CN111893219A - Method for catalyzing hydrolysis of polysaccharide by carbon-based solid acid catalyst - Google Patents
Method for catalyzing hydrolysis of polysaccharide by carbon-based solid acid catalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000011973 solid acid Substances 0.000 title claims abstract description 60
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- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 45
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- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 40
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- 238000000034 method Methods 0.000 title claims abstract description 25
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- 229930006000 Sucrose Natural products 0.000 claims description 4
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 claims description 4
- 239000008101 lactose Substances 0.000 claims description 4
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- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- FTSSQIKWUOOEGC-RULYVFMPSA-N fructooligosaccharide Chemical compound OC[C@H]1O[C@@](CO)(OC[C@@]2(OC[C@@]3(OC[C@@]4(OC[C@@]5(OC[C@@]6(OC[C@@]7(OC[C@@]8(OC[C@@]9(OC[C@@]%10(OC[C@@]%11(O[C@H]%12O[C@H](CO)[C@@H](O)[C@H](O)[C@H]%12O)O[C@H](CO)[C@@H](O)[C@@H]%11O)O[C@H](CO)[C@@H](O)[C@@H]%10O)O[C@H](CO)[C@@H](O)[C@@H]9O)O[C@H](CO)[C@@H](O)[C@@H]8O)O[C@H](CO)[C@@H](O)[C@@H]7O)O[C@H](CO)[C@@H](O)[C@@H]6O)O[C@H](CO)[C@@H](O)[C@@H]5O)O[C@H](CO)[C@@H](O)[C@@H]4O)O[C@H](CO)[C@@H](O)[C@@H]3O)O[C@H](CO)[C@@H](O)[C@@H]2O)[C@@H](O)[C@@H]1O FTSSQIKWUOOEGC-RULYVFMPSA-N 0.000 claims description 3
- 229940107187 fructooligosaccharide Drugs 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 5
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- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000002016 disaccharides Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 150000004043 trisaccharides Chemical class 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 241000220479 Acacia Species 0.000 description 1
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- 229920002527 Glycogen Polymers 0.000 description 1
- 229920002683 Glycosaminoglycan Polymers 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
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- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K3/00—Invert sugar; Separation of glucose or fructose from invert sugar
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention relates to a method for hydrolyzing polysaccharide by using a carbon-based solid acid catalyst, which comprises the steps of mixing the carbon-based solid acid catalyst and the polysaccharide in water, and then carrying out hydrolysis reaction, wherein the temperature of the hydrolysis reaction is not higher than 100 ℃ and the time is less than 3 hours, so that monosaccharide can be obtained; the carbon-based solid acid catalyst is an acidified carbon solid material with a pore structure; the preparation method of the carbon-based solid acid catalyst comprises the steps of dissolving a carbohydrate in water, adding liquid acid, stirring, carrying out heat treatment at 80-200 ℃ for 1-24 h, and roasting at a temperature higher than 200 ℃ in a protective atmosphere to obtain an acidified carbon solid material with a pore structure, namely the carbon-based solid acid catalyst. The acidified carbon solid material with the pore structure, which is prepared by the invention, is used as a catalyst for catalyzing and hydrolyzing the polysaccharide, has higher activity for catalyzing and hydrolyzing the polysaccharide, and can obtain the polysaccharide conversion rate of more than 95% in a short time of hydrolysis at lower temperature.
Description
Technical Field
The invention relates to the technical field of carbohydrate hydrolysis, in particular to a method for catalyzing polysaccharide hydrolysis by a carbon-based solid acid catalyst.
Background
Sugars are an important class of organic compounds that are widely distributed in nature. Sucrose, starch in grains, cellulose in plants, glucose in human blood, and the like, which are eaten daily, are sugars. The saccharides can be classified into monosaccharides, oligosaccharides (oligosaccharides), polysaccharides, and complex saccharides.
