CN102898547B - Method for separating non-wood lignocellulosic biomass hemicellulose by complex solvent - Google Patents
Method for separating non-wood lignocellulosic biomass hemicellulose by complex solvent Download PDFInfo
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- CN102898547B CN102898547B CN201210275657.XA CN201210275657A CN102898547B CN 102898547 B CN102898547 B CN 102898547B CN 201210275657 A CN201210275657 A CN 201210275657A CN 102898547 B CN102898547 B CN 102898547B
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Abstract
The invention relates to a method for separating non-wood lignocellulosic biomass hemicellulose by a complex solvent, which comprises a separation step and an extraction step. According to the invention, mass wheat straw hemicellulose is successfully separated through a sodium hydroxide/urea/thiourea/aqueous solution system under low temperature, the yield of hemicellulose can reach 78%, and a hemicellulose chemical structure can be protected. The time span during the separation process is short in 16 minutes, and the treated material has better reactive accessibility, and is in favor of refining subsequent organisms.
Description
Technical field
The invention belongs to biological field, in particular to a kind of method using double solvents to be separated non-wood material wood fiber biomass hemicellulose.
Background technology
Hemicellulose is the second largest saccharan material of nature, is mainly present in the plants such as timber, careless class and agricultural crop straw.Content in plant materials is about 20%-35%.Hemicellulose is the heterogeneous polymer be made up of pentose, hexose and uronic acid.Abundant wood sugar, pectinose, seminose, glucose and uronic acid is comprised in hemicellulose macromolecular structure.Wherein xylan is the main saccharan forming hemicellulose.The sugared content that hemicellulose enriches and loose structure thereof have huge biorefinery to be worth.Hemicellulose, as the by product of wood fibre biorefining process, can utilize hemicellulose to produce fuel (ethanol, butanols and Virahol etc.), chemical (finings, stablizer and furans etc.) and biomaterial (taking hemicellulose derivative as the mould material of matrix).The byproduct making full use of hemicellulose production high value is conducive to the Financial cost reducing biorefining process.Fully extract hemicellulose from biomass, the Mierocrystalline cellulose that is conducive to be separated, dissolve or hydrolysis, lignin separation, thus improve the economic benefit of biorefining process.Hemicellulose mainly extracts at the pretreatment stage of biomass.
Pretreatment process main at present has Physical (pulverizing, radiation, pyrolysis and explosion etc., see Fig. 1), chemical method (acid-hydrolysis method, alkali density method and method of organic solvent extraction etc., see Fig. 2), biological process (not listing as main method).Physical be conducive to improve raw material accessibility, reduce cellulosic degree of crystallinity, but energy consumption is high; Chemical method is conducive to improving raw material accessibility, reducing cellulose crystallity and hemicellulose level, is the treatment process of full blast, but needs exacting terms and more chemical cost amount; Biological process can reduce the content of hemicellulose, but processing efficiency is low.
Summary of the invention
Therefore, the object of the invention is to set up a kind of new hemicellulose separation method, it at least meets following one or more of or whole standard: 1, the yield of hemicellulose wants high; 2, sepn process hemicellulose structure does not change; 3, sepn process should be simple, repeatable strong.In order to realize above object, the present invention by the following technical solutions.
One aspect of the present invention relates to a kind of hemicellulose extracting method, it is characterized in that comprising the steps: by pretreated barley seeding food (or with straw, cotton stalk, ramulus mori, obtain, reed, awns bar, Herba Poae Sphondylodis, waste of flax and/or pulp be for raw material) and compound aqueous solution precooling under the temperature condition of-5 DEG C or following of sodium hydroxide or potassium hydroxide, urea and thiocarbamide, the temperature of precooling can be identical, also can be different; By compound aqueous solution and barley seeding food mix and blend 2-15min, then centrifugation obtains supernatant liquor; Supernatant liquor uses acid for adjusting pH value between 5-9; Again with two volumes alcohol settling; Pelleting centrifugation, and by washing with alcohol to neutral, vacuum-drying.
In a preferred embodiment of the present invention, described pre-treatment refers to the barley seeding food successively by Benzene-ethanol extraction and hot-water extraction.But, also can not be treated as industrial application instead of Structural Identification.
In a preferred embodiment of the present invention, in described compound aqueous solution, the part by weight of three kinds of components is 8-12: 6-10: 4.5-8.5, is preferably 9-11: 7-9: 5.5: 7.5, more preferably 10: 8: 6.5.
In a preferred embodiment of the present invention, it is characterized in that described mix and blend and centrifugation are all carry out under the temperature condition of-5 DEG C or following.
In a preferred embodiment of the present invention, described extraction step is no more than 20 minutes, preferably more than 18 minutes, further preferably more than 17 minutes.
