CN105754114B - A kind of method of eutectic ionic liquid separation and Extraction straw lignin - Google Patents
A kind of method of eutectic ionic liquid separation and Extraction straw lignin Download PDFInfo
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- CN105754114B CN105754114B CN201610108426.8A CN201610108426A CN105754114B CN 105754114 B CN105754114 B CN 105754114B CN 201610108426 A CN201610108426 A CN 201610108426A CN 105754114 B CN105754114 B CN 105754114B
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- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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Abstract
The present invention relates to a kind of processes with eutectic ionic liquid separation and Extraction straw lignin, its step is that stalk powder raw material and eutectic ionic liquid are added by certain mass ratio in normal pressure reactor, after being mixed at 110 DEG C~160 DEG C, being stirred to react a period of time, the pH value of the mixture is adjusted to 11 or so with alkali, high speed centrifugation retains upper solution.Sediment is washed with distilled water after the pH value of the solution is adjusted to 3 hereinafter, centrifuging again with acid again, centrifuges to supernatant and is in neutrality, last sediment is freeze-dried to obtain lignin.Its main feature is that using cheap and nontoxic choline chloride and hydrogen bond donor as raw material, eutectic ionic liquid is prepared in very mild conditions, the lignin in its separation and Extraction rice straw is used in combination, its raw material is easy to get, it is cheap, process is simple, mild condition, reaction is easily controllable and can effectively reduce energy consumption.
Description
Technical field
The invention belongs to chemical industry application fields, and in particular to a kind of wooden with eutectic ionic liquid separation and Extraction stalk
The technique of element.
Background technology
In China, annual rice straw yield is up to 2.3 hundred million tons, is a kind of renewable biomass resources of enormous amount, and right
Natural reproducible resource is efficiently used, and one of the key of mankind nowadays sustainable development is had become.And lignin is rice
One of main ingredient in straw, content is only second to cellulose, increasingly in short supply with petroleum resources, and lignin is as can
Unique aromatic rings source, needs more to be explored in regenerated resources, replaces oil that can synthesize moreization with lignin
Work and daily necessities.But due to wide variety, complicated, the no pure model object of chemical constitution etc., the extracting and developing of lignin
It is still a great problem in this field with application.Log lignin greatly and lacks lyophily group due to relative molecular mass,
Dissolubility in water and in usual solvents is poor, essentially insoluble solution.The tradition side of lignin is extracted from biological material
Method is reacted with the concentrated sulfuric acid or dilute sulfuric acid, although efficient, environmental pollution is larger, is not suitable for large-scale promotion.It is organic molten
Agent lignin dissolves in dioxane, pyridine, methanol, ethyl alcohol, acetone and sig water, but must be in these solvents plus a little
Water, it is otherwise almost insoluble.Therefore the research hotspot that a kind of separation method of new lignin is current is found.Ionic liquid be by
The salt of organic cation and inorganic anion composition, is in a liquid state at normal temperatures.Stablize in recent years with performance because of it, it is pollution-free,
Easily recycling, and be concerned improving reaction rate, selectivity and catalytic action etc. presentation clear superiority, it enjoys " green
The reputation of color solvent ".Also there are related application, especially traditional imidazole-like ionic liquid such as chlorine in lignin dissolution and catalytic pyrolysis
It is all relatively strong to the solvability of lignin and cellulose for 1- butyl -3- methylimidazoles ([Bmim] Cl) etc., but due to its biology
Degradability is poor, has certain toxicity, and cost is 2~4 times of usual vehicle even higher, therefore, it is difficult to be answered extensively
With.Eutectic ionic liquid be also known as eutectic solvent (Deep Eutectic Solvents, DES) be one kind by quaternary ammonium salt or metal
The eutectic mixture of salt and hydrogen bond donor composition.With conventional ion liquid phase ratio, preparation process is simple, raw material easily takes, price is low
It is honest and clean, without environment side effect, but it there is no application in terms of the extraction to lignin from biomass.Disclosed by the invention is to use
One-step synthesis prepares choline chloride system eutectic ionic liquid, is natural reproducible to the separation and Extraction lignin from stalk
The extraction of resource has important economic implications and social effect with using a kind of new method is provided.
