KR20160112109A - Method of Producing Biomass Hydrolysate by Using Solid Acid Catalyst - Google Patents

Abstract

The present invention relates to a method for producing a biomass-derived saccharification liquid using a solid acid and a liquid acid catalyst. More specifically, the present invention relates to a method for producing a biomass-derived saccharification liquid, involving the production of monosaccharide from solid biomass using both solid acid and liquid acid. According to the present invention, since solid acid is used as the catalyst in the saccharification liquid production method, separation of saccharification liquid and solid acid becomes easy, and thus devices used for neutralization or base separation requiring huge costs are not needed. In addition, the method also ensures excellent saccharification efficiency compared to the case involving a single use of the solid acid or the liquid acid respectively. Thus, method can be useful to produce saccharification liquid with low costs.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a biomass-derived saccharified liquid using a solid acid catalyst,

The present invention relates to a process for producing a biomass-derived glycosylated liquid using a solid acid as a main catalyst, and more particularly, to a process for producing a biomass-derived glycosylation product by using a minimal amount of liquid acid as a co- And a method for producing the biomass-derived saccharified liquid.

Currently, raw materials (substrates) used in bio-energy and compound production are mostly sugars obtained from cereal-derived starch or tropical crops. In the United States, most bioethanol is produced from glucose, which is obtained by hydrolyzing corn starch, and Brazil produces bioethanol from sugar from sugar cane. However, the use of food crops for human consumption as an energy source is criticized at a time when a considerable number of humans are suffering from food shortages, and because it fails to meet the demand for bioethanol, which will increase rapidly in the future, Respectively. Therefore, research on the production of bioenergy using microalgae biomass resources which can not be used as raw materials but used by human beings as a stable source of bioenergy resources is under way (Ge., Renewable Energy (2009); Lee, J. Korean Ind., 36: 84-89 (2011); Harun., Renewable and Sustainable Energy Reviews, In press: 2011; Adams., J. Appl. Phycol., 21: 569-574 Ueno, J. of Fermentation and Bioengineering, 86 (3): 290-295 (2009); Isa., J. of the Japan Institute of Energy, 88: 912-917 1: 38-43 (1998); Brennan Owende, Renew, Sustain. Energy Rev. 14: 557-577 (2010); John., Bioresource Technology, 102: 186-193 (2011); : 5330-5336 (2010)).

Woody biomass is a complex of 40-50% of cellulose, 25-35% of hemicellulose and 15-20% of lignin. Here, cellulose is tightly enclosed by lignin and hemicellulose, and it is difficult to pre-treat and saccharify due to the crystalline structure of cellulose. Currently, physico-chemical methods such as dilute acid hydrolysis, steeping or ateam explosion (STEX), ammonia fiver expansion (AFEX), wet oxidation (WO), and hot water pretreatment are known for pretreatment and saccharification of biomass.

Microalgae are freshwater species that grow in freshwater and marine microalgae that grow in seawater. In particular, microalgae containing a large amount of various kinds of carbohydrates such as starch can be produced by saccharification of various monosaccharides such as glucose, xylose, galactose or mannose Can be produced.

Major algal species are red algae, brown algae and green algae, and red algae, brown algae, and green algae can be decomposed into various sugars through saccharification process. Firstly, the green algae consist mainly of cellulose, mannose, xylane, starch, fructan, etc. The red algae are composed of galactan, agar, Carrageenan, xylan, mannan, etc., and brown algae are composed of alginate, fucoidan, laminaran, and the like. As such, the giant algae are composed of a wide variety of polysaccharides, so a saccharification process is needed to disassemble them.

In addition to these woody biomes, algae (microalgae and giant algae), which are recently attracting attention as new natural resources, have a higher growth rate than the other biomass, so that they can be harvested four to six times a year, Competition with crops and the encroachment of cultivated land are also unnecessary. In addition, it is much more competitive than other biomass because it has a wide area of available cultivation due to the use of wide seas and little production cost. In addition, marine algae has an annual carbon dioxide absorption of 36.7 tonnes per hectare, which is 5 to 7 times higher than lignocellulosic carbon dioxide.