In a preferred embodiment of the present invention, described extraction step adds 1-4 times of volume ethanol, hemicellulose is separated out with precipitation forms after comprising extracting solution acidifying extraction obtained, and precipitation is extremely neutral with washing with alcohol again, vacuum-drying.
The invention still further relates to above-mentioned compound aqueous solution and extracting the application in hemicellulose, described extraction carries out at the temperature of-5 DEG C or following and strong stirring condition.
The present invention is by utilizing sodium hydroxide/urea/sulphur urea/water solution system to be successfully separated a large amount of wheat straw hemicellulose at low temperatures, and the solubility rate of half fiber reaches 85%, and extraction rate reached is to 75%.The very short needs of time span of sepn process 16 minutes, and effectively protect hemicellulose molecule chain structure.Accompanying drawing explanation
Fig. 1: Physical (the representative steam explosion leaching process) separation process of hemicellulose;
Fig. 2: chemical method (the representative alkaline hydrogen peroxide leaching process) preparation flow of hemicellulose;
Fig. 3: low-temperature alkaline composite solution hemicellulose is separated schematic diagram;
Fig. 4: the gas chromatogram of extract: 1,2,5,6-pectinose; 3,4,7,8-wood sugar; 9,14-seminose; 10,11,13-semi-lactosi; 12,16-glucose; 15-inositol;
Embodiment
separation process:
Also 3 separation process are described by reference to the accompanying drawings below by specific embodiment: wheat straw defoliation, fringe, sheath and joint, 40-60 order grass meal is got by plant grinder mill, again through (ethanol and benzene, volume ratio is 1: the 3) extracting of benzene alcohol and hot-water extraction, air-dry for subsequent use.Take the grass meal being equivalent to 6g over dry to stir as 500ml polyethylene bottle, and-10 DEG C of precoolings 3 hours, each 20g, 16g, 13g and 139g mixing of weighing sodium hydroxide, urea, thiocarbamide and deionized water was on average poured in 2 500ml polyethylene bottles in-10 DEG C of precoolings 3 hours.
Precooling terminates, and get one bottle of alkali composite solution and pour into fast and be equipped with in the blender jar of grass meal, 8000rpm stirs 3 minutes, is transferred in 500ml centrifugal bottle immediately, in-10 DEG C of environment with 12000rpm centrifugal 10 minutes.Collect centrifugate and residue respectively.Residue is chilled to-10 DEG C again in advance, and mixes with another bottle of precooling liquid, and 8000rpm stirs 3 minutes, is transferred in 500ml centrifugal bottle immediately, in-10 DEG C of environment with 12000rpm centrifugal 10 minutes.Collect centrifugate and residue, two times centrifugal liquid mixes.Residue is washed with water to neutrality, and the solubility rate of hemicellulose reaches 85%.Centrifugate 12%HCl low temperature is acidified to pH5; Add 2 times of volume ethanol, centrifugation precipitates, and precipitate with washing with alcohol to neutral, vacuum-drying, obtains hemicellulose, and through weighing, hemicellulose yield reaches 75%.
Gas chromatographic detection condition:
Sulphuric acid hydrolysis.Take the beaker that 300mg (over dry) extract is placed in 25ml, add the sulphuric acid soln of 3ml72%, stir, then beaker is placed in the water-bath 1 hour of 30 ± 0.5 DEG C.Measuring 84ml deionized water transfers in high voltage bearing vial by the sugared sample in beaker completely, vial is placed in high-pressure sterilizing pot in 121 DEG C 1 hour, take out and the volume of accurate measuring hydrolyzed solution after cooling.
The neutralization of hydrolyzed solution and concentrated.Precision measures 10ml each monose hydrolysis sugar sample in 25ml beaker, drips several bromophenol blue indicators, adds the hydrated barta powder of oven dry under the condition of magnetic agitation in hydrolysis sugar sample, until the color of solution becomes bluish voilet from yellow.Solution is transferred in the centrifuge tube of 50ml, centrifugal 15min under the condition of 12000r/min, take out clear liquid, clear liquid obtains follow-up clear liquid through syringe filters again, accurate measuring 5ml clear liquid is in 25ml pears type bottle, rotary evaporation in vacuo under 50 DEG C of water-baths, the sample after evaporate to dryness is placed in P2O5 vacuum drier dried overnight, obtains sugared sample.
The Silanization reaction of sugar sample.Precision measure 0.5ml pyridine add dried after sugared sample in, rock gently to sugared sample and be dissolved in completely in pyridine, precision measures 100 μ l in the centrifuge tube of 1.5ml, and add the BSTFA derivatization reagent of 100 μ l, in 70 DEG C of baking ovens, constant temperature took out after 1 hour, be cooled to room temperature, the sugared sample extracting 1 μ l derivatize good is analyzed for GC.
