CN107474261A - A kind of method that biomass lignin is extracted using quaternary ammonium base - Google Patents
A kind of method that biomass lignin is extracted using quaternary ammonium base Download PDFInfo
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- CN107474261A CN107474261A CN201710872500.8A CN201710872500A CN107474261A CN 107474261 A CN107474261 A CN 107474261A CN 201710872500 A CN201710872500 A CN 201710872500A CN 107474261 A CN107474261 A CN 107474261A
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- lignin
- quaternary ammonium
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- biomass
- ammonium base
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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
Abstract
The invention discloses a kind of method that biomass lignin is extracted using quaternary ammonium base, and quaternary ammonium aqueous alkali, heating water bath extraction, filtering are added into biomass material；Filtrate adjusts pH5.0 ~ 6.0, is concentrated under reduced pressure, Ethanol Treatment and filtering with three times volume；Ethanol is distilled off in filtrate decompression, adjusts pH2.0 3.0, centrifuges, and freeze-drying, products obtained therefrom is biomass lignin.The method of quaternary ammonium base that the present invention uses extraction biomass lignin, extraction process cost is low, mild condition, the cycle is short, lignin recovery rate is high.Through various structure characterization methods measure extraction lignin component purity is high, lignin functional structure keeps more complete, extraction lignin also to keep preferable chemism in separation regenerative process.
Description
Technical field
It is specifically a kind of to utilize quaternary ammonium base extraction biology the present invention relates to a kind of extracting method of high-molecular compound
The method of matter lignin.
Background technology
Biomass is mainly made up of cellulose, hemicellulose and lignin.From structure with chemical composition, lignin
Structure is the most complicated, is to be through the unordered 3 D complex structure being polymerized by the benzene oxide monomer of hydroxyl or methoxy substitution
The affluent resources of aromatic feedstock in chemical production.
The rapid development of the increasingly depleted of fossil energy, the abundant reserves of lignin, lignin science determines the economy of lignin
The sustainable developability of benefit.Lignin cost is relatively low, and lignin and its derivative have several functions, can be used as scattered
Agent, adsorbent/strippant, petroleum recovery auxiliary agent, asphalt emulsifier, lignin to human kind sustainable development major contribution the most just
It is to provide stabilization, lasting organic substance source, its application prospect is very wide.Study the pass of lignin performance and structure
System, degradable, reproducible polymer is manufactured using lignin.
As understanding the problems such as mankind's environmental pollution and crisis of resource deepens continuously, possessed by natural polymer
Renewable, degradable, the property such as property is increasingly subject to pay attention to.The recycling of discarded object and the utilization of renewable resource, it is contemporary warp
Ji and the key subjects of social development, and the new demand to contemporary science and technology proposition.In nature, the storage of lignin
Amount is only second to cellulose, and annual all with 50,000,000,000 tons of speed regeneration.But so far, the lignin more than 95 % still with
" black liquor " is burnt up after being directly discharged into rivers or concentration, is seldom utilized effectively.Therefore, using easy, low cost, mild condition
Method separation and Extraction lignin research it is particularly significant.
The basic structural unit of lignin can be divided into following three kinds：Guaiacyl（G）, lilac base（S）And to hydroxyl
Phenyl（H）, these three elements constitute different types of polymer by covalently polymerizeing, and partial polymer is again by intermolecular
Attraction or covalent bond are finally cross-linked to form the 3 D stereo lignin polymerization of with highly branched chain, degree of polymerization height and high degree of dispersion
Body.This structure often results in and a small amount of hemicellulose etc. is remained in separating lignin, and lignin overall separation is inefficient.At present,
The biomass lignin separation method reported is a lot, can be divided into following four here according to the type of processing solvent：
1）Neutral or alkalescence condition separating lignin.Such as traditional pulp-making method.Deficiency：Traditional pulp-making method, in the process of slurrying
It is middle to produce a large amount of waste water, contain large amount of organic, especially lignin in waste water, not only cause environmental pollution to also result in resource
It is a large amount of to waste.
2）Acid condition extracts lignin.Point of extraction biomass lignin can be realized using the dioxane of subacidity
From extraction.Simultaneously lignin can also be extracted and it is separated out in water using the certain density benzene sulfonate aqueous solution and be spread out
Biology, i.e. water-soluble lignin.
3）Inorganic salts reagent extracts lignin.Such as plant is carried out under the conditions of 130 DEG C using sulfite solution
Processing, it is that lignosulfonates are soluble in water to derive its lignin component.Deficiency：This method simultaneously can be molten by cellulosic component
Solution.