Invention content
The purpose of the present invention：It is intended to provide a kind of raw material to be easy to get, the simple lignin of cheap, mild condition, process
Extracting method.It, only need to be by the chlorination of certain mol proportion when preparing eutectic ionic liquid by the quaternary amine structure of choline chloride
Choline and hydrogen bond donor be mixed to be incorporated in heating stirring under certain temperature until forming uniform colourless liquid, and as solvent at
Straw powder is managed, lignin is therefrom extracted.
Technical scheme of the present invention：Synthesis under normal pressure is added by certain mass ratio in stalk powder raw material and eutectic ionic liquid
After in device, being mixed at 110 DEG C~160 DEG C, being stirred to react a period of time, this is mixed with a concentration of 10% sodium hydroxide solution
The pH value for closing object is adjusted to 11, and high speed centrifugation retains upper solution.The pH value of the solution is adjusted to 3 with a concentration of 10% sulfuric acid
Hereinafter, repeatedly being washed, being centrifuged to the aobvious neutrality of supernatant with distilled water by sediment after centrifuging again, last sediment is chilled
It is dried to obtain lignin；The eutectic ionic liquid is existed respectively as raw material with urea, glycerine, citric acid using choline chloride
70~100 DEG C of temperate condition is down toward the transparent obtained choline chloride system eutectic ionic liquid of reaction solution, wherein choline chloride
With the ratio between the amount of substance of urea be the ratio between amount of substance of 1: 1~1: 3, choline chloride and glycerine it is 1: 1~1: 2, chlorination
The ratio between amount of substance of choline and citric acid is 1: 1~3: 1；
(1) method described in, wherein stalk powder raw material be by the stalk after drying after crushing, ball milling, screening, take 40
The mesh powder of mesh~100 is dried to obtained by over dry；
(2) method described in, wherein the mass ratio of eutectic ionic liquid and stalk powder raw material is 100: 5~20；
(3) method described in, wherein the insulation reaction time is 1h~10h.
Compared with the prior art, the present invention has the following advantages：
(1) solvent used in the present invention is choline chloride system eutectic ionic liquid, is with cheap and nontoxic chlorination
Choline and hydrogen bond donor are the raw material for preparing eutectic ionic liquid, preparation-obtained in very mild conditions, are prepared
Process is easy, and reaction temperature is low, and the time is short.
(2) present invention is by the multiple synergistic effect such as the solvent of eutectic ionic liquid, catalysis, activation, separation and Extraction stalk
In lignin, treatment conditions are mild, and extraction process is simple, and reaction is easily controllable, and significantly reduces energy consumption.
Description of the drawings
Fig. 1 is the ultraviolet spectrogram that four kinds of ionic liquids extract rice straw lignin, and the maximum absorption band of four curves of gained is equal
210~220nm or so is appeared in, to be conjugated the absorption band of ethylene linkage, illustrates that dissolving gained lignin has larger unsaturation；
In addition, coming from the π of the phenol (phenyl ring) of non-condensation in lignin component there are one the absorption peak of moderate strength near 280nm
→ π * electron transitions illustrate there is phenolic hydroxyl group, carbon-carbon double bond and the biphenyl knot being conjugated with α carbonyls in the lignin structure of extraction
Structure.