Simple monosaccharides are generally polyhydroxyaldehydes or polyhydroxyketones having 3 to 7 carbon atoms, such as glucose, fructose, galactose, etc., belonging to the class of monosaccharides. Oligosaccharide (oligosaccharide) polymerized from 2-10 monosaccharide molecules, which can be hydrolyzed to generate monosaccharide including disaccharide, trisaccharide, tetrasaccharide, etc.; common disaccharides include lactose, sucrose, maltose, and the like; common trisaccharides such as raffinose and the like. The polysaccharide is polymerized from more than 10 monosaccharide molecules, and can generate a plurality of monosaccharides or oligosaccharides after hydrolysis. Such as acacia, glycogen, starch, cellulose, etc. to generate isomonose after hydrolysis; such as mucopolysaccharide, hemicellulose and the like, generate different types of monosaccharide after hydrolysis.
The polysaccharide can act with water and be hydrolyzed into corresponding monosaccharide molecules. The chemical equation is: (C)6H10O5)n+n H2O＝nC6H12O6The coefficients n are the same for all three. From this equation, it can be seen that, if there are 100 kg of polysaccharide, 111 kg of monosaccharide can be obtained after hydrolysis, and the amount of product obtained is greater than the amount of raw material used, which is one of the advantages of the hydrolysis industry.
However, the above reaction must be carried out under certain conditions of temperature and catalyst, for example, the hydrolysis reaction is accelerated by raising the reaction temperature, but the sugar is unstable at high temperature and carbonizes the sugar. The addition of a suitable catalyst can accelerate the hydrolysis reaction. The catalyst for hydrolysis may be organic or inorganic, and generally, the catalyst for hydrolysis can release hydrogen ions in water to release hydrogen ionsCombining with water to form H3O+Can promote the divalent oxygen atom on the glycosidic bond in the polysaccharide to be changed into unstable tetravalent oxygen atom, finally combined with water to be split, and finally totally split to generate monosaccharide with the prolongation of hydrolysis time.
When polysaccharide is hydrolyzed, monosaccharide is decomposed in a reaction system, because monosaccharide is also an unstable compound, particularly under the action of high temperature and hydrogen ions, monosaccharide can be continuously decomposed into sugar decomposition products such as furfural and humic acid, and monosaccharide is not a final product of polysaccharide hydrolysis but only an intermediate product. Hydrolysis kinetics are involved in the hydrolysis process, the yield of the hydrolyzed sugar depends on the hydrolysis speed of the polysaccharide to generate monosaccharide and the decomposition speed of the monosaccharide, and if the hydrolysis speed of the polysaccharide is higher than the decomposition speed of the monosaccharide to the non-sugar, the yield of the hydrolyzed sugar is high.
At present, inorganic acid is mainly used for hydrolyzing polysaccharide as protonic acid, most of the inorganic acid is strong acid, but the application of inorganic acid such as HI and HBr is limited due to high price, and most of common hydrochloric acid, sulfuric acid and the like have strong corrosivity on metal equipment, can generate waste acid pollution and are difficult to separate. How to obtain a method for hydrolyzing saccharides, which has mild conditions, is green and economic and has reusable catalyst, is a key problem to be solved.
Disclosure of Invention
In order to obtain a method for hydrolyzing saccharides under mild conditions, which is green and economic and has reusable catalyst, and overcome the technical problems of serious pollution, high energy consumption, difficult recovery of the catalyst, more side reactions and the like in the prior art, the method for catalyzing the hydrolysis of polysaccharides by using the carbon-based solid acid catalyst is provided.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a method for hydrolyzing polysaccharide with carbon-based solid acid catalyst comprises mixing carbon-based solid acid catalyst and polysaccharide in water, and performing hydrolysis reaction at a temperature not higher than 100 deg.C for less than 3 hr to obtain monosaccharide;
the carbon-based solid acid catalyst is an acidified carbon solid material with a pore structure.
Further, the preparation method of the carbon-based solid acid catalyst comprises the following steps: dissolving a saccharide compound in water to form a saccharide solution, adding liquid acid into the saccharide solution, stirring to obtain a mixed solution, carrying out heat treatment on the mixed solution at the temperature of 80-200 ℃ for 1-24 h, and roasting at the temperature higher than 200 ℃ in a protective atmosphere to obtain an acidified carbon solid material with a pore structure, namely the carbon-based solid acid catalyst.
