TWI615398B - Method for preparing sugars - Google Patents

Abstract

The present disclosure provides a solid catalyst comprising: a core particle composed of activated carbon, lignin or iron oxide; and a plurality of hydroxyl groups and a sulfonic acid group formed on the surface of the core particle. The present disclosure further provides a method for preparing a saccharide, comprising: mixing an organic acid with the solid catalyst to form a mixed solution; adding a fibrous biomass to the mixed solution to perform a dissolution reaction; and adding water to In the mixture, a hydrolysis reaction is carried out to obtain a hydrolyzate.

Description

Preparation method of sugar

The present disclosure relates to a solid catalyst, and more particularly to a method for preparing a solid catalyst having a plurality of hydroxyl groups and a sulfonic acid group formed on the surface and a saccharide using the catalyst.

Biomass are generally found in the form of organic matter such as grass, wood, crops and their residues and waste. The first generation of biofuels are mainly produced from raw alcohol and biodiesel produced from sugar, starch and vegetable oil. However, the first generation of biofuels faced the problem of competition between raw materials and food; in addition, the fertile soil that can provide these biomass growth is limited, limiting the application of first-generation biofuels.

In order to overcome the shortcomings of the first generation of raw fuel sources, the second generation of biofuels uses lignocellulose as a raw material. Lignocellulose can grow on poor land. There are approximately 22 billion tons (dry basis) of biomass in the world (energy content is about 45EJ), of which lignocellulose accounts for 70~95%. Lignocellulose is mainly composed of three components, namely cellulose (40-50%), hemicellulose (25~35%) and lignin (15-20%), of which cellulose is most utilized. After being converted to glucose, it is considered to be the most promising option to replace petroleum base fuels by fermentation to produce biomass alcohol or dehydration into platform molecules.

Cellulose is a main component of lignocellulose, which is a polymer in which glucose monomers are combined via β-1,4 glycosidic bonds. The β-1,4 glycosidic bond can be destroyed by an acid, and the cellulose is hydrolyzed to form a compound such as glucose or oligosaccharide. The acid that was first applied to the hydrolysis of cellulose to produce sugar is a mineral acid; however, the presence of these inorganic acids may cause problems such as difficulty in separation of the product, corrosion of the reactor, difficulty in recycling the catalyst, and wastewater treatment, which need to be improved and overcome. The recent development of solid catalyst technology can solve the above problems. However, the solid catalyst has a small contact area with the reactants, low acidity of the catalyst, and weak mechanical strength, resulting in a small contact area between the reactant and the catalyst, poor hydrolysis efficiency of the cellulose, and disintegration due to the decrease in mechanical strength for long-term use. .

One embodiment of the present disclosure provides a solid catalyst comprising: a core particle composed of activated carbon, lignin or iron oxide; and a plurality of hydroxyl groups and a sulfonic acid group formed on the surface of the core particle.

An embodiment of the present invention provides a method for preparing a saccharide, comprising: mixing an organic acid with a solid catalyst to form a mixed solution; adding a fibrous biomass to the mixed solution, To carry out a dissolution reaction; and to add water to the mixture to carry out a hydrolysis reaction to obtain a hydrolyzate.

The above described objects, features and advantages of the present invention will become more apparent and understood.

1 is a FTIR spectrum of a sulfonated activated carbon solid catalyst according to an embodiment of the present disclosure; and FIG. 2 is a FTIR spectrum of a sulfonated lignin solid catalyst according to an embodiment of the present disclosure; 3 is a FTIR spectrum of a solid catalyst for direct sulfonation/reflow carbonization, resulfonation/high temperature carbonization and resulfonation of sugarcane after sugar production according to an embodiment of the present disclosure; and FIG. 4 is one of the disclosures according to the present disclosure. EXAMPLES An FTIR spectrum of a sulfonated iron oxide solid catalyst.

One embodiment of the present disclosure provides a solid catalyst comprising: a core particle composed of activated carbon, lignin or iron oxide; and a plurality of hydroxyl groups and a sulfonic acid group formed on the surface of the core particle.

In some embodiments, the core particles are composed of activated carbon having a particle size of 10 to 60 microns.

In some embodiments, the core particles are composed of lignin having a particle size between 100 and 300 microns.

In some embodiments, the core particles are composed of iron oxide and have a particle size of 0.5 to 20 microns.

In some embodiments, the solid catalyst has an acidity of generally between 0.6 and 5.8 mmol [H ⁺ ]/g of catalyst.

The functional groups such as a hydroxyl group and a sulfonic acid group formed on the surface of the solid catalyst particle can effectively increase the affinity with the cellulosic biomass.

An embodiment of the present disclosure provides a method for preparing a saccharide, The method comprises the steps of: mixing a organic acid with a solid catalyst to form a mixed solution; adding a fibrous biomass to the mixed solution to perform a dissolution reaction; and adding water to the mixed solution to carry out a hydrolysis reaction to obtain a Hydrolyzate.

In some embodiments, the above organic acid may include formic acid, acetic acid, or a mixture thereof.

In some embodiments, the weight ratio of the above organic acid to the mixed solution is generally between 75 and 95% by weight.

In some embodiments, the solid catalyst may include: a core particle composed of activated carbon, lignin or iron oxide; and a plurality of hydroxyl groups and a sulfonic acid group formed on the surface of the core particle.

In some embodiments, the core particles are composed of activated carbon having a particle size of 10 to 60 microns.

In some embodiments, the core particles are composed of lignin having a particle size between 100 and 300 microns.

