developing advanced energy technologies to escape the oil-dependent economy through the development of renewable energy technologies. As part of its efforts to develop ethanol production technology, the ethanol production base for corn fuel is expanding.

Biofuel manufacturing technology using wood based materials has not yet reached the commercialization stage, so there are no observed industrial trends. However, Canada's Iogen is actively developing manufacturing technology using wood-based biomass, and the US is the next generation biomass, with a budget of $ 150 million in 2007 to commercialize the technology to extract ethanol from agricultural waste and plant raw materials by 2012. The company plans to replace ethanol with 30% of the total transportation fuel.

On the other hand, algae are largely divided into macroalgae and microalgae, and large algae include red algae, brown algae, green algae, microalgae, chlorella and spirulina. Algae have much better growth than other biomass in the past (4 to 6 times a year in the subtropical region), and because of the large seas available, the available cultivation area is large, and the cost of fresh water, land, fertilizer, etc. Has the advantage of using less resources. In addition, in the case of wood, there is no lignin component to be removed, so the manufacturing process of the biofuel is simple, and the total energy conversion yield is high. In addition, algae have an annual uptake of 36.7 tons of carbon dioxide, which is 5 to 7 times higher than that of wood, and the annual greenhouse gas reduction rate is about 27% assuming that E20 (20% ethanol-added gasoline) is used. This translates into approximately $ 300 billion in carbon tax savings (Table 1).

[Table 1] Comparison of Characteristics of Land Plants and Marine Plants

division Land plants Marine plants Sugar / Starch System Wood Seaweed Raw material Sugar cane, corn Timber Barley, flied, kotoni Raw material production cycle 1 ~ 2 times a year At least 8 years 4 to 6 times a year Raw material production per unit area (tons / ha) 180 9 565 CO ₂ absorption per unit area (tons / ha) 5-10 4.6 36.7 Manufacture process simple Complex (Leignin Removal) Simple (no lignin) Cultivation environment Solar, CO ₂ , Freshwater, Land, Fertilizer Solar, CO ₂ , Freshwater, Land, Fertilizer Solar, CO ₂ , Seawater

However, until now, algae have been mainly used in fine chemicals and medical materials such as electrophoretic reagents, fertilizers, emulsifiers, and anticancer agents, or used only as health foods such as edible and medicinal products. to be.

The present invention has been made to improve the problems in the conventional biofuel manufacturing method as described above. By using seaweed as a raw material instead of sugar, starch or wood based raw materials, which are used as raw materials for conventional biofuels, it overcomes the low glycosylation efficiency that occurs when using existing raw materials and uses fermentation upon saccharification using an ionic liquid having acidic groups as an acid glycosylation catalyst. An object of the present invention is to provide a method for preparing a saccharified solution capable of inhibiting or minimizing the production of 5-HMF (5-hydroxymethylfurfural) as an inhibitor and a method for producing a biofuel using the saccharified solution thereof.

The present invention provides a method for producing a saccharified solution that generates monosaccharides by treating an acidic ionic liquid catalyst with a polysaccharide material extracted from seaweeds or seaweeds.

In addition, the present invention is a method for producing a saccharified solution, characterized in that the acidic ionic liquid catalyst is selected from the group consisting of imidazolium, phosphonium, ammonium, morpholinium, choline represented by the following formula (1-5) to provide:

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently C ₁ to C ₈ alkyl, phenyl, benzyl or fluorinated alkyl, and A is SO ₄ , SO ₃ , BH ₃ , n (AlCl ₃ ) (n = 1 or 2), molecules that may have Bronsted acidity such as CF ₃ COO, CH ₃ COO, HPO ₄ , p-CH ₃ (C ₆ H ₄ ) SO _3, and the like.

In addition, the present invention is the acidic ionic liquid catalyst [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] (1-methylimidazolium hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1-alkyl-3-methylimidazolium chloroaluminate) (R = C _It provides a method for producing a saccharified solution, characterized in that selected from the group consisting of ₁ ~ C ₈ ).

In addition, the present invention is that the extraction solvent at the time of extraction is selected from the group consisting of H ₂ SO ₄ , HCl, HBr, HNO ₃ , CH ₃ COOH, HCOOH, HClO ₄ , H ₃ PO ₄ , PTSA and commercial solid acid Provided is a method for producing a saccharified solution.

The present invention also provides a method for producing a saccharified solution, wherein the polysaccharide material is selected from the group consisting of agar, starch, carrageenan, alginic acid and fibrin.

In addition, the present invention provides a method for producing a saccharified solution, characterized in that the algae is a large algae or a microalgae.

In addition, the present invention provides a method for producing a saccharified solution, characterized in that the large algae is selected from the group consisting of red algae, brown algae and green algae.

In addition, the present invention, the red algae wormwood, kotoni, dog gambling, laver, round seaweed, ox radish, buckwheat, green leaf starfish, stalks, jindubal, sesame gambling, spiny radish, silk grass, scabbard, stone star, stone and Jinu It provides a method for producing a saccharified solution, characterized in that selected from the group consisting of Ari.

In addition, the present invention the brown alga is a group consisting of seaweed, kelp, barn horse, minji horse, shellfish, hooked seaweed, seaweed iron, Ecklonia cava, gompi, rhubarb, iron seaweed cousin, mabanban, hoesaeng mabanban, jichung and 이 It provides a method for producing a saccharified solution, characterized in that selected from.

The present invention also provides a method for producing a saccharified solution, wherein the green alga is selected from the group consisting of Cheongtae, Hakkham, green onion, hearing, bead hearing, jade and salt sake.

