CN107501571B - A kind of method that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover - Google Patents
A kind of method that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover Download PDFInfo
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Abstract
The invention discloses a kind of methods that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover.By corn straw smashing and drying, then using 1- butyl -3- methylimidazole villaumite-LiCl-DMF compound system as solvent, sulfur trioxide pyridine complex is added and carries out high shear sulfonation processing at a certain temperature, treated that material is filtered, washed and is dried in vacuo up to highly sulfonated fibrillation corn stover for sulfonation.1- butyl -3- methylimidazole villaumite is combined with LiCl in the present invention effectively swollen corn stalk fiber and to discharge free hydroxyl group, weakened the cohesive force of raw material, improved the sulfonation modifying efficiency of sulfur trioxide pyridine complex.The present invention can substantially reduce the degradation of the hemicellulose and lignin components of corn stover, and modified technique is simple and easy, and the modified product yield and sulfonation degree of microfibre are high, and large specific surface area realizes the immortalized utilization of agricultural wastes, and modification liquid is easily recycled.
Description
Technical field
The invention belongs to the processing modified method fields of plant fiber, in particular to one kind is using corn stover as raw material, in 1-
It is micro- to prepare highly sulfonated for high shear treatment in butyl -3- methylimidazole villaumite-LiCl-DMF (dimethylformamide) dicyandiamide solution
The method of fibrillated fibers.
Background technique
Plant fiber is one of the most abundant renewable resource on the earth, accumulates and stores up huge biomass energy.Biomass money
The main component in source is cellulose, hemicellulose and lignin.Cellulose is the chief component of plant cell wall；Hemicellulose
Element is incorporated between cellulose and lignin as molecule binder；There is lignin reticular structure cell to be made to be connected, as branch
Support bone frame surrounds and reinforces cellulose and hemicellulose.Currently, energy shortage, atmospheric warming effect and petroleum in global range
The problems such as in short supply, promotes the research of biorefinery.
Plant fiber has reproducibility and biological degradability, and application concentrates on textile and paper industry at present.With each
The exploitation of kind functional fiber keeps it also more and more extensive in the application of food, pharmacy, Material Field.Sulfonated cellulose is function
One of the staple product of energy property fiber, can be used as antivirotic and anticoagulant agent living, and sulfonate fibers are used as heavy metal ion suction at present
Attached dose that there are sulfonation degrees is low, and fibre morphology and group are distributed poor controllability.
Plant fiber supermolecule is the state that crystal region and amorphous region coexist, this directly influences the chemical reaction of fiber
Performance and homogeneity.Therefore, usually it is pre-processed before modification.Preprocess method has chemical method, physical method and life
Object method.Chemistry examination pretreatment can achieve dewaxing, disappear brilliant, swollen and extraction cellulose and other effects.The chemical reagent of dewaxing has first
Benzene/ethyl alcohol, chloroform/ethanol and hot hexane etc..Liquefied ammonia, methylamine and ethamine pretreatment are known as the brilliant effect that disappears to fiber.Alkali process is
It was found that earliest most efficient method, method for modifying fibers is carried out on the basis of alkali swollen mostly.Physics pretreatment method packet
Include Mechanical Method, high energy electron irradiation, high temperature, microwave treatment and steam explosion technology etc..Low energy consumption for biologic pretreatment method, operation
Simply, clean and environmental protection, but its long processing period and inefficient.
The highly crystalline supramolecular structure of cellulose keeps its not soluble in water and ordinary organic solvents.Some dicyandiamide solutions, such as LiCl/
Dimethyl acetamide and dimethylformamide/N2O4Cellulose can be dissolved, but because its strong toxicity, unstable, at high cost and solvent are difficult
The disadvantages of to recycle, makes it be difficult to be widely applied.Swatloski takes the lead in developing the 1- alkyl -3- methyl miaow of dissolved cellulose
Azole ionic liquid.Lu has developed N- methylimidazole/dimethyl sulfoxide and tetrabutylammonium/DMSO dissolution system obtains completely
The ball milling plant cell wall solution that do not degrade.
Its raw material sources of non-wood plant fibre are extensive, cheap, renewable, biodegradable, have good parent
Aqueous and porous structure, and multiple functions group can be introduced on hydroxyl, it purifies native cellulose and its derivative is removed and is used for
Outside the traditional industries such as textile and paper, degradation plastic, adsorbent, ion-exchanger and seperation film etc. can also be manufactured.Tradition
Plant fiber it is modified because the compactness of its structure causes reactivity worth poor, plant fiber cells are difficult to efficiently separate, and accordingly change
Property method need to pass through multi-step chemical, biology or mechanical treatment, modification is at high cost, and pollution is big, and properties of product are poor.
