CN106883428A - A kind of subcritical Ethanol Method extracts disaggregating property lignin method high - Google Patents
A kind of subcritical Ethanol Method extracts disaggregating property lignin method high Download PDFInfo
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- CN106883428A CN106883428A CN201710195768.2A CN201710195768A CN106883428A CN 106883428 A CN106883428 A CN 106883428A CN 201710195768 A CN201710195768 A CN 201710195768A CN 106883428 A CN106883428 A CN 106883428A
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- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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Abstract
Disaggregating property lignin method high is extracted the present invention relates to a kind of subcritical Ethanol Method.The present invention extracts lignin by subcritical Ethanol Method in high-temperature high-pressure reaction kettle from mao bamboon；Then reacted in ethanol lignin and absolute ethyl alcohol being added into SLP type Micro high-temperature autoclaves；Separation of solid and liquid is finally carried out using sand core funnel.The advantage that the subcritical Ethanol Method of the present invention extracts disaggregating property lignin high is that the yield of the ethanol lignin for extracting is higher, and depolymerisation conditions are more gentle simple, and depolymerization rate is high and relative amount of phenolic compound is higher.
Description
Technical field
It is that a kind of subcritical Ethanol Method extracts solution high specifically the present invention relates to the method for the high efficiency extraction of lignin
Poly- characteristic lignin method.
Background technology
Because the fossil fuels such as oil ground is deficient, environmental pollution is increasingly severe in addition, and increasing people focus on
The development and utilization of green energy resource, and lignin is used as the lignocellulosic that cellulose reserves first are only second in the Nature, it
It is primarily present in the non-timbers such as timber and agricultural crop straw, due to its complicated molecular structure and aggregated structure, although its
There is certain achievement in research in the field such as synthetic resin and surface reactive material, but do not obtain and petrochemical cost performance phase yet
The product for matching in excellence or beauty, it may be said that lignin high added value and energy utilization technology are still at an early stage.As lignin is efficiently sharp
With carrying out in a deep going way for research, preparing bio oil or aldehydes matter as feed degradation with lignin becomes another study hotspot.
Asia/supercritical fluid is strong with dissolubility as nearest popular trend, diffusivity is good, it is easily controllable the advantages of.And
Ethanol can dissolve most of organic matter, and produce a large amount of hydroperoxyl radicals, and the presence of excessive hydroperoxyl radical can play staypak
Quality β-ehter bond homolysis forms the effect of free radical.Research shows that Asia/Supercritical Ethanol depolymerization lignin can effectively improve solution
Dimerization product income, widens its application field, and the lignin tool of high yield pulp1 and high activity is extracted in this discovery to subcritical Ethanol Method
There is great importance.
The method that lignin macromolecular is depolymerized to small molecule monomer is had much at present, is broadly divided into biological depolymerization, physics
Depolymerization and chemical depolymerization method.The nonaqueous phase liquid product referred to as bio oil that biomass degradation is obtained, mainly by containing carbonyl, carboxyl
Oxygenatedchemicals with the functional group such as phenolic hydroxyl group is constituted.The bio oil that lignin degradation is produced can be used for preparing liquid fuel with
And the chemicals such as phenol, acid, aldehyde, ester.The raw material that lignin degradation prepares bio oil is generally the biomass containing lignin, such as wood
Matter cellulose, or industrial lignin accessory substance, and the lignin that other methods are extracted.Liquefying lignin catabolite is answered
Miscellaneous, current research contents is mainly：With liquefying lignin bio oil as target product, various technological parameters are inquired into for biology
The influence of oily yield and composition, probes into possible degradation reaction mechanism.Having carried out one for the process conditions of lignin degradation is
Row are explored.Select the key that suitable liquefier is liquefying lignin degraded.In recent years, as people are to the general of supercritical technology
All over concern, the focus of research is turned into using supercritical technology liquefaction lignin or biomass.Conventional supercritical solvent has super
Critical, supercritical methanol, Supercritical Ethanol etc..Saisu etc. is ground respectively from water, the mixture of water-phenol as solvent
Lignin liquefaction is at supercritical conditions studied carefully.Research thinks that lignin occurs solvation first in supercritical water,
Next is hydrolyzed and dealkylation reaction, ultimately results in the generation of lignin degradation small molecule segment.
