CN105622980A - Method for preparing wood fiber gel material from LiCl/DMSO dissolved lignocelluloses - Google Patents
Method for preparing wood fiber gel material from LiCl/DMSO dissolved lignocelluloses Download PDFInfo
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Abstract
The invention relates to a method for preparing a wood fiber gel material from LiCl/DMSO dissolved lignocelluloses, belongs to the field of lignocellulose composite materials, and aims to provide a wood fiber gel material preparation method which is simple in process, low in production cost, high in water absorption rate and high in porosity. The method comprises the following steps: dissolving a certain amount of soybean straw powder or microcrystalline cellulose complex treated by using ethylenediamine into an 8% LiCl/DMSO solution, performing magnetic stirring for 24 hours at the room temperature, and continuously stirring for 2 hours on a constant-temperature magnetic stirrer of 60 DEG C, thereby obtaining a uniform viscous solution; after the viscous solution is cooled to the room temperature, performing vacuum defoamation, after vacuum defoamation is completed, pouring into a mold, soaking into absolute ethyl alcohol for gelatinization, replacing absolute ethyl alcohol every day to wash hydrogel till Cl<-> cannot be detected from AgNO3, replacing water or absolute ethyl alcohol in the gel by using tertiary butanol, and finally performing freeze drying, thereby obtaining an aerogel material.
Description
Technical field
The invention belongs to lignocellulose based composites field, relate generally to the method that a kind of LiCl/DMSO lignocellulose dissolved prepares wood fibre gel rubber material.
Background technology
Gel rubber material (hydrogel and aeroge) is that a kind of Specific surface area is filled with liquid or the highly porous material of gas (usually water or air). The disperse medium of aerogel material is gas, it is as the solid-phase of gel network skeleton, and the gap structure of network is Nano grade, this continuous three-dimensional manometer network structure makes it have the performance of uniqueness, such as high porosity, high-specific surface area, low heat conduction coefficient, low-k, low optical index, the low velocity of sound etc. Current research shows, including pure cellulose, cellulose compound and cellulose mixed gel etc. based on cellulose aquagel material has many good performances, and such as hydrophilic, biological degradability, biocompatibility, transparency is high, cost is low, nontoxic. Cellulose aquagel is with a wide range of applications in fields such as organizational project, controlled delivery system, blood purification, sensor, agricultural and Water warfare.
Along with the environmental pollution that quick disappearance and the petroleum chemicals consumption of petroleum resources cause, start to make the whole world begin to focus on reproducible Wooden Biomass resource as the alternate resources that can replace petrochemical industry resource. Lignocellulose biomass resource includes wood waste, papermaking residue, the non-edible part of crops, resource crop etc. Lignocellulose is the biomass that on the earth, content is the abundantest, is present in widely in woody, herbaceous plant. It is mainly composed of the macromolecules such as cellulose, hemicellulose and lignin, and cellulose is wrapped in by hemicellulose, and outer layer is closely embedded by lignin again, and be combined with each other the cell wall becoming firm. Wherein cellulose is about 35-50%, hemicellulose is 20-35%, and lignin is about 5-30%.
Cellulose gel glue material generally can be obtained by regeneration after cellulose dissolution, most cellulose solutions, such as cellulose Calcium rhodanate aqueous solution, cellulose lithium chloride/dimethyl acetylamide (LiCl/DMAc) solution, cellulose sodium hydrate aqueous solution and 4-methyhnorpholine-N-oxide (NMMO) solution etc. can form translucent gels. Cellulose gel glue material has been done substantial amounts of research by many researcheres, such as the impact that cellulose gel is prepared by cellulose origin, solvent, regeneration, drying mode etc., has been achieved for bigger progress. But, current reported cellulose gel glue material is based on pure cellulose component, not yet carries out in a deep going way about not separating the applied research preparing gel rubber material under each component state of lignocellulose raw material.