Summary of the invention
In order to overcome above-mentioned deficiency, the present invention provides one kind using corn stover as raw material, in 1- butyl -3- methylimidazole chlorine
The method of highly sulfonated fibrillation fiber is prepared in salt-LiCl-DMF dicyandiamide solution.Reduce the half fiber of corn stover significantly
The degradation of dimension element and lignin components, modified technique is simple and easy, and the modified product yield and sulfonation degree of microfibre are high, specific surface area
Greatly, the immortalized utilization of agricultural wastes is realized, and modification liquid is easily recycled.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of fibrillation corn stover sulfonate fibers, the sulfonation degrees 1.21 of the fibrillation corn stover sulfonate fibers~
1.36mmol/g fiber, 50.1~52.9m of specific surface area2/g。
The present invention is directed to plant fiber design feature, in conjunction with solvent processing, chemical modification reagent response characteristic and high shear
The response characteristics for handling lower fibre structure propose that it is micro- to prepare highly sulfonated for one-step method in BmimCl-LiCl-DMF dicyandiamide solution
Fibrillation corn stover, the present invention can substantially reduce the degradation of the hemicellulose and lignin components of corn stover, and modified technique is simple
Easy, modified product yield and sulfonation degree are high, and large specific surface area realizes the immortalized utilization of agricultural wastes, and modification liquid can
Reuse.Preferably, the crystallinity 53.9~56.4% of the fibrillation corn stover sulfonate fibers, length are 41.4~43.4 μ
m。
The present invention also provides a kind of methods for preparing highly sulfonated fibrillation fiber as raw material using corn stover, comprising:
It is spare by corn straw smashing, drying；
1- butyl -3- methylimidazole villaumite-is added in treated corn stover, sulfur trioxide pyridine complex
In LiCl-DMF composite solvent system, high shear sulfonation processing is carried out；
Collect sulfonation treated corn stover, washing, it is dry to get.
It is chanced in present invention research: it is different from general homogeneous solubilising reagent, using 1- butyl -3- methylimidazole chlorine
Salt is combined with LiCl effectively swollen corn stalk fiber and to discharge free hydroxyl group, weaken the cohesive force of raw material, especially pair
In the sulfonating reaction of corn stover, using 1- butyl -3- methylimidazole villaumite-LiCl-DMF dicyandiamide solution can strengthen high shear and
Separation and fiber fibrillating of the chemical action to corn stalk fiber cell, improve the modification efficiency of sulfonating agent.
Preferably, the 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system, solvent group become: 1- fourth
The content of base -3- methylimidazole villaumite is 4.0~14.0wt%, and LiCl content is 1.0%~3.0wt%, and DMF content is 83.0
~95.0wt%.
Preferably, the condition of the high shear sulfonation processing are as follows: in 20~70 DEG C, dispersion 10000~16000rpm of revolving speed
Lower progress high shear sulfonation handles 40~180min.
Since 1- butyl -3- methylimidazole villaumite-LiCl-DMF dicyandiamide solution mainly plays profit to corn stover in the present invention
Rise effect, corn stover is not dissolved completely in 1- butyl -3- methylimidazole villaumite-LiCl-DMF solvent, reaction still for it is non-
Phase reaction.Therefore, in order to guarantee that sulfonating reaction is stable and the high-purity of product, the present invention is to existing sulfonating agent in 1- butyl-
Reaction mechanism in 3- methylimidazole villaumite-LiCl-DMF dicyandiamide solution has carried out system research, gropes by large scale experiment
Find afterwards: when using sulfur trioxide pyridine complex as sulfonating agent, reaction rate is steady, by-product is few, the sulphonation rate of product
It gets a promotion with specific surface area.
Preferably, the mass ratio of the corn stover and sulfur trioxide pyridine complex are as follows: 1:0.8~2.5.
No. CAS of sulfur trioxide pyridine complex in the present invention are as follows: 26412-87-3 is sulfur trioxide and pyridine by regulation
Ratio compounding, belong to commercial product.
Preferably, the corn stover is dense in 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system
Degree is 3.0-7.0wt%.
The present invention also provides the highly sulfonated fibrillation fibers of any above-mentioned method preparation.
The present invention also provides any above-mentioned fibrillation corn stover sulfonate fibers to prepare antivirotic, anticoagulant agent living
Or the application in adsorbent for heavy metal.