Further, the saccharide compound is one or more of glucose, fructose, sucrose, maltose, lactose, starch and dextrin; the liquid acid is one or more of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and chlorosulfonic acid.
Still further, the mass ratio of the saccharide compound to the liquid acid is 1 (1-5); the concentration of the saccharide compound in the water is 0.2-1 g/mL.
Further, the protective atmosphere is one of nitrogen, argon and helium; the roasting temperature is 300-400 ℃ and the roasting time is 2-8 h.
Further, the polysaccharide is one of fructooligosaccharide, xylooligosaccharide, cellulose and starch.
Further, the amount of the carbon-based solid acid catalyst is 4-50% of the mass of the polysaccharide; the mass ratio of the polysaccharide to the water is (0.6-1) to (10-25).
The beneficial technical effects are as follows:
compared with the traditional method for catalyzing polysaccharide hydrolysis by using a protonic acid catalyst, the acidified carbon solid material with a pore structure, which is prepared by the invention, is used as the catalyst for catalyzing polysaccharide hydrolysis, has higher activity for catalyzing polysaccharide hydrolysis, and can obtain the polysaccharide conversion rate of more than 95% in a short time by hydrolyzing at a lower temperature; the carbon-based solid acid catalyst is environment-friendly, insoluble in water, easy to separate, not easy to cause equipment corrosion, low in preparation cost, simple in synthetic route, economical and easy to implement, and has wide application prospects in various aspects such as industrial catalysis, water treatment, electrochemistry and the like; in addition, the carbon-based solid acid catalyst is solid, has higher specific surface area, adjustable acid sites and better chemical stability, is simple to separate in a hydrolysis system and can be repeatedly used, and the catalytic efficiency is not obviously reduced after the repeated use.
Drawings
FIG. 1 is a transmission electron microscope photograph of a carbon-based solid acid catalyst prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
Example 1
The preparation method of the carbon-based solid acid catalyst comprises the following steps: dissolving 1g of glucose in 1mL of deionized water, stirring at room temperature for 3h to obtain a glucose solution, adding 1.0g of 98 wt% sulfuric acid into the glucose solution, stirring for 2h to obtain a mixed solution, drying the mixed solution at 100 ℃ for 12h, and roasting at 300 ℃ for 8h in a nitrogen atmosphere to obtain an acidified carbon solid material, namely the carbon-based solid acid catalyst.
The carbon-based solid acid catalyst obtained in this example was observed by a Transmission Electron Microscope (TEM) showing a TEM image as shown in FIG. 1As can be seen, the carbon-based solid acid catalyst prepared in this example has a pore structure, and the BET test of the carbon-based solid acid catalyst has a specific surface area of 345.3m2/g。
A method for catalyzing polysaccharide hydrolysis by a carbon-based solid acid catalyst comprises the following steps: taking 0.3g of the carbon-based solid acid catalyst and 1.2g of xylo-oligosaccharide, adding 20mL of water, reacting at 80 ℃ for 60min, filtering the reaction liquid to separate out the carbon-based solid acid catalyst, and measuring the monosaccharide yield to be 95.3%.
The carbon-based catalyst can be continuously recycled after being recovered and washed and dried, the recycling frequency can reach more than 3 times, the yield of monosaccharide obtained by catalyzing and hydrolyzing cellulose after being recycled for 3 times is more than 90%, and the catalytic activity is not obviously reduced.
Example 2
The preparation method of the carbon-based solid acid catalyst comprises the following steps: dissolving 1g of fructose in 5mL of deionized water, stirring at room temperature for 3h to obtain a glucose solution, adding 1.25g of 89 wt% phosphoric acid into the fructose solution, stirring for 2h to obtain a mixed solution, drying the mixed solution at 80 ℃ for 24h, and roasting at 350 ℃ for 4h in an argon atmosphere to obtain an acidified carbon solid material, namely a carbon-based solid acid catalyst.