Summary of the invention
In order to overcome the deficiency of background technology, the invention provides the method that a kind of LiCl/DMSO lignocellulose dissolved prepares wood fibre gel rubber material. Mainly solve existing method to prepare cellulose gel glue material and be based on the limitation of pure cellulose component.
The technical solution adopted in the present invention is: the method that the lignocellulose that a kind of LiCl/DMSO dissolves prepares wood fibre gel rubber material, comprises the following steps:
(1) take a certain amount of lignocellulosic material, adopt microphyte pulverizer to be ground into powder;
(2) screen a certain amount of uniform lignocellulose powder, filter and lyophilization after immersing ethylenediamine (EDA) solution at room temperature magnetic agitation 24h, obtain the lignocellulose after ethylenediamine processes;
(3) take the uniform lignocellulosic material of a certain amount of pulverizing and be dissolved in LiCl/DMSO solution after ethylenediamine (EDA) pretreatment, magnetic agitation 24h under room temperature, it is subsequently placed in 60 DEG C of constant temperature blender with magnetic force and continues stirring 2h, and obtain homogeneous viscous solution;
(4) treat that the LiCl/DMSO wood fibre cellulose solution dissolved is cooled to room temperature final vacuum deaeration, pour in mould after deaeration completely, and immerse gelation in dehydrated alcohol;
(5) absolute ethanol washing wood fibre hydrogel is changed, until AgNO3Inspection is without Cl-Exist, then displace the water in gel or dehydrated alcohol with the tert-butyl alcohol (TBA);
(6) to lignocellulose gel rubber material lyophilization, volatilize dehydrated alcohol, obtains lignocellulose aerogel material.
In the method technique that patent of the present invention provides, the lignocellulosic material described in step (1) includes all biomass materials containing cellulose and lignin such as soybean stalk powder, soybean stalk, wood powder, grass meal, wood pulp, straw pulp.
In the method technique that patent of the present invention provides, the uniform lignocellulosic material powder of pulverizing described in step (2) is 40-80 order.
In the method technique that patent of the present invention provides, the homogeneous viscous solution described in step (3) is lignocellulose powder-ethylenediamine complex.
In the method technique that patent of the present invention provides, the LiCl/DMSO solution concentration described in step (4) is 8%.
The invention difference from existing technology is in that, the present invention achieves following technique effect: the soybean stalk flour complexes taking a certain amount of ethylenediamine pretreatment is dissolved in 8%LiCl/DMSO solution, magnetic agitation 24h under room temperature, it is subsequently placed in 60 DEG C of constant temperature blender with magnetic force and continues stirring 2h, and obtain homogeneous viscous solution. Treat that solution is cooled to room temperature final vacuum deaeration, pour in mould after deaeration completely, and immerse gelation in dehydrated alcohol, change absolute ethanol washing hydrogel, until AgNO3Inspection is without Cl-Exist, then displace the water in gel or dehydrated alcohol with the tert-butyl alcohol, last lyophilization, obtain lignocellulose aerogel material.
The invention have the advantages that
1, the lignocellulosic material used due to the present invention belongs to environment-friendly material, safety non-toxic and can be degradable, both the lignocellulose gel of preparation will not be produced toxicity, cause environment pollution without equipment is produced burn into, also can reduce cost.
2, owing to the core freezing equipment of present invention use is simply common, it is not necessary to add expensive equipment, therefore can realize green preparation process at low cost.
3, the lignocellulose aerogel prepared by the present invention has green non-poisonous advantage, and form is good, and material is light, porous nickel and have certain mechanical strength.
4, the method technique preparing wood fibre gel rubber material provided by the invention is simple, and technique is easily controlled and production cost is low.
5, the lignocellulose aerogel material applications that prepared by the present invention is extensive, can be used for insulating against sound, the specific demand such as heat insulation, oil suction and load nano particle, belongs to high value added product. Preparation method can efficiently utilize low-quality biomass resource, widens the purposes of low quality of biomass, improves its use value, for efficiently utilizing low-quality biomass resource to provide new thinking and approach.