The present invention also provides a method for producing a saccharified solution, characterized in that the monosaccharide is selected from the group consisting of galactose, galactose derivatives, 3,6-anhydrogalactose, glucose, fucose, rhamnose, xylose and mannose. to provide.

In addition, the present invention provides a method for producing a saccharified solution, characterized in that the monosaccharide is produced by reacting with aerosol at 0 ~ 6 hours at a temperature of 60 ~ 200 ℃ using an acidic ionic liquid catalyst of 0.05 ~ 30% concentration. to provide.

In addition, the present invention is a method for producing a saccharified liquid, characterized in that the monosaccharide is produced by reacting the fiber with an acidic ionic liquid catalyst at a concentration of 0.05 to 50% at a temperature of 80 to 300 ℃ more than 0 to 6 hours. To provide.

In addition, the present invention is a method for producing a saccharified liquid, characterized in that the monosaccharide is produced by reacting with the acidic ionic liquid catalyst at a concentration of 0.05 to 50% with respect to the raw seaweeds at 60 to 300 ℃ temperature for more than 0 to 6 hours To provide.

In addition, the present invention, after the monosaccharide is reacted with the acidic ionic liquid catalyst of 0.05 ~ 50% concentration to the algae vinegar at 60 ~ 300 ℃ temperature for more than 0 to 6 hours, the target for the remaining cellulose or starch Provided is a method for producing a saccharified solution, which is produced by a secondary or tertiary saccharification reaction under reaction conditions.

In addition, the present invention comprises the steps of treating the acidic ionic liquid catalyst to the polysaccharide material extracted from seaweeds or algae to produce monosaccharides; And

In addition, the present invention provides a method for producing a biofuel comprising the step of fermenting the monosaccharides by a microorganism.

The present invention also provides a method for producing a biofuel, characterized in that the biofuel is selected from the group consisting of C ₁ to C ₄ alcohol and C ₂ to C ₄ ketone.

In addition, the present invention is the fermentation microorganisms Saccharomyces cerevisiae, Sarcina ventriculum, Kluyberomyces prasilis, Zygomonas Mobilis, Kluyberomyces maxianus IMB3, Bretanomyces custersii , Clostridium acetobutylicum, Clostridium Baierinkie, Clostridium aurantibutyllicum and Clostridium tetanomorphium are provided. .

Hereinafter, the present invention will be described in detail.

Method for producing saccharified solution of the present invention or method for producing biofuel,

Treating the acidic ionic liquid catalyst with a polysaccharide material extracted from seaweed grass or seaweed to produce monosaccharides; And

Fermenting the monosaccharide by a microorganism.

In the present invention, the biofuel may be C ₁ to C ₄ alcohol, C ₂ to C ₄ ketone, and the like, of which methanol, ethanol, propanol, butanol or acetone is preferable, but is not limited thereto. It is not. In addition, the polysaccharide material may include, but is not limited to, radish, starch, fiber, carrageenan, alginic acid, and the like.

Algae used in the biofuel production method of the present invention can be used without limitation large algae or microalgae, the large algae include red algae, brown algae, green algae and the like, chlorella, spirulina and the like. As the red algae, wood starfish, laver, kotoni, dog gambling, round stone laver, ox radish, buckwheat, green grass, walnut, jindubal, sesame gourd, spiny radish, silk grass, vulgaris, stone star, stone tree, jinari But it is not limited thereto, and among them, it is preferable to use a stump. The most diverse species of red algae are the most diverse and excellent in their growth ability.The dry weight of wormwood is about 15-25% of cellulose, cellulose, and about 50-70% of galaxan-based radish. In addition, it consists of less than 15% 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 used, but are not limited to Cheongtae, Hakkham, blue, auditory, bead hearing, jade, salt-jumping, and the like. Green algae have chlorophyll and make starch by photosynthesis. Looking at the components of brown algae and green algae, brown algae contain about 30-40% of alginic acid and about 5-6% of fibrin, and green algae contain about 40-50% of starch, the main component of carbohydrate, and 5% of fibrin. It contains less than.

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 cellulose-based material, which is about 15-25% of the total content of woodworms. 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 method for extracting polysaccharide materials such as radish, cellulose, starch, carrageenan, alginic acid and the like from the seaweed is not particularly limited, and any method known in the art may be used. According to one preferred embodiment, the seaweeds are immersed in an aqueous alkaline solution for a certain time and washed with water, and the washed seaweeds are immersed in an extraction solvent made of an acidic drug for a predetermined time to extract the radish, carrageenan, alginic acid component, and then remaining fibrin and The step of collecting starch may extract the radish, carrageenan, alginic acid and starch or fiber. At this time, the extraction temperature is not particularly limited, but is preferably in the range of 80 ~ 150 ℃. 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), PTSA (para-toluene sulfonic acid) or a commercial solid. Acids and the like, but is not necessarily limited thereto, and the alkali aqueous solution may include potassium hydroxide, sodium hydroxide, calcium hydroxide, aqueous ammonia solution, but is not necessarily limited thereto.

Monosaccharides can be obtained by treating and saccharifying a hydrolysis catalyst containing an acidic ionic liquid suitable for extracting polysaccharides such as radish, starch, fibrin, carrageenan, alginic acid and the like. The monosaccharides include galactose, 3,6-anhydrogalactose, glucose, fucose, rhamnose, xylose, mannose, and the like, but are not limited thereto.

The saccharification process of the present invention can be broadly divided into a direct saccharification method and an indirect saccharification method. Hereinafter, the two saccharification processes and a biofuel fermentation method using the saccharification liquid obtained therefrom will be described.