The present invention also provides a kind of processing methods of leaded ion waste water, by any above-mentioned fibrillation corn stover sulphur
10~20min of stirring and adsorbing in leaded ion waste water is added in chemical fibre dimension；
Wherein, the mass ratio of the lead ion and fibrillation corn stover sulfonate fibers is 7~10:200；The suction of lead ion
Attached rate is up to 96.5%.
Beneficial effects of the present invention
(1) 1- butyl -3- methylimidazole villaumite combines the knot that can be specifically directed to corn stover with LiCl in the present invention
Structure, effective swollen corn stalk fiber simultaneously discharge free hydroxyl group, weaken the cohesive force of raw material.
(2) solvent enhances corn stalk fiber cell to the physical mechanical effect of the high shear of raw material and chemical action
Separation and fiber fibrillating, and then improve the sulfonation modifying efficiency of sulfur trioxide pyridine complex.
(3) present invention can substantially reduce the degradation of the hemicellulose and lignin components of corn stover, and modified technique is simply easy
Row, the modified product yield and sulfonation degree of microfibre are high, and large specific surface area realizes the immortalized utilization of agricultural wastes, and
Modification liquid is easily recycled.
(4) preparation method of the present invention is simple, sulfonation is high-efficient, practical, easy to spread.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
A method of highly sulfonated fibrillation corn stover being prepared, in 1- butyl -3- methylimidazole villaumite-LiCl-DMF
The method that highly sulfonated fibrillation fiber is prepared in dicyandiamide solution belongs to the processing modified method field of plant fiber.The present invention will
Corn straw smashing and drying are added three then using 1- butyl -3- methylimidazole villaumite-LiCl-DMF compound system as solvent
Sulfur oxide pyridine complex carries out high shear sulfonation processing at a certain temperature, sulfonation treated material is filtered, washed and
It is dried in vacuo up to highly sulfonated fibrillation corn stover.
The present invention is achieved by the following measures:
A method of highly sulfonated fibrillation fiber being prepared by raw material of corn stover, using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.07--0.09MPa, 30-50 DEG C of temperature,
Time 6.0-8.0h is dried under vacuum to moisture content less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 4.0-14.0wt%, and LiCl content is 1.0%-3.0wt%, and DMF content is 83.0-
95.0wt%.
(3) high shear sulfonation processing is carried out in dicyandiamide solution, and the sulfur trioxide pyrrole of 0.8-2.5g/g corn stover is added
Pyridine compound, corn stover concentration 3.0-7.0wt% are carried out high at 20-70 DEG C of temperature, dispersion revolving speed 10000-16000rpm
It shears sulfonation and handles 40-180min.
(4) corn stover is filtered cleaning after sulfonation processing, is cleaned using the DMF of its 3-5 times of quality, DMF cleaning solution
And it disposes waste liquid and carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water.
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.08--
0.09MPa, temperature are 30-45 DEG C, time 7.0-10.0h, dry after the completion up to target product.
1- butyl -3- methylimidazole villaumite is combined with LiCl in the present invention effectively swollen corn stalk fiber and to discharge
Free hydroxyl group, weakens the cohesive force of raw material, and solvent enhances jade to the physical mechanical effect of the high shear of raw material and chemical action
The separation of rice stalk fibre cell and fiber fibrillating, and then improve the sulfonation modifying effect of sulfur trioxide pyridine complex
Rate.The present invention can substantially reduce the degradation of the hemicellulose and lignin components of corn stover, and modified technique is simple and easy, microfibre
Modified product yield and sulfonation degree it is high, large specific surface area realizes the immortalized utilization of agricultural wastes, and modification liquid is easy to
It recycles.
Embodiment 1
A method of highly sulfonated fibrillation fiber being prepared by raw material of corn stover, using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.08MPa, 30 DEG C of temperature, time 8.0h
Moisture content is dried under vacuum to less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 8.0wt%, and LiCl content is 2.0wt%, and DMF content is 90.0wt%.
(3) high shear sulfonation processing is carried out in dicyandiamide solution, the sulfur trioxide pyridine that 1.5g/g corn stover is added is multiple
It closes object (No. CAS are as follows: 26412-87-3), is added corn stover 40g (concentration 4.0wt%), in 20 DEG C of temperature, dispersion revolving speed
High shear sulfonation is carried out under 16000rpm handles 40min.
(4) sulfonation processing after corn stover be filtered cleaning, using its 3 times of quality DMF cleaning, DMF cleaning solution and
It disposes waste liquid and carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water.
