CN109337090A - A method of high activity lignin is extracted using stabilizer - Google Patents
A method of high activity lignin is extracted using stabilizer Download PDFInfo
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- CN109337090A CN109337090A CN201811170852.XA CN201811170852A CN109337090A CN 109337090 A CN109337090 A CN 109337090A CN 201811170852 A CN201811170852 A CN 201811170852A CN 109337090 A CN109337090 A CN 109337090A
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- lignin
- stabilizer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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Abstract
The invention discloses a kind of methods for extracting high activity lignin using stabilizer, and steps are as follows: (1) first using pulverizer crushed biomass, take it less than 60 mesh part below, drying；(2) biomass after drying is dissolved in organic solvent, wherein the reaction of small molecule stabilizer heating stirring is added；(3) mixed liquor after reaction is filtered, sodium bicarbonate solution is added in filtrate, filtered；(4) excessive deionized water is added in filtrate, organic solvent lignin, drying is precipitated.The present invention utilizes small molecule stabilizer and lignin reaction, obtains that molecular weight is small, the lignin of high activity.
Description
Technical field:
The present invention relates to a kind of lignin extraction methods, are specifically extracted from biomass using micromolecule additive
The method of high activity lignin.
Background of invention:
In recent years, as traditional fossil energy constantly consumes, biomass gradually enters people as reproducible new energy
The visual field, include three big components in biomass, cellulose accounts for about 40%, and hemicellulose accounts for about 30%, and lignin accounts for about 25%, raw
Substance has the characteristics of renewable, low pollution, abundance.
Lignin has carboxyl, aldehyde as a kind of biomass polymers abundant, the existing phenolic hydroxyl group of structure, alcoholic extract hydroxyl group
Base etc., this unique structure allow lignin and other compounds synthetic resin under certain condition；According to its surface
Active characteristic can also be prepared into nonionic surfactant, anionic surfactant, cationic surfactant and two
Property surfactant.The application of lignin application in these areas is so that its added value is much higher than as recycling heat after fuel combustion
Measure added value.Common organic solvent extracting method obtains lignin and is easy to be condensed during the extraction process, not only makes wooden
Element extracts difficult but also the pyrolysis of back lignin and hydrogenolysis are difficult to depolymerization.Fast pyrogenation is as a kind of heavy in biomass conversion
The means wanted, the lignin that common organic solvent extracts will appear more carbon distribution in fast pyrogenation, and needed for making us
Liquid product it is lower.
In view of the problem during current lignin extraction and difficult, a kind of new extracting method is needed now to solve
The extracting method problem in the past.
Summary of the invention:
The present invention is to provide a kind of method of lignin extraction, and the method provided through the invention reaches lignin
The purpose of high extraction and high activity.
Technical scheme is as follows:
(1) for example by biomass material: poplar, herbaceous plant etc. are crushed by pulverizer, are taken wherein less than 60 purposes
Part dries smashed biomass in 110 DEG C；
(2) the stand-by sample of drying in step (1) is dissolved in organic solvent, 5% hydrochloric acid (concentration of volume fraction is added
37%) and the stabilizer of volume fraction 10%, heating stirring reacts 4-8h at 60-110 DEG C；By the mixed liquor mistake after reaction
Filtrate is collected in filter；
(3) in filtrate be added 1mol/L sodium bicarbonate solution be used in and excessive acid, by the reaction solution after neutralization
Filtrate is collected in filtering；
(4) deionized water is added in filtrate obtained in step (3) to be precipitated, the mixed liquor mistake that will be obtained after being sufficiently stirred
Filter, obtains organic solvent lignin solid；It is dried at 50 DEG C.
Further, in step (2) organic solvent be dioxane, arboxylic acid, ethyl alcohol, acetone equal solvent system, surely
Determine agent for small molecule aldehyde, ketone and carboxylic acids, such as: formaldehyde, acetaldehyde, propionic aldehyde, formic acid, acetone.
Further, deionized water additional amount is usually 5-10 times of organic solvent in step (4).
The present invention has following superiority:
(1) bigger than normal with the extracted lignin molecule amount of organic solvent, and the dispersion degree of molecular weight improves；
(2) recovery rate for the organic solvent lignin being added after small molecule stabilizer is obviously improved, and stabilizer and wood
Quality reacts, and improves the pyrolysis activity of lignin；
Detailed description of the invention:
Fig. 1 is lignin extraction process schematic provided in an embodiment of the present invention.
Fig. 2 is the thermal multigraph of the lignin provided in an embodiment of the present invention after formaldehyde and water pretreatment extract.
