CN107286353A - A kind of method of the dicyandiamide solution dissolved lignin based on gamma-valerolactone - Google Patents
A kind of method of the dicyandiamide solution dissolved lignin based on gamma-valerolactone Download PDFInfo
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- CN107286353A CN107286353A CN201610204759.0A CN201610204759A CN107286353A CN 107286353 A CN107286353 A CN 107286353A CN 201610204759 A CN201610204759 A CN 201610204759A CN 107286353 A CN107286353 A CN 107286353A
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- CN
- China
- Prior art keywords
- lignin
- valerolactone
- solvent
- gamma
- dicyandiamide solution
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
Abstract
The present invention relates to a kind of method of the dicyandiamide solution dissolved lignin based on γ valerolactones, belong to chemical industry application field.Specifically lignin is added in γ valerolactone dicyandiamide solutions, under different temperatures, lignin is effectively dissolved in these systems.Design obtains lignin solvent's system of different solvabilities in the present invention, is made up of γ valerolactones and another solvent.γ valerolactones dicyandiamide solution can be regulated and controled to the solvability of lignin by the solvent species and ratio of mixing.Finally, the recycling of lignin can be realized by adding anti-solvent.Easy, quick and green of the invention, pass through the interaction of hydrogen bond between solvent and lignin, lignin is effectively dissolved in dicyandiamide solution, lignin can be isolated again by adding anti-solvent, significant structure change does not occur for lignin during this.Therefore, this process has important promotional value for the application of lignin.
Description
Technical field
The present invention relates to chemical industry application field, a kind of dicyandiamide solution dissolving based on gamma-valerolactone is specifically related to
The method of lignin.
Background technology
Lignin is the important component of lignocellulosic, is renewable and reserves extremely abundant high-molecular compound,
And contain substantial amounts of aromatised fraction in its molecular structure, be most abundant renewable fragrant carbon resource.But, overwhelming majority wood
Quality is not utilized effectively.With becoming increasingly conspicuous for resource and environment problem, the higher value application of lignin is increasingly
Paid close attention to by people.
In the higher value application of lignin, often handled with acid/base, the dissolving of the means such as high temperature pyrolysis/gasification and degraded wood
Quality, but these processes can produce a large amount of charing accessory substances and salt for being difficult to separate etc..Therefore, grind and seek suitable lignin solvent
System turns into one of study hotspot.
By trying to explore, at present it has been found that can have many shortcomings with the dicyandiamide solution of dissolved lignin,
The high volatile and toxicity of such as organic solvent, the strong basicity of sodium hydroxide and severe corrosive, the high cost of ionic liquid and height
Viscosity, liquefied ammonia are to high request of equipment etc., and this makes these solvents have certain limitation in actual industrialization application.Together
When, on the one hand the diversity and the property complicated and changeable of composition in lignin source cause the regular poor of lignin dissolution, another
Aspect difference lignin needs the dicyandiamide solution of different solubility properties.Therefore, regulatable novel dissolvent system is further built
Come effective dissolved lignin, it has also become promote the bottleneck problem of lignin higher value application.
Gamma-valerolactone is a kind of important can be served many purposes from platform chemicals derived from lignocellulosic.With
Biomass conversion and the development using field, gamma-valerolactone is also regarded as a kind of important biomass-based solvent, as can be again
The substitute of raw conventional aprotic polar organic solvent is applied in a variety of chemical reactions.
With gamma-valerolactone and water and other organic solvents (DMSO, DMF), the ion of dissolved lignin is also commonly used to
Liquid ([Bmim] OAc, [Amim] Cl) constitutes mixed solvent system, can meet the dissolving demand of separate sources lignin.
The content of the invention
The invention aims to solve the deficiency that existing lignin dissolution method is present, separate sources lignin is met
Dissolving demand, invented a kind of method of the dicyandiamide solution dissolved lignin based on gamma-valerolactone.
The invention provides a kind of mixed solvent system for being capable of effective dissolved lignin, by gamma-valerolactone and another
Solvent is constituted, and they are water, dimethyl sulfoxide (DMSO) (DMSO), dimethylformamide (DMF), ionic liquid 1- butyl -3- first respectively
Base imidazoles acetate ([Bmim] OAc) and 1- pi-allyl -3- methylimidazole villaumites ([Amim] Cl).The wherein weight of mixed dissolution
Percentage is 10~90%, and the chemical structural formula of the ionic liquid used is：
Wherein left side molecular formula represents ionic liquid [Bmim] OAc, and the right molecular formula represents ionic liquid [Amim] Cl.
The gamma-valerolactone constitutes the mass percent of mixed solvent for 10wt%, 30wt%, 50wt% with water,
70wt% and 90wt%.
The gamma-valerolactone constitutes the mass percent of mixed solvent for 10wt%, 30wt%, 50wt% with DMSO,
70wt% and 90wt%.
The gamma-valerolactone constitutes the mass percent of mixed solvent for 10wt%, 30wt%, 50wt% with DMF,
70wt% and 90wt%.
