CN115820943A - Method for preparing glucose by converting corn straws in molten salt hydrate acid system - Google Patents
Method for preparing glucose by converting corn straws in molten salt hydrate acid system Download PDFInfo
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- CN115820943A CN115820943A CN202211549749.2A CN202211549749A CN115820943A CN 115820943 A CN115820943 A CN 115820943A CN 202211549749 A CN202211549749 A CN 202211549749A CN 115820943 A CN115820943 A CN 115820943A
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- molten salt
- corn straws
- glucose
- acid system
- salt hydrate
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 36
- 239000008103 glucose Substances 0.000 title claims abstract description 36
- 240000008042 Zea mays Species 0.000 title claims abstract description 31
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 title claims abstract description 31
- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 31
- 235000005822 corn Nutrition 0.000 title claims abstract description 31
- 239000010902 straw Substances 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 16
- 150000003839 salts Chemical class 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 13
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 abstract description 21
- 229920002678 cellulose Polymers 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000002028 Biomass Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- -1 glucose monosaccharides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- 125000002353 D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing glucose by converting corn straws in a molten salt hydrate acid system, which comprises the steps of crushing and drying the corn straws, weighing a certain amount of the corn straws and a proper amount of an acidic lithium bromide molten salt solution, mixing the corn straws and the acidic lithium bromide molten salt solution, adding the mixture into a thick-wall pressure-resistant pipe, placing the thick-wall pressure-resistant pipe into an oil bath pot, and reacting for a specific time at a certain temperature to obtain the high-yield glucose. The molten salt solution used in the process has excellent swelling and capability of dispersing and dissolving the corn straws, and can destroy the hydrogen bond structure of cellulose in the corn straws and reduce the crystallinity of the corn straws. The addition of the acid accelerates the dissolution and stripping rates of the corn straws in the molten salt solution, promotes the corn straws to be hydrolyzed into glucose, and improves the yield of the glucose.
Description
Technical Field
The invention relates to the field of energy chemical technology and preparation of high-added-value chemicals by using biomass, in particular to a method for preparing glucose by converting corn straws in a molten salt hydrate acid system.
Background
At present, the social energy source structure mainly adopts fossil energy, and the large-scale exploitation of the fossil energy promotes social development, simultaneously leads to exhaustion of non-renewable fossil energy, and also brings serious pollution problems of atmosphere, water environment and the like. The biomass resource is the only carbon-containing renewable energy resource with huge reserves in the world at present, and the efficient utilization of the biomass resource is beneficial to solving the current energy and environmental problems. Lignocellulose has the characteristics of regeneration and carbon neutralization as a main biomass resource, has a quite abundant chemical structure, is considered to be one of the most abundant sources in renewable biomass fuels, and can be used as an effective raw material for realizing carbon-neutralized biomass-based chemicals. The high-efficiency utilization of the lignocellulose is beneficial to sustainable and renewable development of resources, energy sources and ecology in China, and lays a foundation for realizing carbon neutralization.
In the lignocellulosic component, cellulose comprises about 40% to about 60% of the dry weight of the lignocellulose. Cellulose is a linear glucose polymer linked by D-glucose units through β -1, 4-glycosidic linkages, and can be hydrolyzed to produce glucose monosaccharides, which are in turn synthetic precursors for many value-added chemicals and fuels. Such as various alcohols, 5-hydroxymethylfurfural (5-HMF) and levulinic acid. Among the most attractive platform chemicals is 5-HMF, which can be further converted to 2, 5-furandicarboxaldehyde (DFF) and 2, 5-furandicarboxylic acid (FDCA), which are extremely useful intermediates in the preparation of polymers and petrochemistry. However, the cellulose has high crystallinity characteristics caused by strong hydrogen bonds in and among internal molecules, so that the cellulose is insoluble in water and common organic solvents at normal temperature, the accessibility of homogeneous and heterogeneous catalysts to catalytic sites is greatly limited, and the cellulose is difficult to hydrolyze to release glucose. Some technologies such as mechanocatalytic depolymerization technology, ionic liquids, and molten salt hydrates have been developed to this end, wherein the mechanocatalytic depolymerization technology and the ionic liquids can effectively degrade cellulose into glucose or Total Reducing Sugars (TRS), such as paul dornath, etc. by co-impregnating crystalline cellulose with sulfuric acid and glucose, followed by ball milling of the crystalline cellulose, followed by hydrolysis with a carbon-based catalyst, a glucose yield of 91.2% can be obtained; silvia Morales-delaRosa et al dissolve cellulose in ionsLiquid [ BMIM]Cl for 60min, from H at 378K 2 SO 4 Catalytic hydrolysis was carried out for 180min to obtain a glucose yield of 81.5%. However, the mechanical catalytic depolymerization technology and the ionic liquid have the disadvantages of high energy consumption, high cost, high requirement on equipment, complex synthesis process, certain toxicity and the like. Whereas Molten Salt Hydrate (MSH) is easy to prepare, easy to handle, low in toxicity and has excellent ability to swell, disperse cellulose, and can be handled under a wider range of reaction conditions.
