WO2016148535A1 - Biomass saccharification method using solid acid catalyst - Google Patents

Abstract

The present invention relates to a biomass saccharification method using solid acid and liquid acid catalysts, and more specifically, to a biomass saccharification method for generating a monosaccharide from a solid biomass by using solid acid and liquid acid simultaneously. The saccharification method, according to the present invention, uses solid acid as a catalyst, thereby enabling the easy separation of hydrolysate and solid acid, and thus a neutralization device or salt separating device by which much cost is consumed are unnecessary, and since saccharification efficiency is more excellent compared to when exclusively using solid acid or liquid acid, hydrolysate may be produced at a low cost.

Description

Saccharification Method of Biomass Using Solid Acid Catalyst

The present invention relates to a method for saccharifying biomass using a solid acid as a main catalyst, and more particularly, by using a minimum amount of liquid acid as a cocatalyst to supplement the performance of a solid acid as a main catalyst, the glycation efficiency is dramatically improved. It relates to a biomass saccharification method characterized in that.

Most of the raw materials (substrates) used in the production of bioenergy and compounds are sugars obtained from starches or tropical crops derived from cereals. In the United States, most bioethanol is produced from glucose obtained by hydrolyzing corn starch, and Brazil produces bioethanol from sugar obtained from sugar cane. However, the use of crops for human consumption as energy sources is still a critical limitation because many human beings are criticized at the time of the food shortage and cannot meet the rapidly increasing demand for bioethanol. It has Therefore, research on bioenergy production using microalgae biomass resources that can not be used as food as a source of food, but as a stable source of bioenergy is being conducted (Brennan Owende, Renew. Sustain). Energy Rev. 14: 557-577 (2010); John., Bioresource Technology, 102: 186-193 (2011).

Wood-based biomass is a complex of 40-50% of cellulose, 25-35% of hemicellulose and 15-20% of lignin. Here, cellulose is tightly wrapped by lignin and hemicellulose, and it is not easy to pretreat and saccharify because of the crystalline structure of cellulose. At present, biochemical pretreatment and saccharification are known as physicochemical methods such as dilute acid hydrolysis, steeming or ateam explosion (STEX), ammonia fiver expansion (AFEX), wet oxidation (WO), and hot water pretreatment.

In addition to woody biomass, seaweeds (microalgae and giant algae), which have recently been spotlighted as a new natural resource, are fast growing so that they can be harvested 4 to 6 times a year compared to other biomass, as shown in Table 1. It also has the advantage of no competition with the fields and no erosion of cultivated land. In addition, the use of a large sea makes it much more competitive than other biomass because of its large cultivation area and little production cost. In addition, marine algae absorbs carbon dioxide at an annual rate of 36.7 tons / ha, which is 5 to 7 times higher than that of wood.

Microalgae include freshwater species that grow in freshwater and marine microalgae that grow in seawater. In particular, microalgae containing a large amount of various carbohydrates, such as starch, are glycosylated to produce various monosaccharides such as glucose, xylose, galactose or mannose. Can produce.

Giant algae are mostly marine and can be classified into red algae, brown algae and green algae. These macroalgae can be broken down into various sugars through the saccharification process. First of all, the algae consists mainly of cellulose, mannose, xylene, xylane, starch and fructan, and the red algae are galactan agar and carrageenan. carrageenan, xylan, mannan and the like. Brown algae are also composed of alginate, fucoidan, laminaran and the like. As such, macroalgae are composed of a wide variety of polysaccharides, so a saccharification process is required to break them down.

For the saccharification of such biomass, ionic liquids, strong acids, and strong bases are used as catalysts, and these catalysts are difficult or practically impossible to recycle separately from saccharified liquids. In particular, when acid or alkali is used, a neutralization process is required as a subsequent process. In addition, since a large amount of salt generated during the neutralization process must be removed, additional material costs and process costs may occur. Even if the neutralization process is not necessary, the acid and alkali catalysts are burdened with the environment if they are released as they are, so they can be discharged through an additional treatment process. Therefore, it is absolutely necessary to use a catalyst in a form that can be easily separated from the saccharified solution after the reaction and can be recycled and does not require a subsequent treatment process such as neutralization and desalination.