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.08MPa, temperature
Degree is 45 DEG C, time 7.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 74.2%, sulfonation degree 1.25mmol/g fiber, crystallization
Degree 56.4%, length are 42.8 μm, specific surface area 51.2m2/g。
Embodiment 2
A method of highly sulfonated fibrillation fiber being prepared by raw material of corn stover, using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.07MPa, temperature 50 C, time 7.0h
Moisture content is dried under vacuum to less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 4.0wt%, and LiCl content is 1.0wt%, and DMF content is 95.0wt%.
(3) high shear sulfonation processing is carried out in dicyandiamide solution, the sulfur trioxide pyridine that 2.5g/g corn stover is added is multiple
It closes object (No. CAS are as follows: 26412-87-3), is added corn stover 200g (concentration 3.0wt%), in temperature 50 C, dispersion revolving speed
High shear sulfonation is carried out under 14000rpm handles 180min.
(4) sulfonation processing after corn stover be filtered cleaning, using its 4 times of quality DMF cleaning, DMF cleaning solution and
It disposes waste liquid and carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water.
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.09MPa, temperature
Degree is 35 DEG C, time 10.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 75.6%, sulfonation degree 1.31mmol/g fiber, crystallization
Degree 54.9%, length are 41.6 μm, specific surface area 51.4m2/g。
By above-mentioned thin stillage recycling to sulfonation processing section, other processing parameters are same as above, final prepared fibrillation corn stalk
Stalk sulfonate fibers yield is 76.2%, sulfonation degree 1.21mmol/g fiber, crystallinity 55.2%, and length is 43.4 μm, specific surface
Product 50.1m2/ g, the solvent of reuse still have good performance, the sulfonate fibers function admirable of preparation.
Embodiment 3
A method of highly sulfonated fibrillation fiber being prepared by raw material of corn stover, using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.09MPa, 30 DEG C of temperature, time 6.0h
Moisture content is dried under vacuum to less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 10.0wt%, and LiCl content is 1.5wt%, and DMF content is 88.5wt%.
(3) high shear sulfonation processing is carried out in dicyandiamide solution, the sulfur trioxide pyridine that 0.8g/g corn stover is added is multiple
It closes object (No. CAS are as follows: 26412-87-3), is added corn stover 50g (concentration 7.0wt%), in temperature 70 C, dispersion revolving speed
High shear sulfonation is carried out under 12000rpm handles 90min.
(4) sulfonation processing after corn stover be filtered cleaning, using its 5 times of quality DMF cleaning, DMF cleaning solution and
It disposes waste liquid and carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water.
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.085MPa,
Temperature is 40 DEG C, time 8.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 72.9%, sulfonation degree 1.15mmol/g fiber, crystallization
Degree 53.2%, length are 44.9 μm, specific surface area 50.7m2/g。
Prepared sulfonate fibers are used for the processing of leaded ion waste water, plumbum ion concentration 70.0mg/L, sulfonate fibers
Dosage is 2.0g/L, and the adsorption rate of lead ion is up to 96.5% after adsorption treatment 20min.
Embodiment 4
A method of highly sulfonated fibrillation fiber being prepared by raw material of corn stover, using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.08MPa, 40 DEG C of temperature, time 7.0h
Moisture content is dried under vacuum to less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 14.0wt%, and LiCl content is 3.0wt%, and DMF content is 83.0wt%.
(3) high shear sulfonation processing is carried out in dicyandiamide solution, the sulfur trioxide pyridine that 2.4g/g corn stover is added is multiple
It closes object (No. CAS are as follows: 26412-87-3), is added corn stover 80g (concentration 6.0wt%), in temperature 50 C, dispersion revolving speed
High shear sulfonation is carried out under 10000rpm handles 40min.
(4) sulfonation processing after corn stover be filtered cleaning, using its 4 times of quality DMF cleaning, DMF cleaning solution and
It disposes waste liquid and carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water.