In some embodiments, the core particles are composed of iron oxide and have a particle size of 0.5 to 20 microns.

In some embodiments, the solid catalyst has an acidity of generally between 0.6 and 5.8 mmol [H ⁺ ]/g of catalyst.

In some embodiments, the weight ratio of the solid catalyst to the mixed liquid is generally between 0.5 and 21% by weight.

In some embodiments, the above fibrous biomass may comprise whole cellulose, hemicellulose or lignin.

In some embodiments, the weight ratio of the fibrous biomass to the mixed liquid is generally between 5 and 25 wt%.

In some embodiments, the fibrous biomass may be derived from wood, grass, leaves, algae, waste paper, corn stover, corn cob, rice straw, rice husk, wheat straw, bagasse, bamboo or crop straw.

In some embodiments, the method for preparing a saccharide of the present invention further comprises adding an azeotropic agent to the mixed solution to carry out the above dissolution reaction.

In some embodiments, the azeotroping agent described above may include esters, ketones or alkanes such as n-hexane.

In some embodiments, the weight ratio of the azeotrope to the mixture in the mixture is generally between 15 and 45 wt%.

In some embodiments, the method for preparing a saccharide of the present invention further comprises adding a mineral acid to the mixed solution to carry out the above dissolution reaction.

In some embodiments, the above inorganic acid may include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or a mixture thereof.

In some embodiments, the weight ratio of the above inorganic acid to the mixed solution is generally between 0.5 and 3% by weight.

In some embodiments, the reaction temperature of the above dissolution reaction is generally between 60 and 101 °C.

In some embodiments, the reaction time of the above dissolution reaction is generally between 60 and 240 minutes.

In some embodiments, the reaction pressure of the dissolution reaction is generally between 0.9 and 1.1 atm.

In some embodiments, the weight ratio of the water to the mixed liquid is generally between 25 and 100% by weight.

In some embodiments, the reaction temperature of the above hydrolysis reaction is generally Between 100~110 °C.

In some embodiments, the reaction time of the hydrolysis reaction is generally between 30 and 180 minutes.

In some embodiments, the reaction pressure of the hydrolysis reaction is generally between 0.9 and 1.1 atm.

In some embodiments, the method for preparing a saccharide further comprises adding a mineral acid to the hydrolyzate to perform a secondary hydrolysis.

In some embodiments, the above inorganic acid may include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or a mixture thereof.

In some embodiments, the weight ratio of the above inorganic acid to the hydrolyzed product is generally between 0.5 and 3% by weight.

The invention discloses that the biochemical or cellulose is esterified with an organic acid under a specific solid catalyst catalytic environment to form a soluble organic acid fiber ester, which has low crystallinity and high solubility, and is favorable for subsequent hydrolysis and sugar production. And in the above esterification reaction, the present disclosure uses an azeotropic agent such as a ketone, an ether or an alkane (preferably n-hexane) to cause the water produced by the esterification reaction to form an azeotrope with the azeotrope. The esterification system can effectively improve the esterification efficiency and increase the sugar yield of the subsequent hydrolysis; in addition, the entraining agent can assist the removal of the organic acid after the esterification reaction, and improve the purity of the organic acid, so that the organic acid can be used to prepare the sugar. Reuse in the process; the entrainer helps to lower the temperature of the esterification reaction and avoid the degradation of sugars. In addition, a small amount of inorganic acid may be added to the primary hydrolysis product to carry out secondary hydrolysis to increase the sugar production rate, and the overall reaction procedure can be carried out at a temperature of °101 ° C and a pressure of 1 atm. In addition, in order to facilitate the separation of the solid catalyst after the reaction, the present disclosure is based on, for example, a magnetic iron oxide (Fe ₃ O ₄ ) having a Lewis acid property as a core, and a surface sol-gelation hydrophobic treatment with TEOS. The surface is subjected to a sulfonation reaction to prepare a bifunctional magnetic solid catalyst having both a hydroxyl group and a sulfonic acid group, which has high reactivity and product selectivity in the cellulose and formate system, and the surface of the iron oxide It is protected by the sol-gelling substance, and therefore, it is not eluted by the acid, and the surface sol-gelled iron oxide is further impregnated with dilute sulfuric acid, and after drying, it has a Bronsted acid, and the acidity is, for example, 0.76 mmol [ A magnetic solid catalyst of H ⁺ ]/g is used in the field of cellulose hydrolysis to produce sugar.

40m²/g，酸度≧0.7mmol[H⁺]/g之磁性固體觸媒，(2)磁性觸媒於反應結束後，因表面溶膠-凝膠化物質保護，例如上述的鐵氧化物不會被溶出，可以磁選方式，進行產物與觸媒分離，觸媒回收率

98wt%，纖維素水解產醣率

50wt%，(3)利用共沸製程，降低纖維素酯化溶解過程中水分的產生，增加纖維素溶解率，提高纖維素水解產醣效率，(4)若以傳統Amberlyst 15為觸媒，搭配上述共沸製程，並將一次水解產物再以稀酸進行二次水解，可大幅提升纖維素水解產物產醣率，以及(5)若以磁性觸媒搭配共沸製程，並添加稀酸進行生質物酯化水解產醣試驗，生質物水解產醣率