Comparison of 1,2,3 generation biomass (Source: Korea Institute of Industrial Technology) Sugar- and Starch-
based biomass
(1 ^st generation) Wood-based biomass
(2 ^nd generation) Marine algae
(3 ^rd generation) Raw material Sugarcane, corn wood Chlorella ,
Gelidium amansii Harvest interval 1 2 times / year At least 8 years 4 6 times / year Yield / unit area
[tons / ha] 180 9 565 CO ₂ absorption / unitare [tons / ha] 5 10 4.6 36.7 Production process Simple Complex
(lignin elimination) Simple
(lignin absent) Cultivation environment Sunlight, CO2,
irrigation water, soil fertilizer Sunlight, CO ₂ , irrigation water, soil
fertilizer Sunlight, CO ₂ ,
marine water

For the saccharification of such biomass, ionic liquid, strong acid, strong base, etc. are used as catalysts. It is difficult or practically impossible to separate these catalysts from glycans and recycle them. Particularly, when acid or alkali is used, a neutralization process is required as a follow-up process. In addition, there may be a need to remove a large amount of salt generated during the neutralization process, resulting in additional material cost and process cost. Even if the neutralization process is not necessary, the acid and alkali catalysts are burdened to the environment when they are released. Therefore, it is absolutely necessary to use a catalyst which can be easily separated from the glycation solution after the reaction and can be recycled, and which does not require subsequent treatment steps such as neutralization, desalting and the like.

Korean Patent Laid-Open Publication No. 2013-0001627 discloses a method of pretreating brown algae with an imidazolium-based ionic liquid and hydrolyzing the same with a liquid acid catalyst to extract the sugar. The yield is higher than when the liquid acid catalyst alone is used, but it is necessary to neutralize the content of the liquid acid to 10 to 30 wt% of the algae content.

Korean Patent Registration No. 1254662 describes a method for producing a high glucose-containing glycoside from a horse and algae biomass using a catalyst. This patent directly obtains a high concentration of monosaccharide through enzymatic hydrolysis or chemical hydrolysis from algae without special pretreatment. However, as a catalyst for hydrolysis, a liquid acid such as sulfuric acid, nitric acid, hydrochloric acid, or a liquid such as sodium hydroxide, potassium hydroxide It is disadvantageous in that an additional neutralization process is required.

Korean Patent Laid-Open Publication No. 2009-0039470 describes the glycation method of woody biomes using acid catalyst and supercritical water. In the present invention, the saccharification time is shortened by using the supercritical water. Liquid acid catalyst is used, so that an additional neutralization process is required and the separation process is complicated when the supercritical water is regenerated.

As a result, the inventors of the present invention have found that there is no need for a subsequent step of neutralization and desalting in order to supplement the saccharification performance insufficient as solid acid alone, while using a solid acid catalyst that can be recovered after re- By using a small amount of liquid acid catalyst as a co-catalyst, the present inventors have accomplished the present invention. As a result, a method has been developed which can remarkably improve the economical efficiency of the saccharification process by reducing the cost required for the subsequent neutralization and desalination processes, while the saccharification efficiency is higher than in any case where the solid acid catalyst and the liquid acid catalyst are used alone .

It is an object of the present invention to provide a method for producing a biomass-derived saccharified liquid having a saccharification efficiency and an economical efficiency simultaneously by using a solid acid as a main catalyst and using a small amount of liquid acid as an auxiliary catalyst.

In order to achieve the above object, the present invention provides a process for producing a biomass catalyst comprising the steps of: (a) introducing a biomass feedstock, a solid acid catalyst and a liquid acid catalyst into a reactor; (b) heating the reactor to sacrifice the biomass to produce a saccharified solution; And (c) separating the solid acid catalyst from the glycated solution prepared in the step (b).

In order to increase the saccharification efficiency of the solid acid catalyst while using the solid acid catalyst as the main catalyst, a small amount of the liquid acid catalyst is used in parallel, and the liquid acid takes charge of the liquefaction of the solid raw material and the saccharification of the solid acid catalyst.

Since the method for producing a saccharified liquid according to the present invention uses a solid acid as a catalyst, the saccharified liquid and the solid acid can be easily separated from each other, which makes it possible to recycle the saccharified liquid, The saccharification efficiency is excellent as compared with the case of using only a solid acid or a liquid acid so that the production cost of biomass saccharified liquid can be greatly reduced.