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.085MPa,
Temperature is 40 DEG C, time 9.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 72.1%, sulfonation degree 1.36mmol/g fiber, crystallization
Degree 53.9%, length are 41.4 μm, specific surface area 52.9m2/g。
Embodiment 5
Routine prepares sulfonate fibers method, and corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.08MPa,
30 DEG C of temperature, time 8.0h is dried under vacuum to moisture content less than 2.0wt%, prepares 1- butyl -3- methylimidazole villaumite-DMF
Composite solvent system, solvent group become: the content of 1- butyl -3- methylimidazole villaumite is 75.0wt%, and DMF content is
25.0wt%.The sulfur trioxide pyridine complex (No. CAS are as follows: 26412-87-3) of 1.4g/g corn stover, corn stover is added
30g (concentration 6.0wt%) handles 40min in 30 DEG C of sulfonation of temperature.Corn stover is filtered cleaning after sulfonation processing, uses
The DMF of its 3 times of quality is cleaned, and DMF cleaning solution and is disposed waste liquid and is carried out Treatment for Reuse；Material after DMF cleaning uses distilled water
Continue cleaning to pH value neutrality.Microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree-
0.08MPa, temperature are 45 DEG C, time 10.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 74.8%, sulfonation degree 0.63mmol/g fiber, crystallization
Degree 51.2%, length are 232.1 μm, specific surface area 11.0m2/g。
Embodiment 6
Routine prepares sulfonate fibers method, and corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.08MPa,
Temperature 45 C, time 7.5h is dried under vacuum to moisture content and is less than 2.0wt%, using 1- butyl -3- methylimidazole villaumite as solvent,
The sulfur trioxide pyridine complex (No. CAS are as follows: 26412-87-3) of 2.5g/g corn stover, corn stover 50g (concentration is added
7.0wt%), high shear sulfonation is carried out at temperature 60 C, dispersion revolving speed 14000rpm handle 180min.Corn after sulfonation processing
Stalk is filtered cleaning, is cleaned using the DMF of its 4 times of quality, DMF cleaning solution and disposes waste liquid and carries out Treatment for Reuse；DMF is clear
Material after washing continues cleaning to pH value neutrality using distilled water.It is dry that microfibre corn stalk fiber after cleaning carries out vacuum
Dry, drying condition is vacuum degree -0.085MPa, and temperature is 35 DEG C, time 8.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 72.8%, sulfonation degree 0.56mmol/g fiber, crystallization
Degree 50.2%, length are 242.1 μm, specific surface area 11.2m2/g。
Embodiment 7
Routine prepares sulfonate fibers method, and corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.07MPa,
Temperature 50 C, time 6.0h are dried under vacuum to moisture content less than 2.0wt%, are with 1- butyl -3- methylimidazole villaumite-LiCl
Solvent, the content of 1- butyl -3- methylimidazole villaumite are 97.0wt%, and LiCl content is 3.0wt%.1.5g/g corn stalk is added
The chlorosulfonic acid of stalk, corn stover 200g (concentration 7.0wt%) handle 90min in 25 DEG C of sulfonation of temperature.Corn stalk after sulfonation processing
Stalk is filtered cleaning, is cleaned using the DMF of its 4 times of quality, DMF cleaning solution and disposes waste liquid and carries out Treatment for Reuse；DMF cleaning
Material afterwards continues cleaning to pH value neutrality using distilled water.Microfibre corn stalk fiber after cleaning is dried in vacuo,
Drying condition is vacuum degree -0.085MPa, and temperature is 35 DEG C, time 8.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 72.5%, sulfonation degree 0.34mmol/g fiber, crystallization
Degree 48.0%, length are 273.1 μm, specific surface area 9.1m2/g.In addition, generating a large amount of by-products in reaction process, product is caused
Separation is difficult.
Embodiment 8
Routine prepares sulfonate fibers method, and corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.08MPa,
35 DEG C of temperature, time 7.0h is dried under vacuum to moisture content less than 2.0wt%, and using DMF as solvent, 2.5g/g corn stover is added
Sulfur trioxide pyridine complex (No. CAS are as follows: 26412-87-3), corn stover 60g (concentration 7.0wt%), temperature 60 C,
Disperse under revolving speed 14000rpm to carry out high shear sulfonation processing 180min.Corn stover is filtered cleaning after sulfonation processing, adopts
It is cleaned with the DMF of its 4 times of quality, DMF cleaning solution and disposes waste liquid and carry out Treatment for Reuse；Material after DMF cleaning is using distillation
Water continues cleaning to pH value neutrality.Microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree-
0.085MPa, temperature are 35 DEG C, time 8.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 73.5%, sulfonation degree 0.36mmol/g fiber, crystallization
Degree 51.2%, length are 262.1 μm, specific surface area 9.5m2/g。
Conclusion: through the foregoing embodiment with the comparison of comparative example it is found that relative to conventional method, " 1- butyl -3- methyl miaow
The process combination of the chloro- LiCl-DMF composite solvent system of azoles+high shear sulfonation processing " obtains fibrillation corn stover sulfonate fibers
Sulfonation degree, crystallinity and specific surface area all significantly improve.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (4)
1. a kind of method that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover, feature exist
In using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.08MPa, 30 DEG C of temperature, time 8.0h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 8.0wt%, and LiCl content is 2.0wt%, and DMF content is 90.0wt%；
(3) high shear sulfonation processing is carried out in dicyandiamide solution, and the sulfur trioxide pyridine complex of 1.5g/g corn stover is added,
No. CAS are as follows: 26412-87-3 is added corn stover 40g, makes its concentration 4.0wt%, in 20 DEG C of temperature, dispersion revolving speed
High shear sulfonation is carried out under 16000rpm handles 40min；
(4) corn stover is filtered cleaning after sulfonation processing, is cleaned using the DMF of its 3 times of quality, DMF cleaning solution and processing
Waste liquid carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water；
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.08MPa, and temperature is
It is 45 DEG C, time 7.0h, dry after the completion up to target product.
