CN107459659A - A kind of method of mixed solvent two-step method extraction lignin - Google Patents
A kind of method of mixed solvent two-step method extraction lignin Download PDFInfo
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- CN107459659A CN107459659A CN201610389928.2A CN201610389928A CN107459659A CN 107459659 A CN107459659 A CN 107459659A CN 201610389928 A CN201610389928 A CN 201610389928A CN 107459659 A CN107459659 A CN 107459659A
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- 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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Abstract
A kind of method of mixed solvent two-step method extraction lignin, this method is using two kinds of mixed solvents of different nature as extractant, continuous extraction in two steps under inert conditions, so as to efficiently separate the lignin in lignocellulose biomass.Used mixed solvent is respectively alcohol/aqueous systems and ether/aqueous systems；After extracting lignin, solvent for use can be reclaimed, recycled.Method provided by the present invention can efficiently separate lignin, and isolated ligninolytic activity is preferable, be easy to the further higher value application of lignin, have important application value.
Description
Technical field
The present invention relates to the field of comprehensive utilization of lignocellulose biomass, specifically belongs to a kind of utilization
The method of lignin in mixed solvent two-step method extraction lignocellulose biomass.
Background technology
Biomass resource, rich reserves, green are renewable；Comprehensively utilize the biomass resource in nature
It is the needs of sustainable development.Lignin is one of main composition of lignocellulose biomass, in nature
Content in boundary is only second to cellulose；Its various structures, be by phenylpropyl alcohol alkyl structure unit by C-C or
The unformed three-dimensional netted high polymer that C-O key connections form.So far, lignin be in nature only
One can provide the natural resources of renewable compound aromatic base.However, lignin is mainly as pulping and paper-making
Discarded object discharge in industry, is not fully used, also creates environmental pollution.Therefore, it is comprehensive
Efficiently utilize the lignin in lignocellulose biomass that there is important Research Significance.But lignin
The architectural characteristic of itself makes it difficult to directly degrade, and by certain pretreatment mode, destroys in various degree
Itself complicated structure, it is the key that high-efficiency comprehensive utilization is carried out to lignin or even biomass.
The method for the separation and Extraction lignin reported mainly have acid hydrolyzation, sulphite process, ball-milling method,
Organic solvent method etc. (Chem.Rev.2010,110,3552).Solvent used by organic solvent method
It can reclaim, to lignin, this body structure can preferably be kept, while the lignin that extraction obtains is practically free of
Sulphur, molecular weight is relatively low, and purity is high, is the technology of separating lignin proper at present.It is but existing
Method, mostly using acid or base catalysis, extraction time is longer, takes time and effort；And the wood that extraction obtains
Quality degrading activity is relatively low.Such as industrial Alcell methods, using ethanol-water, process itself is utilized
In caused acid be used as catalyst, delignification under the conditions of 200 DEG C；Because the presence of acid, delignification
During can produce degradation by-products, add separating difficulty；Sun Run storehouses et al. are catalyzed using inorganic acid
The aqueous solution of agent, organic acid or organic low-carbon alcohols extracts wooden in wheat stalk as extraction system
Element, 85 DEG C of extraction 4h, lignin yield highest can be 94% (Ind.Crops Prod., 2006,23,
180)；Pan Xuejun et al. extracts the lignin in poplar under the conditions of higher than 195 DEG C using ethanol water,
Because of the excessive polymerization after generation scission of link, so as to which extraction efficiency reduces, while the lignin extracted is active
Also not high (Ind.Eng.Chem.Res., 2010,49,12156).
Therefore, the method for extracting lignin of exploitation efficiently, economic, for comprehensively utilizing lignocellulosic
Biomass, while reduce environmental pollution there is important Research Significance and wide application prospect.
Organic solvent of different nature has different dissolvings to different component in lignocellulose biomass
Property, the method for the step of mixed solvent two synthesis extraction lignin provided by the invention, the separative efficiency of lignin
Height, isolated ligninolytic activity is preferable, organic solvent recoverable used；For wooden fibre
The comprehensive utilization of dimension cellulosic biomass provides more possibilities.
The content of the invention
It is an object of the invention to provide a kind of method of mixed solvent two-step method extraction lignin.
The technical solution adopted in the present invention is：
A kind of method of mixed solvent two-step method extraction lignin, this method use two kinds of mixing of different nature
Dicyandiamide solution, the lignin under inert conditions in two-step method continuous high-efficient extraction lignocellulose biomass.
