CN103194924A - Method for extracting cellulose from straw stalk by using imidazole ion liquid - Google Patents
Method for extracting cellulose from straw stalk by using imidazole ion liquid Download PDFInfo
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- CN103194924A CN103194924A CN2013101085233A CN201310108523A CN103194924A CN 103194924 A CN103194924 A CN 103194924A CN 2013101085233 A CN2013101085233 A CN 2013101085233A CN 201310108523 A CN201310108523 A CN 201310108523A CN 103194924 A CN103194924 A CN 103194924A
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- methylimidazole
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Abstract
The invention discloses a method for extracting cellulose from straw stalk by using imidazole ion liquid. Firstly, the straw stalk is crushed into 100-mesh powder, and then an ion liquid 1-allyl-3-methylimidazole chloride (AMIMCI) is used for extracting the cellulose in an ultrasonic environment, wherein the ion liquid 1-allyl-3-methylimidazole chloride (AMIMCI) is formed by synthesizing N-methylimidazole and allyl chloride. The method disclosed by the invention has the following advantages: by adopting ultrasonic oscillation to assist the ion liquid to dissolve the straw stalk powder, the method contributes to removal of lignin, can be used for effectively releasing connection of ester bonds between the lignin and a carbohydrate, effectively eliminating the coating effect of the lignin to the cellulose and hemicellulose, enhancing solution of the cellulose in the ion liquid, realizing efficient treatment of the straw stalk, improving the utilization efficiency of biomass resources and solving the problem that the straw stalk is hard to degrade and recycle, and has far-reaching social meaning and economical value.
Description
Technical field
The present invention relates to the biomass processes technology, particularly a kind ofly from rice straw, extract cellulosic method with glyoxaline ion liquid.
Background technology
Follow day being becoming tight of gradually exhausted, the energy of disposable fossil fuel resource and resource, how regenerative resource---biomass energy has become the topic of countries in the world common concern for high-efficiency comprehensive utilization and digestion.Cellulose is the living beings macromolecule that the occurring in nature distribution is the widest, reserves are maximum, and by β-1, the 4-glycosidic bond connects and the glucan of formation its structure by glucose molecule.Usually containing thousands of glucose units, is the main component of plant cell wall.Annual plant can produce 1,000 hundred million tons cellulose by photosynthesis, simultaneously owing to plurality of advantages such as pollution-free, biocompatibility, readily degradable, wide material sources, be considered to be inexhaustible, nexhaustible renewable resource is widely used in departments such as weaving, light industry, chemical industry, medicine and the energy.
The research of ionic liquid aspect dissolving cellulos has at present had swift and violent development.The ionic liquid of discovering numerous species has solvability to cellulose.Zwitterion in the ionic liquid is for the dissolving cellulos decisive role.Except glyoxaline ion liquid, minority pyridines ionic liquid also has the certain dissolubility energy to cellulose at present, but the pyridines ionic liquid makes that than harsh conditions such as serious and solution temperature height research is less at present to cellulose degradation.And imidazole ion liquid because of its preferably stability and more excellent dissolution process condition study more.
The complex structure of native cellulose exists in the molecule and intermolecular hydrogen bond in the strand, and with multilayer disc around mode constitute the cellulose crystalline texture of high crystalline; Lignin and hemicellulose and cellulosic combination simultaneously makes that the contact area of cellulose and ionic liquid is littler.More than these characteristics restricted the dissolving of cellulose in ionic liquid.Ultrasonic wave can destroy the hydrogen bond in the cellulosic molecule effectively, reduces its degree of polymerization.Therefore, adopt the sonic oscillation method auxiliary, can increase the dissolving of cellulose in ionic liquid greatly, enhance productivity.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and from rice straw, extract cellulosic method with glyoxaline ion liquid, this method equipment needed thereby is simple, technology is easy, treatment temperature is low, mild condition, and can not cause additional environmental hazard, realize the high-efficiency pretreatment of rice straw, improved biomass resource utilization efficient.
Technical scheme of the present invention:
A kind ofly extract cellulosic method with glyoxaline ion liquid from rice straw, step is as follows:
1) rice straw was ground into 100 order rice straw powder;
2) be that 1:20-40 mixes and obtains mixture with rice straw powder and ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) according to mass ratio;
3) said mixture is placed ultrasonator, ultrasonic power is 80-120W, in 60-80 ℃ of reaction 1-2h, obtains reactant;
4) with above-mentioned reactant with the centrifugal 10min of 12000r/min rotating speed, Separation of Solid and Liquid is got supernatant then;
5) in the supernatant that above-mentioned separation obtains, add absolute ethyl alcohol, supernatant is 1:5 with going the volume ratio of absolute ethyl alcohol, obtains containing sedimentary mixed liquor, behind the suction filtration sediment oven dry that obtains is preserved, be the target product cellulose, the filtrate behind the suction filtration is reclaimed;
6) ionic liquid 1-allyl-3-methylimidazole villaumite, repetitive cycling utilization are reclaimed in filtrate decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators of reclaiming.