4）Inorganic acid extracts insoluble lignin.Such as the sulfuric acid solution with mass fraction 72%（Or 40% hydrochloric acid solution）Water
Cellulose and other carbohydrate components in solution removing plant, residue obtained is " acid lignin ", if being using sulphuric acid hydrolysis
Claim ligninsulfonate or Kelly Clarkson lignin；If claim hydrochloric acid lignin or Weir Stuart lignin using hydrochloric acid hydrolysis.No
Foot：Sourwood quality is acted on during separation by acid, and chemical change can occur for its structure.
In lignin technique is extracted, distinct methods and separation condition can cause the connecting key between lignin structure unit
The difference of type and functional group, and then cause the difference of recovery rate.For example, it can be produced in traditional handicraft pulping process substantial amounts of useless
Water, contain substantial amounts of organic matter, especially lignin, the more difficult recovery of lignin in waste water, and environmental pollution can be caused；It is acid
Condition extracts lignin, and during by acid treatment, its structure can change sourwood quality；Jiying Zhu are applied
For anaerobic digestion assisted extraction through the pretreated Spruce lignin of diluted alkaline, recovery rate is not high, and only 46.2%.Tarim Basin is big
Learn Zhao Jian ripples and lignin is extracted from glycyrrhiza extract using NaOH, by way of optimal conditions, the recovery rate of obtained lignin
Only 5% or so, and base amount is big, solid-to-liquid ratio is 1 under optimal conditions:30.Wuhan University of Technology Liu Yun wild geese are using NaOH as alkali
Lignin in liquid extraction chestnut shell, the dosage of alkali lye is big, and solid-to-liquid ratio is 1 under optimal conditions:40, and the recovery rate of lignin is only
Reach 10% or so, what is obtained is rugose wood element, and the purity of lignin is not high.How to obtain high activity lignin extraction rate is to grind
The key studied carefully.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide one kind to utilize quaternary ammonium base extraction biomass lignin
Method, its production method is easy, energy consumption and production cost are low, and the lignin yield extracted is higher, quality better, lignin
With preferable dissolubility.
To solve prior art problem, the technical scheme that the present invention takes is：
A kind of method that biomass lignin is extracted using quaternary ammonium base, is comprised the following steps：
1）Quaternary ammonium aqueous alkali, heating water bath extraction, filtering are added into biomass material；
2）Filtrate adjusts pH5.0-6.0, is concentrated under reduced pressure, Ethanol Treatment and filtering with three times volume；
3）Ethanol is distilled off in filtrate decompression, adjusts pH2.0-3.0, centrifuges, freeze-drying, and products obtained therefrom is that biomass is wooden
Element.
Described biomass material includes but is not limited to peanut shell, stalk, wood chip, rice husk, cornstalk, bark etc..
Described quaternary ammonium aqueous alkali species, there is TMAH, tetraethyl ammonium hydroxide, TPAOH
And TBAH.
As mass fraction, quaternary ammonium alkali concn is 20-26% to described quaternary ammonium aqueous alkali.
The temperature of described heating water bath is 40-60 DEG C.
The time of described quaternary ammonium base water-bath pretreatment is 10-18h.
The solid-to-liquid ratio of described stalk amount and quaternary ammonium base water-soluble liquid measure is 1:10-1:20（g/mL）.
The volumetric concentration of the ethanol is 95%.
Step 2）It is preferred that use second acid for adjusting pH, step 3）In preferably use salt acid for adjusting pH, the concentration of hydrochloric acid is preferred
For 6 mol/L.
The principle of the present invention：
The present invention is reacted with the quaternary ammonium base of low concentration with biomass material, make in biomass material lignin and cellulose and
Key between hemicellulose is broken, and so as to realize the separation of lignin and cellulose and hemicellulose, then is adjusted with acetic acid
The hemicellulose in solution is separated out, then carries out alcohol precipitation, is filtered off except hemicellulose, filtrate decompression concentration is gone after ethanol plus salt
Acid separates out lignin.
Beneficial effect：
The method of quaternary ammonium base that the present invention uses extraction biomass lignin, extraction process cost is low, mild condition, cycle are short,
The recovery rate of lignin is high.Sampled analysis, after filtered through gauze in remaining stalk residue the content of lignin be about 10~
15%, the content of lignin is about 5~10% in discarded solution, lignin in remaining hemicellulose residue after vacuum filtration
Content is about 3~5%, and the recovery rate of lignin is up to 79.6%.
The extraction conditions of the present invention are gentle, and avoid conventional method influences on the structure of lignin in raw material, and wooden
The dissolution loss of element.The production cost of the present invention is low, and the cycle is short, discarded biomass material can be used, effectively
Protect environment.
The lignin component purity height of extraction is measured through various structure characterization methods, separates lignin function in regenerative process
Structure keeps more complete, extraction lignin also to keep preferable chemism.