Specifically, the first step carries out separation of solid and liquid, solid is direct using alcohol/aqueous systems extraction after cooling
Carry out ether/aqueous systems extraction of second step；It is organic molten that the extract solution obtained twice is evaporated under reduced pressure removing respectively
Agent, merge；Obtained final extract solution adds excessive distilled water, and filtering is stood after being stirred vigorously, is dried
(30-50 DEG C), produce lignin.
The lignocellulose biomass includes cork wood chip, hardwood wood chip, various agricultural crop straws, each
Kind shell etc., it is preferred that lignocellulose biomass is made to the particle of 20-50 mesh.
Described two mixed solvents of different nature, it is respectively alcohol/aqueous systems and ether/aqueous systems that it, which is formed,.
The volume ratio of alcohol and water is 1 in the alcohol/aqueous systems:1~1:10, ether and water in the ether/aqueous systems
Volume ratio be 1:1~1:10.
Alcohol/the aqueous systems are the mixed system of low-carbon alcoholic solvent and water, and low-carbon alcoholic solvent is methanol, ethanol
Or one or both of normal propyl alcohol or three kinds；Ether/the aqueous systems are the mixing of material of organic ethers solvent and water
System, material of organic ethers solvent are tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, glycol monoethyl ether or ethylene glycol two
It is more than one or both of methyl ether.
During extraction, in two steps in addition to used dicyandiamide solution difference, other operating conditions are identical：
In inert atmosphere, under the conditions of 100~200 DEG C of temperature, the time is 0.5~3h.
The inert atmosphere is nitrogen.
The mass ratio that dicyandiamide solution used and lignocellulosic are extracted in two-step method is 1：10:~1:100.
Extraction of the present invention refers to different dicyandiamide solutions to wooden in lignocellulose biomass
Element is extracted.
The advantages of the present invention：
The present invention is using in two kinds of mixed solvent two-step method extraction lignocellulose biomass of different nature
Lignin.Carried out under this method inert conditions, lignin separation efficiency high, solvent is easy to be recycled；Together
When the ligninolytic activity that extracts it is preferable, be advantageous to the further high-valued application of lignin.Extraction wood
After quality, solvent for use can be reclaimed, recycled.The invention provides a kind of high efficiency extraction is wooden
The method of lignin in cellulose biomass, it is related to biomass comprehensive and utilizes field.
Embodiment
The lignocellulose biomass such as wood chip, shell, stalk are crushed through pulverizer first, ball mill machine
Tool processing, obtains the mesh of particle diameter about 40, is then directly added into Parr kettles and is extracted.
Embodiment 1
Take 5.0g to treat lignocellulosic to add in 300m L Parr kettles, be firstly added 80mL first
Alcohol, 20mL water, after nitrogen displacement 3 times, 100 DEG C of reaction 1h, cool, filter；Filter
Slag is rejoined in kettle, adds 80mL tetrahydrofurans, 20mL water, after nitrogen displacement 3 times, 120 DEG C
1h is reacted, is cooled, is filtered；The extract solution obtained twice be evaporated under reduced pressure respectively remove organic solvent,
Merge；Excessive distilled water is added in final extract solution, stood after being stirred vigorously, filter, be drying to obtain wood
Quality 4.3g.
Embodiment 2
Take 10.0g to treat lignocellulosic to add in 300m L Parr kettles, be firstly added 80mL
Ethanol, 20mL water, after nitrogen displacement 3 times, 100 DEG C of reaction 1h, cool, filter；
Filter residue is rejoined in kettle, adds 80mL Isosorbide-5-Nitraes-dioxane, 20mL water, nitrogen displacement 3
After secondary, 140 DEG C of reaction 1h, cool, filter；The extract solution obtained twice is evaporated under reduced pressure respectively
Remove organic solvent, merge；Excessive distilled water is added in final extract solution, is stood after being stirred vigorously, mistake
Filter, dry (40 DEG C) produce lignin 7.5g.
Embodiment 3
Take 6.0g to treat lignocellulosic to add in 300m L Parr kettles, be firstly added 50mL first
Alcohol, 50mL water, after nitrogen displacement 3 times, 120 DEG C of reaction 0.5h, cool, filter；
Filter residue is rejoined in kettle, adds 80mL glycol monoethyl ethers, 20mL water, nitrogen displacement 3
After secondary, 100 DEG C of reaction 0.5h, cool, filter；The extract solution obtained twice depressurizes steaming respectively
Distillation is removed organic solvent, merged；Excessive distilled water is added in final extract solution, stood after being stirred vigorously,
Filter, be drying to obtain lignin 4.5g.