The content of the invention
The present invention is in view of the shortcomings of the prior art, there is provided a kind of subcritical Ethanol Method extracts disaggregating property lignin side high
Method
To realize object above, the present invention is achieved through the following technical solutions：
Step one：Prepare ethanol lignin.Section is removed into bamboo section, peeling is crushed, acetone extraction, after natural air drying, by ball
Mill, obtains the bamboo powder that particle diameter is 20 ~ 60 mesh.With（Bamboo powder raw material+Pd/C catalyst）：Ethanol solution is 1:20 in high temperature and high pressure kettle
（KFC-0.5）In, the reaction time is 60min, and reaction temperature is 85 ~ 200 DEG C, records reaction pressure, mixture is obtained, by G4
Type sand core funnel is filtered, and obtains solid residue and lignin liquor, and lignin liquor is in the acid deionized water that pH value is 2.0
8 h are stood, is filtered using G5 types sand core funnel, solid obtained ethanol lignin by the freeze-drying of 24 hours.Weigh ethanol
The quality of lignin, calculates yield.
Step 2：The depolymerization of ethanol lignin.0.6 g ethanol lignin samples and 30 mL absolute ethyl alcohols are added into SLP types
In Micro high-temperature autoclave, it is 180 DEG C and 240 DEG C to set reaction temperature, and the reaction time is 4 h, records reaction pressure.Press
According to the facts test to impose a condition and reacted, reactor is quickly cooled to room temperature after terminating, then entered using the sand core funnel of G5 types
Row separation of solid and liquid, washs colourless to solution using isopropanol and tetrahydrofuran.Solid product is placed in 50 DEG C of thermostatic drying chamber drying
To constant weight, weigh and determine the residual burnt yield of solid phase.Liquid product isopropanol is settled to 100 mL, takes and is placed in 50 DEG C of constant temperature in right amount
Drying box is dried to constant weight.Finally, the liquid product after constant volume is taken, is first removed water with anhydrous sodium sulfate again with isopropanol, after
Through organic filter membrane filtration, the liquid product for obtaining carries out gas chromatography/mass spectrometry technology（GC/MS）Analysis, obtains wherein
The relative amount of phenolic product.
The present invention is that by subcritical Ethanol Method and ethanol lignin is added into Pd/C catalyst, and solution high is extracted from mao bamboon
The ethanol lignin of poly- characteristic, wherein yield are the ratio of the quality with the quality of lignin in mao bamboon in theory of the lignin for obtaining
Value, and the size of disaggregating property is mainly by ethanol lignin under the undercritical conditions in the depolymerization rate and depolymerization product of depolymerization
Phenolic product relative amount size is judged.
The yield of the ethanol lignin that the present invention is extracted is higher, and depolymerisation conditions are more gentle simple, depolymerization rate it is high and
The relative amount of phenolic compound is higher.
Specific embodiment
Subcritical Ethanol Method of the invention presented below extracts the specific embodiment of disaggregating property lignin method high, carries altogether
For 3 embodiments, but the embodiment the invention is not restricted to be provided.
Embodiment 1
First, the bamboo powder after ball milling is sieved, takes the g of 20 g and Pd/C catalyst of bamboo powder 0.2 in high temperature and high pressure kettle（KFC-0.5）
In, add the ethanol solution of 400 mL（70% 95% absolute ethyl alcohol）, the reaction time as 60 min is set, reaction temperature is 160
DEG C, record reaction pressure is 0.8 MPa, and the mixture for obtaining obtains solid residue and wooden by the filtering of G4 types sand core funnel
Plain solution, lignin liquor stands 8 h in the acid deionized water that pH value is 2.0, is filtered using G5 types sand core funnel, solid
Ethanol lignin is obtained by the freeze-drying of 24 h.The quality of ethanol lignin is weighed, yield is calculated.Then, by 0.6 g second
Alcohol lignin and 30 mL absolute ethyl alcohols are added in SLP type Micro high-temperature autoclaves, and it is 240 DEG C to set reaction temperature, instead
It is 4 h between seasonable, record reaction pressure is 7.5 MPa.Imposed a condition according to experiment and reacted, it is after terminating that reactor is quick
Be cooled to room temperature, separation of solid and liquid carried out using the sand core funnel of G5 types, solid product using isopropanol and tetrahydrofuran wash to
It is colourless.Solid product is placed in 50 DEG C of thermostatic drying chambers and dries to constant weight, weighs and determines the residual burnt yield of solid phase.Liquid product isopropyl
Alcohol is settled to 100 mL, takes 40 mL and pours into disposable plastic culture dish, is placed in 50oC thermostatic drying chambers are dried to constant weight.Most
Afterwards, the liquid product after constant volume is taken, is first removed water by anhydrous sodium sulfate again with isopropanol, by organic filter membrane filtration,
The liquid product for obtaining carries out gas chromatography/mass spectrometry technology（GC/MS）Analysis, obtains wherein the relative of phenolic product and contains
Amount.