The research of preparing glucose by taking cellulose as a raw material has been widely concerned by researchers at home and abroad for a long time, the yield of glucose prepared by cellulose is high at present, and Liu and the like combine cellulose and P 2 O 5 (MMC) mixed grinding to efficiently depolymerize cellulose I to amorphous cellulose, followed by H 2 And recrystallizing in O to obtain the easily hydrolyzed cellulose II, and finally obtaining the glucose yield of 68 percent. JamesKong-WinChang et al used 72wt.% H at 30 deg.C 2 SO 4 Pretreating cellulose (H) 2 SO 4 Mass ratio/dry cellulose 36) 2H, then partially neutralized (H) with 20wt.% NaOH + the/OH molar ratio is 2.3-2.5) and hydrolysis is carried out for 10min at 121 ℃, and the glucose yield close to 100 percent can be obtained. The process for preparing glucose by cellulose is popularized to the process for preparing glucose by converting biomass, and the defects of low glucose yield, difficult separation and recovery of products and the like which are not suitable occur. Therefore, the design of a more efficient and more economical biomass catalytic reaction system for directly converting biomass to prepare high-yield glucose has important significance.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for preparing glucose by converting corn straws in a molten salt hydrate acid system, which comprises the following steps:
(1) Adding the crushed and dried corn straws and the acidic lithium bromide molten salt solution containing sulfuric acid into a thick-wall pressure-resistant pipe;
the mass ratio of the corn straw to the acidic lithium bromide molten salt solution in the step (1) is 0.1g:6g, sulfuric acid 0.05mol/L.
The molar ratio of the lithium bromide to the water in the acidic lithium bromide molten salt solution in the step (1) is 3.2.
(2) Placing in an oil bath pan for full reaction to obtain glucose reaction solution.
In the step (2), the reaction temperature is 85-95 ℃ and the reaction time is 40-55 min.
Further preferably, the reaction temperature in the step (2) is 90 ℃ and the reaction time is 45min.
According to the invention, the specific acid amount is added into the lithium bromide molten salt hydrate, and the corn straw is catalyzed and converted under the appropriate reaction condition, so that the high-yield glucose is obtained. In the method, the molten salt solution has excellent swelling and capability of dispersing and dissolving the corn straws, and can destroy the hydrogen bond structure of cellulose in the corn straws and reduce the crystallinity of the corn straws. The addition of the acid accelerates the dissolution and stripping rates of the corn straws in the molten salt solution, promotes the corn straws to be hydrolyzed into glucose, and improves the yield of the glucose.
Detailed Description
The embodiments of the present invention will be described in further detail. However, the shi 2 mode of the present invention is not limited to the following examples.
Transforming corn straws by a molten salt hydrate acid system: 0.1g of corn straw and 6g of acidic lithium bromide molten salt solution (the molar ratio of lithium bromide to water is 3.2, and the sulfuric acid content is 0.05 mol/L) are weighed and added into a thick-wall pressure-resistant pipe, the thick-wall pressure-resistant pipe is sealed and placed into an oil bath pot, and the thick-wall pressure-resistant pipe is kept for 45min at 90 ℃. After the reaction, the thick-walled pressure-resistant tube was taken out to water and cooled, and after cooling, the reaction solution was filtered with a 0.22 μm organic filter membrane, and the filtrate was collected and subjected to HPLC analysis to obtain a glucose yield of 86.38%.