Korean Unexamined Patent Publication No. 2013-0001627 discloses a method of extracting sugar by pretreatment of brown algae with an imidazolium-based ionic liquid, followed by hydrolysis with a liquid acid catalyst. Although the yield was higher than when only the liquid acid catalyst was used, there is a disadvantage in that a step of neutralizing the liquid acid content to 10 to 30 wt% of the algal content is required.

Republic of Korea Patent No. 1254662 discloses a method for producing a high glucose-containing glycosylated solution from the net and algae biomass using a catalyst. This patent obtains high concentrations of monosaccharides directly from enzymatic hydrolysis or chemical hydrolysis from algae without special pretreatment, but as a catalyst for hydrolysis, liquid acids such as sulfuric acid, nitric acid, hydrochloric acid, or liquids such as sodium hydroxide and potassium hydroxide. The use of bases has the disadvantage of requiring additional neutralization steps.

Korean Patent Laid-Open Publication No. 2009-0039470 discloses a saccharification method of woody biomass using an acid catalyst and a supercritical water. Although this patent uses supercritical water to shorten the glycosylation time very short. The liquid acid catalyst requires additional neutralization and has a disadvantage in that the separation process is complicated during supercritical water regeneration.

Accordingly, the present inventors have made diligent efforts to solve the above problems, but using a solid acid catalyst that can be recovered and reused after the reaction, so that there is no necessity of a subsequent process of neutralization and desalting to compensate for the insufficient saccharification performance of the solid acid. By using a trace amount of the liquid acid as an auxiliary catalyst, it was confirmed that the saccharification efficiency was remarkably improved, and the present invention was completed. As a result, a method of improving the economic efficiency of the saccharification process has been developed through higher saccharification efficiency than the case of using a solid acid catalyst and a liquid acid catalyst alone, and at the same time, the cost of subsequent neutralization and desalination processes is reduced.

The above information described in this Background section is only for improving the understanding of the background of the present invention, and therefore does not include information that forms a prior art known to those of ordinary skill in the art. You may not.

Summary of the Invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a saccharification method of biomass, which has a saccharification efficiency and economy at the same time by using a solid acid as a main catalyst and a trace liquid as a cocatalyst.

In order to achieve the above object, the present invention comprises the steps of (a) adding a solid acid catalyst and a liquid acid catalyst to the biomass raw material, and then heating to saccharify the biomass; And (b) separating the solid acid catalyst from the saccharification liquid.

FIG. 1 shows the results of saccharification of Golenkinia using 9.23 g / L Emberist 36 and nitric acid according to each concentration.

FIG. 2 shows the results of saccharification of Golenkinia using 0.01 N nitric acid and 9.23 g / L Emberist 36. FIG.

Figure 3 shows the results of saccharification of golenkinia using 0.05N nitric acid and 9.23 g / L Emberist 36.

Fig. 4 shows the results of saccharification of cellulose using 0.05N nitric acid and 9.23 g / L emblem 36.

FIG. 5 shows the results of 2,3-BDO production using crab ciella oxytoca strain from Golenkinia saccharified solution treated with 0.01 N nitric acid.

Detailed description and specifics of the invention Embodiment

Unless defined otherwise, 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 saccharified solution was prepared using a solid acid and a liquid acid, and the separation of the prepared saccharified liquid and the solid acid was easy, and it was confirmed that the saccharification efficiency was superior to the single use of the solid acid.

In an embodiment of the present invention, a microalgae raw material, a solid acid and a liquid acid catalyst were added to a stainless steel reactor to perform a saccharification reaction, and a saccharification rate was increased as compared with a solid acid catalyst or a liquid acid catalyst alone. It was confirmed that.