80wt%，使用後，觸媒之飽和磁性強度大於60emu/g，可以磁選方式，進行產物與觸媒分離，磁選後，觸媒再生後，重複使用3次，產醣率仍可維持在80wt%左右。 The main functions of the present disclosure include: (1) performing sol-gel hydrophobic treatment on the surface of iron oxide powder by a sol-gel method, and then impregnating the powder with dilute sulfuric acid to prepare a saturated magnetic strength of e60 emu/g. ≦10μm, specific surface area

40m ² /g, a magnetic solid catalyst with an acidity of mmol0.7mmol [H ⁺ ]/g, (2) after the end of the reaction, the magnetic catalyst is protected by a surface sol-gelling substance, such as the above iron oxide. Dissolved, magnetic separation, separation of product and catalyst, catalyst recovery

98wt%, cellulose hydrolysis yield rate

50wt%, (3) using the azeotropic process to reduce the production of water during the esterification and dissolution of cellulose, increase the dissolution rate of cellulose, and improve the efficiency of cellulose hydrolysis and sugar production. (4) If the traditional Amberlyst 15 is used as a catalyst, The azeotropic process described above, and the secondary hydrolysis of the hydrolyzed product by dilute acid can greatly increase the sugar production rate of the cellulose hydrolyzate, and (5) if the magnetic catalyst is combined with the azeotropic process, and the dilute acid is added for growth. Quality esterification hydrolysis sugar production test, biomass hydrolysis rate

80wt%, after use, the saturation magnetic strength of the catalyst is greater than 60emu/g, and the product can be separated from the catalyst by magnetic separation. After magnetic separation, after the catalyst is regenerated, it can be reused 3 times, and the sugar yield can still be maintained at 80wt%. about.

Example / Comparative Example

Example 1

Preparation of solid catalyst (1) (activated carbon after sulfonation)

Take a mixture of activated carbon/fuming sulfuric acid with a weight ratio of 1/10, stir and heat to 80~120 °C, stir for 8~16 hours, carry out activated carbon sulfonation reaction, and wash the mixture to the washing liquid after the reaction is finished [H ⁺ ] The concentration is 1.5~3.0N. After filtering, the filter cake is dried (105 ° C) and ground to be activated carbon after sulfonation.

The sulfonated activated carbon solid catalyst (code name Wako ACS) prepared in this example was subjected to FTIR structure identification with an unsulfonated activated carbon raw material (code name Wako AC), and the results are shown in Fig. 1. The sulfonated activated carbon solid catalyst prepared in this example showed an -OH functional group at 2,500-3,500 cm ^-1 on the FTIR spectrum, and an S=O functional group at 1,035-1,180 cm ^-1 . It can be confirmed that the sulfonated activated carbon solid catalyst prepared in this example does have a hydroxyl group (-OH) and a sulfonic acid group (-SO ₃ H) difunctional group.

Example 2

Preparation of solid catalyst (2) (lignin after sulfonation)

Take a mixture of lignin/fuming sulfuric acid with a weight ratio of 1/10, stir and heat to 80~120 °C, stir for 8~16 hours, carry out lignin sulfonation reaction, and wash the mixture to the washing liquid after the reaction is finished [H ⁺ ] The concentration is 1.5~3.0N. After filtering, the filter cake is dried (105 °C) and ground to obtain lignin after sulfonation.

The sulfonated lignin solid catalyst (code name Lignin-S) prepared in this example was identified by FTIR structure with unsulfonated lignin (code name Lignin), and the results are shown in Fig. 2. The sulfonated lignin solid catalyst prepared in this example exhibited an -OH functional group at 2,500-3,500 cm ^-1 on the FTIR spectrum, and an S=O functional group at 1,035-1,180 cm ^-1 . It can be confirmed that the sulfonated lignin solid catalyst prepared in the present example does have a hydroxyl group (-OH) and a sulfonic acid group (-SO ₃ H) bifunctional group.

Example 3

The disclosure discloses the preparation of solid catalyst (3) (direct sulfonation of bagasse after sugar production)

Take the sugar-bearing bagasse/fuming sulfuric acid mixture with a weight ratio of 1/10, stir and heat to 80~120 °C, stir for 8~16 hours, carry out the sulfonation reaction of sugarcane after sugar production, and wash the mixture after the reaction is finished. The washing liquid [H ⁺ ] concentration is 1.5~3.0N, the filter cake after filtration, dried (105 ° C), and ground, which is the direct sulfonation product of bagasse after sugar production.

The FTIR structure was identified by the solid catalyst (code BRS) directly sulfonated after the sugar-producing bagasse prepared in this example, and the unsulfonated raw bagasse (code RBR) and the unsulfonated sugar-bearing bagasse (code BR). As shown in Figure 3. The solid catalyst for direct sulfonation of bagasse after sugar production prepared in this example showed an -OH functional group at 2,500-3,500 cm ^-1 on the FTIR spectrum, and an S==O functional group at 1,035-1,180 cm ^-1 . Therefore, it can be confirmed that the solid catalyst for direct sulfonation of the bagasse after sugar production in the present embodiment does have a hydroxyl group (-OH) and a sulfonic acid group (-SO ₃ H) bifunctional group.

