CN104292471A - Method for preparing protolignin by using corn cob residues - Google Patents
Method for preparing protolignin by using corn cob residues Download PDFInfo
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- CN104292471A CN104292471A CN201410579754.7A CN201410579754A CN104292471A CN 104292471 A CN104292471 A CN 104292471A CN 201410579754 A CN201410579754 A CN 201410579754A CN 104292471 A CN104292471 A CN 104292471A
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Abstract
The invention discloses a method for preparing protolignin by using corn cob residues, by which lignin in corn cob residues are effectively separated by taking high-boiling alcohol as a solvent and under the action of a catalyst. According to the invention, the biomass resources of waste gas are fully used, and lignin in corn cob residues is effectively separated. By detecting, the ash content of obtained lignin is low, the molecular weight of the lignin is about 5000, and the dispersancy index of the lignin is about 1, so that the obtained lignin is high in purity, good in activity, and narrow in molecular weight distribution, therefore, the lignin is a high-quality lignin. According to the invention, the problems of environmental pollution and cost raise caused by the volatilization of low-boiling-point solvents are solved; and because used solvents are high-boiling-point solvents and water, the problems of volatilization and cycle use of the solvents are effectively solved. The method disclosed by the invention solves the problem of corn cob residue resource waste, and the extraction rate of lignin in corn cob residues is 60-75%.
Description
Technical field
The present invention relates to a kind of method utilizing the high alcohol separating xylose slag xylogen that boils.
Background technology
Along with the day by day scarcity of the fossil class energy, utilizing reproducible biomass resource to obtain all kinds of chemical becomes one of emphasis of mankind nowadays Sustainable development.Research in this respect mainly concentrates at present and transforms hemicellulose and Mierocrystalline cellulose aspect, but research in xylogen is less.Xylogen is the three-dimensional netted polymer aromatics of poly-phenols be formed by connecting by ehter bond and carbon-carbon bond by benzene oxide unit, can be used for preparing gasoline, diesel oil, methyl alcohol and aromatic compound etc., is the potential effective substitutes of petroleum resources.The method mainly inorganic acid alkali boiling of current industrial separating lignin, but xylogen is violent owing to being hydrolyzed, and causes molecular weight dispersion degree high, and chemical transformation is large, and therefore use value is lower.Current research shows, it is higher that organic solvent method can obtain molecular weight, and range of molecular weight distributions is narrow, the good lignin product of purity.Xylose residue produces a large amount of acid solid waste residues produced in the process of wood sugar, and be a kind of lignocellulosic sources of high-quality, main component comprises Mierocrystalline cellulose, hemicellulose and xylogen.According to the yearly capacity of Chinese Enterprises, there are 13-26 ten thousand tons of wood sugar waste sludge discharges every year.Therefore these wood sugar waste residues of Appropriate application, not only protect environment, and turn waste into wealth, and create great economic benefit.Containing a large amount of sulfate radical in xylose residue, directly burning causes topsoil, produces gac and levulinic acid added value of product is low, and it is bad to produce fertilizer aspect market outlook, does not therefore make xylose residue be used adequately reasonably with upper type.Research finds, utilizes xylose residue can obtain high purity lignin product for raw material, increases Business Economic Benefit.