Described ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) is synthetic by N-methylimidazole and allyl chloride, and its preparation methods steps is as follows:
1) N
2Protection mixes with allyl chloride the N-methylimidazole down with mass ratio 1.0:1.2;
2) in 40 ℃ of water-baths, add hot reflux 12h, after the removal of impurity, can make 1-allyl-3-methylimidazole villaumite.
Advantage of the present invention and beneficial effect are:
1) adopts the dissolving of the auxiliary rice straw powder of sonic oscillation, help the removal of lignin, can effectively remove lignin and be connected with ester bond between the carbohydrate, effectively broken the package action of lignin to cellulose, hemicellulose;
2) adopt 1-allyl-3-methylimidazole villaumite (AMIMCl) to extract cellulose, it is strong and be easy to reclaim, can not volatilize to cellulosic solvability, can extract cellulose effectively from rice straw and can not cause the resource excess waste;
3) this method equipment needed thereby is simple, technology is easy, treatment temperature is low, mild condition and can not cause additional environmental hazard, realized the high-efficiency pretreatment of rice straw, improve biomass resource utilization efficient, solved that rice straw is difficult to degrade, the difficult problem of recycling, had extremely far-reaching social effect and an economic worth.
The specific embodiment
The present invention is described in further detail by following examples, but the technology contents that present embodiment is narrated is illustrative, rather than determinate, should not limit to protection scope of the present invention according to this.
Embodiment 1:
A kind ofly extract cellulosic method with glyoxaline ion liquid from rice straw, step is as follows:
1) rice straw was ground into 100 order rice straw powder;
2) be that 1:20 mix with ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) according to mass ratio with the rice straw powder, obtain mixture;
3) said mixture is placed ultrasonator, use ultrasonic power 110W, in 60 ℃ of reaction 2h, obtain reactant;
4) with above-mentioned reactant with the centrifugal 10min of 12000r/min rotating speed, Separation of Solid and Liquid is got supernatant then;
5) in the supernatant that above-mentioned separation obtains, add absolute ethyl alcohol, supernatant is 1:5 with going the volume ratio of absolute ethyl alcohol, obtains containing sedimentary mixed liquor, behind the suction filtration sediment oven dry that obtains is preserved, be the target product cellulose, the filtrate behind the suction filtration is reclaimed;
6) ionic liquid 1-allyl-3-methylimidazole villaumite, repetitive cycling utilization are reclaimed in filtrate decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators of reclaiming.
Described ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) is to be synthesized with the mass ratio of 1.0:1.2 by N-methylimidazole, allyl chloride, and its preparation methods steps is as follows:
1) N
2Protection mixes with allyl chloride the N-methylimidazole down with mass ratio 1.0:1.2;
2) in 40 ℃ of water-baths, add hot reflux 12h, after the removal of impurity, can make 1-allyl-3-methylimidazole villaumite.
Testing result shows: ultrasonic wave is down auxiliary, extract through 1-allyl-3-methylimidazole villaumite (AMIMCl), the cellulosic recovery rate of gained is 75%, and described recovery rate is the ratio of cellulose quality in the cellulose quality of dissolving in the ionic liquid and the rice straw.Ionic liquid decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators is reclaimed, and the rate of recovery is 95%
Embodiment 2:
A kind ofly extract cellulosic method with glyoxaline ion liquid from rice straw, step is as follows:
1) rice straw was ground into 100 order rice straw powder;
2) be that 1:30 mix with ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) according to mass ratio with the rice straw powder, obtain mixture;
3) said mixture is placed ultrasonator, use ultrasonic power 100W, in 60 ℃ of reaction 2h, obtain reactant;
4) with above-mentioned reactant with the centrifugal 10min of 12000r/min rotating speed, Separation of Solid and Liquid is got supernatant then;
5) in the supernatant that above-mentioned separation obtains, add absolute ethyl alcohol, supernatant is 1:5 with going the volume ratio of absolute ethyl alcohol, obtains containing sedimentary mixed liquor, behind the suction filtration sediment oven dry that obtains is preserved, be the target product cellulose, the filtrate behind the suction filtration is reclaimed;
6) ionic liquid 1-allyl-3-methylimidazole villaumite, repetitive cycling utilization are reclaimed in filtrate decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators of reclaiming.