The carbon-based solid acid catalyst obtained in this example was observed by a Transmission Electron Microscope (TEM) having a pore structure similar to that of FIG. 1 and having a BET specific surface area of 298.4m2/g。
A method for catalyzing polysaccharide hydrolysis by a carbon-based solid acid catalyst comprises the following steps: taking 0.2g of the carbon-based solid acid catalyst and 1.2g of starch, adding 40mL of water, reacting at 100 ℃ for 60min, filtering the reaction liquid to separate out the carbon-based solid acid catalyst, and measuring the monosaccharide yield to be 97%.
Example 3
The preparation method of the carbon-based solid acid catalyst comprises the following steps: dissolving 1g of lactose in 3mL of deionized water, stirring at room temperature for 3h to obtain a glucose solution, adding 5g of 37% hydrochloric acid into the fructose solution, stirring for 2h to obtain a mixed solution, drying the mixed solution at 150 ℃ for 2h, and roasting at 400 ℃ for 2h in a nitrogen atmosphere to obtain an acidified carbon solid material, namely the carbon-based solid acid catalyst.
The carbon-based solid acid catalyst obtained in this example was observed by a Transmission Electron Microscope (TEM) having a pore structure similar to that of FIG. 1 and having a BET specific surface area of 367.3m2/g。
A method for catalyzing polysaccharide hydrolysis by a carbon-based solid acid catalyst comprises the following steps: taking 0.2g of the carbon-based solid acid catalyst and 1.2g of fructo-oligosaccharide, adding 40mL of water, reacting at 90 ℃ for 50min, filtering the reaction liquid to separate out the carbon-based solid acid catalyst, and measuring the monosaccharide yield to be 99%.
Example 4
The preparation method of the carbon-based solid acid catalyst comprises the following steps: adding 1g of dextrin into 1mL of deionized water, stirring for 3 hours at room temperature to obtain a dextrin solution, adding 1g of 98 wt% sulfuric acid and 1g of chlorosulfonic acid into the dextrin solution, stirring for 2 hours to obtain a mixed solution, drying the mixed solution at 100 ℃ for 24 hours, and roasting at 300 ℃ for 4 hours in a nitrogen atmosphere to obtain an acidified carbon solid material, namely the carbon-based solid acid catalyst.
The carbon-based solid acid catalyst obtained in this example was observed by a transmission electron microscope to have a pore structure in a TEM image similar to that of FIG. 1, and a BET test showed a specific surface area of 351.7m2/g。
A method for catalyzing polysaccharide hydrolysis by a carbon-based solid acid catalyst comprises the following steps: taking 0.3g of the carbon-based solid acid catalyst and 1.2g of polysaccharide, adding 40mL of water, reacting at 90 ℃ for 2.5h, filtering the reaction liquid to separate out the carbon-based solid acid catalyst, and measuring the monosaccharide yield to be 97.5%.
Example 5
The carbon-based solid acid catalyst was prepared in the same manner as in example 1.
A method for catalyzing polysaccharide hydrolysis by a carbon-based solid acid catalyst comprises the following steps: taking 0.05g of the carbon-based solid acid catalyst and 1.2g of xylo-oligosaccharide, adding 20mL of water, reacting at 100 ℃ for 2.8h, filtering the reaction liquid to separate the carbon-based solid acid catalyst, and measuring the monosaccharide yield to be 95%.
Comparative example 1
The carbon-based solid acid catalyst of this comparative example was prepared as follows: directly roasting glucose in a nitrogen atmosphere at 300 ℃ for 8h to obtain a carbon material, then soaking the obtained carbon material in 98 wt% sulfuric acid for acidification and etching for 12h to obtain an acidified carbon solid material, and observing the acidified carbon solid material by adopting a TEM (transmission electron microscope) to obtain the same porous structure.
The hydrolysis of xylo-oligosaccharides was catalyzed according to the formulation and method of example 1, and the monosaccharide yield was determined to be 49%.