Brief description of the drawings
Fig. 1 is wheat lignin and separating lignin ultraviolet spectrogram in embodiment 1；
Fig. 2 is the 1H-NMR analysis collection of illustrative plates of Spruce lignin in embodiment 2.
Embodiment
The present invention is further described with specific embodiment below in conjunction with the accompanying drawings.Unless stated otherwise, the present invention uses
Reagent, apparatus and method be the art routinely reagent, equipment and conventional use of method purchased in market.
Embodiment 1
A kind of method that wheat lignin is extracted using TMAH:
By dried wheat stalk in apparatus,Soxhlet's, using volume ratio as 2:1 benzene:Ethanol solution is stripped, and is taken out
Time 6h is carried, residue is dried, obtains this experiment degreasing sample used.1.000g degreasings dewaxing stalk is taken, with Klason methods
The content of lignin in wheat stalk is determined, parallel survey three times, is averaged.
The accurate wheat stalk for weighing 10g drying, the TMAH that 200ml mass concentrations are 24% is added,
Water bath with thermostatic control handles 14h under the conditions of temperature 50 C, while hot filtered through gauze, and filtrate adjusts pH 5.5 with acetic acid, is concentrated under reduced pressure, and uses
95% Ethanol Treatment of three times volume is simultaneously filtered by vacuum.Filtrate decompression is adjusted after ethanol is distilled off with 6 mol/L HCl solution
PH2.0, centrifuge, freeze-drying, obtain wheat lignin.Lignin high purity more than 90% is surveyed by Klason methods, most
Alkali lye dosage is few under the conditions of excellent, solid-to-liquid ratio 1:14 measure its molecular weight as 4500 through GPC technologies, calculate the recovery rate of lignin
79.6%。
The present embodiment extraction wheat lignin standard lignin and separating lignin ultraviolet spectrogram as shown in Fig. 1,
It can be seen that the position at the characteristic ultraviolet absorption peak that two kinds of materials show is essentially identical：Wavelength in 280-290nm and
Occurs obvious absworption peak at 260nm, the absworption peak that its medium wavelength is located at 280-290nm comes from non-conjugated phenol in lignin
Hydroxyl（I.e. typical guaiacyl G）, and absworption peak of the wavelength at 260nm is then the characteristic absorption peak of lignin phenyl ring, this two
Place's absworption peak is the feature ultraviolet absorption peak of lignin.Meanwhile the absorption peak strength of separate substance and standard lignin also pole
It is close, shows that the lignin component containing high-purity, impurity content are less in separate substance indirectly；Separation is also indicated that simultaneously again
Lignin functional structure is kept more complete during life.
Embodiment 2
A kind of method that Spruce lignin is extracted using tetraethyl ammonium hydroxide：
Maize straw is cleaned into drying, pulverizer crushes standby.1.000g degreasings dewaxing stalk is taken, wheat is determined with Klason methods
The content of lignin in stalk, parallel survey three times, are averaged as 12.78%.
The accurate maize straw weighed after 10g drying, 200ml 20% tetraethyl ammonium hydroxide is added, in temperature 50 C
Under the conditions of water bath with thermostatic control processing 10h, filtered through gauze while hot, filtrate adjusts pH 5.5 with acetic acid, is concentrated under reduced pressure, with three times volume
95% Ethanol Treatment and be filtered by vacuum.Filtrate decompression is distilled off adjusting pH2.0, centrifugation with 6 mol/L HCl solution after ethanol
Separation, freeze-drying, products obtained therefrom is Spruce lignin, and the recovery rate for calculating lignin is 75.3%.
This research carries out infrared spectrum analysis using infrared spectrum to separate substance and standard alkaline type lignin sample, as a result
As shown in Fig. 2 separating lignin is essentially identical in the position of characteristic diffraction peak with standard lignin sample, only in feature peak intensity
It is upper to be slightly different with standard lignin, show using TMAH processing stalk without the chemistry for substantially changing lignin
Structure.In infrared spectrum absorpting peak, strong absworption peak near 3445cm-1 is hydroxyl O-H stretching vibration peak, 2924 Hes
Absworption peak at 2852cm-1 comes from the C-H stretching vibration peaks on methyl and methylene, shows to contain lignin in separate substance
Side chain building block.Meanwhile the absworption peak at 1653cm-1 comes from C=O of contraposition substituted aroma ketone；Positioned at 1410-
1550cm-1 characteristic absorption peak shows to contain lignin benzene ring structure, the absworption peak especially at 1457cm-1 in separate substance
For C-H on phenyl ring and methyl deformation vibration peak.Absworption peak at 1124cm-1 is lilac base（S）Characteristic absorption peak；
Absworption peak at 1031cm-1 is the C-H deformation vibrations peak in fragrant plane of a loop；Absworption peak at 835cm-1 is guaiacyl virtue
C-H stretching vibration peaks outside fragrant plane of a loop.Show that separate substance contains the architectural feature of H-G-S- type lignin, illustrate separation wood
Quality has preferable chemism.