Therefore, in one aspect, the present invention comprises the steps of: (a) adding a solid acid catalyst and a liquid acid catalyst to the biomass raw material, and then heating to saccharify the biomass; And (b) separating the solid acid catalyst from the saccharification liquid, and a method for saccharifying biomass using the solid acid and liquid acid catalysts.

In the present invention, the biomass raw material may be characterized in that the microalgae raw material, microalgae dry powder, microalgae residue, wood-based biomass or macroalgae biomass. The microalgae can be used in the form of primula, and it is preferable to use the microalgae in the form of dry powder for ease of transportation, storage and reaction. It is also possible to use a microalgae residue form in which carbohydrates are present. In addition, various types of biomass such as wood-based biomass and algae can be used.

In the present invention, the microalga is genus Nannochloropsis sp., Golenkinia sp., Oranthiochitrium sp., Aurantiochytrium sp., Schizochytrium sp. ), Chlorella sp., Spirulina sp., Dunaliella sp., Botryococcus sp., Thraustochytrium sp., Japono Japonochytrium sp., Ulkenia sp., Crypthecodinium sp., Halphthoros sp., Chlamydomonas sp. Porphyridium sp. May be selected from the group consisting of. Microalgae that produce carbohydrates in the saccharification reaction using biomass can be used without limitation, but it is more preferable to use the genus Golenkinia of the microalgal group.

In the present invention, the macroalgae may be selected from the group consisting of red algae, brown algae and green algae. Giant algae are divided into red algae, brown algae, and green algae. In the present invention, algae that generate carbohydrates as a raw material of saccharified liquid can be used without limitation.

In the present invention, the wood-based biomass may be selected from the group consisting of corncob, corn stover, wood chip, wood pellets and waste wood. Wood-based biomass is classified into herbaceous biomass and wood-based biomass. A large amount of herbaceous biomass is produced and it is preferable to use corn which is disposed of as waste. In particular, corncaps or cornstalks that are discarded after harvesting grains from corn can be used without limitation. Wood-based biomass may also use waste wood or wood chips or wood pellets for ease of transportation.

In the present invention, a small amount of liquid acid catalyst is used in parallel to increase the saccharification efficiency of the solid acid and the solid acid catalyst, which are the main catalysts, but the liquid acid mainly liquefies the solid raw material, and the solid acid catalyst mainly plays a role of saccharification. In this case, the acid catalyst is mixed with biomass to perform a chemical hydrolysis reaction, and in the present invention, a solid acid catalyst is used to facilitate separation from the saccharified solution.

The term solid acid of the present invention refers to a solid that acts as a proton donor or electron acceptor. Solid acids have the property of discoloring basic indicators or adsorbing bases, just like normal acids. Naturally produced clay minerals such as acidic clay, silica alumina mixed with various ratios of silica and alumina, cation exchange resins, and solid acids (eg, silica gel, alumina, sulfuric acid, phosphoric acid, etc.) And inorganic chemicals such as aluminum oxide. In particular, it is known that the properties as a catalyst is important and excellent in activity and selectivity as compared to a homogeneous acid solvent.

In the present invention, the solid acid catalyst is zeolite, bentonite, benolinite, kaolinite, attapulgite, 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 ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), 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 ), chromium phosphate (CrPO ₄ ), copper phosphate (Cu ₃ (PO ₄ ) ₂ ), zinc phosphate (Zn ₃ (PO ₄ ) ₂ ), magnesium phosphate (Mg ₃ (PO ₄ ) ₂ ), aluminum chloride (AlCl ₃ ), titanium chloride (TiCl ₄ ), calcium chloride (CaCl ₂ ), calcium fluoride (CaF ₂ ), barium fluoride (BaF ₂ ), calcium carbonate (C aCO ₃ ), magnesium carbonate (MgCO ₃ ) and a cation exchange resin, it may be characterized in that the cation exchange resin (trade name: Amberlyst 15, A21, 36, 70), more preferably Amberlyst36 can be used.