Summary of the invention
The object of the invention is to avoid the deficiency of existing organic solvent method in separating lignin and Mierocrystalline cellulose process, a kind of method utilizing the high alcohol separating xylose slag xylogen that boils is provided.The invention solves the problem of Liginon Resource waste in xylose residue, the xylogen ash content being separated preparation is low, active high, the molecular-weight average of xylogen is about 5000, with the detection of nucleus magnetic resonance, the polydispersity index of xylogen, about 1, infraredly proves that the xylogen be separated belongs to guaiacyl-Syringa oblata Lindl. fundamental mode xylogen.The invention solves because low boiling point solvent volatilizees the rising of the environmental pollution that causes and cost, the solvent used is high boiling solvent, the problem effectively solving solvent evaporates and recycle, leaching process has stopped the generation of waste water,waste gas and industrial residue.The xylogen purity be separated to is high, quality better, can be used for the lignin derivative product obtaining high added value further.Utilize a method for the high alcohol separating xylose slag xylogen that boils, its step and condition as follows: xylose residue is placed in the autoclave with temperature control and stirring rake by (1), adds catalyzer, adds height and boils alcohol and water as solvent; Xylose residue and catalyst quality are than being 100:3-100:7; The boil volume ratio of alcohol and water of height is 6:4-10:4; Xylose residue quality (g) is 1:4-1:10 with volume (ml) proportioning of the high alcohol solution that boils; Temperature of reaction is 160-220 DEG C, reaction times 1-3 hour; Xylogen is dissolved in height and boils in alcohol solution, and filter and remove Mierocrystalline cellulose, the Mierocrystalline cellulose obtained can otherwise processed and utilization.(2) be injected in water by filtrate, the volume ratio of filtrate and water is 1:1-1:4, and xylogen forms precipitation.(3) filter, the lignin product 30-60 DEG C of warm water washing obtained, obtains xylogen after drying; Containing the filtrate of the high alcohol that boils through underpressure distillation, after sloughing moisture, high boiling solvent (hbs) can recycle; Described catalyzer is Mg(NO
3)
26H
2o, AlCl
36H
2o, MgCl6H
2one in O; The described height alcohol that boils is the one of butyleneglycol, ethylene glycol and propylene glycol.The present invention takes full advantage of the biomass resource of waste gas, effectively isolates xylogen in xylose residue.The xylogen ash content obtained after testing is low, and lignin molecule amount is about 5000, and xylogen polydispersity index is about 1, and therefore visible gained xylogen purity is high, activity is good, range of molecular weight distributions is narrow, is high-quality lignin.The invention solves because low boiling point solvent volatilizees the rising of the environmental pollution that causes and cost, the solvent used is high boiling solvent and water, the problem effectively solving solvent evaporates and recycle.The invention solves the problem of the xylose residue wasting of resources, in xylose residue, the extraction yield of xylogen is at 60%-75%.
specific embodiment mode:embodiment 1: xylose residue is placed in the autoclave with temperature control and stirring rake, add BDO and water as solvent, the volume ratio of BDO and water is 6:4; Xylose residue quality (g) is 1:4 with volume (ml) proportioning of the high alcohol solution that boils; Temperature of reaction is 180 DEG C, and the reaction times is 1 hour, and xylogen is dissolved in high boiling solvent (hbs); Filter and remove Mierocrystalline cellulose, the Mierocrystalline cellulose obtained utilizes separately; Be injected in water by filtrate again, the volume ratio of filtrate and water is 1:1; Xylogen forms precipitation, and filter, the lignin product obtained 40 DEG C of warm water washings, obtain xylogen after drying, and lignin extraction rate is 60%; Contain the filtrate of the high alcohol that boils through underpressure distillation, after sloughing moisture, high boiling solvent (hbs) can recycle.
Embodiment 2: xylose residue is placed in the autoclave with temperature control and stirring rake, adds Mg(NO
3)
26H
2o is as catalyzer, and add BDO and water as solvent, the volume ratio of BDO and water is 7:4; Xylose residue and catalyst quality are than being 100:3; Xylose residue quality (g) is 1:6 with volume (ml) proportioning of the high alcohol solution that boils; Temperature of reaction is 220 DEG C, and the reaction times is 2 hours, and xylogen is dissolved in high boiling solvent (hbs); Filter and remove Mierocrystalline cellulose, the Mierocrystalline cellulose obtained utilizes separately; Be injected in water by filtrate again, the volume ratio of filtrate and water is 1:2; Xylogen forms precipitation, and filter, the lignin product obtained 60 DEG C of warm water washings, obtain xylogen after drying, and lignin extraction rate is 67%; Contain the filtrate of the high alcohol that boils through underpressure distillation, after sloughing moisture, high boiling solvent (hbs) can recycle.