First, the indirect glycosylation method is a method of extracting a polysaccharide material from the seaweed herb and then making the polysaccharide material into a monosaccharide. As an example of the saccharification method using the indirect saccharification method, a method of saccharification using a radish as a starting material will be described. In the radish, galactan, a galactose polymer, comprises most of the components, and the galactan may be converted into fermentable monosaccharide galactose or 3,6-anhydrogalactose through an appropriate saccharification process (low molecular weight process). In this case, a hydrolysis method using an acidic ionic liquid catalyst is used for the saccharification process, and as a catalyst which can be used, [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [ HSO ₄ ] (1-methylimidazolium hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1-alkyl-3-methylimidazolium chloroaluminate) (R = C ₁ ~ C ₈ ). At this time, it is preferable that the concentration of the used acid, the reaction temperature and the reaction time are well set so that the saccharification yield of galactose is maximized and the resulting galactose is not decomposed to produce 5-HMF. According to a preferred embodiment of the present invention, the monosaccharide is [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] (1-methylimidazolium) at a concentration of 0.05 to 30% relative to radish. hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1-alkyl- It is produced by reacting for 0-6 hours at a temperature of 60-200 ℃ using an acidic ionic liquid catalyst such as 3-methylimidazolium chloroaluminate) (R = C ₁ ~ C ₈ ).

As a saccharification method using the indirect saccharification method, a method of saccharification using fiber as a starting material will be described. Fibrin is a substance made of cellulose and can be hydrolyzed using an acidic ionic liquid catalyst to be converted into glucose. Catalysts for hydrolyzing cellulose include [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] (1-methylimidazolium hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H2PO4] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1-alkyl-3-methylimidazolium chloroaluminate) (R = C ₁ to C ₈ ) In this case, it is preferable that the glycation yield of glucose is maximized by controlling the concentration of the acid used, the reaction temperature and the reaction time, and the resulting glucose is not decomposed to produce 5-HMF. According to one preferred embodiment of the invention, the monosaccharide is [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] -methylimidazolium hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1- It is produced by reacting with an acidic ionic liquid catalyst such as alkyl-3-methylimidazolium chloroaluminate) (R = C ₁ ~ C ₈ )) at a temperature of 80 to 300 ° C. over 0 to 6 hours. According to another preferred embodiment of the invention,

As a saccharification method using the indirect saccharification method, a method of saccharification using starch as a starting material will be described. Starch is a substance composed of glucose. Acidic ionic liquid catalysts that hydrolyze starch include [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] (1-methylimidazolium hydrogensulfate). , [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1-alkyl-3- methylimidazolium chloroaluminate) (R = C ₁ ~ C ₈ ) can be used, and by controlling the acid concentration, reaction temperature, and reaction time, etc., the maximum glycosylation yield is maximized while glucose is overly degraded. Preferably, 5-HMF is not produced.

The saccharification method using the direct saccharification method uses seaweeds containing all of fibrin and / or agar, carrageenan, or seaweeds containing starch and / or alginic acid and fiber as starting materials, and extracts the above materials without extracting polysaccharides. It is a method of saccharifying directly to monosaccharides. In this case, a hydrolysis method using an acidic ionic liquid as a catalyst may be used. As described above, an acidic ionic liquid catalyst system used in an indirect glycosylation process may be used. At this time, by appropriately adjusting the concentration of the acid catalyst, the reaction temperature and the reaction time, it is necessary to find the conditions for the saccharification yield of the produced glucose and galactose to the maximum, and the reaction conditions for preventing the resulting monosaccharides from being over-degraded to produce 5-HMF. It is important. In the case of saccharifying the algae raw material as a starting material, the collected seaweeds are washed with water to remove impurities and washed. Then, the dried seaweeds are completely dried using a hot air dryer or a natural drying method, and the dried seaweeds are chopped using a raw material grinder. It is preferable to use after converting the particle into a fine powder form. According to one preferred embodiment of the present invention, the monosaccharide is [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] -methylimidazolium hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1- It is produced by reacting more than 0 to 6 hours at a temperature of 60 to 300 ℃ using an acidic ionic liquid catalyst system such as alkyl-3-methylimidazolium chloroaluminate) (R = C ₁ ~ C ₈ ). According to another preferred embodiment of the present invention, the monosaccharide is [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] at a concentration of 0.05 to 50% relative to the algae raw material by using the multistage saccharification method. [HSO ₄ ] (1-methylimidazolium hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1-alkyl-3-methylimidazolium chloroaluminate) (R = C ₁ ~ C ₈ ) was reacted for more than 0 to 6 hours at a temperature of 60 ~ 300 ℃ using a catalyst selected from the group consisting of acidic ionic liquid Then, it is produced by secondary or tertiary glycosylation reaction on the remaining cellulose or starch under the above reaction conditions.

The saccharified solution comprising galactose, 3,6-anhydrogalactose, glucose, or a mixture thereof produced as described above can be converted to bioalcohol using a strain for biofuel fermentation such as yeast. Fermented yeast that can be used in the present invention is Clostridium acetobutylicum (Clostridium acetobutylicum), Clostridium Bayeringki (Clostridium beijerinckii), Clostridium aurantibutylicum (Clostriduim aurantibutylicum) Or Clostridium Tetanomorph (Clostridium tetanomorphum) And the like, but are not limited thereto, and they are more preferable in butanol and acetone fermentation. In addition, Saccharomyces cerevisiae (Saccharomyces cerevisiae), Sarcina Ventriculy (Sarcina ventriculi), Kluyveromyces pragilis (Kluyveromyces fragilis), Zagomonas Mobiles (Zygomomonas mobilis) Or Kluiberomyces maximans (Kluyveromyces marxianus) IMB3, Bretanomyces Custersy (Brettanomyces custersii) May be used, and these are more preferred for ethanol fermentation.