Example 4

The disclosure discloses the preparation of solid catalyst (4) (carbonization and resulfonation of bagasse after sugar production)

The sugar-bearing bagasse/10% sulfuric acid/toluene mixture with a weight ratio of 40/100/62.5 was subjected to reflux carbonization at 85 ° C for 24 hours, and the reactants were taken out until the pH of the washing liquid was 6-7, and the filter cake was filtered. After drying (105 ° C), grinding, that is, the carbonized sample of the bagasse after sugar production. Take a weight ratio of 1/10 of sugar-bearing bagasse back to carbonization sample / fuming sulfuric acid mixture, stir and heat to 80 ~ 120 ° C, stirring time is 8 ~ 16 hours, after the sugar-bearing bagasse reflux carbonization sample sulfonation reaction, reaction After the end, the mixture is washed to a water washing liquid [H ⁺ ] concentration of 1.5 to 3.0 N, and the filter cake is filtered, dried (105 ° C), and ground to be a carbonized resulfonated product after sugar production.

The FTIR structure was identified by the solid catalyst (code name BRCS-RC) prepared by the carbonization and resulfonation of the bagasse after the production of sugar in the present example, and the results are shown in Fig. 3. In the present embodiment, the solid catalyst for carbonization and resulfonation of the bagasse after sugar production showed an -OH functional group at 2,500-3,500 cm ^-1 on the FTIR spectrum, and an S=O functional group at 1,035-1,180 cm ^-1 . . Therefore, it can be confirmed that the solid catalyst for the carbonization and resulfonation of the bagasse after the sugar production in the present embodiment does have a hydroxyl group (-OH) and a sulfonic acid group (-SO ₃ H) bifunctional group.

Example 5

The disclosure discloses the preparation of solid catalyst (5) (high temperature carbonization and resulfonation of bagasse after sugar production)

After the sugar-bearing bagasse is carbonized at 600 ° C for 24 hours, it is taken out and ground, which is a high-temperature carbonized sample of the bagasse after sugar production. Take a weight ratio of 1/10 of the sugar-bearing bagasse high-temperature carbonized sample/fuming sulfuric acid mixture, stir and heat to 80~120 °C, and stir for 8~16 hours to carry out the sulfonation reaction of the bagasse high-temperature carbonization sample after sugar production. After the end, the mixture is washed to a water washing liquid [H ⁺ ] concentration of 1.5 to 3.0 N, and the filter cake after filtration is dried (105 ° C) and ground to obtain a high-temperature carbonized resulfonation product of sugar-bearing bagasse.

The FTIR structure was identified by the solid catalyst (code name BRCS-HT) prepared by high temperature carbonization and resulfonation of sugar-bearing bagasse after the production of sugar in the present example, and the results are shown in Fig. 3. The solid catalyst for high-temperature carbonization and resulfonation of bagasse after sugar production in this example has an -OH functional group at 2,500-3,500 cm ^-1 on the FTIR spectrum, and an S=O functional group at 1,035-1,180 cm ^-1 . . Therefore, it can be confirmed that the solid catalyst for high-temperature carbonization and resulfonation of the bagasse after sugar production in the present embodiment does have a hydroxyl group (-OH) and a sulfonic acid group (-SO ₃ H) bifunctional group.

Example 6

Preparation of solid catalyst (6) (iron oxide after sulfonation)

1 g of Fe ₃ O ₄ powder was placed in a water/ethanol/ammonia mixture at a weight ratio of 20/60/1.5, and the Fe ₃ O ₄ particles were dispersed by ultrasonic vibration. The system temperature was 50 ° C, and the weight ratio was slowly added. 0.45/10 TEOS/water mixture, stirred for 12 hours, magnetically obtained with Fe ₃ O ₄ as the core, the surface covered with SiO ₂ , with -OH particles, washed with methanol until the pH of the washing liquid is 7~8, After the sample was dried, 1 g was taken, and the sample was impregnated in a 3 wt% sulfuric acid solution, and the surface of the catalyst was partially sulfonated at 80 ° C. The sample was washed, dried, and ground to obtain iron oxide after sulfonation.

The sulfonated iron oxide solid catalyst (code: Fe ₃ O ₄ -SiO ₂ -SO ₃ H) prepared in this example and the unsulfonated iron oxide raw material (code: Fe ₃ O ₄ ) were identified by FTIR structure. Figure 4 shows. The sulfonated iron oxide solid catalyst prepared in this example showed an -OH functional group at 2,500-3,500 cm ^-1 on the FTIR spectrum, and an S=O functional group at 1,035-1,180 cm ^-1 . It can be confirmed that the sulfonated iron oxide solid catalyst prepared in this example does have a hydroxyl group (-OH) and a sulfonic acid group (-SO ₃ H) bifunctional group.

Example 7

The present invention discloses the sugar efficiency test of the solid catalyst (1)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the sulfonated activated carbon solid catalyst prepared by Example 1 (code: Wako ACS) / (fibres) The weight ratio of vitamin + formic acid was 15.6%, and the cellulose dissolution reaction was carried out in a reflux system. After the cellulose dissolution reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 100 ° C for 3 hours to complete the cellulose esterification hydrolysis sugar generating reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 8

The present invention discloses the sugar yield test of solid catalyst (2)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code TYPE 1 ACS) / (cellulose + formic acid) after sulfonation using commercially available activated carbon was 15.6%, and refluxed. The cellulose dissolution reaction is carried out in the system. After the cellulose dissolution reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 100 ° C for 3 hours to complete the cellulose esterification hydrolysis sugar generating reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 9

The present invention discloses the sugar efficiency test of the solid catalyst (3)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code Kraft Lignin S) / (cellulose + formic acid) after sulfonation using commercially available lignin was 15.6%, and refluxed. The cellulose dissolution reaction is carried out in the system. After the cellulose dissolution reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 100 ° C for 3 hours to complete the cellulose esterification hydrolysis sugar generating reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 10

The present invention discloses a sugar-melting efficiency test of a solid catalyst (4)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code BRCS-RC) / (cellulose + formic acid) of the sugarcane residue after carbonization and resulfonation after the sugar production in Example 4 was taken. At 15.6%, the cellulose dissolution reaction was carried out in a reflux system. After the cellulose dissolution reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 100 ° C for 3 hours to complete the cellulose esterification hydrolysis sugar generating reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar comprises glucose, xylose, mannose, arabinose and oligosaccharide, etc., of the embodiment The results of the sugar production test are shown in Table 1 below.