Fig. 2 is the infrared spectrogram that four kinds of ionic liquids extract rice straw lignin, the appearance profile line phase of four curves in figure
Closely, there are several characteristic absorption peaks of lignin：3400cm-1~3450cm-1It is the stretching vibration absorption peak of-OH, 2920cm-1It is the absorption peak of methyl, methylene and methine, 1735cm-1、1655cm-1It is to be stretched with the non-conjugated and conjugation of aromatic rings respectively
Contracting vibration performance peak, the characteristic absorption of phenyl ring are mainly reflected in 1600cm-1、1510cm-1And 1420cm-1Be in infrared spectrum most
Apparent absorption peak.Compared with [Bmim] Cl ionic liquids of comparative example 1 extraction lignin curve, three kinds of self-control choline chlorides
It is 1600cm of the eutectic ionic liquid extraction lignin curve in characterization phenyl ring skeleton stretching vibration-1And 1512cm-1Absorption peak is equal
It shows stronger absorption, illustrates after eutectic ionic liquid is handled, the skeleton structure of lignin has obtained good protection.
Specific implementation mode
Embodiment 1
Choline chloride 35g is weighed, urea 30g is separately added into the reaction vessel of sealing, 40min is stirred at 80 DEG C, instead
It answers liquid transparent, obtains Ch-U eutectic ionic liquids.It is slowly added to rice straw powder 3.25g, when being warming up to 150 DEG C or so, insulation reaction
Modified lignin resin and DES mixtures are obtained after 5h.The sodium hydroxide solution for being about 10% with concentration is by the pH value tune of the mixture
To 11 or so, high speed centrifugation retains upper solution.The pH value of the solution is adjusted to 3 hereinafter, again by the sulfuric acid for being about 10% with concentration
Sediment is repeatedly washed with distilled water after secondary centrifugation, is centrifuged to the aobvious neutrality of supernatant, last sediment is freeze-dried to be obtained
To lignin 0.195g.
Embodiment 2
Choline chloride 35g is weighed, glycerine 46g is separately added into the reaction vessel of sealing, and 40min is stirred at 80 DEG C,
Reaction solution is transparent, obtains Ch-G eutectic ionic liquids.It is slowly added to rice straw powder 4.05g, when being warming up to 150 DEG C or so, heat preservation is anti-
Modified lignin resin and DES mixtures are obtained after answering 5h.The sodium hydroxide solution for being about 10% with concentration is by the pH value of the mixture
11 or so are adjusted to, high speed centrifugation retains upper solution.The sulfuric acid for being about 10% with concentration by the pH value of the solution be adjusted to 3 hereinafter,
Sediment is repeatedly washed with distilled water after centrifuging again, is centrifuged to the aobvious neutrality of supernatant, last sediment is freeze-dried
Obtain lignin 0.505g.
Embodiment 3
Choline chloride 35g is weighed, citric acid 48g is separately added into the reaction vessel of sealing, and 80min is stirred at 80 DEG C,
Reaction solution is transparent, obtains Ch-C eutectic ionic liquids.It is slowly added to rice straw powder 4.15g, when being warming up to 150 DEG C or so, heat preservation is anti-
Modified lignin resin and DES mixtures are obtained after answering 5h.With the sodium hydroxide solution for being about 10% with concentration by the pH of the mixture
Value is adjusted to 11 or so, and high speed centrifugation retains upper solution.The sulfuric acid for being about 10% with concentration by the pH value of the solution be adjusted to 3 with
Under, sediment is repeatedly washed with distilled water after centrifuging again, is centrifuged to the aobvious neutrality of supernatant, last sediment is chilled dry
It is dry to obtain lignin 0.65g.
Embodiment 4
Choline chloride 35g is weighed, citric acid 48g is separately added into the reaction vessel of sealing, and 80min is stirred at 80 DEG C,
Reaction solution is transparent, obtains Ch-C eutectic ionic liquids.It is slowly added to rice straw powder 4.15g, when being warming up to 150 DEG C or so, heat preservation is anti-
Modified lignin resin and DES mixtures are obtained after answering 2h.The sodium hydroxide solution for being about 10% with concentration is by the pH value of the mixture
11 or so are adjusted to, high speed centrifugation retains upper solution.The sulfuric acid for being about 10% with concentration by the pH value of the solution be adjusted to 3 hereinafter,
Sediment is repeatedly washed with distilled water after centrifuging again, is centrifuged to the aobvious neutrality of supernatant, last sediment is freeze-dried
Obtain lignin 0.61g.