In particular, biobutanol having a gasoline-like component in biofuel is a biobutanol fuel mixture in which the main characteristics satisfy the criteria of a good fuel, including properties such as energy density, volatility control, sufficient octane number, low impurities, etc. Is very similar to gasoline fuel, and the energy density of biobutanol is close to that of unleaded gasoline. Biobutanol, unlike bioethanol, does not generate phase separation even if water is present, and has a low oxygen content, so that biobutanol may be mixed with gasoline at a high concentration.

The method for preparing a saccharified solution using the ionic liquid as an acid saccharification catalyst according to the present invention is 5-HMF (5-hydroxymethylfurfural), which is known as an inhibitor during subsequent microbial fermentation, compared to the conventional saccharification method by acid hydrolysis of seaweed using sulfuric acid. By suppressing or minimizing the production of biofuel using the conventional saccharification liquid can be maximized. In addition, the use of conventional wood-based raw materials do not require the lignin removal process, which is essential, can reduce the process cost, and in addition to glucose, most of the sugar components contained in seaweed such as galactose, 3,6-anhydrogalactose as biofuel It can be converted to lower the production cost of fuel, which can solve the energy resource problem. In addition, the algae has excellent CO ₂ absorption capacity, which contributes to the reduction of nationwide greenhouse gas and actively respond to international environmental regulations. It is economically and environmentally advantageous.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.

In this example, the experiment was performed using the following saccharification device, experimental materials, and analytical methods.

One. Saccharification  Device

A saccharification system consisting of a reactor and a control box for carrying out saccharification experiments is shown in FIG. 1. The reactor was made into a cylinder of 500 ml capacity (effective volume: 400 ml) with an inner height of 12.5 cm and an inner diameter of 7 cm, and a temperature jacket was installed to reach a set reaction temperature. A thermocouple was fitted to measure the temperature inside the reactor and a coolant was circulated to the outside of the reactor to prevent overheating. In order to facilitate sampling during the reaction, high-pressure N ₂ gas can be introduced from the outside of the reactor, an N ₂ gas reservoir and a sample port are installed, and a control box is equipped with an RPM meter, a digital temperature controller, and a pressure gauge. .

2. Experimental Materials

2.1. temperament

In this embodiment, Moroccan loot, Jeju loot, Kotani, kotoni were used as red algae, auditory was used as green alga, and kelp was used as brown algae.

In this embodiment, the experiment was conducted by dividing into direct glycosylation method using the urticaria as a raw material and indirect glycosylation method using the fibrin and the radish separated / extracted from the urticaria as a raw material. For direct saccharification, after washing the distilled water with distilled water, dried at 40 ℃ and pulverized, it was used by powdering into 106, 300 mesh. For the indirect glycosylation method, Umbrella was immersed in a solution of Moroccan loach for a certain time in KOH aqueous solution, washed with distilled water and then semi-dried, extracted with distilled water or ethyl alcohol or methyl alcohol, dried and pulverized at 40 ° C. fibrin is the residual fibrin that two times (1h / 1 times) after the bleaching and twice (1.5h / 1 times) bleached with CIO ₂ eseo 60 ℃, H ₂ O ₂ at 80 ℃ with O ₃ after the extraction of the agar Bleached twice (1h / 1 time) was used.

2.2. Strains and Media

In this example, Saccharomyces cerevisiae DKIC413 and Bretanomyces custersii kccm 11490 were used, and <YAPD medium (yeast extract 10 g / ℓ), as a culture medium <purchased by the Korean spawn association> peptone 20 g / l, dextrose 20 g / l). The medium was used after sterilization at 121 ° C. for 15 minutes in a high pressure reactor (Woosung Scientific co., Korea).

3. Analysis method

3.1. Sugar analysis

The saccharified solution was analyzed using HPLC equipped with a current detector (ICS-3000, Dionex Co., USA), Carbopac PA 1 (4250 mm, Dionex Co., USA) and Carbopac PA 1 (450 mm, Dionex Co.) , USA) was used as a column. The mobile phase used a 16 mM NaOH solution, the flow rate was 1 ml / min and the column temperature was 30 ° C. Glucose and galactose concentrations were quantitatively analyzed using calibration curves of standards, and the yields of glucose and galactose were calculated as the yields of glucose and galactose produced relative to the total carbohydrates contained in the dry feed according to Equation 1.

C = concentration of glucose or galactose (g / l)

V = Total amount of solvent used for saccharification (ℓ)

S = total carbohydrate in dry ingredients (g)

3.2. Protein analysis Semi - micro Kjeldahl method)

To analyze the protein, 0.5 g of the sample was taken and placed in a protein digestion tube, whereupon 20 ml of sulfuric acid and a decomposition promoter (K ₂ SO ₄ : CuSO ₄ 5H ₂ 0 = 9: 1) 5 g was added to decompose the protein. After the decomposition was completed, 70 ml of distilled water was added, 75 ml of 32% NaOH was added to the distillation, and then distilled using a protein distillation apparatus. Ammonia generated by distillation was collected with 100 ml of 3% boric acid and then titrated with 0.1 N HCl to calculate the total nitrogen content according to Equation 2.

V ₀ = 0.1 N HCl consumption of blank sample (ml)

V ₁ = 0.1 N HCl consumption (mL) of this sample

f = Factor of 0.1 N HCl

N = nitrogen coefficient

s = sample amount (mg)

0.0014: Nitrogen amount (g) corresponding to 1 ml of 0.1 N HCl

3.3. Ash analysis (dry painting method)

The crucible was heated in a 550 ° C. incineration furnace until weighed, then cooled in a desiccator and weighed. 2 g of the sample was placed in a weighed crucible and incubated in a 550 ° C. incinerator until white or off-white ash remained, then cooled to 200 ° C. in the incinerator, transferred to a desiccator, and cooled to room temperature. Ash content (%) was calculated according to equation (3).