FIG. 1 is a graph showing the results of saccharification reaction of Golenchinae using 9.23 g / L amber list 36 and nitric acid according to each concentration.
Fig. 2 is a graph showing the results of saccharification reaction of Golenchnia using 0.01 N nitric acid and 9.23 g / L amberlest.
FIG. 3 is a graph showing the glycation reaction results of Golenchnia using 0.05 N nitric acid and 9.23 g / L amberlest.
4 is a graph showing a saccharification reaction result of cellulose using 0.05 N nitric acid and 9.23 g / L amberlest.
FIG. 5 is a graph showing the production result of 2,3-BDO from Saccharomyces cerevisiae saccharides treated with 0.01 N nitric acid.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, a glycation solution was prepared using solid acid and liquid acid, and it was confirmed that the glycated liquid and the solid acid can be easily separated from each other and the saccharification efficiency is superior to that of a single use of solid acid.

In one embodiment of the present invention, the microbial feedstock, the solid acid, and the liquid acid catalyst are added to a stainless steel reactor to perform the glycation reaction. The saccharification rate is increased compared to the case where the solid acid catalyst or the liquid acid catalyst is used alone .

Accordingly, in one aspect, the present invention provides a process for the preparation of a biomass feedstock comprising: (a) feeding a biomass feedstock, a solid acid catalyst and a liquid acid catalyst into a reactor; (b) heating the reactor to sacrifice the biomass to produce a saccharified solution; And (c) separating the solid acid catalyst from the glycated liquid prepared in the step (b). The present invention also relates to a method for producing a biomass-derived glycated solution using the solid acid and liquid acid catalyst.

In the present invention, the biomass feedstock may be microalgae, microalgae dry powder or microalgae residues, woody biomass, or giant algae biomass. Microalgae can be used in the form of a primate, preferably in the form of a dry powder for ease of transportation, storage and reaction. Residues of microalgae in the presence of carbohydrates can also be used. Various types of biomass such as woody biomass and giant algae are available.

In the present invention, the microalgae are selected from the group consisting of Nannochloropsis sp ., Golenkinia sp ., Aurantiochytrium sp ., Schizochytrium sp . ), Chlorella sp ., Spirulina sp ., Dunaliella sp ., Botryococcus sp ., Thraustochytrium sp ., Zapono sp . Such as Japanese chrysanthemum spp ., Japonochytrium sp ., Ulkenia sp. , Crypthecodinium sp ., Haliphthoros sp. , Chlamydomonas sp. sp .) and the genus Porphyridium sp .) may be one or more selected from the group consisting of The microalgae producing carbohydrates in the glycation reaction using biomass can be used without limitation, but it is more preferable to use the microalgae among the microalgae.

In the present invention, the macro alga may be at least one selected from the group consisting of red algae, brown algae and green algae. Giant algae are classified into red algae, brown algae, and green algae. In the present invention, giant algae producing carbohydrate as a raw material of saccharified liquid can be used without limitation.

In the present invention, the wood-based biomes may be at least one selected from the group consisting of corncob, corn stover, wood chip, wood pellet, and waste wood. have. Woody biomass is divided into herbaceous biomass and tree-based biomass, which produces a large amount of herbaceous biomass, and it is preferable to use corn that is discarded as waste. Especially, corncobs and cornstarchs that are discarded after harvesting corn from corn can be used without limit. Wood-based biomass may also use wood chips or lignocellulosic pellets for the convenience of transportation or use of waste wood.

In the present invention, the solid acid catalyst is kaolinite (kaolinite), bentonite (bentonite), attapulgite (attapulgite), zeolite (zeolite), montmorillonite (montmorillonite), zinc oxide (ZnO), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO _2), cesium oxide (CeO _2), vanadium oxide (V ₂ O _5), silicon oxide (SiO _2), chromium oxide (Cr ₂ O _3), calcium sulfate (CaSO _4), manganese sulfate (MnSO ₄ ), nickel sulfate (NiSO ₄ ), copper sulfate (CuSO ₄ ), cobalt sulfate (CoSO ₄ ), cadmium sulfate (CdSO ₄ ), magnesium sulfate (MgSO ₄ ), iron sulfate (FeSO ₄ ) ₂ (SO _{4) 3),} zinc sulfate (ZnSO _4), calcium nitrate _{(Ca (NO 3) 2)} , zinc nitrate _{(Zn (NO 3) 2)} , iron nitrate _{(Fe (NO 3) 3)} , aluminum phosphate (AlPO _4), iron phosphate (FePO _4), chromate phosphate (CrPO _4), phosphoric acid copper _{(Cu 3 (PO 4) 2} ), zinc phosphate _{(Zn 3 (PO 4) 4} ), magnesium phosphate (Mg ₃ (PO _{4) 2),} aluminum chloride (AlCl _3), titanium chloride (TiCl _4), calcium chloride (CaCl _2), silver chloride (AgCl), calcium fluoride (CaF _{2 1} ) selected from the group consisting of barium fluoride (BaF ₂ ), anhydrous sulfuric acid (SO ₃ ), sulfamic acid, citric acid, succinic acid, maleic acid, phthalic acid and cation exchange resins (trade name: Amberlyst 15, A21, Or more. The acid catalyst is mixed with the biomass to perform a chemical hydrolysis reaction. In the present invention, a solid acid catalyst is used to facilitate separation from the glycation solution, and preferably a cation exchange resin, more preferably Amberlyst 36 can be used.