Example 11

The present invention discloses the sugar yield test of the solid catalyst (5)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code name BRCS-HT) / (cellulose + formic acid) obtained by high temperature carbonization and sulfonation of the sugar-bearing bagasse prepared in Example 5 was taken. At 15.6%, the cellulose dissolution reaction was carried out in a reflux system. After the cellulose dissolution reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 100 ° C for 3 hours to complete the cellulose esterification hydrolysis sugar generating reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 12

The present invention discloses the sugar efficiency test of the solid catalyst (6)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 1)/(cellulose + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The cellulose dissolution reaction is carried out in a reflux system. After the cellulose dissolution reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 100 ° C for 3 hours to complete the cellulose esterification hydrolysis sugar generating reaction, and the product is collected for sugar production. Rate analysis.

The samples were determined by the 3,5-dinitrosalicylic acid method (DNS method). The reducing sugar content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 13

The present invention discloses the sugar yield test of solid catalyst (7)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2) / (cellulose + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 3.9%. The cellulose dissolution reaction is carried out in a reflux system. After the cellulose dissolution reaction is completed, 50 wt% of the weight of the mixture is added to the product, and the hydrolysis reaction is carried out at 60 ° C for 3 hours to complete the cellulose esterification hydrolysis and sugar production reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 14

The present invention discloses the sugar efficiency test of the solid catalyst (8)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2) / (cellulose + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 7.8%. The cellulose dissolution reaction is carried out in a reflux system. After the cellulose dissolving reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 60 ° C, and the hydrolysis time is 3 hours. At the time, the cellulose esterification hydrolysis reaction is completed, and the product is collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 15

The present invention discloses the sugar efficiency test of the solid catalyst (9)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2) / (cellulose + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The cellulose dissolution reaction is carried out in a reflux system. After the cellulose dissolution reaction is completed, 50 wt% of the weight of the mixture is added to the product, and the hydrolysis reaction is carried out at 60 ° C for 3 hours to complete the cellulose esterification hydrolysis and sugar production reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 16

The present invention discloses the sugar yield test of the solid catalyst (10)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2) / (cellulose + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 3.9%. , cellulose in a reflux system Dissolve the reaction. After the cellulose dissolution reaction is completed, 50 wt% of the weight of the mixture is added to the product, and the hydrolysis reaction is carried out at 60 ° C for 3 hours to complete the cellulose esterification hydrolysis and sugar production reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 17

The present invention discloses the sugar yield test of solid catalyst (11)

Taking the weight ratio of cellulose/formic acid to 10% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2) / (cellulose + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 3.9%. The cellulose dissolution reaction is carried out in a reflux system. After the cellulose dissolution reaction is completed, 50 wt% of water of the mixture is added to the product, and hydrolysis reaction is carried out at 100 ° C for 3 hours to complete the cellulose esterification hydrolysis sugar generating reaction, and the product is collected for sugar production. Rate analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 1 below.

Example 18

The present invention discloses the sugar efficiency test of the solid catalyst (12)

Taking the weight ratio of corn stalk/formic acid to 15% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The corn stover dissolution reaction was carried out in a reflux system at 101 ° C for 3 hours. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 19

The present invention discloses the sugar yield test of solid catalyst (13)

Taking the weight ratio of corn stalk/formic acid to 15% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The corn stover dissolution reaction was carried out in a reflux system at 101 ° C for 3 hours. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours. 10 g of the primary hydrolysis reaction product was added, and 10 g of sulfuric acid (3 M) and 15 g of deionized water were added, and a second hydrolysis reaction was carried out at 100 ° C for a hydrolysis time of 0.5 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 20

The present invention discloses the sugar efficiency test of the solid catalyst (14)

Taking the weight ratio of corn stalk/formic acid to 15% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The weight ratio of the azeotrope n-hexane/(corn stalk + formic acid) was 18.25%, and 1 wt% of sulfuric acid was added, and the corn stover dissolution reaction was carried out for 3 hours in a reflux system of 64 °C. After the corn stalk dissolution reaction was completed, the product was collected for sugar yield analysis.

The sample was determined by the 3,5-dinitrosalicylic acid method (DNS method) to determine the total reducing sugar content by HPLC (High-performance liquid). Chromatography, high performance liquid chromatography) Determination of glucose content. The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 21

The present invention discloses the sugar efficiency test of the solid catalyst (15)

Taking the weight ratio of corn stalk/formic acid to 15% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The weight ratio of the azeotrope n-hexane/(corn stalk + formic acid) was 18.25%, and 1 wt% of sulfuric acid was added, and the corn stover dissolution reaction was carried out for 3 hours in a reflux system of 64 °C. After the corn stalk dissolving reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 1 hour, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 22

The present invention discloses the sugar efficiency test of the solid catalyst (16)