In the present invention, the liquid acid catalyst may be selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, bromic acid, perchloric acid and acetic acid, preferably nitric acid may be used. The liquid acid catalyst is used to increase the saccharification reaction efficiency of the solid acid catalyst and to reduce the saccharification reaction time. Although the saccharification reaction proceeds even when the solid acid is used alone, the efficiency of the saccharification reaction when used in parallel with a small amount of the liquid acid catalyst is used. This rises even more. In addition, when the saccharification reaction proceeds only with a liquid acid catalyst, a neutralization process is additionally required in order to control the acidity of the product, and a desalting process is required to remove salts generated therein. In this case, when the liquid acid is supplied to the fermentation process without removing the liquid acid, the activity of the microorganism is lowered by the acid, so that the smooth fermentation process cannot be performed. However, when used in parallel with the solid acid catalyst, since a small amount (10 parts by weight or less) of the liquid acid is used, the saccharified solution can be used in the fermentation process without the neutralization process, and no additional desalting process is required.

In the present invention, the saccharification of step (a) may be performed for 0.5 to 5 hours at a temperature of 80 ~ 200 ℃. The pyrolysis temperature of the general sugar is known as about 200 ℃ but it is preferable to perform the reaction below 200 ℃ so that the resulting sugar is not pyrolyzed. In addition, when the temperature is low, since the reaction rate is lowered and the overall efficiency decreases, the reaction is preferably performed at 80 ° C. or higher, and more preferably, at 150 ° C. The reaction time is preferably within 4 hours, the time at which the sugar is decomposed by the acid at 0.5 hours, which is the shortest time for the sugar to be produced, more preferably 1 to 3 hours.

In the present invention, the amount of the solid acid catalyst and the liquid acid catalyst added is 1 to 150 parts by weight and 0.006 to 6.3 parts by weight, preferably 60 to 120 parts by weight and 0.315 to 3.15 parts by weight, based on 100 parts by weight of the biomass, respectively. More preferably, 92.3 parts by weight and 0.63 parts by weight may be used. Among the solid acid catalysts, the emblem has maximum activity when 0.63 parts by weight is added, but when using other solid acid catalysts, since the activity of the catalyst changes, an appropriate concentration can be selected according to the activity of the solid acid. . In addition, when the solid acid catalyst is less than 1 part by weight, the effect of hydrolysis by the solid acid catalyst is remarkably inferior, and when it exceeds 150 parts by weight, glycolysis by acid may occur. In addition, when the amount of the liquid acid catalyst is less than 0.006 parts by weight, the activation effect of the solid acid catalyst by the liquid acid catalyst is lowered. When the amount of the liquid acid catalyst is greater than 6.3 parts by weight, glycolysis by the liquid acid catalyst occurs and further neutralization and desalting of the product is required.

In the present invention, the saccharified liquid is glucose, galactose, rhamnose, xylose, mannose, fucose, arabinose. It may be characterized by including one or more selected from the group consisting of (arabinose) and ribose (ribose). The saccharification liquid produced by the saccharification reaction may include various monosaccharides, but in the present invention, mixed monosaccharides including glucose, galactose, and the like may be obtained.

Example

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

Example 1: Raw Material of Saccharification Reaction and Configuration of Saccharification Reactor

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

In order to quantify the monosaccharides produced by the saccharification process, high performance liquid chromatography was used. It consists of a pump made by Waters, an autosampler that automatically injects a certain amount of samples, and a column oven that keeps the temperature of the column constant. The sugar in the saccharified solution was detected through an evaporative light scattering detector.

In the present example, microalgae Golenkinia sp. Was used, which is just one example and is not limited to the substrate used in the present invention. Golenkinia was dried in an oven at 70 ° C. and ground to produce a powder having a particle size of 1 mm or less and used for saccharification experiments.

A liquid acid catalyst was used as a 70% nitric acid solution, and a solid acid catalyst was purchased from Amberlyst 36_wet purchased from Sigma Aldrich.