Embodiment 4
Take 8.0g to treat lignocellulosic to add in 300m L Parr kettles, be firstly added 75mL second
Alcohol, 25mL water, after nitrogen displacement 3 times, 140 DEG C of reaction 0.5h, cool, filter；
Filter residue is rejoined in kettle, adds 50mL glycol dimethyl ethers, 50mL water, nitrogen displacement 3
After secondary, 100 DEG C of reaction 1h, cool, filter；The extract solution obtained twice is evaporated under reduced pressure respectively
Remove organic solvent, merge；Excessive distilled water is added in final extract solution, is stood after being stirred vigorously, mistake
Filter, be drying to obtain lignin 5.9g.
Claims (10)
- A kind of 1. method of mixed solvent two-step method extraction lignin, it is characterised in that:This method uses two kinds of mixed solvent systems of different nature, the lignin under inert conditions in two-step method continuous high-efficient extraction lignocellulose biomass.
- 2. in accordance with the method for claim 1, it is characterised in that：The first step carries out separation of solid and liquid, solid directly carries out ether/aqueous systems extraction of second step using alcohol/aqueous systems extraction after cooling；The extract solution obtained twice is evaporated under reduced pressure removing organic solvent respectively, merges；Obtained final extract solution adds excessive distilled water, and filtering is stood after being stirred vigorously, dries, produce lignin.
- 3. according to the method described in claim 1 or 2, it is characterised in that：The lignocellulose biomass is included more than one or both of cork wood chip, hardwood wood chip, various agricultural crop straws or various shells.
- 4. in accordance with the method for claim 3, it is characterised in that：Preferably, lignocellulose biomass is made to the particle of 20-50 mesh.
- 5. in accordance with the method for claim 1, it is characterised in that：Described two mixed solvents of different nature, it is respectively alcohol/aqueous systems and ether/aqueous systems that it, which is formed,.
- 6. in accordance with the method for claim 5, it is characterised in that：The volume ratio of alcohol and water is 1 in the alcohol/aqueous systems:1~1:10, the volume ratio of ether and water is 1 in the ether/aqueous systems:1~1:10.
- 7. according to the method described in claim 2 or 5, it is characterised in that：Alcohol/the aqueous systems are the mixed system of low-carbon alcoholic solvent and water, and low-carbon alcoholic solvent is one or both of methanol, ethanol or normal propyl alcohol or three kinds；Ether/the aqueous systems are the mixed system of material of organic ethers solvent and water, and material of organic ethers solvent is more than one or both of tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, glycol monoethyl ether or glycol dimethyl ether.
- 8. in accordance with the method for claim 2, it is characterised in that：During extraction, in two steps in addition to used dicyandiamide solution difference, other operating conditions are identical：In inert atmosphere, under the conditions of 100~200 DEG C of temperature, the time is 0.5~3h.
- 9. in accordance with the method for claim 8, it is characterised in that：The inert atmosphere is nitrogen.
- 10. according to the method described in claim 1 or 2, it is characterised in that：The mass ratio that dicyandiamide solution used and lignocellulosic are extracted in two-step method is 1：10:~1:100.
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Cited By (1)
| 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 |
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| CN101121735A (en) * | 2007-07-06 | 2008-02-13 | 陈培豪 | Plant fibre raw material hydrolysis solution and method for preprocessing plant fibre raw material using the same |
| CN101712698A (en) * | 2009-11-25 | 2010-05-26 | 大连工业大学 | Ionic liquid based method for extracting lignin by two-liquid-phase system |
| CN102162199A (en) * | 2011-05-03 | 2011-08-24 | 浙江农林大学 | Method for extracting lignin from raw grass |
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2016
- 2016-06-02 CN CN201610389928.2A patent/CN107459659A/en active Pending
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| CN101121735A (en) * | 2007-07-06 | 2008-02-13 | 陈培豪 | Plant fibre raw material hydrolysis solution and method for preprocessing plant fibre raw material using the same |
| CN101712698A (en) * | 2009-11-25 | 2010-05-26 | 大连工业大学 | Ionic liquid based method for extracting lignin by two-liquid-phase system |
| CN102162199A (en) * | 2011-05-03 | 2011-08-24 | 浙江农林大学 | Method for extracting lignin from raw grass |
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Cited By (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 |
| CN108179644B (en) * | 2017-12-21 | 2019-11-12 | 中国科学院青岛生物能源与过程研究所 | A method of extracting lignin from biomass |
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