The term " solid acid " of the present invention refers to a solid acting as a proton donor or an electron acceptor. Solid acids have the property of discoloring basic indicators like base acids or adsorbing bases. Naturally occurring clay minerals such as acid clay, silica alumina mixed with various ratios of silica and alumina, cation exchange resin, solid volcanic acid (for example, silica gel or alumina attached with sulfuric acid, phosphoric acid, etc.) And inorganic chemicals such as aluminum oxide. In particular, it is known that the properties of the catalyst are important and are superior in activity and selectivity to homogeneous acid solvents.

      In the present invention, the liquid acid catalyst may be at least one member selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, bromic acid, perchloric acid and acetic acid, preferably nitric acid. The liquid acid catalyst is used to increase the saccharification reaction efficiency of the solid acid catalyst and to reduce the saccharification reaction time. Even when the solid acid is used singly, the saccharification reaction proceeds, but when used in combination with a small amount of liquid acid catalyst, . In addition, when the glycation reaction proceeds only with the liquid acid catalyst, a neutralization process is further required to adjust the acidity of the product, and a desalination process is required to remove the generated salts. In this case, when the liquid acid is supplied to the fermentation process without removing the acid, the activity of the microorganism is lowered by the acid, so that the smooth fermentation process can not proceed. However, when used in combination with a solid acid catalyst, a small amount (less than 0.05 N) of liquid acid is used, so that the saccharified liquid can be used in the fermentation process without neutralization, and an additional desalination step is not necessary.

In the present invention, the step (b) may be performed at a temperature of 80 to 200 ^° C for 0.5 to 5 hours. Generally, the pyrolysis temperature of a sugar is known to be about 200 ^° C. It is preferable to perform the reaction at a temperature of 200 ^° C or less to prevent pyrolysis of the resulting saccharide. In addition, when the temperature is low, the reaction rate decreases and the overall efficiency decreases. Therefore, the reaction is preferably performed at 80 ^° C or higher, more preferably 150 ^° C. The reaction time is preferably within 4 hours, more preferably from 1 to 3 hours, at which the sugar produced by the shortest time of producing sugar is decomposed by acid.

In the present invention, the solid acid catalyst in the step (a) may be used in an amount of 0.1 to 15 g / L, and the liquid acid catalyst may be used in an amount of 0.0001 to 0.1 N. When the solid acid catalyst content is less than 0.1 g / L, the effect of hydrolysis by the solid acid catalyst is significantly deteriorated, and if it exceeds 15 g / L, acid-induced sugar disintegration may occur. When the liquid acid is 0.0001N or less, the activation effect of the solid acid catalyst by the liquid acid catalyst is poor. When the liquid acid catalyst is more than 0.05N, the liquid acid catalyst causes sugar disintegration and further neutralization and desalting of the product is required.

In the present invention, the monosaccharide is selected from the group consisting of glucose, galactose, rhmnose, xylose, mannose, fucose, arabinose arabinose, and libose. In the present invention, There are various kinds of monosaccharides produced by the glycation reaction, but in the present invention, mixed monosaccharides including glucose, galactose and the like can be obtained.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example  : Glycation  The raw materials of the reaction and Glycation  Configuration of the reactor

The saccharifying device system used for the present embodiment is composed of a reactor made of stainless steel and a control box. The reactor has a cylindrical shape with an inner diameter of 6 cm and an inner height of 10 cm and a reaction volume of 300 ml (effective capacity: 200 ml). The reactor is equipped with an impeller for stirring, a thermocouple for measuring the temperature inside the reactor and a sampling line line is installed on the reactor lid. For ease of sampling, high pressure N ₂ gas can be introduced into the sampling line from the outside of the reactor. The control box is equipped with the RPM of the stirrer, the temperature setting inside the reactor, and the timer.