HPLC was used for quantitative analysis of monosaccharides in microalgal saccharification liquor, and Aminex HPX-87H (Biorad, 300 mm × 7.8 mm) was used as a column. The mobile phase used tertiary distilled water, the flow rate was set to 0.6ml / min, the column temperature was set to 65 ℃. Monosaccharide concentration was quantitatively analyzed using a standard curve. The yield of the produced monosaccharide was calculated by the following equation.

S = monosaccharide concentration quantified by HPLC (g / L)

M = concentration of dried microalgae raw material for the saccharification reaction (g / L)

Example 2: Change in Glycation Reaction Efficiency According to Concentration of Liquid Acid Catalyst

Since lowering the amount of nitric acid used as a cocatalyst to a level where the subsequent neutralization and desalting process is unnecessary or minimized is the most important factor in achieving the object of the present invention, 10 g of biomass is added to 1 L of distilled sand, and then used as the main catalyst. Emberist 36 was glycosylated with varying amounts of nitric acid in the range of 0.00315 to 0.315 g while being fixed at 9.23 g. The amount of the emblem is such that the maximum saccharification yield can be reached by the activation effect of the liquid acid catalyst at the same value as the concentration of 24.3 meqH ⁺ / L of nitric acid. The experiment using only pure 23, 9.23g as a control group was performed. The saccharification of all experiments was performed at 150 ° C. for up to 160 minutes.

As shown in FIG. 1, when only the solid acid catalyst is used, the yield is extremely low, which implies no practicality. In the case of using nitric acid, even when the concentration of nitric acid was lowered to 0.063g (0.01N), the time to reach the maximum yield was slightly longer than that of 0.315g (0.05N), but sufficient sugar yield was obtained. However, if the nitric acid concentration was lower than 0.063g, a sufficient level of yield could not be obtained. Therefore, 0.063 g of nitric acid was found to be the most suitable, so such a low nitric acid concentration is a level which, as judged by conventional knowledge, does not require subsequent neutralization and desalination processes. As a result, by using a small amount of the liquid acid catalyst when using a solid acid catalyst, the saccharification efficiency is significantly increased, but as in the case of using the solid acid alone, it was possible to develop a saccharification method that does not require subsequent neutralization and desalination processes.

Example 3: Synergistic Effect of Parallel Use of Solid Acid Catalyst and Liquid Acid Catalyst

In order to confirm the synergistic effect that can be obtained when the solid acid and the liquid acid catalyst are used in parallel, an additional glycosylation reaction using only the liquid acid catalyst is performed as a control, and the result is combined with the result using only the solid acid. It was compared with the result at the time of use. As shown in FIG. 2, it can be seen that synergistic effects are apparent when 0.063 (0.01N) g of nitric acid is used together with a solid acid. By using the catalyst together, there was an 80% increase in glycation yield (2.1 g / L-> 3.7 g / L based on sugar concentration) compared to the sum ((1) + (2)). Figure 3 shows the results using 0.315g (0.05N) nitric acid, when using both catalysts showed a higher sugar yield than the case of using each catalyst alone, but the synergistic effect is remarkable compared to the use of nitric acid alone There was no.

Example 4: Cellulose Glycation Reaction

The same experimental apparatus as in Example 1 was used, and the same experiment was carried out using cellulose instead of golenkinia. Cellulose was glycosylated using only 0.315 g (0.05 N) nitric acid, only 9.23 g Emberist36, or 0.315 g nitric acid and 9.23 g Emberist 36 in combination The experiment was performed. As a result, as shown in FIG. 4, when the nitric acid and the Emberist 36 were used together, the sugar yield was 25% higher than the sum of the sugar concentrations ((1) + (2)) when the two catalysts were used alone. By showing a high value, the synergy effect of the parallel use of the catalyst was shown.

Example 5: Klebsiella oxytoca strain fermentation from Golenkinia saccharified solution

Golenkinia sp. 0.063 g HNO ₃ 0.063 g and Amberlyst36 9.23 g were prepared in the same manner as in Example 3. The saccharified solution was filtered through a solid acid catalyst with 8m filter paper, and then the supernatant was filtered out after the solid solution precipitated with a centrifuge. Thereafter, the lipid in the saccharified solution was extracted using an excess amount of chloroform as an organic solvent, and the layers were separated by centrifugation to obtain only an aqueous layer. In the case of lipid extraction process, it is a process that can be removed during the preparation of saccharified solution using the degreasing microalgal sample. The glycosylated solution was not subjected to a separate salt treatment process such as electrodialysis.