Embodiment 5
Choline chloride 35g is weighed, citric acid 48g is separately added into the reaction vessel of sealing, and 80min is stirred at 80 DEG C,
Reaction solution is transparent, obtains Ch-C eutectic ionic liquids.It is slowly added to rice straw powder 4.15g, when being warming up to 120 DEG C or so, heat preservation is anti-
Modified lignin resin and DES mixtures are obtained after answering 5h.The sodium hydroxide solution for being about 10% with concentration is by the pH value of the mixture
11 or so are adjusted to, high speed centrifugation retains upper solution.The sulfuric acid for being about 10% with concentration by the pH value of the solution be adjusted to 3 hereinafter,
Sediment is repeatedly washed with distilled water after centrifuging again, is centrifuged to the aobvious neutrality of supernatant, last sediment is freeze-dried
Obtain lignin 0.505g.
Comparison example 1
By [Bmim] Cl ionic liquid 83g, when being warming up to 150 DEG C or so, it is slowly added to rice straw powder 4.15g, keeps the temperature simultaneously magnetic force
It is stirred to react 5h, the pH value of the mixture is adjusted to 11 or so by the sodium hydroxide solution for being about 10% with concentration, and high speed centrifugation is protected
Stay upper solution.The pH value of the solution is adjusted to 3 hereinafter, steaming sediment after centrifuging again by the sulfuric acid for being about 10% with concentration
Distilled water is repeatedly washed, is centrifuged to the aobvious neutrality of supernatant, and last sediment is freeze-dried to obtain lignin 0.505g.
With [Bmim] the Cl ionic liquid phase ratios of outsourcing used in comparison example 1, method of the invention uses homemade eutectic
Ionic liquid, cost of material is cheap, and preparation process is simple, and the treatment conditions temperature of the extraction process for rice straw powder lignin
With.If the embodiment of the present invention 2 is compared with comparison example 1, treatment conditions are identical, the recovery rate higher of lignin.The present invention
Embodiment 5 compared with comparison example 1, when the recovery rate of lignin is identical, Extracting temperature can reduce by 30 DEG C, be effectively reduced
Energy consumption.
Claims (4)
1. a kind of method of eutectic ionic liquid separation and Extraction straw lignin, which is characterized in that by stalk powder raw material with it is low total
Molten ionic liquid is added by certain mass ratio in normal pressure reactor, is mixed at 110 DEG C~160 DEG C, is stirred to react a period of time
Afterwards, the pH value of the mixture is adjusted to 11 with a concentration of 10% sodium hydroxide solution, high speed centrifugation retains upper solution；With
A concentration of 10% sulfuric acid repeatedly washs sediment distilled water after the pH value of the solution is adjusted to 3 hereinafter, centrifuging again, from
For the heart to the aobvious neutrality of supernatant, last sediment is freeze-dried to obtain lignin；The eutectic ionic liquid is with chlorination courage
Alkali is transparent obtained down toward reaction solution in 70~100 DEG C of temperate condition as raw material with urea, glycerine, citric acid respectively
Choline chloride system eutectic ionic liquid, wherein the ratio between amount of substance of choline chloride and urea be 1: 1~1: 3, choline chloride with
The ratio between amount of substance of glycerine is that the ratio between amount of substance of 1: 1~1: 2, choline chloride and citric acid is 1: 1~3: 1.
2. the method for eutectic ionic liquid separation and Extraction straw lignin according to claim 1, it is characterised in that stalk
Powder raw material be by the stalk after drying after crushing, ball milling, screening, take the mesh powder of 40 mesh~100, be dried to over dry.
3. the method for eutectic ionic liquid separation and Extraction straw lignin according to claim 1, it is characterised in that low total
The mass ratio of molten ionic liquid and stalk powder raw material is 100: 5~20.