The gamma-valerolactone constitutes the mass percent of mixed solvent for 10wt%, 30wt% with [Bmim] OAc,
50wt%, 70wt% and 90wt%.
The gamma-valerolactone constitutes the mass percent of mixed solvent for 10wt%, 30wt% with [Amim] Cl,
50wt%, 70wt% and 90wt%.
Use concretely comprising the following steps for the mixed solvent dissolved lignin：Lignin is added to gamma-valerolactone dicyandiamide solution
In, 40 DEG C~70 DEG C are warming up to, mixing speed 250rpm/min is kept for 0.5~2 hour, lignin dissolution is in the solvent.Wood
Quality is 0~40g/100g in the solubility of in the mixed solvent.
Added into the lignin and gamma-valerolactone mixed solution of gained after anti-solvent, agitated, lignin is separated out and sunk
Form sediment, anti-solvent is water, ethanol or acetone, specific consumption is：
1) suitable quantity of water (amount of water/lignin liquor amount >=2, body are added to the lignin gamma-valerolactone mixed solution of gained
Product ratio) after, lignin can flocculation sediment；
2) to the lignin gamma-valerolactone mixed solution of gained add ethanol in proper amount (plus amount of alcohol/lignin liquor amount >=
1, volume ratio), lignin can flocculation sediment；
3) to the lignin gamma-valerolactone mixed solution of gained add proper amount of acetone (plus amounts of acetone/lignin liquor amount >=
1, volume ratio), lignin can flocculation sediment.
The invention provides a kind of method of the dissolved lignin in gamma-valerolactone mixed solvent system.This method is by wood
Quality makes it be dissolved in gamma-valerolactone in the mixed solvent under certain temperature stirring.And add certain volume in backward system
Anti-solvent, makes the lignin dissolved be deposited from gamma-valerolactone in the mixed solvent.
The present invention is related to two processes of dissolving and separation, effectively using gamma-valerolactone mixed solvent system as platform
Lignin is dissolved, and the dissolution properties of solvent can be adjusted by the change of solvent species and solvent proportion of composing
Control, and solvent can be recycled, and whole process does not introduce poisonous organic reagent, green, environmental protection.Lignin exists
Big change does not occur for dissolving front-end geometry, is conducive to continuing with for lignin.
This method is easy, green, passes through the interaction of hydrogen bond between dicyandiamide solution and lignin so that lignin is molten
Effectively dissolved, then separated solvent in agent system by anti-solvent, this process is in miscellaneous lignin
Course of dissolution in have important application and popularization value.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The raw material can be obtained from open commercial sources unless otherwise instructed.
Embodiment 1
The lignin (L0045, Lignin (Dealkaline), TCI, Shanghai) of certain mass is added to γ-penta
In the mixed solvent system of lactone and water (mass percent that wherein gamma-valerolactone is constituted with water is respectively 10wt%,
30wt%, 50wt%, 70wt% and 90wt%), dissolved respectively at 40 DEG C, 50 DEG C, 60 DEG C and 70 DEG C, mixing speed
250rpm/min, is kept for 2 hours, solubility values of the lignin in gamma-valerolactone and water mixed solvent such as following table.
Embodiment 2
The lignin (L0045, Lignin (Dealkaline), TCI, Shanghai) of certain mass is added to γ-penta
In lactone and DMSO mixed solvent system (wherein gamma-valerolactone and the DMSO mass percents constituted are respectively 10wt%,
30wt%, 50wt%, 70wt% and 90wt%), dissolved respectively at 40 DEG C, 50 DEG C, 60 DEG C and 70 DEG C, mixing speed
250rpm/min, is kept for 2 hours, solubility values such as following table of the lignin in gamma-valerolactone and DMSO in the mixed solvents.
Embodiment 3
The lignin (L0045, Lignin (Dealkaline), TCI, Shanghai) of certain mass is added to γ-penta
In lactone and DMF mixed solvent system (wherein gamma-valerolactone and the DMF mass percents constituted are respectively 10wt%,
30wt%, 50wt%, 70wt% and 90wt%), dissolved respectively at 40 DEG C, 50 DEG C, 60 DEG C and 70 DEG C, mixing speed
250rpm/min, is kept for 2 hours, and lignin is in gamma-valerolactone and the solubility values such as following table of DMF in the mixed solvents.
Embodiment 4
The lignin (L0045, Lignin (Dealkaline), TCI, Shanghai) of certain mass is added to γ-penta
(wherein gamma-valerolactone is distinguished with the mass percent that [Bmim] OAc is constituted in lactone and [Bmim] OAc mixed solvent system
For 10wt%, 30wt%, 50wt%, 70wt% and 90wt%), dissolved respectively at 40 DEG C, 50 DEG C, 60 DEG C and 70 DEG C, stirring
Speed 250rpm/min, is kept for 2 hours, lignin gamma-valerolactone and [Bmim] OAc in the mixed solvents solubility values such as
Following table.
