CN104004201A - Method for degrading lignin in acidic eutectic solvent - Google Patents
Method for degrading lignin in acidic eutectic solvent Download PDFInfo
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- CN104004201A CN104004201A CN201410261154.6A CN201410261154A CN104004201A CN 104004201 A CN104004201 A CN 104004201A CN 201410261154 A CN201410261154 A CN 201410261154A CN 104004201 A CN104004201 A CN 104004201A
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Abstract
The invention discloses a method for degrading lignin in a Bronsted acidic eutectic solvent. The method includes the first step of adding lignin raw materials, the eutectic solvent and water into a reactor, the second step of conducting stirring and homogeneous catalytic degradation under the normal pressure and the temperature ranging from 90 DEG C to 130 DEG C, the third step of adding water to deposit residuals of lignin after a reaction product is cooled, and the fourth step of conducting centrifuging, full washing and drying on the residuals to obtain degraded lignin. Rotary steaming is conducted on supermatant liquid to remove moisture, and the eutectic solvent can be recycled through vacuum drying. According to the method, the Bronsted acidic eutectic solvent is used as the solvent and catalysts to degrade the lignin; the eutectic solvent can be recycled, and consequently the method has the advantages of being simple in process, low in cost and the like.
Description
Technical field
The invention belongs to natural biological resources effective utilization field, relate in particular to one and exist
the method of lignin degrading in acid eutectic solvent.
Background technology
Along with the exhaustion of petroleum resources and the aggravation of Greenhouse effect, seek reproducible " green " resource and cause extensive concern.Xylogen is mainly the unformed macromolecular compound being connected to form by ehter bond or C-C by para hydroxybenzene propane unit, guaiacyl phenylpropyl alcohol alkane unit and Syringa oblata Lindl. base phenylpropyl alcohol alkane unit, be only second to Mierocrystalline cellulose and chitin at the content of occurring in nature, and be unique renewable resources containing aromatic structure.Can reduce the macromolecular molecular weight of xylogen by technology such as cracking, bio-transformation and thermochemistry degradeds, increase activity hydroxy group number, generate high value aromatic compound simultaneously.Cracking is carried out conventionally under high temperature (300～600 DEG C), high pressure (10MPa), inert gas conditions, higher to equipment requirements.Bio-transformation is by mushrooms such as fungies, xylogen to be degraded, but degradation process is very slow.Thermochemistry transforms and comprises acid catalysis, base catalysis, metal catalytic, supercutical fluid auxiliary catalysis etc., and conventional thermochemistry transforms the High Temperature High Pressure condition of (being greater than 300 DEG C, 10MPa) that conventionally also needs.
The good physical chemistry features such as steam forces down owing to having, Heat stability is good, designability, ionic liquid comes into one's own gradually in the research in carbohydrate and lignin degradation field.At present, ionic liquid, especially acidic ion liquid are obtained many progress in the research of cellulose degradation conversion aspect, but, need deeply in the research in xylogen field.In addition, the raw material that conventional ion liquid uses is many from petroleum resources, non-renewable, and complicated process of preparation, expensive, has limited its large-scale industrial production application.2003, the discovery urea such as Abbott and quaternary ammonium salt are liquid mixture by forming by certain mol proportion Hybrid Heating under room temperature, and be referred to as eutectic solvent (Deep Eutectic Solvents), this solvent has the physicochemical property similar with ionic liquid, is therefore also referred to as ionic liquid analogue.Eutectic solvent is nontoxic, biodegradable, and atom utilization is 100%.Research discovery subsequently, carbohydrate, xylogen etc. has good solubility energy in some eutectic solvents.Therefore, the Degradation and Transformation of research xylogen in acid eutectic solvent, is the effective way that realizes xylogen high-value-use.
Summary of the invention
The object of this invention is to provide a kind of operating procedure lignin degradation method simple, with low cost.
Technical scheme of the present invention is: xylogen raw material, eutectic solvent and water are joined in reactor, under normal pressure, 90～130 DEG C of conditions, stir and carry out homogeneous catalysis degraded, after question response product is cooling, aqueous precipitation lignin residue, centrifugal, fully washing residue, the dry lignin degrading that obtains.Supernatant liquid revolves to steam removes moisture, the recyclable eutectic solvent of vacuum-drying.
1. the method described in, wherein, described eutectic solvent is choline chloride 60-tosic acid;
2. the method described in, wherein, in eutectic solvent, the mol ratio of choline chloride 60 and tosic acid is 3～7:7～3;
3. the method described in, wherein, raw material wood element is milled wood lignin quality, alkali lignin, enzymolysis xylogen, organic solvent xylogen, one or more in ionic liquid xylogen;
4. the method described in, wherein, eutectic solvent: xylogen: the mass ratio of water is 100:5～20:0.01～5;
5. the method described in, wherein, the reaction times is 0.5～12h.
