CN106632515A - Method for degrading lignin by ionic liquid catalyzed alcohol system - Google Patents
Method for degrading lignin by ionic liquid catalyzed alcohol system Download PDFInfo
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- CN106632515A CN106632515A CN201610873410.6A CN201610873410A CN106632515A CN 106632515 A CN106632515 A CN 106632515A CN 201610873410 A CN201610873410 A CN 201610873410A CN 106632515 A CN106632515 A CN 106632515A
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- lignin
- ionic liquid
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- catalyzed alcohol
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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 relates to a method for degrading lignin by an ionic liquid catalyzed alcohol system. The method specifically comprises the following steps: adding lignin, ionic liquid and alcohol to a reaction kettle, sealing the reaction kettle, stirring in 180-260 DEG C of the temperature, and performing the lignin catalytic degradation; after cooling a reactant, adding distilled water to the reactant, and filtering and separating in vacuum so as to obtain the undegraded lignin; and removing most of the water from filter liquor through the vacuum concentration of a rotary evaporator, extracting by using an organic solvent, and extracting a lignin catalyzed degradation product. The method is capable of using the ionic liquid catalyzed alcohol system to degrade the lignin, and improving the utilization ratio of the lignin, and is good for preparing chemicals by the lignin. The ionic liquid can be recycled and repeatedly used. The method has the advantages of simple process and environment friendliness.
Description
Technical field
The invention belongs to natural biomass resources effective utilization field, more particularly to a kind of ionic liquid-catalyzed alcohol system drop
The method of solution lignin.
Background technology
With petroleum resources increasingly reduction and environmental problem it is increasingly apparent, biomass resource is used as reproducible green
Resource causes extensive concern.Lignin as biomass material one of three big components, rich reserves and be unique tool
There is the renewable resource of aromatic structure, the annual whole world can about produce 6 × 1014Ton, with petroleum replacing resource new energy is become
The potentiality in source.However, because lignin structure is sufficiently complex, molecular weight is big and has a very wide distribution, it is very difficult to directly utilize, system
Lignin of the slurry paper industry more than 95% is not utilized effectively, and lignin black liquor also creates serious environmental problem.Cause
This, by destroying lignin tridimensional network, is degraded to small-molecule substance and is converted into biological-based chemicals, so as to improve
The utilization rate of Liginon Resource, has important practical significance.
The greatest problem using presence of current lignin is the degradation problem of lignin.Thermochemical study, cracking at present
The method of lignin degrading is often higher to equipment requirement, and the bioconversion usual production cycle is longer, and process is slow.Alcohol system pair
It is wooden to have certain dissolubility, the still not good biomass solvent of ionic liquid, its excellent catalytic capability is in lignin
Degradation process in also have important function.Additionally, ionic liquid is used as green solvent, its relatively low vapour pressure and its capable of circulation
The characteristic for using so that larger harm will not be caused during use to environment.
The content of the invention
The invention solves the problems that existing lignin degradation method complex process, higher to equipment requirement, easily cause two secondary environments
The problem of pollution, and a kind of lignin degradation method of environmental protection is provided.
A kind of method of ionic liquid-catalyzed alcohol system lignin degrading, specifically follows the steps below：
First, lignin is added in the mixed solution of polyalcohol and ionic liquid, by magnetic agitation by mixed solution
Stir, close reactor, in system inert gas is passed through.
2nd, the reaction mixture that step one is obtained is positioned in the thermostatical oil bath of 180～260 DEG C of temperature, keeps 0.5
～3h, obtains mixture；
3rd, distilled water and the isolated undegraded lignin of vacuum filtration are added in the reactant liquor obtained to step 2.
4th, to the rotated evaporation under reduced pressure concentration of step 3 gained filtrate, most of moisture is removed, is entered using organic solvent
Row extracting 3-6 time, extracts lignin degradation products therein.