Fig. 3 is the lignin fast pyrogenation gross area provided in an embodiment of the present invention after formaldehyde is mentioned and being taken with water pretreatment
Figure.
Specific embodiment:
Further instruction is given to the present invention below by example, the present invention is not only limited to following specific embodiments,
Illustrated embodiment is not optimum extraction lignin condition yet.
Embodiment 1:
(1) less than 60 mesh white poplar sawdusts in 110 DEG C of drying 12h after taking 1g to crush；
(2) the white poplar sawdust of drying is dissolved in the dioxane of 9ml, the hydrochloric acid (37%) and 1ml of 0.42ml is added
Formaldehyde (37%), 400 revs/min of reaction 5h of heating stirring, then filter mixed liquor at 80 DEG C, with 10ml dioxy six when filtering
Ring washs filter residue in three times, collects filtrate；
(3) in filtrate be added 5ml 1mol/L sodium bicarbonate solution be used in and excessive acid, after being sufficiently mixed will
Reaction solution filtering after neutralization, collects filtrate；
(4) 70ml deionized water is added in filtrate obtained in step (3) to be precipitated, is stirred 15 minutes, is obtained with glass bar
Mixed liquor filtering, obtain organic solvent lignin solid；It is dried at 50 DEG C, the recovery rate of lignin is 81%；
Embodiment 2:
(1) less than 60 mesh white poplar sawdusts in 110 DEG C of drying 12h after taking 1g to crush；
(2) the white poplar sawdust of drying is dissolved in the dioxane of 9ml, the hydrochloric acid (37%) and 1ml of 0.42ml is added
Formic acid (99.9%), 400 revs/min of reaction 8h of heating stirring, then filter mixed liquor at 80 DEG C, with 10ml dioxy when filtering
Six rings wash filter residue in three times, collect filtrate；
(3) in filtrate be added 5ml 1mol/L sodium bicarbonate solution be used in and excessive acid, after being sufficiently mixed will
Reaction solution filtering after neutralization, collects filtrate；
(4) 70ml deionized water is added in filtrate obtained in step (3) to be precipitated, is stirred 15 minutes, is obtained with glass bar
Mixed liquor filtering, obtain organic solvent lignin solid；It is dried at 50 DEG C, obtains high activity lignin, lignin mentions
Taking rate is 65%；
Embodiment 3:
(1) less than 60 mesh white poplar sawdusts in 110 DEG C of drying 12h after taking 10g to crush；
(3) the white poplar sawdust of drying is dissolved in the dioxane of 90ml, the hydrochloric acid (37%) and 10ml of 4.2ml is added
Formaldehyde (37%), 400 revs/min of reaction 8h of heating stirring, then filter mixed liquor at 80 DEG C, collect filtrate；
(4) in filtrate be added 10ml 1mol/L sodium bicarbonate solution be used in and excessive acid, after being sufficiently mixed will
Reaction solution filtering after neutralization, collects filtrate；
(5) 400ml deionized water is added in filtrate obtained in step (3) to be precipitated, stirs 15min with magnetic stir bar,
Obtained mixed liquor filtering, obtains organic solvent lignin solid；It is dried at 50 DEG C, obtains high activity lignin, lignin
Recovery rate be 73%；
Embodiment 4:
(1) less than 60 mesh white poplar sawdusts in 110 DEG C of drying 12h after taking 1g to crush；
(2) the white poplar sawdust of drying is dissolved in the dioxane of 9ml, the hydrochloric acid (37%) and 1ml of 0.42ml is added
Acetaldehyde (99.9%), 400 revs/min of reaction 5h of heating stirring, then filter mixed liquor at 80 DEG C, with 10ml dioxy when filtering
Six rings wash filter residue in three times, collect filtrate；
(3) in filtrate be added 5ml 1mol/L sodium bicarbonate solution be used in and excessive acid, after being sufficiently mixed will
Reaction solution filtering after neutralization, collects filtrate；
(4) 70ml deionized water is added in filtrate obtained in step (3) to be precipitated, is stirred 15 minutes, is obtained with glass bar
Mixed liquor filtering, obtain organic solvent lignin solid；It is dried at 50 DEG C, obtains high activity lignin, lignin mentions
Taking rate is 63%；
Embodiment 5:
(1) less than 60 mesh white poplar sawdusts in 110 DEG C of drying 12h after taking 1g to crush；
(2) the white poplar sawdust of drying is dissolved in the acetic acid of 10ml: formic acid: water=5: in 3: 2 solution, the first of 1ml is added
Aldehyde (37%), first 300 revs/min of reaction 1h of heating stirring at 60 DEG C, then 500 revs/min of the heating stirring reactions at 110 DEG C
Then 3h filters mixed liquor, when filtering is washed at 60 DEG C in three times with the acetic acid solution of 15ml 0.5mol/L, collects filter
Liquid；