W ₁ = Container dose in grams

W ₀ = Container after ashing + ash (g)

S = sample weight (g)

3.4. Cell concentration measurement

Cell concentration was measured at 600 nm using a spectrophotometer (Genesys 10-S, Thermo electron corp., USA). The amount of the dried cells was centrifuged at 3,500 rpm for 10 minutes using a centrifuge (VS-150FN, Vision Science Co., LTD., Korea), and the concentrated solution was washed again with distilled water and centrifuged. It measured by drying at 50 degreeC for 24 hours. The dry cell weight is the dry cell weight of Saccharomyces cerevisiae = 0.3135 absorbance + 0.1811 (correlation coefficient = 0.994), and the dry cell weight of Bretanomyces custersii = 0.1292 absorbance + 0.8554 (correlation coefficient) = 0.999).

3.5. Ethanol analysis

Ethanol concentration in the culture was analyzed using HPLC equipped with RI detector (Breeze HPLC system, Waters Co., USA), the column was Aminex HPX-87H (3007.8 mm, Bio-rad). 5 mM sulfuric acid solution was used for the mobile phase, the flow rate was 0.6 ml / min, the temperature of the column and the RI detector was set to 50 ° C, and the ethanol concentration was quantitatively analyzed using the calibration curve of the standard.

Example  1. Fibers according to seaweeds and Galactan  Ingredient analysis

0.3 g of seaweeds (moroccan loaf, Jeju loaf, skewer, kotoni, auditory, seaweed, kelp) and 3 ml of sulfuric acid solution were added to a glass tube and reacted at 30 ° C. for 2 hours (first hydrolysis). At this time, the glucose and D-galactose were used for the determination of 72% sulfuric acid concentration, and for the determination of 3,6-anhydrogalactose, sulfuric acid concentration of 1% was used to prevent overdegradation. After the reaction, the reaction solution was placed in a 250 ml bottle and 84 ml of distilled water was added and hydrolyzed at 121 ° C. for 1 hour using a high pressure reactor (VS-150FN, Vision Science Co., LTD., Korea) (2 Secondary hydrolysis). After the hydrolysis, take out the bottle when the internal temperature of the high-pressure reactor is 50 ℃, leave it at room temperature, cool it, take 1 ml of this, neutralize with CaCO ₃ and centrifuge (VS-150FN, Vision Science Co., LTD., Korea), and centrifuged at 8,000 rpm for 10 minutes to analyze the cellulose and galactan components.

As a result, as shown in Table 2, depending on the type of seaweed, even the same species showed the difference in the content of the components, the carbohydrate content was the highest in the 70 ~ 80% of the larvae (Morocco, Jeju) Seaweed was the lowest at 41%. In addition, the content of non-hydrated carbohydrate (protein, lipid and other) was the highest in seaweed (59%), and the lowest in the woodworm (Moroccosan, Jeju) was 20-28%, so the red algae was most efficiently used as an ethanol production source. Confirmed that it can. Therefore, in the subsequent experiments, a saccharification / fermentation experiment was performed by selecting a Moroccan loot with a relatively high carbohydrate content.

[Table 2] Chemical Composition of Seaweeds

Seaweed Cellulose (%) Galactan (%) (carbohydrate) (%) protein (%) Other (geological, ash) (%) Red algae Lobsterfish (Morocco) 16.6 58.6 (Gal: 25.6%, AHG: 33.0%) 75.2 17.9 6.9 Wumu 0 88.5 (Gal: 37.5%, AHG: 51.0%) 88.5 7.1 4.4 fibrin 99.7 0 99.7 0.2 0.1 Utsukasari (Jeju) 23.0 56.4 79.4 11.8 8.8 Flirt 19.7 54.4 74.1 11.0 14.9 Kotoni 7.1 43.4 50.5 4.9 44.6 Green algae ear 10.9 47.8 58.7 34.7 6.6 Brown algae Seaweed 2.4 38.7 41.1 24.2 34.7 Kelp 6.7 40.0 46.7 12.2 38.1

Example  2. Sulfate Catalyst and Ionic Liquid Saccharification  Experimental fertilizer

2.1. Indirect glycosylation

2.1.1. Influence by type of catalyst

The yield of saccharification according to the type of catalyst was compared using the separated dried radish as a substrate. The monosaccharides that can be produced because of the substrate are galactose and 3,6-anhydrogalactose (3,6-AHG). 5 g (S / L = 5%) or 10 g (S / L = 10%) of substrate and 10.7, 13.8 wt% of [bmim] [HSO4] (Abdol R. Hajipour et al., Catalyst communication 9, 89-96, 2008) or 100 ml of sulfuric acid and water were placed in a 250 ml Erlenmeyer flask, and the reaction was carried out at 121 ° C. for 15 minutes. , USA), where S / L is the solid / liquid ratio. Table 3 compares the yields of galactose, 3,6-anhydrogalactose and 5-HMF produced according to the type of catalyst under conditions of 121 ° C. for 15 minutes. Yield is the maximum convertible concentration calculated based on the component analysis results of D-galactose 37.5% and 51,3,6-anhydrogalactose 51% in radish (Table 2), when S / L = 5%, D-galactose 27.3 g / L, 3,6-anhydrogalactose 37.1 g / L in yield 100%, for S / L 10%, D-galactose 36.41 g / L, 3,6-anhydrogalactose 49.52 g / L Was derived with a yield of 100%.