TABLE 1
The results of converting corn stover in a molten salt hydrate acid system to produce glucose at different temperatures and times are shown in table 1. The reaction is carried out for 45min at the temperature of 90 ℃, and the glucose with higher yield can be obtained, and the yield reaches 86.38%.
Finally, it should be noted that the above list is only a specific implementation example of the present invention. It is obvious that the invention is not limited to the above embodiment examples, but that many variations are possible. All modifications which can be derived or suggested directly from the disclosure of the present invention by a person skilled in the art are considered to be within the scope of the present invention.
Claims (5)
1. The method for preparing glucose by converting corn straws in a molten salt hydrate acid system is characterized by comprising the following steps:
(1) Adding the crushed and dried corn straws and the acidic lithium bromide molten salt solution containing sulfuric acid into a thick-wall pressure-resistant pipe;
(2) Placing in an oil bath pan for full reaction to obtain glucose reaction solution.
2. The method for preparing glucose by converting corn stalks in a molten salt hydrate acid system according to claim 1, wherein the molten salt hydrate acid system comprises the following steps: the mass ratio of the corn straw to the acidic lithium bromide molten salt solution in the step (1) is 0.1g:6g, sulfuric acid 0.05mol/L.
3. The method for preparing glucose by converting corn stalks in a molten salt hydrate acid system according to claim 2, wherein: the molar ratio of the lithium bromide to the water in the acidic lithium bromide molten salt solution in the step (1) is 3.2.
4. The method for preparing glucose by converting corn stalks in a molten salt hydrate acid system according to claim 1, wherein: in the step (2), the reaction temperature is 85-95 ℃ and the reaction time is 40-55 min.
5. The method for preparing glucose by converting corn stalks in a molten salt hydrate acid system according to claim 1, wherein: in the step (2), the reaction temperature is 90 ℃ and the reaction time is 45min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211549749.2A CN115820943A (en) | 2022-12-05 | 2022-12-05 | Method for preparing glucose by converting corn straws in molten salt hydrate acid system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211549749.2A CN115820943A (en) | 2022-12-05 | 2022-12-05 | Method for preparing glucose by converting corn straws in molten salt hydrate acid system |
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| CN115820943A true CN115820943A (en) | 2023-03-21 |
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| CN202211549749.2A Pending CN115820943A (en) | 2022-12-05 | 2022-12-05 | Method for preparing glucose by converting corn straws in molten salt hydrate acid system |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558112A (en) * | 2012-02-27 | 2012-07-11 | 中国科学技术大学 | Method for converting cellulose into 5-hydroxymethylfurfural (HMF) |
| US20130252302A1 (en) * | 2012-03-25 | 2013-09-26 | Wisconsin Alumni Reserarch Foundation | Saccharification of lignocellulosic biomass |
| CN107937446A (en) * | 2017-12-22 | 2018-04-20 | 天津大学 | A kind of technique using maize straw as waste ethanol |
-
2022
- 2022-12-05 CN CN202211549749.2A patent/CN115820943A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558112A (en) * | 2012-02-27 | 2012-07-11 | 中国科学技术大学 | Method for converting cellulose into 5-hydroxymethylfurfural (HMF) |
| US20130252302A1 (en) * | 2012-03-25 | 2013-09-26 | Wisconsin Alumni Reserarch Foundation | Saccharification of lignocellulosic biomass |
| CN107937446A (en) * | 2017-12-22 | 2018-04-20 | 天津大学 | A kind of technique using maize straw as waste ethanol |
Non-Patent Citations (1)
| Title |
|---|
| WEIHUA DENG等: "Cellulose Hydrolysis in Acidified LiBr Molten Salt Hydrate Media", 《I&EC RESEARCH 》, no. 54, pages 5226 - 5234 * |
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