Below in conjunction with accompanying drawing, the invention will be further described.
Accompanying drawing explanation
Fig. 1 difference wood fibre concentration gel surface and profile scanning electromicroscopic photograph, Stem-1% represents that wood fibre cellulose content is 1%, and Stem-2% represents that wood fibre cellulose content is 2%, and Stem-3% represents that wood fibre cellulose content is 3%
Fig. 2 difference delignification degree wood fibre gel image scanning electromicroscopic photograph, Stem-0h represents the not delignified gel rubber material of lignocellulosic material, Stem-0.5h represents the gel rubber material of lignocellulosic material delignification 0.5h, Stem-1h represents the gel rubber material of lignocellulosic material delignification 1h, and Stem-2h represents the gel rubber material of lignocellulosic material delignification 2h
Fig. 3 difference delignification degree wood fibre gel equilibrium swelling ratio at different temperatures, Stem-0h represents the not delignified gel rubber material of lignocellulosic material, Stem-0.5h represents the gel rubber material of lignocellulosic material delignification 0.5h, Stem-1h represents the gel rubber material of lignocellulosic material delignification 1h, and Stem-2h represents the gel rubber material of lignocellulosic material delignification 2h
Fig. 4 variable concentrations lignocellulose gel rubber material equilibrium swelling ratio at different temperatures, Stem-1h-1% represents gel rubber material that wood fibre cellulose content is 1% equilibrium swelling ratio at different temperatures, and Stem-1h-2% represents gel rubber material that wood fibre cellulose content is 2% equilibrium swelling ratio at different temperatures
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, technical matters step, it is embodied as condition and material, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiments. Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not paying creative work premise, broadly fall into the scope of protection of the invention.
Lignocellulosic material for the present invention can be all biomass materials containing cellulose and lignin such as soybean stalk, wood powder, grass meal, wood pulp, straw pulp. Hereinafter, with soybean stalk for lignocellulosic material, it is embodied as illustrating to the present invention.
Embodiment 1
Take soybean stalk stem stalk part, after microphyte pulverizer is pulverized, filter out the soybean stalk powder of 40-80 order for experiment. Soybean stalk powder removes the organic solvent extracts such as resinic acid therein, terpene compound and fatty acid after benzene-ol mixed liquor (2: 1, v/v) extracting 24h. After extracting, soybean stalk powder fully volatilizees prior to ventilation a small amount of organic solvent of the moisture in powder of straw and residual, then vacuum drying. Dried soybean stalk powder is through sodium chlorite (NaClO2) and glacial acetic acid difference delignification process 0h, 0.5h, 1h, 2h at 75 DEG C, to prepare the raw material of different content of lignin, then vacuum drying.
Embodiment 2
Weigh dry soybean stalk stem stalk raw material 10g, be ground into the powder of 40-80 order, immerse in 200ml ethylenediamine solution, at room temperature filter and lyophilization after magnetic agitation 24h, obtain the soybean stalk stalk powder end of ethylenediamine pretreatment.
Embodiment 3
Preparation is containing 8%LiCl/DMSO solution, then the soybean stalk powder taking a certain amount of ethylenediamine pretreatment is dissolved in this solution, the concentration of soybean stalk powder is respectively configured as 1%, 2%, 3%, and under room temperature, magnetic agitation 24h obtains the stem stalk/LiCl/DMSO mixed solution of homogeneous thickness after being placed in 60 DEG C of constant temperature blender with magnetic force to continue stirring 2h.
Embodiment 4
Preparation 8%LiCl/DMSO solution, soybean stalk powder-the ethylenediamine mixture (Stem-EDA) that soybean stalk powder concentration is 1% taking a certain amount of ethylenediamine pretreatment is dissolved in this solution, magnetic agitation 24h under room temperature, it is subsequently placed in 60 DEG C of constant temperature blender with magnetic force and continues stirring 2h, and obtain homogeneous viscous solution. Treat that solution is cooled to room temperature final vacuum deaeration, pour in mould after deaeration completely, and immerse gelation in dehydrated alcohol, change absolute ethanol washing hydrogel, until AgNO3Inspection is without Cl-Exist, then displace the water in gel or dehydrated alcohol, last lyophilization with the tert-butyl alcohol (TBA), obtain the wood fibre temperature sensitive type semi-intercrossing network aerogel material that lignocellulosic material concentration is 1%.