The invention has the beneficial effects as follows:
1, the method applied in the present invention technique is simple, with low cost;
2, eutectic solvent steam forces down, nontoxic, recyclable recycling;
3, under normal pressure, relatively mild reaction conditions, can realize the degraded of xylogen homogeneous catalysis;
4, lignin degradation molecular weight of product reduces, and hydroxy radical content increases, and has widened its range of application.
Brief description of the drawings
Fig. 1 is gel permeation chromatography (GPC) spectrogram of alkali lignin of degrading in alkali lignin raw material and embodiment 1.The weight-average molecular weight of alkali lignin is 17680g/mol, and polydispersity coefficient is 26.98; The weight-average molecular weight of alkali lignin of degrading in embodiment 1 is 7783g/mol, and polydispersity coefficient is 16.05, proves that degraded has occurred xylogen in acid eutectic solvent treating processes, causes molecular weight to reduce.
Fig. 2 is infrared (FTIR) spectrogram of alkali lignin of degrading in alkali lignin raw material and embodiment 3.Compared with the infrared spectrum of degraded alkali lignin and alkali lignin, 3305cm
-1near hydroxyl (OH) absorption peak strengthens, 1078cm
-1near ehter bond (C-O-C) absorption peak weakens, and proves that xylogen ehter bond generation fracture has generated hydroxyl in treating processes.1510cm
-1near phenyl ring charateristic avsorption band is constant, illustrates that the phenol type structure of xylogen does not have destroyed.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but not as a limitation of the invention.
Embodiment 1:
1g alkali lignin and 250 μ L deionized waters are joined in 20mL eutectic solvent to oil bath magnetic agitation 1h at 130 DEG C, cooling degraded product, add the deionized water of 3 times of eutectic solvent quality, centrifugal, washing, dry, obtain the alkali lignin of degrading, quality is 0.957g.
Embodiment 2:
1g alkali lignin and 250 μ L deionized waters are joined in 20mL eutectic solvent to oil bath magnetic agitation 3h at 130 DEG C, cooling degraded product, add the deionized water of 3 times of eutectic solvent quality, centrifugal, washing, dry, obtain the alkali lignin of degrading, quality is 0.938g.
Embodiment 3:
1g alkali lignin and 250 μ L deionized waters are joined in 20mL eutectic solvent to oil bath magnetic agitation 5h at 130 DEG C, cooling degraded product, add the deionized water of 3 times of eutectic solvent quality, centrifugal, washing, dry, obtain the alkali lignin of degrading, quality is 0.893g.
Embodiment 4:
1g alkali lignin and 250 μ L deionized waters are joined in 20mL eutectic solvent to oil bath magnetic agitation 12h at 130 DEG C, cooling degraded product, add the deionized water of 3 times of eutectic solvent quality, centrifugal, washing, dry, obtain the alkali lignin of degrading, quality is 0.887g.
Claims (6)
- One kind the method of lignin degrading in acid eutectic solvent, it is characterized in that, xylogen raw material, eutectic solvent and water are joined in reactor, under normal pressure, 90～130 DEG C of conditions, stir and carry out homogeneous catalysis degraded, after question response product is cooling, aqueous precipitation lignin residue, centrifugal, fully wash residue, the dry lignin degrading that obtains, supernatant liquid revolves to steam removes moisture, the recyclable eutectic solvent of vacuum-drying.
- According to claim 1 in acid eutectic solvent, the method for lignin degrading, is characterized in that described eutectic solvent is choline chloride 60-tosic acid.
- According to claim 2 the method of lignin degrading in acid eutectic solvent, is characterized in that in eutectic solvent, the mol ratio of choline chloride 60 and tosic acid is 3～7:7～3.
- According to claim 1 in acid eutectic solvent, the method for lignin degrading, is characterized in that xylogen raw material is milled wood lignin quality, alkali lignin, enzymolysis xylogen, organic solvent xylogen, one or more in ionic liquid xylogen.
- According to claim 1 in acid eutectic solvent, the method for lignin degrading, is characterized in that eutectic solvent: xylogen: the mass ratio of water is 100:5～20:0.01～5.