Compared with the example 1, the catalyst prepared by performing high-temperature carbonization and acidification in the comparative example 1 has weak acid site combination, and an active center falls off during the hydrolysis reaction of the catalytic polysaccharide, so that the hydrolysis reaction effect is poor. According to the invention, firstly, saccharide compounds such as glucose and the like are dissolved in water and then added with liquid acid for stirring, the saccharide compounds such as glucose and the like have more hydroxyl active sites and can be better combined with the liquid acid in the water, then, the saccharide compounds such as glucose and the like are subjected to preheating treatment at a lower high temperature, the hydroxyl active sites on the saccharide compounds such as glucose and the like can be more firmly combined with the acid, and the carbon-based solid acid catalyst obtained after roasting has a large number of firmer acidic active sites which act with glycosidic bonds to break the acidic active sites, so that the polysaccharide can be efficiently catalyzed and completely hydrolyzed into monosaccharide.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for catalyzing polysaccharide hydrolysis by a carbon-based solid acid catalyst is characterized in that the carbon-based solid acid catalyst and the polysaccharide are mixed in water and then subjected to hydrolysis reaction, the temperature of the hydrolysis reaction is not higher than 100 ℃, and the time is less than 3 hours, so that monosaccharide can be obtained;
the carbon-based solid acid catalyst is an acidified carbon solid material with a pore structure.
2. The method for hydrolyzing polysaccharide with carbon-based solid acid catalyst as claimed in claim 1, wherein the preparation method of carbon-based solid acid catalyst comprises the following steps:
dissolving a saccharide compound in water to form a saccharide solution, adding liquid acid into the saccharide solution, stirring to obtain a mixed solution, carrying out heat treatment on the mixed solution at the temperature of 80-200 ℃ for 1-24 h, and roasting at the temperature higher than 200 ℃ in a protective atmosphere to obtain an acidified carbon solid material with a pore structure, namely the carbon-based solid acid catalyst.
3. The method for catalyzing polysaccharide hydrolysis by using the carbon-based solid acid catalyst as claimed in claim 2, wherein the sugar compound is one or more of glucose, fructose, sucrose, maltose, lactose, starch and dextrin; the liquid acid is one or more of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and chlorosulfonic acid.
4. The method for hydrolyzing polysaccharide by using carbon-based solid acid catalyst as claimed in claim 2, wherein the mass ratio of the saccharide compound to the liquid acid is 1 (1-5); the concentration of the saccharide compound in the water is 0.2-1 g/mL.
5. The method of claim 2, wherein the protective atmosphere is one of nitrogen, argon, helium; the roasting temperature is 300-400 ℃ and the roasting time is 2-8 h.
6. The method of claim 2, wherein the polysaccharide is one of fructooligosaccharide, xylooligosaccharide, cellulose and starch.
7. The method for hydrolyzing polysaccharide with carbon-based solid acid catalyst as claimed in claim 2, wherein the amount of carbon-based solid acid catalyst is 4-50% of the polysaccharide; the mass ratio of the polysaccharide to the water is (0.6-1) to (10-25).
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| JP2012231683A (en) * | 2011-04-28 | 2012-11-29 | Equos Research Co Ltd | Cellulose saccharification method |
| CN106824226A (en) * | 2017-01-14 | 2017-06-13 | 江苏理工学院 | A kind of preparation method and its usage of carbon-based solid acid |
| CN108950090A (en) * | 2018-07-20 | 2018-12-07 | 江苏理工学院 | A kind of method for hydrolysis of saccharide compound |
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| WO2011036955A1 (en) * | 2009-09-25 | 2011-03-31 | 国立大学法人北海道大学 | Catalyst for hydrolysis of cellulose or hemicellulose, and process for production of sugar-containing solution using the catalyst |
| CN101786015A (en) * | 2010-03-31 | 2010-07-28 | 华南理工大学 | Hydrothermal preparation method of carbon-based solid sulfoacid |
| JP2012231683A (en) * | 2011-04-28 | 2012-11-29 | Equos Research Co Ltd | Cellulose saccharification method |
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