Described ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) is to be synthesized with the mass ratio of 1.0:1.2 by N-methylimidazole, allyl chloride, and its preparation methods steps is as follows:
1) N
2Protection mixes with allyl chloride the N-methylimidazole down with mass ratio 1.0:1.2;
2) in 40 ℃ of water-baths, add hot reflux 12h, after the removal of impurity, can make 1-allyl-3-methylimidazole villaumite.
Testing result shows: ultrasonic wave is down auxiliary, extract through 1-allyl-3-methylimidazole villaumite (AMIMCl), the cellulosic recovery rate of gained is 79%, and described recovery rate is the ratio of cellulose quality in the cellulose quality of dissolving in the ionic liquid and the rice straw.Ionic liquid decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators is reclaimed, and the rate of recovery is 95%
Embodiment 3:
A kind ofly extract cellulosic method with glyoxaline ion liquid from rice straw, step is as follows:
1) rice straw was ground into 100 order rice straw powder;
2) be that 1:40 mix with ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) according to mass ratio with the rice straw powder, obtain mixture;
3) said mixture is placed ultrasonator, use ultrasonic power 80W, in 80 ℃ of reaction 1h, obtain reactant;
4) with above-mentioned reactant with the centrifugal 10min of 12000r/min rotating speed, Separation of Solid and Liquid is got supernatant then;
5) in the supernatant that above-mentioned separation obtains, add absolute ethyl alcohol, supernatant is 1:5 with going the volume ratio of absolute ethyl alcohol, obtains containing sedimentary mixed liquor, behind the suction filtration sediment oven dry that obtains is preserved, be the target product cellulose, the filtrate behind the suction filtration is reclaimed;
6) ionic liquid 1-allyl-3-methylimidazole villaumite, repetitive cycling utilization are reclaimed in filtrate decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators of reclaiming.
Described ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) is synthetic by N-methylimidazole and allyl chloride, and its preparation methods steps is as follows:
1) N
2Protection mixes with allyl chloride the N-methylimidazole down with mass ratio 1.0:1.2;
2) in 40 ℃ of water-baths, add hot reflux 12h, after the removal of impurity, can make 1-allyl-3-methylimidazole villaumite.
Testing result shows: ultrasonic wave is down auxiliary, extract through 1-allyl-3-methylimidazole villaumite (AMIMCl), the cellulosic recovery rate of gained is 71%, and described recovery rate is the ratio of cellulose quality in the cellulose quality of dissolving in the ionic liquid and the rice straw.Ionic liquid decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators is reclaimed, and the rate of recovery is 95%.
Claims (2)
1. one kind is extracted cellulosic method with glyoxaline ion liquid from rice straw, and step is as follows:
1) rice straw was ground into 100 order rice straw powder;
2) be that 1:20-40 mix with ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) according to mass ratio with the rice straw powder, obtain mixture;
3) said mixture is placed ultrasonator, use ultrasonic power 80-120W, in 60-80 ℃ of reaction 1-2h, obtain reactant;
4) with above-mentioned reactant with the centrifugal 10min of 12000r/min rotating speed, Separation of Solid and Liquid is got supernatant then;
5) in the supernatant that above-mentioned separation obtains, add absolute ethyl alcohol, supernatant is 1:5 with going the volume ratio of absolute ethyl alcohol, obtains containing sedimentary mixed liquor, behind the suction filtration sediment oven dry that obtains is preserved, be the target product cellulose, the filtrate behind the suction filtration is reclaimed;
6) ionic liquid 1-allyl-3-methylimidazole villaumite, repetitive cycling utilization are reclaimed in filtrate decompression distillation under 70 ℃ of water bath condition of Rotary Evaporators of reclaiming.