2. a kind of method that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover, feature exist
In using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.07MPa, temperature 50 C, time 7.0h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 4.0wt%, and LiCl content is 1.0wt%, and DMF content is 95.0wt%；
(3) high shear sulfonation processing is carried out in dicyandiamide solution, and the sulfur trioxide pyridine complex of 2.5g/g corn stover is added,
No. CAS are as follows: 26412-87-3 is added corn stover 200g, makes its concentration 3.0wt%, in temperature 50 C, dispersion revolving speed
High shear sulfonation is carried out under 14000rpm handles 180min；
(4) corn stover is filtered cleaning after sulfonation processing, is cleaned using the DMF of its 4 times of quality, DMF cleaning solution and processing
Waste liquid carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water；
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.09MPa, and temperature is
It is 35 DEG C, time 10.0h, dry after the completion up to target product.
3. a kind of method that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover, feature exist
In using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.09MPa, 30 DEG C of temperature, time 6.0h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 10.0wt%, and LiCl content is 1.5wt%, and DMF content is 88.5wt%；
(3) high shear sulfonation processing is carried out in dicyandiamide solution, and the sulfur trioxide pyridine complex of 0.8g/g corn stover is added,
No. CAS are as follows: 26412-87-3 is added corn stover 50g, makes its concentration 7.0wt%, in temperature 70 C, dispersion revolving speed
High shear sulfonation is carried out under 12000rpm handles 90min；
(4) corn stover is filtered cleaning after sulfonation processing, is cleaned using the DMF of its 5 times of quality, DMF cleaning solution and processing
Waste liquid carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water；
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.085MPa, temperature
It is 40 DEG C, time 8.0h, it is dry after the completion up to target product.
4. a kind of method that 1- butyl -3- methylimidazole villaumite-LiCl-DMF system prepares fento corn stover, feature exist
In using following steps:
(1) corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.08MPa, 40 DEG C of temperature, time 7.0h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiCl-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 14.0wt%, and LiCl content is 3.0wt%, and DMF content is 83.0wt%；
(3) high shear sulfonation processing is carried out in dicyandiamide solution, and the sulfur trioxide pyridine complex of 2.4g/g corn stover is added,
No. CAS are as follows: 26412-87-3 is added corn stover 80g, makes its concentration 6.0wt%, in temperature 50 C, dispersion revolving speed
High shear sulfonation is carried out under 10000rpm handles 40min；
(4) corn stover is filtered cleaning after sulfonation processing, is cleaned using the DMF of its 4 times of quality, DMF cleaning solution and processing
Waste liquid carries out Treatment for Reuse；
(5) material after DMF cleaning continues cleaning to pH value neutrality using distilled water；
(6) the microfibre corn stalk fiber after cleaning is dried in vacuo, and drying condition is vacuum degree -0.085MPa, temperature
It is 40 DEG C, time 9.0h, it is dry after the completion up to target product.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126260A (en) * | 1994-05-27 | 1996-07-10 | 金伯特-克拉克公司 | Sulfonated cellulose and method of preparation |
| CN105885058A (en) * | 2014-11-03 | 2016-08-24 | 吴迪 | Method utilizing crop straws to prepare sodium lignosulfonate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1126260A (en) * | 1994-05-27 | 1996-07-10 | 金伯特-克拉克公司 | Sulfonated cellulose and method of preparation |
| CN105885058A (en) * | 2014-11-03 | 2016-08-24 | 吴迪 | Method utilizing crop straws to prepare sodium lignosulfonate |
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