High performance liquid chromatography was used to quantify the monosaccharide produced by the glycation process. It consists of a pump manufactured by Waters, an autosampler which automatically injects a certain amount of samples, and a column oven which keeps the temperature of the column constant. The steam produced by Sedex Co., The sugar in the saccharified liquid was detected through an evaporative light scattering detector.

In this example, microalgae of Golenkinia sp. Were used, which is only one example and is not limited to the substrate used in the present invention. Golenchinia was dried in a 70 ^o C oven and pulverized to produce a powder with a particle size of 1 mm or less.

The liquid acid catalyst used was 70% nitric acid solution purchased from Sigmaaldrich, and the solid acid catalyst was purchased from Amberlyst36_wet purchased from Sigma-Aldrich.

Aminex HPX-87H (Biorad, 300 mm x 7.8 mm) was used as a column for the quantitative analysis of monosaccharides in the microalgae saccharified liquid. The mobile phase used was a third distilled water, the flow rate was set at 0.6 ml / min, and the column temperature was set at 65 ^° C. Concentrations of monosaccharides were quantitatively analyzed using standard curve. The yield of the resulting monosaccharide was calculated by the following equation.

S = monosaccharide concentration quantitatively analyzed on HPLC (g / L)

M = Concentration (g / L) of microalgae dry raw material added for saccharification reaction

Experimental Example  One: Liquid acid  Depending on the concentration of the catalyst Glycation reaction  Efficiency change

Since it is most important to achieve the object of the present invention that the amount of nitric acid to be used as the co-catalyst is reduced to a level where the necessity of subsequent neutralization and desalination is unnecessary or minimized, the amount of amblingrite 36 used as the main catalyst should be 9.23 g / L and the concentration of nitric acid was changed in the range of 0.05N to 0.0005N. Experiments were carried out using pure 9.23 g / L amberlum 36 alone as a control. The concentration of Golenchinia used in all experiments was 10 g / L and the glycosylation was carried out at 150 ^° C for a maximum of 160 min.

As shown in FIG. 1, it can be seen that the use of the solid acid catalyst alone is not practical because the yield is extremely low. In the case of using nitric acid together, even when the concentration of nitric acid was lowered to 0.01 N, the time required for reaching the maximum yield was slightly longer than that of 0.05 N, but sufficient yield of sugar was obtained. However, when the concentration of nitric acid was lower than 0.01 N, a sufficient level of yield could not be obtained. Therefore, it has been found that 0.01 N is the most suitable concentration of nitric acid to be added. Therefore, the concentration of nitric acid to be used at such a low level is not required to be subjected to subsequent neutralization and desalting when judged by conventional knowledge. As a result, when the solid acid catalyst is used, the saccharification efficiency is remarkably increased by using a small amount of the liquid acid catalyst, and it is possible to develop a saccharification method which does not require subsequent neutralization and desalting processes as in the case of using solid acid alone.

Experimental Example  2: Solid acid  Catalyst and Liquid acid  Synergistic effect of simultaneous use of catalyst

In order to confirm the synergistic effect of the simultaneous use of the solid acid and the liquid acid catalyst, a saccharification reaction using only a liquid acid catalyst as a control group was performed, and the result was combined with the result of using the solid acid only, The results were compared with those of the parallel use. As can be seen from FIG. 2, when synergistic effect is apparent when 0.01 N of nitric acid is used together with the solid acid, it can be seen from the viewpoint of 120 minutes when the concentration reaches its maximum, The yield of saccharification increased by about 80% (2.1 g / L -> 3.7 g / L on the basis of sugar concentration) compared to the sum in use. FIG. 3 shows the results using 0.05 N nitric acid. When two catalysts were used together, the yield of sugar was higher than that of each catalyst alone, but there was no remarkable synergistic effect.

Experimental Example  3: Cellulose ( Celluose ) Glycation  reaction

Experiments in which celluloses were saccharified using only 0.05 N nitric acid at 10 g / L (Sigma-Aldrich Korea) or using Amberlyst 36 alone at 9.23 g / L, or in combination with 0.05 N nitric acid and 9.23 g / . As a result, as shown in FIG. 4, when the nitric acid and Amberlyst 36 were used together, the yield per unit was 25% higher than the sum of the sugar contents when the two catalysts were used alone, The synergy effect was clear.