Experimental results showed that when sulfuric acid was used as a catalyst at S / L = 5%, the production of galactose and 3,6-anhydrogalactose was 24.3 g / L (16.6 g / L + 7.70 g / L) at 10.7 wt% of the catalyst. ), 20.04 g / L (17.81 g / L + 2.23 g / L) at 13.8 wt% of catalyst, but the yield when using [bmim] [HSO ₄ ] (1-butyl-3-methylimidazolium hydrogenesulfate) was 10.7 Not only is 1.8 times as high as 31.4 g / L (10.70 g / L + 20.70 g / L) at wt% and 36.5 g / L (13.8 g / L + 22.65 g / L) at 13.8 wt% of catalyst, but also [bmim] [ When HSO ₄ ] is used, the amount of 5-HMF, a fermentation-inducing substance, is also significantly reduced when sulfuric acid is used (4.29-5.10 g / L → 0.05 ~ 0.08 g / L). This trend was also the same when S / L = 10% (Tables 3 and 4).

[Table 3] Comparison of Monosaccharide and 5-HMF Formation Using Sulfuric Acid Catalyst and Ionic Liquid Catalyst as Substrate (S / L = 5%)

catalyst Yield,% (g / L) Kinds wt% D-galactose 3,6-L-AHG 5-HMF H ₂ SO ₄ 10.7 91.4 (16.60) 31.1 (7.70) 10.0 (4.29) 13.8 97.9 (17.81) 9.0 (2.23) 11.9 (5.10) [bmim] [HSO ₄ ] 10.7 58.8 (10.70) 83.6 (20.70) 0.1 (0.05) 13.8 73.5 (13.38) 91.5 (22.65) 0.2 (0.08)

[Table 4] Production of Monosaccharides and 5-HMF using Sulfuric Acid Catalyst and Ionic Liquid Catalyst as Substrates (S / L = 10%)

catalyst Yield,% (g / L) Kinds wt% D-galactose 3,6-L-AHG 5-HMF H ₂ SO ₄ 10.7 88.2 (32.11) 30.8 (11.44) 11.5 (9.88) 13.8 89.6 (32.62) 8.8 (3.27) 13.8 (11.86) [bmim] [HSO ₄ ] 10.7 61.0 (22.21) 75.6 (28.08) 0.3 (0.23) 13.8 71.8 (26.14) 77.6 (28.82) 0.4 (0.37)

2.1.2. Effects of Acidic Ionic Liquid Types

To compare the yield per product according to the type of acidic ionic liquid, [bmim] [HSO ₄ ] (1-butyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] (1-methylimidazolium hydrogensulfate), [bmim] [HSO ₄ ] (1-butyl-3-methylimidazolium hydrogenesulfate) was carried out in an autoclave for 15 minutes at S / L = 10%, 121 ° C. (Table 5).

[Table 5] Production of Monosaccharides and 5-HMF using Sulfuric Acid Catalyst and Ionic Liquid Catalyst as Substrates (S / L = 10%)

catalyst Yield,% (g / L) Kinds wt% D-galactose 3,6-L-AHG 5-HMF [bmim] [HSO ₄ ] 10.7 61.0 (22.21) 75.6 (37.44) 0.3 (0.26) [Ammonium] [HSO ₄ ] 62.3 (22.68) 76.6 (37.93) 0.2 (0.17) [Phosphonium] [HSO ₄ ] 63.0 (22.94) 77.6 (38.43) 0.3 (0.26) [choline] [HSO ₄ ] 60.8 (22.14) 74.8 (37.04) 0.2 (0.17)

2.2. Fibrin Indirect glycosylation

Using the isolated dry fibers as a substrate, the saccharification yield according to the catalyst type was compared. Since the substrate is unagar, the monosaccharide that can be produced is glucose. 20 g of the substrate (S / L = 5%) and 10 wt% of [bmim] [HSO ₄ ] or sulfuric acid and 400 ml of water were added to a 500 ml autoclave for 15 minutes at 210 ° C. After termination, the saccharified solution lowered to room temperature was neutralized and analyzed by HLPC (ICS-3000, Dionex Co., USA). Table 6 compares the yield of glucose and 5-HMF produced according to the type of catalyst. The yield of D-glucose was derived from 100 g of 48 g / L, the maximum convertible concentration calculated on the basis of 99.7% of D-glucose (Table 2), which is a component analysis result in the cellulose. In other words, the amount of D-glucose produced when the saccharification was performed using the raw fiber 50 sulfuric acid as a catalyst yielded a yield of 47.5% at 22.79 g / L, but the amount produced when [bmim] [HSO ₄ ] was used was 28.96 g / L. The yield of 60.3% was shown as L, and the amount of 5-HMF produced was significantly reduced to 6.8 g / L when sulfuric acid was used as catalyst and 0.41 g / L when [bmim] [HSO ₄ ] was used. (Table 6).