Embodiment 5
The lignin (L0045, Lignin (Dealkaline), TCI, Shanghai) of certain mass is added to γ-penta
(wherein gamma-valerolactone is respectively with [Amim] Cl mass percents constituted in lactone and [Amim] Cl mixed solvent system
10wt%, 30wt%, 50wt%, 70wt% and 90wt%), dissolved respectively at 40 DEG C, 50 DEG C, 60 DEG C and 70 DEG C, stirring speed
250rpm/min is spent, is kept for 2 hours, lignin is as follows in gamma-valerolactone and the solubility values of [Amim] Cl in the mixed solvents
Table.
Claims (7)
1. a kind of dicyandiamide solution of the lignin dissolution based on gamma-valerolactone, is made up of gamma-valerolactone and another solvent；
Another solvent is respectively dimethyl sulfoxide (DMSO), dimethylformamide, ionic liquid 1-butyl-3-methyl imidazolium acetate and
1- pi-allyl -3- methylimidazole villaumites.
2. according to the method described in claim 1, it is characterised in that：The quality percentage of gamma-valerolactone and another solvent composition
Than being respectively 10%, 30%, 50%, 70%, 90%.
3. a kind of method of the dicyandiamide solution dissolved lignin based on gamma-valerolactone,
Comprise the following steps：
Lignin is added in gamma-valerolactone dicyandiamide solution, required temperature is warming up to, by stirring, lignin dissolution is in this
In solvent.After dissolving terminates, lignin can be separated from gamma-valerolactone dicyandiamide solution with anti-solvent.
4. according to any described methods of claim 1-3, it is characterised in that：In the dissolving step, temperature is 40-70 DEG C,
Specially 40 DEG C.
5. according to any described methods of claim 1-4, it is characterised in that：The dissolution time is 0.5~2h；Specially
1h。
6. according to any described methods of claim 1-5, it is characterised in that：It is used anti-molten in the anti-solvent step
Agent is water, ethanol or acetone, specially ethanol.
7. according to any described methods of claim 1-6, the specific consumption of anti-solvent is：
1) amount of water/lignin liquor amount >=2, volume ratio, specific volume ratio is 2；
2) amount of alcohol/lignin liquor amount >=1, volume ratio are added, specific volume ratio is 1；
3) amounts of acetone/lignin liquor amount >=1, volume ratio are added, specific volume ratio is 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822304A (en) * | 2018-07-18 | 2018-11-16 | 天津科技大学 | A kind of method of gamma-valerolactone/aqueous systems classification lignin |
| CN109395778A (en) * | 2018-11-13 | 2019-03-01 | 北京林业大学 | A kind of phytic acid niobium supported nano-gold category catalyst system for levulic acid and ester through hydrogenation |
| CN109621851A (en) * | 2018-12-12 | 2019-04-16 | 天津科技大学 | A kind of preparation method of gamma-valerolactone/glycerol system high yield pulp1 lignin micro-nano ball |
| CN113368057A (en) * | 2021-05-11 | 2021-09-10 | 暨南大学 | In-situ functionalized nano lignin and preparation method and application thereof |
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| CN103435577A (en) * | 2013-06-25 | 2013-12-11 | 天津大学 | Method for preparing levulinic acid and co-producing gamma-valerolactone from biomass |
| CN105385722A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Method for pre-processing lignocellulose biomass to increase sugar field of lignocellulose biomass |
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| CN103435577A (en) * | 2013-06-25 | 2013-12-11 | 天津大学 | Method for preparing levulinic acid and co-producing gamma-valerolactone from biomass |
| CN105385722A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Method for pre-processing lignocellulose biomass to increase sugar field of lignocellulose biomass |
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| SILVIA TABASSO等: "Microwave-Assisted γ-Valerolactone Production for Biomass Lignin Extraction: A Cascade Protocol", 《MOLECULES》 * |
| 曾勇等: "木质纤维预处理方法及基质的变化与检测", 《中国沼气》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822304A (en) * | 2018-07-18 | 2018-11-16 | 天津科技大学 | A kind of method of gamma-valerolactone/aqueous systems classification lignin |
| CN109395778A (en) * | 2018-11-13 | 2019-03-01 | 北京林业大学 | A kind of phytic acid niobium supported nano-gold category catalyst system for levulic acid and ester through hydrogenation |
| CN109395778B (en) * | 2018-11-13 | 2021-10-22 | 北京林业大学 | Niobium phytate supported nano metal catalytic system for levulinic acid and ester hydrogenation |
| CN109621851A (en) * | 2018-12-12 | 2019-04-16 | 天津科技大学 | A kind of preparation method of gamma-valerolactone/glycerol system high yield pulp1 lignin micro-nano ball |
| CN109621851B (en) * | 2018-12-12 | 2021-04-30 | 天津科技大学 | Preparation method of gamma-valerolactone/glycerol system high-yield lignin micro-nanospheres |
| CN113368057A (en) * | 2021-05-11 | 2021-09-10 | 暨南大学 | In-situ functionalized nano lignin and preparation method and application thereof |
| CN113368057B (en) * | 2021-05-11 | 2022-11-29 | 暨南大学 | In-situ functionalized nano lignin and preparation method and application thereof |
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