GC analysis condition.Post initial temperature is 100 DEG C, and gasification temperature is 260 DEG C, and detected temperatures is 270 DEG C.Pillar adopts two sections of intensifications, heating schedule be 100 DEG C with the ramp to 190 DEG C of 15 DEG C/min, more then with the ramp to 260 DEG C of 3 DEG C/min.
Known through gas chromatographic detection, the sample extracted contains the complete monosaccharide components of hemicellulose: wood sugar, pectinose, seminose, glucose and semi-lactosi.And pass through the Infrared spectroscopy of extracted sample, found that the polysaccharide of easy reaction is connected with the ester bond between forulic acid, illustrate that the structure of hemicellulose obtains good protection due to low temperature sharp separation.
Should be understood that; specific embodiments of the invention are only the objects for exemplary illustration; it limits protection scope of the present invention never in any form; those skilled in the art can be improved according to the above description or be converted, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (7)
1. a hemicellulose extracting method, it is characterized in that the compound aqueous solution precooling under the temperature condition of-5 DEG C or following comprised the steps: pre-treatment or undressed raw material and sodium hydroxide or potassium hydroxide, urea and thiocarbamide, raw material is identical with the temperature of compound aqueous solution precooling or different; By compound aqueous solution and barley seeding food mix and blend 2-15min, then centrifugation obtains supernatant liquor; Supernatant liquor uses acid for adjusting pH value between 5-9; Again with two volumes alcohol settling; Pelleting centrifugation, and by washing with alcohol to neutral, vacuum-drying; Described raw material is selected from barley seeding food, straw, cotton stalk, ramulus mori, obtains, reed, awns bar, Herba Poae Sphondylodis, one or more combination in waste of flax and/or pulp; Described extraction step is no more than 20 minutes.
2. hemicellulose extracting method according to claim 1, in described compound aqueous solution, the part by weight of three kinds of components is 8-12: 6-10: 4.5-8.5.
3. hemicellulose extracting method according to claim 1, it is characterized in that described stirring and centrifugation are all carry out under the temperature condition of-5 DEG C or following, described stirring is strong stirring.
4. the hemicellulose extracting method according to claims 1 to 3 any one, described extraction step is no more than 18 minutes.
5. hemicellulose extracting method according to claim 4, described extraction step adds 1-4 times of volume ethanol, hemicellulose is separated out with precipitation forms after comprising extracting solution acidifying extraction obtained, and precipitation is extremely neutral with washing with alcohol again, vacuum-drying.
6. hemicellulose extracting method according to claim 5, described extraction carries out under the temperature condition of-5 DEG C or following.
7. the extracting method of hemicellulose according to claim 1, described pre-treatment refers to that, successively by Benzene-ethanol extraction and hot-water extraction raw material, described raw material is wheat straw.
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| CN103333274B (en) * | 2013-07-11 | 2015-10-28 | 宜宾丝丽雅集团有限公司 | A kind of extraction recovery method squeezing hemicellulose in salkali waste |
| CN105113236B (en) * | 2015-10-14 | 2017-08-25 | 浙江超凡制衣有限公司 | A kind of low skin irritability flax material and its preparation technology |
| CN107475323A (en) * | 2017-08-31 | 2017-12-15 | 齐鲁工业大学 | A kind of processing method of waste straw cellulase hydrolysis saccharification |
| CN107475324A (en) * | 2017-08-31 | 2017-12-15 | 齐鲁工业大学 | A kind of method for changing wood-cellulose crystal structure and promoting its enzymatic saccharification |
| CN111690075B (en) * | 2019-03-15 | 2021-10-15 | 中国海洋大学 | Water-soluble beta-glucan, preparation method thereof and application thereof in preparation of immune enhancement and anti-tumor medicines and health-care products |
| CN115075031B (en) * | 2022-06-06 | 2024-02-09 | 赣南师范大学 | Method for removing hemicellulose in bleached bamboo pulp, bamboo dissolving pulp and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932209A (en) * | 1969-02-24 | 1976-01-13 | Personal Products Company | Low hemicellulose, dry crosslinked cellulosic absorbent materials |
| CN1955347A (en) * | 2005-10-26 | 2007-05-02 | 中国科学院过程工程研究所 | Preparing method of straw type fibre spinning solution |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932209A (en) * | 1969-02-24 | 1976-01-13 | Personal Products Company | Low hemicellulose, dry crosslinked cellulosic absorbent materials |
| CN1955347A (en) * | 2005-10-26 | 2007-05-02 | 中国科学院过程工程研究所 | Preparing method of straw type fibre spinning solution |
Non-Patent Citations (2)
| Title |
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| "玉米秆半纤维素的碱法提取与表征";程合丽等;《中国造纸学报》;20110915;第26卷(第3期);第26-29页 * |
| 查纯喜等."纤维素在氢氧化钠/硫脲/尿素/水溶液中的溶解合溶液特性".《东华大学学报(自然科学版)》.2008,第34卷(第1期),第20-23页,第43页. * |
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