Wherein, magnetic agitation and inert gas is passed through in order to guarantee system is uniform, discharge air in step one.In step 2
Using ionic liquid-catalyzed alcohol system lignin degrading, ionic liquid is added in order to improve the catalytic degradation efficiency of lignin.Step
In rapid three the catalytic degradation product of undegraded lignin and lignin is separated using vacuum filtration.Add in step 4 organic molten
Agent extracts the catalytic degradation product of lignin.Lignin degradation method of the present invention is had certain based on alcohols to lignin
Dissolution characteristics and the stronger solvability of ionic liquid and catalysis activity, degraded using ionic liquid-catalyzed alcohol system wooden
Element, obtains small-molecule substance, is conducive to preparing chemicals using lignin, meets the principle of lignin higher value application.
The invention has the beneficial effects as follows：
1st, the method applied in the present invention is simple to operate, and equipment requirement is low, with short production cycle, and low toxicity, environmental pollution are little.
2nd, the method does not produce pernicious gas, ionic liquid recoverable, environmental protection.3rd, ionic liquid can greatly improve wooden
Plain degradation efficiency, obtains small-molecule substance, is advantageously implemented lignin higher value application, meets the requirement of biorefining.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, also including each specific embodiment it
Between any combination.
Specific embodiment one：What present embodiment was specifically followed the steps below：
First, 1g lignin is added in the mixed solution of 1,2-PD and 1- butyl -3- N-Methylimidazoleacetic salt, is led to
Cross magnetic agitation mixed solution stirs, close reactor, nitrogen 15min is passed through in system.
2nd, the reaction mixture that step one is obtained is positioned in the thermostatical oil bath of 200 DEG C of temperature, keeps 0.5h, obtained
To mixture；
3rd, distilled water and the isolated undegraded lignin of vacuum filtration are added in the reactant liquor obtained to step 2.
4th, to the rotated evaporation under reduced pressure concentration of step 3 gained filtrate, most of moisture is removed, is taken out using ethyl acetate
Carry 4 times, extract lignin degradation products therein.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Alcohols used in step one
For 1,2- butanediols, ionic liquid is 1- ethyl-3-methylimidazole acetates.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment from unlike specific embodiment one：Thermostat water bath in step 2
Temperature be 240 DEG C, keep 2h.Other are identical with specific embodiment one.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：
A kind of method of ionic liquid-catalyzed alcohol system lignin degrading of the present embodiment, specifically follows the steps below
's：
First, 0.5g coir lignin is added to into 15mL glycerine and 0.5g 1- butyl -3- methylimidazolium hydrogen sulphate salt
Mixed solution in, mixed solution is stirred by magnetic agitation, close reactor, nitrogen 15min is passed through in system.
2nd, the reactor equipped with mixed solution in step one is placed in the thermostatical oil bath of 240 DEG C of temperature, keeps 1h；
3rd, 100mL distilled water is added in the reactant liquor obtained to step 2, and by nylon leaching film that aperture is 0.45 μm
Vacuum filtration is carried out, undegraded lignin solid residue is obtained.
4th, by the rotated evaporation under reduced pressure concentration of step 3 gained filtrate, most of moisture is removed, is entered using ethyl acetate
Row extracting 4 times, extracts lignin degradation products therein.
The present embodiment, the degradation rate of coir lignin is 28.1%, and main catabolite has polynary ether-ether and 2,
The lignin monomer compounds such as 6- syringol, 2- methoxyl group -4- propylphenols, 4- hydroxy 3-methoxybenzene acetone.
Claims (6)
1. a kind of method of ionic liquid-catalyzed alcohol system lignin degrading, it is comprised the following steps that：
First, lignin is added in the mixed solution of alcohol and ionic liquid, mixed solution is stirred by magnetic agitation,
Reactor is closed, in system inert gas is passed through；
2nd, the reactor equipped with mixed solution in step one is positioned in the thermostatical oil bath of 200～260 DEG C of temperature, is kept
0.5～3h, applies all the time magnetic agitation during this；
3rd, distilled water and the isolated undegraded lignin of vacuum filtration are added in the reactant liquor obtained to step 2.