Embodiment 2
Bamboo powder after ball milling is sieved, takes the g of 20 g and Pd/C catalyst of bamboo powder 0.2 in high temperature and high pressure kettle（KFC-0.5）In, plus
Enter the ethanol solution of 400 mL（70% 95% absolute ethyl alcohol）, the reaction time as 60 min is set, reaction temperature is 180 DEG C, note
Record reaction pressure is 1.5 MPa, and the mixture for obtaining is filtered by G4 types sand core funnel, obtains solid residue and lignin is molten
Liquid, lignin liquor stands 8 h in the acid deionized water that pH value is 2.0, is filtered using G5 types sand core funnel, and solid passes through
The freeze-drying of 24 h obtains ethanol lignin.The quality of ethanol lignin is weighed, yield is calculated.Then, by 0.6 g ethanol wood
Quality and 30 mL absolute ethyl alcohols are added in SLP type Micro high-temperature autoclaves, and it is 240 DEG C to set reaction temperature, during reaction
Between be 4 h, record reaction pressure be 7.5 MPa.Imposed a condition according to experiment and reacted, quickly cool down reactor after terminating
To room temperature, separation of solid and liquid is carried out using the sand core funnel of G5 types, solid product is washed to colourless using isopropanol and tetrahydrofuran.
Solid product is placed in 50 DEG C of thermostatic drying chambers and dries to constant weight, weighs and determines the residual burnt yield of solid phase.Liquid product is fixed with isopropanol
Hold to 100 mL, take 40 mL and pour into disposable plastic culture dish, be placed in 50oC thermostatic drying chambers are dried to constant weight.Finally,
The liquid product after constant volume is taken, is first removed water by anhydrous sodium sulfate again with isopropanol, by organic filter membrane filtration, obtained
Liquid product carry out gas chromatography/mass spectrometry technology（GC/MS）Analysis, obtains the relative amount of wherein phenolic product.
Embodiment 3
Bamboo powder after ball milling is sieved, takes the g of 20 g and Pd/C catalyst of bamboo powder 0.2 in high temperature and high pressure kettle（KFC-0.5）In, plus
Enter the ethanol solution of 400 mL（70% 95% absolute ethyl alcohol）, the reaction time as 60 min is set, reaction temperature is 200 DEG C, note
Record reaction pressure is 2.5 MPa, and the mixture for obtaining is filtered by G4 types sand core funnel, obtains solid residue and lignin is molten
Liquid, lignin liquor stands 8 h in the acid deionized water that pH value is 2.0, is filtered using G5 types sand core funnel, and solid passes through
The freeze-drying of 24 h obtains ethanol lignin.The quality of ethanol lignin is weighed, yield is calculated.Then, by 0.6 g ethanol wood
Quality and 30 mL absolute ethyl alcohols are added in SLP type Micro high-temperature autoclaves, and it is 240 DEG C to set reaction temperature, during reaction
Between be 4 h, record reaction pressure be 7.5 MPa.Imposed a condition according to experiment and reacted, quickly cool down reactor after terminating
To room temperature, separation of solid and liquid is carried out using the sand core funnel of G5 types, solid product is washed to colourless using isopropanol and tetrahydrofuran.
Solid product is placed in 50 DEG C of thermostatic drying chambers and dries to constant weight, weighs and determines the residual burnt yield of solid phase.Liquid product is fixed with isopropanol
Hold to 100 mL, take 40 mL and pour into disposable plastic culture dish, be placed in 50oC thermostatic drying chambers are dried to constant weight.Finally,
The liquid product after constant volume is taken, is first removed water by anhydrous sodium sulfate again with isopropanol, by organic filter membrane filtration, obtained
Liquid product carry out gas chromatography/mass spectrometry technology（GC/MS）Analysis, obtains the relative amount of wherein phenolic product.
From detection, 160oThe yield of the ethanol lignin that C is extracted is 18.00%, the solution in 240 DEG C of depolymerization
Poly- rate is 78.571%, and the phenols relative amount for obtaining is 35.89%.As temperature is increased to 180oThe ethanol that C is extracted is wooden
The yield of element is 22.59%, and the depolymerization rate in 240 DEG C of depolymerization is 79.796%, and the phenols relative amount for obtaining is 56.06%.
200oThe yield of the ethanol lignin that C is extracted is 43.56%, and the depolymerization rate in 240 DEG C of depolymerization is 87.635%, is obtained
Phenols relative amount is 58.18%.There it can be seen that being increased to 200 DEG C, the yield of ethanol lignin from 160 DEG C with temperature
From 18.00% to 43.56%, phenols relative amount increases to 58.18% from 35.89% in depolymerization liquid product.This explanation present invention
Can improve the extraction yield of ethanol lignin, and income to phenols relative amount in depolymerization rate and depolymerization product has necessarily
Influence, while there is provided a kind of method that ethanol lignin is extracted under more gentle simple undercritical conditions.