[Table 6] Production of Monosaccharides and 5-HMF using Sulfate Catalyst and Ionic Liquid Catalyst as Fiber Substrate (S / L = 5%)

catalyst Yield,% (g / L) Kinds wt% D-glucose 5-HMF H ₂ SO ₄ 10 47.5 (22.79) 14.1 (6.8) [bmim] [HSO ₄ ] 60.3 (28.96) 0.9 (0.41)

2.3. Multi-level using raw grass Saccharification

Saccharification yield according to catalyst type was compared using Moroccan loot as a substrate. Monosaccharides that can be produced because the substrate is a native fern are D-galactose, 3,6-anhydrogalactose (3,6-AHG), D-glucose. 10 g of the substrate (S / L = 10%) and 10 wt% of [bmim] [HSO ₄ ] or sulfuric acid and 100 ml of water were added to a 250 ml Erlenmeyer flask, followed by reaction at 121 ° C. for 60 minutes. After termination, the saccharified solution lowered to room temperature was neutralized and analyzed by HLPC (ICS-3000, Dionex Co., USA). Table 7 compares the yields of galactose, glucose and 3,6-anhydrogalactose and 5-HMF produced according to the type of catalyst at 121 ° C. for 60 minutes. The yield of monosaccharide was calculated as the maximum convertible concentration of D-glucose 15.5 based on the component analysis results of D-glucose 16.6%, D-galactose 25.6%, 3,6-anhydrogalactose 33.0% g / L, D-galactose 23.8 g / L, 3,6-anhydrogalactose 30.7 g / L were derived as the yield 100%. When glycosylated using sulfuric acid as a catalyst, the amounts of D-glucose and D-galactose and 3,6-anhydrogalactose were 0.19 g / L, 19.1 g / L, and 6.23 g / L, respectively, while [bmim] [HSO ₄ ] was about twice as high as 0.17 g / L, 20.1 g / L, and 27.8 g / L, respectively. In addition, when [bmim] [HSO ₄ ] was used, 5- The production of HMF is also 97% lower than when using sulfuric acid (7.35 g / L → 0.21 g / L) (Table 7). However, in the case of D-glucose, the yield was very low (1%) because the saccharification temperature did not satisfy the fiber saccharification conditions (about 200-220 ° C.). The results are shown in Table 8. As a result, as shown in Table 8, when [bmim] [HSO ₄ ] is used, the yield was 27.91 g / L, yielding 57.9%, and 5-HMF was produced when sulfuric acid was used as a catalyst. When 7.85 g / L and [bmim] [HSO ₄ ] were used, it was found that the reduction was 96% to 0.34 g / L.

[Table 7] Production of Monosaccharides and 5-HMF using Sulfate Catalyst and Ionic Liquid Catalyst as Raw Materials (S / L = 5%)

catalyst Yield,% (g / L) Kinds wt% D-glucose D-galactose 3,6-L-AHG 5-HMF H ₂ SO ₄ 4.8 1.2 (0.19) 80.3 (19.1) 20.3 (6.23) 10.5 (7.35) [bmim] [HSO ₄ ] 4.8 1.1 (0.17) 84.6 (20.1) 90.6 (27.8) 0.3 (0.21)

[Table 8] Comparison of Monosaccharide and 5-HMF Production using Sulfate Catalyst and Ionic Liquid Catalyst as Residual Fiber as Substrate (S / L = 5%)

catalyst Yield,% (g / L) Kinds wt% D-glucose 5-HMF H ₂ SO ₄ 10 40.6 (19.60) 16.3 (7.85) [bmim] [HSO ₄ ] 57.9 (27.91) 0.7 (0.34)

Example  3. Ethanol Production Culture

3.1. On the saccharification method  Growth Characteristics of Different Fermentation Strains

An experiment was performed to compare the growth pattern of the ethanol producing strain, Bretanomyces custersii, for the saccharified solution using sulfuric acid prepared in Example 2 and the saccharified solution using the ionic liquid of the present invention. Figure 3 shows the growth curve of Bretanomyces custersii in the saccharification solution using sulfuric acid and the saccharification solution using [bmim] [HSO ₄ ]. In the case of saccharified solution using sulfuric acid (5-HMF concentration: 4.29 g / L), the cell concentration was 1.4 (OD600 nm). However, saccharified solution using [bmim] [HSO ₄ ] was used. Concentration: 0.05 g / L) showed a high growth rate of 4 cells (OD600 nm) in the experiment, so that saccharified solution using sulfuric acid with high concentration of 5-HMF was less fermented than ionic liquid. It was confirmed that the growth of the strain is inhibited due to the presence of the substance 5-HMF, whereas the saccharified solution using the ionic liquid was confirmed that the strain grows well without such fermentation inhibitory action.

3.2. Saccharification  Fermentation

4 and 5 show the results of fermentation when the brethan solution using sulfuric acid and the brethan solution using the catalyst [bmim] [HSO ₄ ] of the present invention as a strain. In the case of saccharified solution using sulfuric acid (5-HMF concentration: 4.29 g / L), the sum of the concentrations of D-glucose and galactose (D-galactose + 3,6-AHG) is 15 g after 50 hours at 50 g / L. Ethanol was produced at 6.2 g / L while being consumed as / L, but when the saccharified solution using sulfuric acid was used in the experiment on the saccharified solution (5-HMF concentration: 0.05 g / L) using [bmim] [HSO ₄ ] As the monosaccharide was consumed faster, the monosaccharide concentration was consumed as 3.2 g / L after 48 hours at 50 g / L, resulting in twice as much ethanol as 12.3 g / L. In the case of saccharified solution using sulfuric acid with high concentration of 5-HMF, it was confirmed that the production of ethanol was reduced due to the growth inhibition effect of the strain due to the presence of 5-HMF, which is a fermentation inhibitor, than the ionic liquid. In the case of saccharification liquid using a sex liquid, it was confirmed that ethanol was produced without this inhibitory effect.

1 is a schematic representation of a glycosylation device, comprising: (a) batch reactor, (b) sampling port, (c) pressure gauge, (d) N ₂ gas regulator, (e) N ₂ gas cylinder, (f) control box and (g) a N ₂ gas reservoir.

2 is a chemical structural formula showing the binding structure of agarose.

3 shows a growth curve of Bretanomyces custersii in a saccharified solution using sulfuric acid and a saccharified solution using [bmim] [HSO ₄ ] as a catalyst of the present invention.

