CN101402659B - Method for removing hemicellulose in biomass raw material - Google Patents
Method for removing hemicellulose in biomass raw material Download PDFInfo
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- CN101402659B CN101402659B CN2008102270175A CN200810227017A CN101402659B CN 101402659 B CN101402659 B CN 101402659B CN 2008102270175 A CN2008102270175 A CN 2008102270175A CN 200810227017 A CN200810227017 A CN 200810227017A CN 101402659 B CN101402659 B CN 101402659B
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- hemicellulose
- xylo
- biomass material
- biomass materials
- xylogen
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Abstract
The present invention discloses a method for removing hemicellulose in biomass materials. The method comprises the following steps: hydrolysis reaction that utilizes Fe<3+> to catalyze the biomass materials is carried out so as to remove the hemicellulose from the biomass materials and to transfer the hemicellulose into xylose and xylo-oligosaccharide. The method adopts Fe<3+> as a catalyst, which can accelerate the degradation rate of the hemicellulose and shorten the pretreatment time, or lower the pretreatment temperature with the same pretreatment time, thereby reducing part energy consumption in industrial production; when degrading the hemicellulose into the xylo, the Fe<3+> can also ensure the high yield of xylo and simultaneously reduce the side product of furfural, improve the recovery rate of the xylo and does not cause the degradation of great amount of cellulose and xylogen, thus realizing the separation of a monocomponent of the biomass materials. The Fe<3+> is recyclable and no effluent and waste are discharged in the production process. The method is an environment-friendly green production technology.
Description
Technical field
The present invention relates to a kind of method of removing hemicellulose in the biomass material.
Background technology
In recent years, the complete utilization of biomass material was mentioned by people more and more.In the biomass material three big components from the separation of industrial significance with utilize situation, hemicellulose generally in sepn process direct hydrolysis obtain wood sugar and xylo-oligosaccharide, be used as foodstuff additive, fodder additives or functional foodstuff etc.; Cellulosic separation and utilization account for absolute dominant position, and the Mierocrystalline cellulose of resulting separation is mainly used in papermaking and weaving, and in addition, the monose behind the cellulose hydrolysis can be used for a plurality of fields such as ethanol fermentation; Remaining lignin residue is taken as fuel mostly and directly utilizes after the pre-treatment.
In numerous pretreatment processs, sour pre-treatment and alkali pre-treatment are comparative maturities and use two kinds of maximum methods.Though acid solution can make hemicellulose almost completely remove, under the high-temperature acidic condition, wood sugar is easy to further be degraded into furfural.Though make hemicellulose can reach very high clearance, recovery utilization rate is lower.Be accompanied by the removal of hemicellulose, Mierocrystalline cellulose also has degraded significantly; Under the effect of high temperature and proton, xylogen produces carbonium ion under acidic conditions simultaneously, and easy and other aromatic nucleus generation condensation reactions of carbonium ion generate more stable superpolymer, thereby make xylogen modification to a certain extent.It is the alkaline cooking of pulping and paper-making aspect that the alkali pre-treatment is used maximum, and this method is to be based upon to keep most Mierocrystalline celluloses, removes hemicellulose and xylogen to greatest extent, even is cost with the active structure that destroys this component.Since the intensive chemical modification make himself activity and using value by brokenization, having no alternative becomes the by product that can't further utilize in the component sepn process and can only select burned its heat energy that utilizes, and loses the original utility value of this component.In addition, a large amount of black liquor of alkali pre-treatment generation also are difficult problems that needs to be resolved hurrily.
In general, the problem of existing component separate mode maximum is this three big component not to be done a comprehensive comprehensive value assessment, and employed separation method is often attended to one thing and lose sight of another.Therefore, in order to promote the using value of hemicellulose and xylogen raw material in the sepn process, really solve the low problem of biomass three big component utilization ratios, we wish three kinds of components to be separated one by one and be used respectively.Therefore, must consider in wherein a kind of component of high efficiency separation, to guarantee that other two kinds of components are not affected as much as possible.Like this, just can make the real pattern that realizes efficient complete utilization of hemicellulose in the biomass material, Mierocrystalline cellulose and xylogen three big components.Based on this theory, at first separate the easiest removed hemicellulose and become the crucial the first step.