Taking the weight ratio of corn stalk/formic acid to 15% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The weight ratio of the azeotrope n-hexane/(corn stalk + formic acid) was 18.25%, and 1 wt% of sulfuric acid was added, and the corn stover dissolution reaction was carried out for 3 hours in a reflux system of 64 °C. After the corn stalk dissolution reaction is over, To the product, 50% by weight of water of the mixture was added, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for analysis of sugar yield.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 23

The present invention discloses the sugar efficiency test of solid catalyst (17)

Taking the weight ratio of corn stalk/formic acid to 15% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The weight ratio of the azeotrope n-hexane/(corn stalk + formic acid) was 18.25%, and 1 wt% of sulfuric acid was added, and the corn stover dissolution reaction was carried out for 3 hours in a reflux system of 64 °C. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours. 10 g of the primary hydrolysis reaction product was added, and 10 g of sulfuric acid (3 M) and 15 g of deionized water were added, and a second hydrolysis reaction was carried out at 100 ° C for a hydrolysis time of 0.5 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 24

The present invention discloses the sugar efficiency test of the solid catalyst (18)

Taking the weight ratio of corn stalk/formic acid to 20% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The corn stover dissolution reaction was carried out for 3 hours in a 40 ° C reflux system. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 25

The present invention discloses the sugar yield test of solid catalyst (19)

Taking the weight ratio of corn stalk/formic acid to 20% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The corn stover dissolution reaction was carried out for 3 hours in a reflux system at 60 °C. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). Reducing sugar package Glucose, xylose, mannose, arabinose and oligosaccharide, etc., the results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 26

The present invention discloses the sugar efficiency test of the solid catalyst (20)

Taking the weight ratio of corn stalk/formic acid to 20% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The corn stover dissolution reaction was carried out for 3 hours in a reflux system at 80 °C. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 27

The present invention discloses the sugar yield test of solid catalyst (21)

Taking the weight ratio of corn stalk/formic acid to 20% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The corn stover dissolution reaction was carried out for 3 hours in a 100 ° C reflux system. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The samples were determined by the 3,5-dinitrosalicylic acid method (DNS method). The reducing sugar content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 28

The present invention discloses the sugar efficiency test of the solid catalyst (22)

Taking the weight ratio of corn stalk/formic acid to 20% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 1.95%. The corn stover dissolution reaction was carried out for 3 hours in a 100 ° C reflux system. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 29

The present invention discloses the sugar yield test of solid catalyst (23)

The weight ratio of corn stalk/formic acid was 20% by weight as a reactant, and the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 3.90%. The corn stover dissolution reaction was carried out for 3 hours in a 100 ° C reflux system. After the corn stalk dissolution reaction is completed, in the product, 50% by weight of water of the mixture is added, and a hydrolysis reaction is carried out at 100 ° C. The hydrolysis time was 2 hours, and the product was collected for analysis of sugar yield.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 30

The present invention discloses the sugar efficiency test of the solid catalyst (24)

The weight ratio of corn stalk/formic acid was 20% by weight as a reactant, and the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 7.80%. The corn stover dissolution reaction was carried out for 3 hours in a 100 ° C reflux system. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 31

The present invention discloses the sugar efficiency test of the solid catalyst (25)

Taking the weight ratio of corn stalk/formic acid to 20% by weight as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. Take the azeotrope n-hexane / (corn stalk) The weight ratio of + formic acid was 18.25%, and the corn stover dissolution reaction was carried out for 3 hours in a 64 ° C reflux system. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 32

The present invention discloses the sugar efficiency test of the solid catalyst (26)

Taking the weight ratio of corn stalk/formic acid to 25 wt% as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The corn stover dissolution reaction was carried out for 3 hours in a reflux system at 60 °C. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 33

The present invention discloses the sugar efficiency test of solid catalyst (27)

Taking the weight ratio of corn stalk/formic acid to 25 wt% as a reactant, the weight ratio of the solid catalyst (code BRS 2)/(corn stalk + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The weight ratio of the azeotrope n-hexane/(corn stalk + formic acid) was 18.25%, and the corn stover dissolution reaction was carried out for 3 hours in a reflux system of 64 °C. After the corn stalk dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 34

The present invention discloses the sugar efficiency test of the solid catalyst (28)

The bagasse/formic acid weight ratio was 20 wt% as a reactant, and the weight ratio of the solid catalyst (code BRS 2)/(bagasse + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 15.6%. The bagasse dissolution reaction was carried out for 3 hours in a 60 ° C reflux system. After the bagasse dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for analysis of sugar yield.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar comprises glucose, xylose, mannose, arabinose and oligosaccharide, etc., of the embodiment The results of the sugar production test are shown in Table 2 below.

Example 35

The present invention discloses the sugar efficiency test of solid catalyst (29)

The bagasse/formic acid weight ratio was 20 wt% as a reactant, and the weight ratio of the solid catalyst (code BRS 2)/(bagasse + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 20.4%. The bagasse dissolution reaction was carried out for 3 hours in a 60 ° C reflux system. After the bagasse dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for analysis of sugar yield.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 36

The present invention discloses the sugar efficiency test of the solid catalyst (30)

The bagasse/formic acid weight ratio was 25 wt% as a reactant, and the weight ratio of the solid catalyst (code BRS 2)/(bagasse + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 20.4%. The bagasse dissolution reaction was carried out for 3 hours in a 60 ° C reflux system. After the bagasse dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for analysis of sugar yield.