(3) in filtrate be added 5ml 1mol/L sodium bicarbonate solution be used in and excessive acid, after being sufficiently mixed will
Reaction solution filtering after neutralization, collects filtrate；
(4) 50ml deionized water is added in filtrate obtained in step (3) to be precipitated, is stirred 15 minutes, is obtained with glass bar
Mixed liquor filtering, obtain organic solvent lignin solid；It is dried at 50 DEG C, obtains high activity lignin, lignin mentions
Taking rate is 66%；
Embodiment 6:
(1) less than 60 mesh white poplar sawdusts in 110 DEG C of drying 12h after taking 1g to crush；
(2) the white poplar sawdust of drying is dissolved in the dioxane of 9ml, the hydrochloric acid (37%) and 1ml of 0.42ml is added
Deionized water-comparison, 400 revs/min of reaction 8h of heating stirring, then filter mixed liquor at 80 DEG C, with 10ml bis- when filtering
Six ring of oxygen washs filter residue in three times, collects filtrate；
(3) in filtrate be added 5ml 1mol/L sodium bicarbonate solution be used in and excessive acid, after being sufficiently mixed will
Reaction solution filtering after neutralization, collects filtrate；
(4) 70ml deionized water is added in filtrate obtained in step (3) to be precipitated, is stirred 15 minutes, is obtained with glass bar
Mixed liquor filtering, obtain organic solvent lignin solid；It is dried at 50 DEG C, the recovery rate of lignin is 36%；
The above embodiments show:, can be wooden by extracting in organic solvent using method provided in the present invention
A small amount of small molecule aldehyde and carboxylic acids, which is added, as stabilizer during element can significantly improve mentioning for organic solvent lignin
Rate is taken, especially has lower molecular weight and high activity by the lignin of this procedure extraction.
Claims (7)
1. a kind of method for extracting high activity lignin using stabilizer, it is characterised in that: in dioxane solvent or formic acid
In acetic acid solvent, a small amount of hydrochloric acid conditioning solution pH, heating stirring is added as stabilizer in the aldehydes or carboxylic acids that small molecule is added
Extract lignin.
2. it is according to claim 1 using stabilizer extract high activity lignin method, it is characterised in that: addition it is small
Stabilizer molecule is aldehydes: formaldehyde, acetaldehyde, propionic aldehyde；Carboxylic acids: one of formic acid.
3. the method according to claim 1 for extracting high activity lignin using stabilizer, it is characterised in that: above-mentioned used
Organic solvent, be not limited only to dioxane, arboxylic acid dicyandiamide solution also includes alcohols: methanol, alcohol solvent system.
4. the method according to claim 1 for extracting high activity lignin using stabilizer, it is characterised in that: the heating
Stirring, being heated to temperature is 60-110 DEG C, and stirring rate is 300-500 revs/min.
5. the method according to claim 1 for extracting high activity lignin using stabilizer, it is characterised in that: in after reaction
With alkali used, it is not limited only to sodium bicarbonate, also includes sodium carbonate, sodium hydroxide.
6. the method according to claim 1 for extracting high activity lignin using stabilizer, it is characterised in that: the acid of addition
It is not limited only to hydrochloric acid, also includes sulfuric acid, trifluoromethanesulfonic acid.
7. it is according to claim 1 using stabilizer extract high activity lignin method, it is characterised in that: addition it is small
The volume of stabilizer molecule is the 7-10% of organic solvent.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108179644A (en) * | 2017-12-21 | 2018-06-19 | 中国科学院青岛生物能源与过程研究所 | A kind of method that lignin is extracted from biomass |
| US20180201870A1 (en) * | 2014-12-01 | 2018-07-19 | Council Of Scientific And Industrial Research | An eco-friendly process for the isolation of biopolymers from agricultural residues |
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- 2018-10-08 CN CN201811170852.XA patent/CN109337090A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180201870A1 (en) * | 2014-12-01 | 2018-07-19 | Council Of Scientific And Industrial Research | An eco-friendly process for the isolation of biopolymers from agricultural residues |
| CN108179644A (en) * | 2017-12-21 | 2018-06-19 | 中国科学院青岛生物能源与过程研究所 | A kind of method that lignin is extracted from biomass |
Non-Patent Citations (1)
| Title |
|---|
| LUTERBACHER, J: "Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization", 《SCIENCE》 * |
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