Embodiment 5
Preparation 8%LiCl/DMSO solution, soybean stalk powder-the ethylenediamine mixture (Stem-EDA) that soybean stalk powder concentration is 2% taking a certain amount of ethylenediamine pretreatment is dissolved in this solution, magnetic agitation 24h under room temperature, it is subsequently placed in 60 DEG C of constant temperature blender with magnetic force and continues stirring 2h, and obtain homogeneous viscous solution. Treat that solution is cooled to room temperature final vacuum deaeration, pour in mould after deaeration completely, and immerse gelation in dehydrated alcohol, change absolute ethanol washing hydrogel every day, until AgNO3Inspection is without Cl-Exist, then displace the water in gel or dehydrated alcohol, last lyophilization with the tert-butyl alcohol (TBA), obtain the wood fibre temperature sensitive type semi-intercrossing network aerogel material that lignocellulosic material concentration is 2%.
Embodiment 6
Preparation 8%LiCl/DMSO solution, soybean stalk powder-the ethylenediamine mixture (Stem-EDA) that soybean stalk powder concentration is 3% taking a certain amount of ethylenediamine pretreatment is dissolved in this solution, magnetic agitation 24h under room temperature, it is subsequently placed in 60 DEG C of constant temperature blender with magnetic force and continues stirring 2h, and obtain homogeneous viscous solution. Treat that solution is cooled to room temperature final vacuum deaeration, pour in mould after deaeration completely, and immerse gelation in dehydrated alcohol, change absolute ethanol washing hydrogel every day, until AgNO3Inspection is without Cl-Exist, then displace the water in gel or dehydrated alcohol, last lyophilization with the tert-butyl alcohol (TBA), obtain the wood fibre temperature sensitive type semi-intercrossing network aerogel material that lignocellulosic material concentration is 3%.
Every technical staff's notice: although the present invention describes according to above-mentioned detailed description of the invention, but the invention thought of the present invention is not limited to that invention, the repacking of any utilization inventive concept, all will include in this patent scope of patent protection.
Claims (5)
1. the method that the lignocellulose of a LiCl/DMSO dissolving prepares wood fibre gel rubber material, it is characterised in that comprise the following steps:
(1) take a certain amount of lignocellulosic material, adopt microphyte pulverizer to be ground into powder;
(2) screen uniform lignocellulose powder, filter and lyophilization after immersing ethylenediamine (EDA) solution at room temperature magnetic agitation 24h, obtain the lignocellulose after ethylenediamine processes;
(3) take the uniform lignocellulosic material of a certain amount of pulverizing and be dissolved in LiCl/DMSO solution after ethylenediamine (EDA) pretreatment, magnetic agitation 24h under room temperature, it is subsequently placed in 60 DEG C of constant temperature blender with magnetic force and continues stirring 2h, and obtain homogeneous viscous solution;
(4) treat that the LiCl/DMSO wood fibre cellulose solution dissolved is cooled to room temperature final vacuum deaeration, pour in mould after deaeration completely, and immerse gelation in dehydrated alcohol;
(5) absolute ethanol washing wood fibre hydrogel is changed, until AgNO3Inspection is without Cl-Exist, then displace the water in gel or dehydrated alcohol with the tert-butyl alcohol (TBA);
(6) to lignocellulose gel rubber material lyophilization, volatilize dehydrated alcohol, obtains lignocellulose aerogel material.
2. the method preparing wood fibre gel rubber material according to claim 1 LiCl/DMSO lignocellulose dissolved, it is characterised in that the lignocellulosic material described in step (1) includes all biomass materials containing cellulose and lignin such as soybean stalk powder, wood powder, grass meal, wood pulp, Straw Pulp.