Claims (5)
1. a kind of subcritical Ethanol Method extracts disaggregating property lignin method high, it is characterised in that：
First, the bamboo powder that mao bamboon obtains after past, peeling, crushing, extracting, ball milling is placed in high-temperature high-pressure reaction kettle,
In the setting reaction time, change the temperature extracted from 85 DEG C ~ 200 DEG C, add catalyst, tested in ethanol solution, lead to cold
But water is cooled to suitable temperature, takes out mixture, is filtered while hot with G4 type sand core funnels；
Then, by filtrate by rotary evaporation to 5 ~ 10 mL, it is placed in the acid deionized water that pH value is 2.0 and stands 8
H, after Precipitation, is filtered using G5 types sand core funnel, and solid obtained ethanol lignin by the freeze-drying of 24 hours；
Then, by 0.6 g ethanol lignin and 30 mL absolute ethyl alcohols addition SLP type Micro high-temperature autoclaves, set anti-
It is 180 DEG C and 240 DEG C to answer temperature, and the reaction time is 4 h, records reaction pressure；Imposed a condition according to experiment and reacted, tied
Reactor is quickly cooled to room temperature after beam；
Finally, separation of solid and liquid is carried out using G5 sand core funnels；Solid product is washed to colourless using isopropanol and tetrahydrofuran, Gu
Phase product is placed in 50 DEG C of thermostatic drying chambers and dries to constant weight, weighs and determines the residual burnt yield of solid phase；Liquid product isopropanol constant volume
To 100 mL, in taking the disposable plastic culture dish that 40 mL pour into a diameter of 9 cm, be placed in 50 DEG C of thermostatic drying chambers dry to
Constant weight.
2. a kind of subcritical Ethanol Method according to claim 1 extracts disaggregating property lignin method high, it is characterised in that：
Lignin is separated by filtration the sand core funnel for using model G4, vacuumizing filtration.
3. a kind of subcritical Ethanol Method according to claim 1 extracts disaggregating property lignin method high, it is characterised in that：
The volume ratio of the alcohol water in ethanol solution is 7:3, the temperature of rotary evaporation is 45 DEG C.
4. a kind of subcritical Ethanol Method according to claim 1 extracts disaggregating property lignin method high, it is characterised in that：
Mass fraction >=99.7% of absolute ethyl alcohol；Reaction temperature during extraction is specifically 160 DEG C, 180 DEG C or 200 DEG C, during reaction
Pressure must not exceed 10 MPa, and logical cooling water is cooled to 60 DEG C by reactor；Actual temp during depolymerization is 240 DEG C, reaction
When pressure must not exceed 10 MPa, allow reactor to be quickly cooled to room temperature using cold bath.
5. a kind of subcritical Ethanol Method according to claim 1 extracts disaggregating property lignin method high, it is characterised in that：
The separation of the solid-liquid product of depolymerization uses the sand core funnel of model G5, vacuumizing filtration；Isopropanol is high-efficiency liquid chromatographic-grade,
Its mass fraction >=99.9%；Mass fraction >=99% of tetrahydrofuran.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342918A (en) * | 2017-12-26 | 2018-07-31 | 浙江金昌特种纸股份有限公司 | A kind of method that subcritical ethanol/water pretreatment prepares nanometer microfibril |
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|---|---|---|---|---|
| WO2012079021A2 (en) * | 2010-12-09 | 2012-06-14 | Virdia Ltd. | Methods and systems for processing lignocellulosic materials and related compositions |
| CN103524283A (en) * | 2013-10-12 | 2014-01-22 | 浙江大学 | Method for extracting monophenol compounds and pyrolysis lignin from biological oil |
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2017
- 2017-03-29 CN CN201710195768.2A patent/CN106883428A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012079021A2 (en) * | 2010-12-09 | 2012-06-14 | Virdia Ltd. | Methods and systems for processing lignocellulosic materials and related compositions |
| CN103524283A (en) * | 2013-10-12 | 2014-01-22 | 浙江大学 | Method for extracting monophenol compounds and pyrolysis lignin from biological oil |
Non-Patent Citations (3)
| Title |
|---|
| JAE-YOUNG KIM等: ""Effects of various reaction parameters on solvolytical depolymerization of lignin in sub- and supercritical ethanol"", 《CHEMOSPHERE》 * |
| WILLIAM B. HEWSON等: ""Studies on Lignin and Related Compounds. LVIII. The Mechanism of the Ethanolysis of Maple Wood at High Temperatures"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| YUEYUAN YE等: ""Novel Method for Production of Phenolics by Combining Lignin Extraction with Lignin Depolymerization in Aqueous Ethanol"", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342918A (en) * | 2017-12-26 | 2018-07-31 | 浙江金昌特种纸股份有限公司 | A kind of method that subcritical ethanol/water pretreatment prepares nanometer microfibril |
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