4th, step 3 gained filtrate is removed into most of moisture by Rotary Evaporators reduced pressure concentration, is extracted using organic solvent
3-6 time, extract lignin degradation products therein.
2. a kind of method of ionic liquid-catalyzed alcohol system lignin degrading according to claim 1, it is characterised in that step
Lignin described in rapid one is organic solvent lignin, lignosulfonates, alkali lignin.
3. a kind of method of ionic liquid-catalyzed alcohol system lignin degrading according to claim 1, it is characterised in that step
Alcohols used is dihydroxylic alcohols, trihydroxylic alcohol of the boiling point more than 100 DEG C in rapid one.
4. a kind of method of ionic liquid-catalyzed alcohol system lignin degrading according to claim 1, it is characterised in that step
Ionic liquid described in rapid one is by alkyl-substituted glyoxaline cation and HSO4 -、CH3COO-、SO42-Anion is constituted.
5. a kind of method of ionic liquid-catalyzed alcohol system lignin degrading according to claim 1, it is characterised in that step
The ratio of lignin raw material, polyalcohol and ionic liquid is 1 in rapid one:10～30：0.5～2 (m/v/m).
6. a kind of method of ionic liquid-catalyzed alcohol system lignin degrading according to claim 1, it is characterised in that step
Temperature is controlled in rapid two at 200～300 DEG C, the reaction time is in 0.5～3h.
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| CN201610873410.6A CN106632515A (en) | 2016-10-03 | 2016-10-03 | Method for degrading lignin by ionic liquid catalyzed alcohol system |
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| CN201610873410.6A CN106632515A (en) | 2016-10-03 | 2016-10-03 | Method for degrading lignin by ionic liquid catalyzed alcohol system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276253A (en) * | 2018-03-16 | 2018-07-13 | 中国科学院过程工程研究所 | A kind of method of photocatalytic oxidation degradation lignin and its model compound |
| CN111302906A (en) * | 2020-03-31 | 2020-06-19 | 河北工业大学 | Method for preparing guaiacol by catalyzing lignin with binuclear sulfonic acid type ionic liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103194924A (en) * | 2013-03-29 | 2013-07-10 | 南开大学 | Method for extracting cellulose from straw stalk by using imidazole ion liquid |
| CN103467750A (en) * | 2013-07-29 | 2013-12-25 | 北京林业大学 | Degradation method for lignin |
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2016
- 2016-10-03 CN CN201610873410.6A patent/CN106632515A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194924A (en) * | 2013-03-29 | 2013-07-10 | 南开大学 | Method for extracting cellulose from straw stalk by using imidazole ion liquid |
| CN103467750A (en) * | 2013-07-29 | 2013-12-25 | 北京林业大学 | Degradation method for lignin |
Non-Patent Citations (2)
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| 李利芬等: "离子液体在木质素研究中的应用", 《林产化学与工业》 * |
| 程芳超: "基于离子液体的农林生物质组分分离及催化转化研究", 《中国博士学位论文全文数据库 农业科技辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276253A (en) * | 2018-03-16 | 2018-07-13 | 中国科学院过程工程研究所 | A kind of method of photocatalytic oxidation degradation lignin and its model compound |
| CN108276253B (en) * | 2018-03-16 | 2021-01-22 | 中国科学院过程工程研究所 | Method for degrading lignin and model compound thereof by photocatalytic oxidation |
| CN111302906A (en) * | 2020-03-31 | 2020-06-19 | 河北工业大学 | Method for preparing guaiacol by catalyzing lignin with binuclear sulfonic acid type ionic liquid |
| CN111302906B (en) * | 2020-03-31 | 2022-09-13 | 河北工业大学 | Method for preparing guaiacol by catalyzing lignin with binuclear sulfonic acid type ionic liquid |
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Application publication date: 20170510 |