3. the method preparing wood fibre gel rubber material according to claim 1 LiCl/DMSO lignocellulose dissolved, it is characterised in that the uniform lignocellulosic material powder of pulverizing described in step (2) is 40-80 order.
4. the method preparing wood fibre gel rubber material according to claim 1 LiCl/DMSO lignocellulose dissolved, it is characterised in that the homogeneous viscous solution described in step (3) is lignocellulose powder-EDA complex.
5. the method preparing wood fibre gel rubber material according to claim 1 LiCl/DMSO lignocellulose dissolved, it is characterised in that the LiCl/DMSO solution concentration described in step (4) is 8%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117571A (en) * | 2016-08-04 | 2016-11-16 | 南京林业大学 | A kind of silane coupler strengthens the preparation method of lignocellulose base composite gel material |
| CN108051389A (en) * | 2018-02-05 | 2018-05-18 | 南京林业大学 | A kind of method for quantitative determining content of lignin in wood fibre without isolation |
| CN109749120A (en) * | 2019-03-06 | 2019-05-14 | 中国科学院过程工程研究所 | A kind of method that stalk directly prepares fiber-rich element aeroge |
| CN112358642A (en) * | 2020-10-12 | 2021-02-12 | 武汉纺织大学 | Method for preparing cellulose/polyester fiber composite aerogel by adopting waste textiles |
| CN113087959A (en) * | 2021-05-18 | 2021-07-09 | 北华大学 | Preparation method of crop straw full-component aerogel, product and application thereof |
| CN115109426A (en) * | 2022-08-09 | 2022-09-27 | 大连工业大学 | Preparation method of wood fiber all-component super-hydrophobic aerogel material |
-
2015
- 2015-11-27 CN CN201510852214.6A patent/CN105622980A/en active Pending
Non-Patent Citations (2)
| Title |
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| YUJI MATSUMOTO, ET AL.: "DISSOLUTION OF ETHYLENEDIAMINE-PRETREATED LIGNOCELLULOSIC MATERIAL IN LICL/DMSO AND PREPARATION OF LIGNOCELLULOSE AEROGELS", 《第十六届木材、纤维及制浆化学国际会议论文集（第Ⅱ卷）》 * |
| 潘永康等: "《现代干燥技术》", 31 May 2007, 化学工业出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117571A (en) * | 2016-08-04 | 2016-11-16 | 南京林业大学 | A kind of silane coupler strengthens the preparation method of lignocellulose base composite gel material |
| CN106117571B (en) * | 2016-08-04 | 2018-05-15 | 南京林业大学 | A kind of preparation method of silane coupling agent enhancing lignocellulosic base composite gel material |
| CN108051389A (en) * | 2018-02-05 | 2018-05-18 | 南京林业大学 | A kind of method for quantitative determining content of lignin in wood fibre without isolation |
| CN108051389B (en) * | 2018-02-05 | 2020-04-21 | 南京林业大学 | Method for quantitatively determining content of lignin in wood fiber without separation |
| CN109749120A (en) * | 2019-03-06 | 2019-05-14 | 中国科学院过程工程研究所 | A kind of method that stalk directly prepares fiber-rich element aeroge |
| CN112358642A (en) * | 2020-10-12 | 2021-02-12 | 武汉纺织大学 | Method for preparing cellulose/polyester fiber composite aerogel by adopting waste textiles |
| CN112358642B (en) * | 2020-10-12 | 2022-11-04 | 武汉纺织大学 | Method for preparing cellulose/polyester fiber composite aerogel by adopting waste textiles |
| CN113087959A (en) * | 2021-05-18 | 2021-07-09 | 北华大学 | Preparation method of crop straw full-component aerogel, product and application thereof |
| CN115109426A (en) * | 2022-08-09 | 2022-09-27 | 大连工业大学 | Preparation method of wood fiber all-component super-hydrophobic aerogel material |
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Application publication date: 20160601 |