Embodiment 3: xylose residue is placed in the autoclave with temperature control and stirring rake, adds MgCl6H
2o is as catalyzer, and add ethylene glycol and water as solvent, the volume ratio of ethylene glycol and water is 9:4; Xylose residue and catalyst quality are than being 100:5; Xylose residue quality (g) is 1:8 with volume (ml) proportioning of the high alcohol solution that boils; Temperature of reaction is 200 DEG C, and the reaction times is 3 hours, and xylogen is dissolved in high boiling solvent (hbs); Filter and remove Mierocrystalline cellulose, the Mierocrystalline cellulose obtained utilizes separately; Be injected in water by filtrate again, the volume ratio of filtrate and water is 1:3; Xylogen forms precipitation, and filter, the lignin product obtained 30 DEG C of warm water washings, obtain xylogen after drying, and lignin extraction rate is 69%; Contain the filtrate of the high alcohol that boils through underpressure distillation, after sloughing moisture, high boiling solvent (hbs) can recycle.
Embodiment 4: xylose residue is placed in the autoclave with temperature control and stirring rake, adds AlCl
36H
2o is as catalyzer, and add propylene glycol and water as solvent, the volume ratio of propylene glycol and water is 10:4; Xylose residue and catalyst quality are than being 100:7; Xylose residue quality (g) is 1:10 with volume (ml) proportioning of the high alcohol solution that boils; Temperature of reaction is 160 DEG C, and the reaction times is 3 hours, and xylogen is dissolved in high boiling solvent (hbs); Filter and remove Mierocrystalline cellulose, the Mierocrystalline cellulose obtained utilizes separately; Be injected in water by filtrate again, the volume ratio of filtrate and water is 1:3; Xylogen forms precipitation, and filter, the lignin product obtained 50 DEG C of warm water washings, obtain xylogen after drying, and lignin extraction rate is 75%; Contain the filtrate of the high alcohol that boils through underpressure distillation, after sloughing moisture, high boiling solvent (hbs) can recycle.
Claims (8)
1. utilize a method for the high alcohol separating xylose slag xylogen that boils, it is characterized in that, xylose residue is placed in the autoclave with temperature control and stirring rake by its step and condition following (1), adds catalyzer, adds height and boil alcohol and water as solvent; Xylose residue and catalyst quality are than being 100:3-100:7; The boil volume ratio of alcohol and water of height is 6:4-10:4; Xylose residue quality (g) is 1:4-1:10 with volume (ml) proportioning of the high alcohol solution that boils; Temperature of reaction is 160-220 DEG C, reaction times 1-3 hour; Xylogen is dissolved in height and boils in alcohol solution, filters and removes Mierocrystalline cellulose, and the Mierocrystalline cellulose obtained can otherwise processed and utilization; (2) be injected in water by filtrate, the volume ratio of filtrate and water is 1:1-1:4, and xylogen forms precipitation; (3) filter, the lignin product 30-60 DEG C of warm water washing obtained, obtains xylogen after drying; Containing the filtrate of the high alcohol that boils through underpressure distillation, after sloughing moisture, high boiling solvent (hbs) can recycle; Described catalyzer is Mg(NO
3)
26H
2o, AlCl
36H
2o, MgCl6H
2one in O; The described height alcohol that boils is the one of butyleneglycol, ethylene glycol and propylene glycol.
2. the method utilizing the high alcohol separating xylose slag xylogen that boils according to claim 1, is characterized in that, the boil volume ratio of alcohol and water of described height is 6:4-10:4.
3. the method utilizing the high alcohol separating xylose slag xylogen that boils according to claim 1, it is characterized in that, described xylose residue and the mass ratio of catalyzer are 100:3-100:7.
4. the method utilizing the high alcohol separating xylose slag xylogen that boils according to claim 1, is characterized in that, described xylose residue quality (g) and height alcohol solution volume (ml) proportioning of boiling is 1:4-1:10.