Embodiment 3
A kind of method that wheat lignin is extracted with TBAH:
Wheat stalk is cleaned into drying, pulverizer crushes standby.1.000g degreasings dewaxing stalk is taken, wheat is determined with Klason methods
The content of lignin in stalk, parallel survey three times, average 18.75%.
The accurate wheat stalk weighed after 10g drying, adds the tetraethyl ammonium hydroxide that appropriate concentration is 20%, in temperature
Water bath with thermostatic control handles 15h under the conditions of 50 DEG C, while hot filtered through gauze, and filtrate adjusts pH 5.5 with acetic acid, is concentrated under reduced pressure, with three times
95% Ethanol Treatment of volume is simultaneously filtered by vacuum.Filtrate decompression distillation is adjusted with after removing ethanol with 6 mol/L HCl solution
PH2.0, centrifuge, freeze-drying, products obtained therefrom is wheat lignin, and the recovery rate for calculating lignin is 72.9%.
Corn lignin ultraviolet of the present embodiment extraction as a result, maximum absorption band is located at 282 nm, while
Occurs an acromion at 312 nm.Conjugated molecule structure is corresponded at 282 nm to absorb as caused by electron transition in aromatic rings,
Strong absorption at 312 nm corresponds to p-Coumaric Acid and the absorption to forulic acid.Show lignin with reference to infrared spectrum analysis
In contain more chemical active radical, there is preferable chemism.
The extracting method mild condition of the present invention is can be seen that by embodiment 1-3, it is green, it is simple and quick, lignin
Recovery rate is high, obtained lignin quality better, contains more chemical active radical, platform chemical combination preferably in lignin
Thing, it can substitute petrochemicals by MOLECULE DESIGN and modified synthesis high polymer material, there is significant application value.
The lignin component purity height of extraction is measured through various structure characterization methods, separates lignin function in regenerative process
Structure keeps more complete, extraction lignin also to keep preferable chemism.
Claims (10)
- A kind of 1. method that biomass lignin is extracted using quaternary ammonium base, it is characterised in that comprise the following steps：1）Quaternary ammonium aqueous alkali, heating water bath extraction, filtering are added into biomass material；2）Filtrate adjusts pH5.0-6.0, is concentrated under reduced pressure, Ethanol Treatment and filtering with three times volume；3）Ethanol is distilled off in filtrate decompression, adjusts pH2.0-3.0, centrifuges, freeze-drying, and products obtained therefrom is that biomass is wooden Element.
- 2. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：Described life Raw material of substance is at least one of peanut shell, wheat stalk, wood chip, rice husk, cornstalk or bark.
- 3. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：Described season Ammonium alkali be TMAH, tetraethyl ammonium hydroxide, TPAOH and TBAH at least It is a kind of.
- 4. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：Described season Ammonium aqueous alkali, as mass fraction, quaternary ammonium alkali content are 20-26%.
- 5. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：Described water The temperature of bath heating is 40-60 DEG C.
- 6. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：Described season The time of ammonium buck bath is 10-18h.
- 7. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：Described life The solid-to-liquid ratio of raw material of substance and quaternary ammonium aqueous alkali is 1:10-1:20.
- 8. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：The ethanol Volumetric concentration be 95%.
- 9. the method according to claim 1 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：Step 2）Or Step 3）Middle regulation pH uses acetic acid or hydrochloric acid.
- 10. the method according to claim 9 that biomass lignin is extracted using quaternary ammonium base, it is characterised in that：The salt Acid concentration is 6 mol/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641397A (en) * | 2006-10-26 | 2010-02-03 | 希乐克公司 | biomass processing |
| CN102492150A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method for liquefying straws by ionic liquid |
| 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 |
-
2017
- 2017-09-25 CN CN201710872500.8A patent/CN107474261A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641397A (en) * | 2006-10-26 | 2010-02-03 | 希乐克公司 | biomass processing |
| CN102492150A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method for liquefying straws by ionic liquid |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| CHAO ZHONG ET AL.: ""Enhanced saccharification of lignocellulosic biomass by pretreatment with quaternary ammonium hydroxide"", 《JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY》 * |
| CHAO ZHONG ET AL.: ""Enhanced saccharification of wheat straw with the application of ultrasonic-assisted quaternary ammonium hydroxide pretreatment"", 《PROCESS BIOCHEMISTRY》 * |
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Application publication date: 20171215 |