(G / L) 9 to 100 ml of the prepared saccharified solution; 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 using sodium hydroxide.

As a result of culturing crab ciella oxytoca strain, as shown in Figure 5, the strain was grown well without a separate salt treatment process, it was confirmed that the production of 2,3-BDO.

Since the saccharification method according to the present invention uses a solid acid as a catalyst, it is easy to separate the saccharified liquid and the solid acid, so that a costly neutralization device or a salt separation device is not necessary, and the solid acid or liquid acid is used alone. Since the saccharification efficiency is excellent, it is useful for producing saccharified solution at low cost.

As described above in detail specific parts of the present invention, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

1. Method of saccharifying biomass using solid acid and liquid acid catalyst comprising the following steps:

   (a) adding a solid acid catalyst and a liquid acid catalyst to the biomass feedstock and then heating to saccharify the biomass; And

   (b) separating the solid acid catalyst from the saccharified solution.
2. The method of claim 1,

   The biomass raw material is a microalgae raw material, microalgae dry powder, microalgae residue, macroalgae biomass or wood-based biomass, characterized in that the saccharification method.
3. The method of claim 2,

   The microalgae include the genus Nannochloropsis sp., Golenkinia sp., Aurantiochytrium sp., Schizochytrium sp., And Chlorella genus. Chlorella sp.), Spirulina sp., Dunaliella sp., Botryococcus sp., Thraustochytrium sp., Japonochytrium sp.), the genus Ulkenia sp., the genus Crypthecodinium sp., the genus Halifthoros sp., the genus Chlamydomonas sp., and the genus Porphyridium. Porphyridium sp.) Glycosylation method, characterized in that selected from the group consisting of.
4. The method of claim 2,

   The giant algae is saccharification method, characterized in that selected from the group consisting of red algae, brown algae and green algae.
5. The method of claim 2,

   The wood-based biomass is a saccharification method, characterized in that selected from the group consisting of corncob (corncob), corn stover (corn stover), wood chip (wood chip), wood pellets and waste wood.
6. The method of claim 1,

   The solid acid catalyst is zeolite, bentonite, kaolinite, kaolinite, attapulgite, 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 )} , aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), 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 ), Chromium Phosphate (CrPO ₄ ), Copper Phosphate (Cu ₃ (PO ₄ ) ₂ ), Zinc Phosphate (Zn ₃ (PO ₄ ) ₂ ), Magnesium Phosphate (Mg ₃ (PO ₄ ) ₂ ), Aluminum Chloride (AlCl ₃ ), Titanium chloride (TiCl ₄ ), calcium chloride (CaCl ₂ ), calcium fluoride (CaF ₂ ), barium fluoride (BaF ₂ ), calcium carbonate (CaCO ₃ ), magnesium carbonate Saccharification method, characterized in that selected from the group consisting of calcium (MgCO ₃ ) and cation exchange resin.
7. The method of claim 1,

   The liquid acid catalyst is a saccharification method, characterized in that selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, bromic acid, perchloric acid and acetic acid.
8. The method of claim 1,

   The saccharification step (a) is characterized in that the saccharification method is performed for 0.5 to 5 hours at a temperature of 80 ~ 200 ℃.
9. The method of claim 1,

   The amount of the solid acid catalyst and the liquid acid catalyst added is 1 to 150 parts by weight and 0.006 to 6.3 parts by weight based on 100 parts by weight of the biomass, respectively.
10. The method of claim 1,

    The saccharified solution is glucose, galactose, rhamnose, rhmnose, xylose, mannose, fucose, arabinose and arabinose. A saccharification solution production method comprising at least one selected from the group consisting of (ribose).

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