Through existing patent retrieval is found, " the continuous dilute acid hydrolysis of biomass is produced the method and the equipment thereof of monose " (publication number CN1927874A), " preparing the alcoholic acid method " (publication number is CN101041835A) by cellulose waste double thin acid hydrolysis, " method for preparing reductive monosaccharide by biomass by hydrolyzation " (publication number CN1432574A), " Processing lignocellulosic materials involves contacting feedstockmaterial with mixture of dilute a
Summary of the invention
The purpose of this invention is to provide a kind of method of removing hemicellulose in the biomass material.
The method of hemicellulose is to use Fe in the removal biomass material provided by the present invention
3+The hydrolysis reaction of catalysis biological raw material is removed the hemicellulose in the biomass material and is translated into wood sugar and xylo-oligosaccharide.
The temperature of reaction of described hydrolysis reaction specifically can be 140-200 ℃, and the reaction times can be 5-30min.
But described biomass material drying, the processing of pulverizing, sieve, making particle diameter is 20-80 purpose particle.
Biomass material described in the present invention, comprise agriculture and forestry organic waste material (maize straw, wheat straw stalk, rice husk, straw, corn cob, lumbering branches and leaves etc.), crop (hybrid white poplar, sugarcane, sweet sorghum etc.) and various waste (urban solid garbage, waste paper, the remaining bagasse of sugaring etc.), be the lignocellulose raw material of polymkeric substance such as containing Mierocrystalline cellulose, hemicellulose and xylogen.
In the system of described reaction, described biomass material and the Fe that is added
3+Proportioning be 1g:5.6-224mg; Wherein, the quality of described biomass material is with dry weight basis.
Described Fe
3+Come from FeCl
3, Fe
2(SO
4)
3Or Fe (NO
3)
3
Adopt method of the present invention that the hemicellulose clearance is reached more than 80%.
The present invention removes that the method for hemicellulose has the following advantages in the biomass material:
(1) method of the present invention has been selected Fe for use in the biomass material preprocessing process
3+Make catalyzer, Fe
3+Can quicken the degradation rate of hemicellulose, shorten pretreatment time, perhaps under the identical time, reduce pretreatment temperature, therefore, can in industrial production, reduce a part of energy consumption;
(2) compare Fe with dilute acid pretreatment
3+When degradation of hemicellulose is wood sugar, guaranteed higher wood sugar yield, also reduced the generation of by product furfural simultaneously, avoided a large amount of losses of wood sugar, improved the recovery utilization rate of wood sugar;
(3) at Fe
3+In the time of degradation of hemicellulose, can not cause the degraded of most of Mierocrystalline cellulose and xylogen, thereby the single component that realizes biomass material is separated;
(4) because Fe
3+Can the subsequent recovery utilization, no waste liquid and waste discharge in the production process are eco-friendly green production technology.
Embodiment
Hemicellulose in embodiment 1, the removal maize straw
Take by weighing maize straw dry weight 1.0g, it is ground into particle diameter is 40-80 purpose particle, and putting into volume then is the stainless steel tubular type reactor of 20ml, and adds 0.02mol/L FeCl
3Solution 5ml makes Fe
3+With the proportioning of maize straw be 5.6mg:1.0g, seal, put into boiling water preheating 2min, transfer to preheating 1min in 220 ℃ the sand bath at once, put into temperature of reaction at last and be 200 ℃ oil bath and react 10min.Reaction finishes the back and with cold water tubular reactor is cooled to room temperature, filters, and collects hydrolyzed solution and residue.Hydrolyzed solution is used to measure the wood sugar and the xylo-oligosaccharide rate of recovery, and residue is used to measure the surplus ratio of hemicellulose clearance and Mierocrystalline cellulose, xylogen.Measuring method with reference to American National Instrument Renewable Energy Laboratory " Determination of StructuralCarbohydrates and Lignin in Biomass " (Amie Sluiter, 2006,
Http:// www.nrel.gov/).After maize straw was handled through aforesaid method, the hemicellulose clearance was 80.52%, and the rate of recovery of wood sugar and solubility xylo-oligosaccharide is 79.43%, and the Mierocrystalline cellulose surplus ratio is 99.57%.Most hemicelluloses are removed, but the content of Mierocrystalline cellulose and xylogen is not produced remarkably influenced.