Experimental Example  4: Golenkinia From saccharified liquid Crabshiella Oxytoka  Strain fermentation

20 g / L Golenkinia prepared using 0.01 N HNO 3 and 9.23 g / L Amberlyst 36 sp . A saccharified liquid was prepared. The saccharified solution is filtered with a 8m filter paper through a solid acid catalyst, and the precipitated solution is centrifuged to precipitate a solid substance, and the supernatant is filtered out. Thereafter, the lipid in the glycosylated liquid is extracted using an excess amount of chloroform, which is an organic solvent, and separated by a centrifugal separator to obtain an aqueous solution layer only. In the process of lipid extraction, it is a process that can be removed when preparing a saccharified liquid using a degreased microalgae sample. The saccharified solution thus prepared was not subjected to a separate salt treatment such as electrodialysis.

To 100 ml of the prepared saccharified liquid, (g / L) 9; yeast extract, 5; _{(NH 4) 2 SO 4,} 6; K ₂ HPO ₄ , 8.7; KH ₂ PO _4, 6.8; MgSO ₄ 7H ₂ O, 0.25; trace metal solution, 2% (v / v) was added and the pH was adjusted to 5.5 with sodium hydroxide.

As shown in FIG. 5, it was confirmed that the strain grew well and produced 2,3-BDO even without a separate salt treatment.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

A method for producing a biomass-derived glycosylated liquid using a solid acid and a liquid acid catalyst comprising the steps of:
(a) introducing a biomass feedstock, a solid acid catalyst and a liquid acid catalyst into a reactor;
(b) heating the reactor to sacrifice the biomass to produce a saccharified solution; And
(c) separating the solid acid catalyst from the glycated liquid prepared in the step (b).
[Claim 7] The method according to claim 1, wherein the biomass raw material is microalgae, microalgae dry powder or microalgae residues, macroalgae biomass, or woody biomass.
The microalgae of claim 2, wherein the microalgae are selected from the group consisting of Nannochloropsis sp ., Golenkinia sp ., Aurantiochytrium sp ., Schizochytrium sp. , Chlorella sp ., Spirulina sp ., Dunaliella sp ., Botryococcus sp ., Thraustochytrium sp ., Chlorella sp ., Spirulina sp . Japanese genus such as Japonochytrium sp ., Ulkenia sp. , Crypthecodinium sp ., Haliphthoros sp. , Chlamydomonas sp . And Porphyridium sp .). ≪ RTI ID = 0.0 > 8. < / RTI >
[Claim 3] The method according to claim 2, wherein the giant algae is at least one selected from the group consisting of red algae, brown algae and green algae.
[5] The method of claim 2, wherein the woody biomass is at least one selected from the group consisting of corncob, corn stover, wood chip, wood pellet, and waste wood A method for producing a saccharified liquid.
The solid acid catalyst according to claim 1, wherein the solid acid catalyst is selected from the group consisting of zeolite, bentonite, kaolinite, attapulgite, montmorillonite, zinc oxide (ZnO) It is also possible to use titanium oxide (TiO2), cerium oxide (CeO2), vanadium oxide (V2O5), silicon oxide (SiO2), chromium oxide (Cr2O3), calcium sulfate (CaSO4), manganese sulfate (MnSO4) (CaSO4), cobalt sulfate (CoSO4), cadmium sulfate (CdSO4), magnesium sulfate (MgSO4), iron sulfate (FeSO4), aluminum sulfate (Al2 (SO4) 3), calcium nitrate Zn (NO3) 2), Fe (NO3) 3, AlPO4, FePO4, CrPO4, Copper Phosphorus (Cu3 PO4) 4), magnesium phosphate (Mg3 (PO4) 2), aluminum chloride (AlCl3), titanium chloride (TiCl4), calcium chloride (CaCl2), calcium fluoride (CaF2), barium fluoride (BaF2) Magnesium carbonate (MgCO3) and cation exchange resin catalyst (Amberly st15, A21, 36, 70). < / RTI >
The method according to claim 1, wherein the liquid acid catalyst is at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, bromic acid, perchloric acid and acetic acid.
The method of claim 1, wherein the step (b) is performed at a temperature of 80 to 200 ^° C for 0.5 to 4 hours.
The method according to claim 1, wherein the solid acid catalyst in step (a) is used in an amount of 0.1 to 15 g / L, and the liquid acid catalyst is used in an amount of 0.0001 to 0.05 N.
The method according to claim 1, wherein the monosaccharide is selected from the group consisting of glucose, galactose, rhmnose, xylose, mannose, fucose, arabinose, wherein the saccharide is at least one selected from the group consisting of arabinose and libose.

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