5. the method utilizing the high alcohol separating xylose slag xylogen that boils according to claim 1, it is characterized in that, described temperature of reaction is 160-220 DEG C.
6. the method utilizing the high alcohol separating xylose slag xylogen that boils according to claim 1, it is characterized in that, the described reaction times is 1-3 hour.
7. the method utilizing the high alcohol separating xylose slag xylogen that boils according to claim 1, it is characterized in that, filtrate is injected in water by described step (2), and the volume ratio of filtrate and water is 1:1-1:4.
8. the method utilizing the high alcohol separating xylose slag xylogen that boils according to claim 1, is characterized in that, described step (3) is filtered, the lignin product 30-60 DEG C of warm water washing obtained.
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| CN201410579754.7A CN104292471A (en) | 2014-10-27 | 2014-10-27 | Method for preparing protolignin by using corn cob residues |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693451A (en) * | 2015-03-23 | 2015-06-10 | 山东福田药业有限公司 | Method for preparing lignin in use of corncob residues as raw materials |
| CN105559095A (en) * | 2015-12-09 | 2016-05-11 | 新疆环拓生物科技有限公司 | Method for preparing and separating plant fiber and lignin from rose flower residues |
| CN107558282A (en) * | 2017-09-30 | 2018-01-09 | 四川金象赛瑞化工股份有限公司 | A kind of preparation method of bamboo explosion high-boiling alcohol lignin |
| CN108179646A (en) * | 2018-01-05 | 2018-06-19 | 四川金象赛瑞化工股份有限公司 | With the method for plant fiber material production xylose, high-boiling alcohol lignin and fiber |
| CN109535440A (en) * | 2018-11-26 | 2019-03-29 | 广州楹鼎生物科技有限公司 | A method of processing plant material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276847A (en) * | 2011-07-29 | 2011-12-14 | 长春工业大学 | Method for separating nut shell lignin by utilizing high-boiling alcohol |
| CN102558571A (en) * | 2011-04-02 | 2012-07-11 | 济南圣泉集团股份有限公司 | Method for preparing alkali lignin by using corncob residues |
| CN103044690A (en) * | 2012-12-19 | 2013-04-17 | 山东龙力生物科技股份有限公司 | Preparation method for high-activity enzymatic hydrolysis lignin |
-
2014
- 2014-10-27 CN CN201410579754.7A patent/CN104292471A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558571A (en) * | 2011-04-02 | 2012-07-11 | 济南圣泉集团股份有限公司 | Method for preparing alkali lignin by using corncob residues |
| CN102276847A (en) * | 2011-07-29 | 2011-12-14 | 长春工业大学 | Method for separating nut shell lignin by utilizing high-boiling alcohol |
| CN103044690A (en) * | 2012-12-19 | 2013-04-17 | 山东龙力生物科技股份有限公司 | Preparation method for high-activity enzymatic hydrolysis lignin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693451A (en) * | 2015-03-23 | 2015-06-10 | 山东福田药业有限公司 | Method for preparing lignin in use of corncob residues as raw materials |
| CN105559095A (en) * | 2015-12-09 | 2016-05-11 | 新疆环拓生物科技有限公司 | Method for preparing and separating plant fiber and lignin from rose flower residues |
| CN107558282A (en) * | 2017-09-30 | 2018-01-09 | 四川金象赛瑞化工股份有限公司 | A kind of preparation method of bamboo explosion high-boiling alcohol lignin |
| CN108179646A (en) * | 2018-01-05 | 2018-06-19 | 四川金象赛瑞化工股份有限公司 | With the method for plant fiber material production xylose, high-boiling alcohol lignin and fiber |
| CN109535440A (en) * | 2018-11-26 | 2019-03-29 | 广州楹鼎生物科技有限公司 | A method of processing plant material |
| CN109535440B (en) * | 2018-11-26 | 2021-04-27 | 广州楹鼎生物科技有限公司 | A method for treating plant material |
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