- According to claim 1 in acid eutectic solvent, the method for lignin degrading, is characterized in that the reaction times is 0.5～12h.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461936A (en) * | 2014-09-12 | 2016-04-06 | 东北林业大学 | Rapid butyrylation modification method of ligninsulfonate |
| CN105503540A (en) * | 2014-09-24 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for preparation of benzene ring phenol compound from alkali lignin |
| CN105754114A (en) * | 2016-02-25 | 2016-07-13 | 南京林业大学 | Method for separating and extracting straw lignin by using eutectic ionic liquid |
| CN106442805A (en) * | 2016-11-23 | 2017-02-22 | 新疆农业科学院农产品贮藏加工研究所 | Method for extracting milled wood lignin from stone cells in Korla fragrant pear fruit |
| CN106987862A (en) * | 2017-04-12 | 2017-07-28 | 中北大学 | A kind of method of the electrochemical degradation lignin in eutectic solvent |
| CN109369886A (en) * | 2017-08-04 | 2019-02-22 | 南京林业大学 | A kind of method that eutectic solvent modified lignin resin is used for epoxy curing agent |
| CN110105619A (en) * | 2019-04-26 | 2019-08-09 | 中国科学院山西煤炭化学研究所 | A kind of controlled degradation recovery method of polyurethane |
| CN110982090A (en) * | 2019-12-04 | 2020-04-10 | 北京林业大学 | Method for extracting lignin in biomass by microwave-assisted eutectic solvent |
| CN111392724A (en) * | 2020-05-15 | 2020-07-10 | 齐鲁工业大学 | Preparation method of chromium ion adsorption activated carbon |
| CN112029115A (en) * | 2020-09-11 | 2020-12-04 | 齐鲁工业大学 | Method for separating and extracting lignin by in-situ synthesis of deep eutectic solvent |
| CN112209360A (en) * | 2020-10-16 | 2021-01-12 | 北京理工大学 | Shrimp shell conversion method based on sulfonic acid type eutectic solvent |
| CN113198428A (en) * | 2021-04-30 | 2021-08-03 | 深圳信息职业技术学院 | Method for preparing three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof |
| CN114800943A (en) * | 2022-05-20 | 2022-07-29 | 嘉兴学院 | Method for recycling waste carpet |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461936A (en) * | 2014-09-12 | 2016-04-06 | 东北林业大学 | Rapid butyrylation modification method of ligninsulfonate |
| CN105503540A (en) * | 2014-09-24 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for preparation of benzene ring phenol compound from alkali lignin |
| CN105754114A (en) * | 2016-02-25 | 2016-07-13 | 南京林业大学 | Method for separating and extracting straw lignin by using eutectic ionic liquid |
| CN106442805A (en) * | 2016-11-23 | 2017-02-22 | 新疆农业科学院农产品贮藏加工研究所 | Method for extracting milled wood lignin from stone cells in Korla fragrant pear fruit |
| CN106987862A (en) * | 2017-04-12 | 2017-07-28 | 中北大学 | A kind of method of the electrochemical degradation lignin in eutectic solvent |
| CN106987862B (en) * | 2017-04-12 | 2018-03-09 | 中北大学 | A kind of method of the electrochemical degradation lignin in eutectic solvent |
| CN109369886A (en) * | 2017-08-04 | 2019-02-22 | 南京林业大学 | A kind of method that eutectic solvent modified lignin resin is used for epoxy curing agent |
| CN110105619A (en) * | 2019-04-26 | 2019-08-09 | 中国科学院山西煤炭化学研究所 | A kind of controlled degradation recovery method of polyurethane |
| CN110982090A (en) * | 2019-12-04 | 2020-04-10 | 北京林业大学 | Method for extracting lignin in biomass by microwave-assisted eutectic solvent |
| CN111392724A (en) * | 2020-05-15 | 2020-07-10 | 齐鲁工业大学 | Preparation method of chromium ion adsorption activated carbon |
| CN111392724B (en) * | 2020-05-15 | 2022-10-11 | 齐鲁工业大学 | Preparation method of chromium ion adsorption activated carbon |
| CN112029115A (en) * | 2020-09-11 | 2020-12-04 | 齐鲁工业大学 | Method for separating and extracting lignin by in-situ synthesis of deep eutectic solvent |
| CN112209360A (en) * | 2020-10-16 | 2021-01-12 | 北京理工大学 | Shrimp shell conversion method based on sulfonic acid type eutectic solvent |
| CN113198428A (en) * | 2021-04-30 | 2021-08-03 | 深圳信息职业技术学院 | Method for preparing three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof |
| CN113198428B (en) * | 2021-04-30 | 2022-04-12 | 深圳信息职业技术学院 | Method for preparing three-dimensional multifunctional adsorbing material in situ by using corn pith and application thereof |
| CN114800943A (en) * | 2022-05-20 | 2022-07-29 | 嘉兴学院 | Method for recycling waste carpet |
| CN114800943B (en) * | 2022-05-20 | 2024-02-20 | 嘉兴学院 | Method for recycling waste carpets |
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Application publication date: 20140827 |