2. from rice straw, extract cellulosic method according to claim 1 is described with glyoxaline ion liquid, it is characterized in that: described ionic liquid 1-allyl-3-methylimidazole villaumite (AMIMCl) is synthetic by N-methylimidazole and allyl chloride, and its preparation methods steps is as follows:
1) N
2Protection mixes with allyl chloride the N-methylimidazole down with mass ratio 1.0:1.2;
2) in 40 ℃ of water-baths, add hot reflux 12h, after the removal of impurity, can make 1-allyl-3-methylimidazole villaumite.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554397A (en) * | 2013-10-25 | 2014-02-05 | 沈阳工业大学 | Functionalized ionic liquid reinforced and modified phenolic resin and preparation method of phenolic resin |
| CN103554522A (en) * | 2013-11-08 | 2014-02-05 | 南开大学 | Method for preparing solvent system capable of dissolving cellulose under room temperature condition |
| CN104650247A (en) * | 2013-11-20 | 2015-05-27 | 中国人民大学 | Method used for fractional separation of cellulose with different polymerization degrees using ionic liquid-carbon dioxide system |
| CN105220552A (en) * | 2015-09-09 | 2016-01-06 | 郑州轻工业学院 | Utilize the cellulosic method of imidazoles asymmetric Gemini ionic liquid extract |
| CN106632515A (en) * | 2016-10-03 | 2017-05-10 | 东北林业大学 | Method for degrading lignin by ionic liquid catalyzed alcohol system |
| CN108822305A (en) * | 2018-06-27 | 2018-11-16 | 西北农林科技大学 | A method of it is pre-processed based on glyoxaline ion liquid and extracts gutta-percha in eucommia bark |
| CN111345428A (en) * | 2020-03-24 | 2020-06-30 | 河北喜之郎食品有限公司 | Konjak gum and preparation method thereof |
| CN114082218A (en) * | 2021-12-03 | 2022-02-25 | 齐鲁工业大学 | Preparation and application of controllable and selective lignin extraction switch type eutectic solvent |
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| CN1851063A (en) * | 2006-05-19 | 2006-10-25 | 东华大学 | Method for preparing cellulose fiber using ion liquid as solvent |
| CN102733224A (en) * | 2012-06-20 | 2012-10-17 | 合肥工业大学 | Method for separating corncob cellulose by using ionic liquid |
| CN102796048A (en) * | 2012-09-07 | 2012-11-28 | 南开大学 | Preparation method of ionic liquid for efficiently extracting cellulose and application thereof |
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Patent Citations (3)
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| CN1851063A (en) * | 2006-05-19 | 2006-10-25 | 东华大学 | Method for preparing cellulose fiber using ion liquid as solvent |
| CN102733224A (en) * | 2012-06-20 | 2012-10-17 | 合肥工业大学 | Method for separating corncob cellulose by using ionic liquid |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554397A (en) * | 2013-10-25 | 2014-02-05 | 沈阳工业大学 | Functionalized ionic liquid reinforced and modified phenolic resin and preparation method of phenolic resin |
| CN103554397B (en) * | 2013-10-25 | 2016-01-20 | 沈阳工业大学 | Functionalized ion liquid enhancing modified resol and preparation method thereof |
| CN103554522A (en) * | 2013-11-08 | 2014-02-05 | 南开大学 | Method for preparing solvent system capable of dissolving cellulose under room temperature condition |
| CN104650247A (en) * | 2013-11-20 | 2015-05-27 | 中国人民大学 | Method used for fractional separation of cellulose with different polymerization degrees using ionic liquid-carbon dioxide system |
| CN104650247B (en) * | 2013-11-20 | 2017-07-14 | 中国人民大学 | The method of the cellulose of separation different polymerization degree is classified using ionic liquid carbon dioxide system |
| CN105220552A (en) * | 2015-09-09 | 2016-01-06 | 郑州轻工业学院 | Utilize the cellulosic method of imidazoles asymmetric Gemini ionic liquid extract |
| CN105220552B (en) * | 2015-09-09 | 2017-03-29 | 郑州轻工业学院 | Using the method for the asymmetric Gemini ionic liquid extracts cellulose of imidazoles |
| CN106632515A (en) * | 2016-10-03 | 2017-05-10 | 东北林业大学 | Method for degrading lignin by ionic liquid catalyzed alcohol system |
| CN108822305A (en) * | 2018-06-27 | 2018-11-16 | 西北农林科技大学 | A method of it is pre-processed based on glyoxaline ion liquid and extracts gutta-percha in eucommia bark |
| CN108822305B (en) * | 2018-06-27 | 2020-11-27 | 西北农林科技大学 | Method for extracting gutta-percha from eucommia bark based on imidazole ionic liquid pretreatment |
| CN111345428A (en) * | 2020-03-24 | 2020-06-30 | 河北喜之郎食品有限公司 | Konjak gum and preparation method thereof |
| CN114082218A (en) * | 2021-12-03 | 2022-02-25 | 齐鲁工业大学 | Preparation and application of controllable and selective lignin extraction switch type eutectic solvent |
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Application publication date: 20130710 |