Hemicellulose in embodiment 2, the removal maize straw
Take by weighing maize straw dry weight 1.0g, it is ground into particle diameter is 40-80 purpose particle, and putting into volume then is the stainless steel tubular type reactor of 20ml, and adds 0.2mol/L Fe
2(SO
4)
3Solution 10ml makes Fe
3+With the proportioning of maize straw be 224mg:1.0g, seal, put into boiling water preheating 2min, transfer to preheating 1min in 160 ℃ the sand bath at once, put into temperature of reaction at last and be 140 ℃ oil bath and react 20min.Reaction finishes the back and with cold water tubular reactor is cooled to room temperature, filters, and collects hydrolyzed solution and residue.Hydrolyzed solution is used to measure the wood sugar and the xylo-oligosaccharide rate of recovery, and residue is used to measure the surplus ratio of hemicellulose clearance and Mierocrystalline cellulose, xylogen.After maize straw was handled through this condition, the hemicellulose clearance was 98.15%, and the rate of recovery of wood sugar and solubility xylo-oligosaccharide is 79.43%, and the Mierocrystalline cellulose surplus ratio is 92.37%.Most hemicelluloses are removed, but the content of Mierocrystalline cellulose and xylogen is not produced remarkably influenced.
Hemicellulose in embodiment 3, the removal maize straw
Take by weighing maize straw dry weight 1.0g, it is ground into particle diameter is 40-80 purpose particle, and putting into volume then is the stainless steel tubular type reactor of 20ml, and adds 0.1mol/L Fe (NO
3)
3Solution 10ml makes Fe
3+With the proportioning of maize straw be 56mg:1.0g, seal, put into boiling water preheating 2min, transfer to preheating 1min in 170 ℃ the sand bath at once, put into temperature of reaction at last and be 150 ℃ oil bath and react 10min.Reaction finishes the back and with cold water tubular reactor is cooled to room temperature, filters, and collects hydrolyzed solution and residue.Hydrolyzed solution is used to measure the wood sugar and the xylo-oligosaccharide rate of recovery, and residue is used to measure the surplus ratio of hemicellulose clearance and Mierocrystalline cellulose, xylogen.After maize straw was handled through this condition, the hemicellulose clearance was 90.77%, and the rate of recovery of wood sugar and solubility xylo-oligosaccharide is 85.47%, and the Mierocrystalline cellulose surplus ratio is 93.57%.Most hemicelluloses are removed, but the content of Mierocrystalline cellulose and xylogen is not produced remarkably influenced.
Hemicellulose in embodiment 4, the removal corn cob
Take by weighing corn cob dry weight 1.0g, it is ground into particle diameter is 40-80 purpose particle, and putting into volume then is the stainless steel tubular type reactor of 20ml, and adds 0.1mol/L FeCl
3Solution 10ml makes Fe
3+With the proportioning of corn cob be 5.6mg:1.0g, seal, put into boiling water preheating 2min, transfer to preheating 1min in 170 ℃ the sand bath at once, put into temperature of reaction at last and be 150 ℃ oil bath and react 10min.Reaction finishes the back and with cold water tubular reactor is cooled to room temperature, filters, and collects hydrolyzed solution and residue.Hydrolyzed solution is used to measure the wood sugar and the xylo-oligosaccharide rate of recovery, and residue is used to measure the surplus ratio of hemicellulose clearance and Mierocrystalline cellulose, xylogen.After corn cob was handled through this condition, the hemicellulose clearance was 100%, and the rate of recovery of wood sugar and solubility xylo-oligosaccharide is 89.53%, and the Mierocrystalline cellulose surplus ratio is 95.17%.Most hemicelluloses are removed, but the content of Mierocrystalline cellulose and xylogen is not produced remarkably influenced.
Hemicellulose in embodiment 5, the removal bagasse
Take by weighing bagasse dry weight 1.0g, it is ground into particle diameter is 20-80 purpose particle, and putting into volume then is the stainless steel tubular type reactor of 20ml, and adds 0.1mol/L FeCl
3Solution 10ml makes Fe
3+With the proportioning of bagasse be 5.6mg:1.0g, seal, put into boiling water preheating 2min, transfer to preheating 1min in 170 ℃ the sand bath at once, put into temperature of reaction at last and be 150 ℃ oil bath and react 10min.Reaction finishes the back and with cold water tubular reactor is cooled to room temperature, filters, and collects hydrolyzed solution and residue.Hydrolyzed solution is used to measure the wood sugar and the xylo-oligosaccharide rate of recovery, and residue is used to measure the surplus ratio of hemicellulose clearance and Mierocrystalline cellulose, xylogen.After bagasse was handled through this condition, the hemicellulose clearance was 94.83%, and the rate of recovery of wood sugar and solubility xylo-oligosaccharide is 91.55%, and the Mierocrystalline cellulose surplus ratio is 94.78%.Most hemicelluloses are removed, but the content of Mierocrystalline cellulose and xylogen is not produced remarkably influenced.