4. the method for eutectic ionic liquid separation and Extraction straw lignin according to claim 1, it is characterised in that reaction
Time is 1h~10h.
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| CN107474261A (en) * | 2017-09-25 | 2017-12-15 | 南京工业大学 | A kind of method that biomass lignin is extracted using quaternary ammonium base |
| CN107904266B (en) * | 2017-12-18 | 2020-12-11 | 湘潭大学 | Pretreatment method for efficiently and environmentally improving lignocellulose enzymolysis saccharification efficiency and application |
| CN108299517A (en) * | 2018-03-07 | 2018-07-20 | 齐鲁工业大学 | A method of extracting low-molecular weight lignin from biomass |
| CN108441530B (en) * | 2018-03-13 | 2021-10-08 | 北京化工大学 | Method for pretreating lignocellulose by using alkaline eutectic solvent |
| CN108554450B (en) * | 2018-06-13 | 2020-03-31 | 青岛科技大学 | Catalyst and process for alcoholysis of polycarbonate |
| CN109485041B (en) * | 2018-11-27 | 2022-05-27 | 南京林业大学 | Method for preparing porous carbon by taking eutectic ionic liquid as pore-forming agent |
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| CN110218335B (en) * | 2019-05-22 | 2022-03-04 | 广东工业大学 | Method for extracting lignin by using ternary deep eutectic solvent |
| CN110804893B (en) * | 2019-11-15 | 2021-11-30 | 齐鲁工业大学 | Method for separating holocellulose in wood fibers by using choline eutectic solvent |
| CN111302910B (en) * | 2020-03-13 | 2023-01-13 | 中国科学院广州能源研究所 | Method for producing acetophenone and acetic acid by biomass directional catalysis |
| CN113603899B (en) * | 2021-07-12 | 2023-03-21 | 华南理工大学 | Method for pretreating lignocellulose by using Lewis base to assist neutral eutectic solvent |
| CN114377717B (en) * | 2022-01-26 | 2023-12-22 | 福建农林大学 | Lignin-based carbon composite graphite phase carbon nitride/Mxene heterojunction photocatalyst and preparation method and application thereof |
| CN114454280B (en) * | 2022-02-15 | 2023-05-23 | 浙江农林大学 | Method for adjusting chromatic aberration of wood veneer |
| CN115232176B (en) * | 2022-07-14 | 2023-06-20 | 华南理工大学 | Method for extracting lignin by using ternary eutectic solvent |
| CN116144039B (en) * | 2022-11-30 | 2024-05-14 | 东北林业大学 | Method for separating natural lignin |
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| CN103739854A (en) * | 2013-12-25 | 2014-04-23 | 东北林业大学 | Method for modifying lignin in eutectic solvent through quaternization |
| CN104004201A (en) * | 2014-06-13 | 2014-08-27 | 东北林业大学 | Method for degrading lignin in acidic eutectic solvent |
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| Title |
|---|
| New natural and renewable low transition temperature mixtures (LTTMs):screening as solvents for lignocellulosic biomass processing;María Francisco等;《Green Chemistry》;20120620(第14期);第18149-18155页,表3和第2156页第3-4段、fig.5、2157页第3段 * |
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Application publication date: 20160713 Assignee: Nanjing Cheng Shan Technology Co., Ltd. Assignor: Nanjing Forestry University Contract record no.: X2019320000341 Denomination of invention: Method for separating and extracting straw lignin by using eutectic ionic liquid Granted publication date: 20180928 License type: Common License Record date: 20191211 Application publication date: 20160713 Assignee: Nanjing Mai Wen environmental protection equipment Engineering Co., Ltd. Assignor: Nanjing Forestry University Contract record no.: X2019320000342 Denomination of invention: Method for separating and extracting straw lignin by using eutectic ionic liquid Granted publication date: 20180928 License type: Common License Record date: 20191211 |