4 and 5 show ethanol fermentation results when Bretanomyces custerssie was used as a strain for saccharification solution using sulfuric acid and saccharification solution using [bmim] [HSO ₄ ], respectively. In the figure, glucose represents D-glucose, and galactose represents the sum of D-galactose and 3,6-AHG.

Claims (18)

A method of producing a saccharified solution in which monosaccharides are produced by treating an acidic ionic liquid catalyst with a polysaccharide material extracted from seaweeds or seaweeds. The method according to claim 1, The acidic ionic liquid catalyst is a method for producing a saccharified solution, characterized in that selected from the group consisting of imidazolium, phosphonium, ammonium, morpholinium, choline represented by the following formula 1-5: [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

Wherein R ¹ , R ² , R ³ , and R ⁴ are each independently C ₁ to C ₈ alkyl, phenyl, benzyl or fluorinated alkyl, and A is SO ₄ , SO ₃ , BH ₃ , n (AlCl ₃ ) (n = 1 or 2), molecules that may have Bronsted acidity such as CF ₃ COO, CH ₃ COO, HPO ₄ , p-CH ₃ (C ₆ H ₄ ) SO _3, and the like. The method according to claim 1, The acidic ionic liquid catalyst is [Rmim] [HSO ₄ ] (1-alkyl-3-methylimidazolium hydrogenesulfate), [Hmin] [HSO ₄ ] (1-methylimidazolium hydrogensulfate), [Rmin] [TFA] (1-alkylimidazolium triflouroacetate ), [Rmim] [H ₂ PO ₄ ] (1-alkyl-3-methylimidazolium dihydrogenphosphate), [Rmim] [Al ₂ Cl ₆ ] (1-alkyl-3-methylimidazolium chloroaluminate) (R = C ₁ -C ₈ ) Method for producing a saccharified solution, characterized in that selected from the group consisting of. The method according to claim 1, The extraction solvent in the extraction is H ₂ SO ₄ , HCl, HBr, HNO ₃ , CH ₃ COOH, HCOOH, HClO ₄ , H ₃ PO ₄ , PTSA and a saccharified solution, characterized in that selected from commercial solid acids Method of preparation. The method according to claim 1, The polysaccharide material is a method of producing a saccharification liquid, characterized in that selected from the group consisting of agar, starch, carrageenan, alginic acid and fibrin. The method according to claim 1, The seaweed is a method of producing a saccharification liquid, characterized in that large algae or microalgae. The method according to claim 6, The large alga is a method of producing a saccharification liquid, characterized in that selected from the group consisting of red algae, brown algae and green algae. The method according to claim 7, The red algae is from the group consisting of wood starfish, kotoni, dog gambling, laver, round stone seaweed, daikon radish, buckwheat, green grass fern, pods, jindubal, sesame gourd, thorn radish, silk grass, vinegar, stone star, stone tree and zinnia Method for producing a saccharified solution, characterized in that selected. The method according to claim 7, The brown alga is characterized in that selected from the group consisting of brown seaweed, kelp, barn horse, folk eggplant, shellfish, hooked seaweed, seaweed, Ecklonia cava, gompi, rhubarb, iron seaweed cousin, mabanban, hoesan mabanban, jichung and 톳 The manufacturing method of the saccharification liquid made into. The method according to claim 7, The green alga is a method of producing a saccharification liquid, characterized in that selected from the group consisting of Cheongtae, Hakkham, green, hearing, bead hearing, jade and salt juju. The method according to claim 1, The monosaccharide is a method of producing a saccharification liquid, characterized in that selected from the group consisting of galactose, galactose derivatives, 3,6- anhydrogalactose, glucose, fucose, rhamnose, xylose and mannose. The method according to claim 1, The monosaccharide is a method for producing a saccharification solution, characterized in that produced by reacting with aerosol in the presence of 0 to 6 hours at 60 ~ 200 ℃ temperature using an acidic ionic liquid catalyst of 0.05 ~ 30% concentration. The method according to claim 1, The monosaccharide is a method for producing a saccharification solution, characterized in that produced by reacting the fiber with an acidic ionic liquid catalyst at a concentration of 0.05 to 50% at a temperature of 80 to 300 ℃ more than 0 to 6 hours. The method according to claim 1, The monosaccharide is a method for producing a saccharified solution, characterized in that produced by reacting with an acidic ionic liquid catalyst at a concentration of 0.05 to 50% with respect to the raw seaweeds at a temperature of 60 to 300 ℃ more than 0 to 6 hours. The method according to claim 1, The monosaccharide was reacted with an acidic ionic liquid catalyst at a concentration of 0.05 to 50% with respect to the algae raw material at 60 to 300 ° C. for more than 0 to 6 hours, and then, in the reaction conditions for the remaining cellulose or starch, Or a saccharification solution produced by tertiary saccharification. Treating the acidic ionic liquid catalyst with a polysaccharide material extracted from seaweed grass or seaweed to produce monosaccharides; And Fermenting the monosaccharides by the microorganisms. 18. The method of claim 16, The biofuel is a method of producing a biofuel, characterized in that selected from the group consisting of C ₁ to C ₄ alcohol and C ₂ to C ₄ ketone. 18. The method of claim 16, The fermentation microorganisms are Saccharomyces cerevisiae, Sarcina ventriculum, Kluyveromyces pragilis, Zygomonas mobilis, Kluyberomyces maximaus IMB3, Bretanomyces custersii, Clostridium aceto A method for producing a biofuel, characterized in that it is selected from the group consisting of butyricum, Clostridium Baieringki, Clostridium aurantibutylricum and Clostridium tetanomorphium.

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