Claims (1)
1. a method of removing hemicellulose in the biomass material is to use Fe
3+The reaction that is hydrolyzed of catalysis biological raw material;
The temperature of reaction of described hydrolysis reaction is 140-200 ℃, and the reaction times is 5-30min;
Described biomass material is maize straw, corn cob or bagasse;
The particle diameter of described biomass material is the 20-80 order;
In the system of described hydrolysis reaction, described biomass material and the Fe that is added
3+Proportioning be 1g: 5.6-224mg; Wherein, the quality of described biomass material is with dry weight basis;
Described Fe
3+Come from FeCl
3, Fe
2(SO
4)
3Or Fe (NO
3)
3
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| CN2008102270175A CN101402659B (en) | 2008-11-18 | 2008-11-18 | Method for removing hemicellulose in biomass raw material |
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| CN101402659B true CN101402659B (en) | 2011-06-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9085735B2 (en) | 2013-01-02 | 2015-07-21 | American Fuel Producers, LLC | Methods for producing synthetic fuel |
| CN104480229A (en) * | 2014-12-01 | 2015-04-01 | 天津大学 | Method for preparing high-concentration pentaglucose solution from lignocellulose |
| CN107385119A (en) * | 2017-08-28 | 2017-11-24 | 华南理工大学 | A kind of method that corncob rapidly and efficiently prepares xylose hydrolysis fluid |
| CN107691712A (en) * | 2017-08-29 | 2018-02-16 | 霍山县长冲中药材开发有限公司 | A kind of preparation method of section of shape stem of noble dendrobium immersion tea |
| CN108118103A (en) * | 2017-12-20 | 2018-06-05 | 南京林业大学 | The method that a kind of iron ion-acetic acid catalysis directionally hydrolyzing hemicellulose produces xylose |
| CN110283947B (en) * | 2019-07-19 | 2022-05-10 | 北京林业大学 | Method for catalytically producing xylooligosaccharide |
| CN113183266B (en) * | 2021-04-27 | 2022-07-26 | 中南林业科技大学 | Method for pretreating poplar fibers by hydrothermal-peroxyacetate metal salt cooperation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998017727A1 (en) * | 1996-10-18 | 1998-04-30 | Kronospan Gmbh | Treatment of lignocellulosic material |
| CN1927874A (en) * | 2006-09-27 | 2007-03-14 | 华东理工大学 | Method and apparatus for preparing monosaccharide with diluent acid continuous catalyzing biomass |
| CN101199944A (en) * | 2007-11-23 | 2008-06-18 | 淮北中润生物能源技术开发有限公司 | Cellulose biomimetic catalysis hydrolysis system and application in liquid fuel production thereof |
| WO2008086115A2 (en) * | 2007-01-03 | 2008-07-17 | Colusa Biomass Energy Corporation | Hydrolyzation of cellulose using carbonic acid |
-
2008
- 2008-11-18 CN CN2008102270175A patent/CN101402659B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998017727A1 (en) * | 1996-10-18 | 1998-04-30 | Kronospan Gmbh | Treatment of lignocellulosic material |
| CN1927874A (en) * | 2006-09-27 | 2007-03-14 | 华东理工大学 | Method and apparatus for preparing monosaccharide with diluent acid continuous catalyzing biomass |
| WO2008086115A2 (en) * | 2007-01-03 | 2008-07-17 | Colusa Biomass Energy Corporation | Hydrolyzation of cellulose using carbonic acid |
| CN101199944A (en) * | 2007-11-23 | 2008-06-18 | 淮北中润生物能源技术开发有限公司 | Cellulose biomimetic catalysis hydrolysis system and application in liquid fuel production thereof |
Non-Patent Citations (3)
| Title |
|---|
| 肖代俊等."硫酸催化蔗髓半纤维素的水解条件研究".《广西科学》.2008,第15卷(第2期),第181-183页. |
| 赵辉等."玉米芯半纤维素常压酸水解技术的研究".《黑龙江大学自然科学学报》.2003,第20卷(第1期),第118-121页. |
| 陈学武等."玉米秸秆半纤维素的水解研究".《河北科技大学学报》.1999,第20卷(第2期),第47-53页. |
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