The sample was determined by the 3,5-dinitrosalicylic acid method (DNS method) to determine the total reducing sugar content by HPLC (High-performance liquid). Chromatography, high performance liquid chromatography) Determination of glucose content. The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 37

The present invention discloses the sugar yield test of solid catalyst (31)

The bagasse/formic acid weight ratio was 25 wt% as a reactant, and the weight ratio of the solid catalyst (code BRS 2)/(bagasse + formic acid) directly sulfonated after the sugar-producing bagasse prepared in Example 3 was 20.4%. The weight ratio of the entrainer n-hexane/(bagasse+formic acid) was 18.25%, and the bagasse dissolution reaction was carried out for 3 hours in a reflux system of 64 °C. After the bagasse dissolution reaction was completed, 50 wt% of water of the mixture was added to the product, and a hydrolysis reaction was carried out at 100 ° C for 2 hours, and the product was collected for analysis of sugar yield.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 2 below.

Example 38

The present invention discloses the sugar efficiency test of the solid catalyst (32)

The sulfonated iron oxide solid catalyst prepared in Example 6 was prepared, and the corn stalk/formic acid weight ratio was 10/90, and the biomass was pretreated, the azeotropic agent, the inorganic acid and the second hydrolysis were used to hydrolyze the raw material. The impact assessment, the results are shown in Table 3 below.

Reactant: 10wt% corn stalk, oxidized iron oxide solid catalyst / (corn stalk + formic acid) = 0.156, n-hexane / (corn stalk + formic acid) = 0.1825, secondary hydrolysis: esterification of sugar production product 10g, added 10g concentration is 3M sulfuric acid, then add 15g Deionized water was reacted at 100 ° C for 30 minutes.

It can be seen from Table 3 that after grinding (corn stalk grinding through mesh no. 30 mesh, particle size <0.59mm), the sugar production effect of the biomass is better than that of the coarse crusher, because the polished biomass is in contact with the solid acid catalyst. The specific surface area is large, and therefore, the reactivity is preferred. The effect of adding an entrainer is preferred in each set of reaction conditions. The corn stalks treated before grinding were treated with n-hexane as an entraining agent. After esterification for 3 hours, 50% by weight of water was added for hydrolysis. After hydrolysis for 2 hours, the sugar yield was 76.6 wt%, and the product was further added with sulfuric acid. Sub-hydrolysis, the sugar production rate can reach 83.3wt%. After the reaction, the catalyst is attracted by a strong magnet, and the catalyst is attracted by the magnet. The catalyst recovery rate is 98% by weight or more. After the catalyst is washed and used, it can be reused three times, and the sugar yield can reach 81% by weight.

Comparative Example 1

Sugar production efficiency test of traditional solid catalyst (1)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of Amberlyst 35 solid catalyst/(cellulose + formic acid) was 15.6%, and the cellulose dissolution reaction was carried out in a reflux system at 101 ° C for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 1.5 hours, and the product was collected for analysis of sugar yield.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 2

Sugar production efficiency test of traditional solid catalyst (2)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of Amberlyst 15 solid catalyst / (cellulose + formic acid) was 15.6%, and the cellulose dissolution reaction was carried out in a reflux system at 101 ° C for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 2 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 3

Sugar production efficiency test of traditional solid catalyst (3)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of titanium dioxide solid catalyst / (cellulose + formic acid) was 20.6%, and the cellulose dissolution reaction was carried out in a reflux system at 101 ° C for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 2 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 4

Sugar production efficiency test of traditional solid catalyst (4)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of Nafion solid catalyst/(cellulose+formic acid) was 8.4%, and the cellulose (esterification) dissolution reaction was carried out in a reflux system at 101 ° C. 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 3 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). Reducing sugar package Glucose, xylose, mannose, arabinose and oligosaccharide, etc., the results of the sugar production test of this example are shown in Table 4 below.

Comparative Example 5

Sugar production efficiency test of traditional solid catalyst (5)

Taking the cellulose/formic acid weight ratio of 5/95 as a reactant, taking the aluminum powder solid catalyst / (cellulose + formic acid) weight ratio of 20.3%, and performing cellulose (esterification) dissolution in a 101 ° C reflux system. Reaction for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 1.5 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 6

Sugar production efficiency test of traditional solid catalyst (6)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of cerium oxide solid catalyst/(cellulose+formic acid) was 8.33%, and the cellulose dissolution reaction was carried out in a reflux system at 101 ° C for 3 hours. . After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 3 hours. Thereafter, the product was collected for sugar yield analysis.

The samples were determined by the 3,5-dinitrosalicylic acid method (DNS method). The reducing sugar content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 7

Sugar production efficiency test of traditional solid catalyst (7)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of HY-zeolite solid catalyst/(cellulose+formic acid) was 15.6%, and the cellulose dissolution reaction was carried out in a reflux system at 101 ° C for 3 hours. . After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 3 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 8

Sugar production efficiency test of traditional solid catalyst (8)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of tin dioxide solid catalyst/(cellulose+formic acid) was 8.3%, and cellulose (esterification) was carried out in a reflux system at 101 ° C. The reaction was dissolved for 3 hours. After the completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 2 hours, after which the product was collected for sugar production. analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 9

Sugar production efficiency test of traditional solid catalyst (9)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of iron oxide solid catalyst/(cellulose+formic acid) was 16.6%, and cellulose (esterification) was dissolved in a reflux system of 101 ° C. Reaction for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 4 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 10

Sugar production efficiency test of traditional solid catalyst (10)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of the heteropoly acid H ₃ PW ₁₂ O ₄₀ solid catalyst / (cellulose + formic acid) was 5%, which was carried out in a reflux system of 101 ° C. The cellulose (esterification) was dissolved for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 1.5 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 11

Sugar production efficiency test of traditional solid catalyst (11)

The weight ratio of cellulose/formic acid was 5/95 as a reactant, and the weight ratio of activated carbon solid catalyst/(cellulose+formic acid) was 18.5%, and cellulose (esterification) was dissolved in a reflux system of 101 ° C. Reaction for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 2 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 12

Sugar production efficiency test of traditional solid catalyst (12)

Take the weight ratio of cellulose/formic acid to 10/90 as the reactant, take The weight ratio of Dowex solid catalyst / (cellulose + formic acid) was 15.6%, and the cellulose (esterification) dissolution reaction was carried out in a reflux system of 101 ° C for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 2 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 13

Sugar production efficiency test of traditional solid catalyst (13)

The weight ratio of cellulose/formic acid was 10/90 as a reactant, and the weight ratio of Amberlyst 35 solid catalyst/(cellulose+formic acid) was 15.6%, and cellulose (esterification) was dissolved in a reflux system of 101 ° C. Reaction for 3 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 2 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

Comparative Example 14

Sugar production efficiency test of traditional solid catalyst (14)

The weight ratio of cellulose/formic acid was 10/90 as a reactant, and the weight ratio of ZSM-5 solid catalyst/(cellulose+formic acid) was 15.6%, and cellulose (esterification) was carried out in a reflux system at 101 ° C. The reaction was dissolved for 4 hours. After completion of the cellulose dissolution reaction, 50 wt% of water of the mixture was added to the product, and hydrolysis reaction was carried out at 100 ° C for 1.5 hours. Thereafter, the product was collected for sugar yield analysis.

The total reducing sugar content was determined by the 3,5-dinitrosalicylic acid method (DNS method), and the glucose content was determined by HPLC (High-performance liquid chromatography). The reducing sugar contains glucose, xylose, mannose, arabinose, oligosaccharide, etc. The results of the sugar production efficiency test of this example are shown in Table 4 below.

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

Claims (24)

A method for preparing a saccharide, comprising: mixing an organic acid with a solid catalyst to form a mixed solution, wherein the solid catalyst comprises a core particle and a plurality of hydroxyl groups and a sulfonic acid group formed on a surface of the core particle, wherein The core particles are composed of activated carbon, lignin or iron oxide; a fibrous biomass is added to the mixed solution to carry out a dissolution reaction; and water is added to the mixed solution to carry out a hydrolysis reaction to obtain a Hydrolyzate. The method for producing a saccharide according to claim 1, wherein the organic acid comprises formic acid, acetic acid or a mixture thereof. The method for preparing a saccharide according to claim 1, wherein the weight ratio of the organic acid to the mixed solution is between 75 and 95% by weight. The method for preparing a saccharide according to claim 1, wherein the weight ratio of the solid catalyst to the mixture is from 0.5 to 21% by weight. The method for preparing a saccharide according to claim 1, wherein the cellulosic biomass comprises whole cellulose, hemicellulose or lignin. The method for preparing a saccharide according to claim 1, wherein the cellulosic biomass is in a weight ratio of 5 to 25 wt% in the mixture. The method for preparing a saccharide according to claim 1, wherein the fibrous biomass is derived from wood, grass, leaves, algae, waste paper, corn stalk, corn cob, rice straw, rice husk, wheat straw , bagasse, bamboo or crop straw stems. The method for preparing a saccharide according to claim 1, further comprising adding an azeotropic agent to the mixture to carry out the dissolution reaction. The method for producing a saccharide according to claim 8, wherein the entraining agent comprises an ester, a ketone or an alkane. The method for producing a saccharide according to claim 9, wherein the entraining agent comprises n-hexane. The method for preparing a saccharide according to claim 8, wherein the weight ratio of the azeotropic agent to the mixed solution is between 15 and 45 wt%. The method for preparing a saccharide according to claim 1, further comprising adding a mineral acid to the mixed solution to carry out the dissolution reaction. The method for producing a saccharide according to claim 12, wherein the inorganic acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or a mixture thereof. The method for preparing a saccharide according to claim 12, wherein the weight ratio of the inorganic acid to the mixed solution is between 0.5 and 3% by weight. The method for preparing a saccharide according to claim 1, wherein the temperature of the dissolution reaction is between 60 and 101 °C. The method for preparing a saccharide according to claim 1, wherein the dissolution reaction time is between 60 and 240 minutes. The method for preparing a saccharide according to claim 1, wherein the pressure of the dissolution reaction is between 0.9 and 1.1 atm. The method for preparing a saccharide according to claim 1, wherein the weight ratio of the water in the mixed solution is between 25 and 100% by weight. The method for preparing a saccharide according to claim 1, wherein the hydrolysis reaction has a temperature of from 100 to 110 °C. The method for preparing a saccharide according to claim 1, wherein the hydrolysis reaction is carried out for a period of from 30 to 180 minutes. The method for preparing a saccharide according to claim 1, wherein the pressure of the hydrolysis reaction is between 0.9 and 1.1 atm. The method for preparing a saccharide according to claim 1, further comprising adding a mineral acid to the hydrolyzate to carry out a second hydrolysis reaction. The method for producing a saccharide according to claim 22, wherein the inorganic acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or a mixture thereof. The method for preparing a saccharide according to claim 22, wherein the weight ratio of the inorganic acid to the hydrolyzed product is between 0.5 and 3% by weight.