CN107501572B - A kind of method that 1- butyl -3- methylimidazole villaumite-LiBr-DMF system prepares fento corn stover - Google Patents
A kind of method that 1- butyl -3- methylimidazole villaumite-LiBr-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-LiBr-DMF system prepares fento corn stover.By corn straw smashing and drying, then using 1- butyl -3- methylimidazole villaumite-LiBr-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 LiBr 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 present invention relates 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-LiBr-DMF (dimethylformamide) dicyandiamide solution
The method of fibrillated fibers.
Background technique
Lignocellulosic is as a kind of renewable natural macromolecular material, and renewable, yield is big, and global annual output is up to
1.0 × 1010 tons, neutral carbon becomes the optimal selection of petroleum industry substitute.China is large agricultural country, annual corn stover,
The agricultural wastes resource yield such as straw, wheat straw is big, Efficient Conversion utilize for increase agricultural incomes, mitigate petroleum resources according to
Bad, exploitation new function material, reduction environmental pollution and waste make full use of significant.
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.
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-LiBr-DMF dicyandiamide solution.Expand the agricultural wastes such as corn stover
Application range and utility value
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-LiBr-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
It can reuse.Preferably, the crystallinity 53.9~56.4% of the fibrillation corn stover sulfonate fibers, length are 41.4~43.4
μm。
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 LiBr-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 LiBr 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-LiBr-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-LiBr-DMF composite solvent system, solvent group become: 1- fourth
The content of base -3- methylimidazole villaumite is 4.5~14.5wt%, and LiBr content is 1.5%~3.5wt%, and DMF content is 82.0
~94.0wt%.
Preferably, the condition of the high shear sulfonation processing are as follows: in 30~70 DEG C, dispersion 10000~16000rpm of revolving speed
Lower progress high shear sulfonation handles 40~180min.
Since 1- butyl -3- methylimidazole villaumite-LiBr-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-LiBr-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-LiBr-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-LiBr-DMF composite solvent system
Degree is 3.0-7.0wt%.
The present invention also provides 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent systems to improve corn stalk
Application in stalk sulfonation efficiency.
The present invention also provides above-mentioned fibrillation corn stover sulfonate fibers to prepare antivirotic, anticoagulant agent living or again
Application in metal ion adsorbent.
The present invention also provides a kind of processing methods of leaded ion waste water, and above-mentioned fibrillation corn stover sulfonation is fine
10~20min of stirring and adsorbing in leaded ion waste water is added in dimension；
Wherein, the mass ratio of the lead ion and fibrillation corn stover sulfonate fibers is 7~10:200.
Beneficial effects of the present invention
(1) 1- butyl -3- methylimidazole villaumite combines the knot that can be specifically directed to corn stover with LiBr 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-LiBr-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-LiBr-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-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 4.5-14.5wt%, and LiBr content is 1.5%-3.5wt%, and DMF content is 82.0-
94.0wt%.
(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 30-70 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 LiBr 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 -0.09MPa, 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-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 9.0wt%, and LiBr content is 2.0wt%, and DMF content is 89.0wt%.
(3) high shear sulfonation processing is carried out in dicyandiamide solution, the sulfur trioxide pyridine that 1.4g/g corn stover is added is multiple
It closes object (No. CAS are as follows: 26412-87-3), is added corn stover 40g (concentration 6.0wt%), in 30 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 10.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 75.3%, sulfonation degree 1.23mmol/g fiber, crystallization
Degree 56.2%, length are 42.1 μm, specific surface area 51.0m2/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 -0.08MPa, temperature 45 C, time 7.5h
Moisture content is dried under vacuum to less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 4.5wt%, and LiBr content is 1.5wt%, and DMF content is 94.0wt%.
(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 7.0wt%), in temperature 60 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 -0.085MPa,
Temperature is 35 DEG C, time 8.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 75.1%, sulfonation degree 1.42mmol/g fiber, crystallization
Degree 54.1%, length are 42.3 μm, specific surface area 51.2m2/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 76.7%, sulfonation degree 1.34mmol/g fiber, crystallinity 55.2%, and length is 44.7 μm, specific surface
Product 50.5m2/ 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 -0.07MPa, temperature 50 C, time 6.0h
Moisture content is dried under vacuum to less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 12.0wt%, and LiBr content is 3.0wt%, and DMF content is 85.0wt%.
(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 60g (concentration 3.0wt%), in temperature 70 C, dispersion revolving speed
High shear sulfonation is carried out under 12000rpm handles 80min.
(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 -0.09MPa, temperature
Degree is 40 DEG C, time 9.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 73.4%, sulfonation degree 1.19mmol/g fiber, crystallization
Degree 53.0%, length are 45.4 μm, specific surface area 50.2m2/g。
Prepared sulfonate fibers are used for the processing of leaded ion waste water, plumbum ion concentration 72.0mg/L, sulfonate fibers
Dosage is 2.5g/L, and the adsorption rate of lead ion is up to 98.1% after adsorption treatment 25min.
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, 35 DEG C of temperature, time 7.0h
Moisture content is dried under vacuum to less than 2.0wt%.
(2) 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -
The content of 3- methylimidazole villaumite is 14.5wt%, and LiBr content is 3.5wt%, and DMF content is 82.0wt%.
(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 50g (concentration 4.0wt%), in temperature 45 C, dispersion revolving speed
High shear sulfonation is carried out under 10000rpm handles 130min.
(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 30 DEG C, time 7.0h, dry after the completion up to target product.
Prepared fibrillation corn stover sulfonate fibers yield is 72.6%, sulfonation degree 1.41mmol/g fiber, crystallization
Degree 53.7%, length are 42.9 μm, specific surface area 52.3m2/g。
Embodiment 5
Routine prepares sulfonate fibers method, and corn stalk powder is broken into 20 mesh grass meal below, in vacuum degree -0.09MPa,
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
60g (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 100g (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-LiBr
Solvent, the content of 1- butyl -3- methylimidazole villaumite are 97.0wt%, and LiBr content is 3.0wt%.1.5g/g corn stalk is added
The chlorosulfonic acid of stalk, corn stover 40g (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 72.8%, sulfonation degree 0.36mmol/g fiber, crystallization
Degree 48.2%, length are 262.1 μm, specific surface area 9.2m2/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 90g (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。
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-LiBr-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 8.0h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 9.0wt%, and LiBr content is 2.0wt%, and DMF content is 89.0wt%；
(3) high shear sulfonation processing is carried out in dicyandiamide solution, and the sulfur trioxide pyridine complex of 1.4g/g corn stover is added,
No. CAS are as follows: 26412-87-3 is added corn stover 40g, makes its concentration 6.0wt%, in 30 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 10.0h, dry after the completion up to target product.
2. a kind of method that 1- butyl -3- methylimidazole villaumite-LiBr-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, temperature 45 C, time 7.5h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 4.5wt%, and LiBr content is 1.5wt%, and DMF content is 94.0wt%；
(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 7.0wt%, in temperature 60 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 -0.085MPa, temperature
It is 35 DEG C, time 8.0h, it is dry after the completion up to target product.
3. a kind of method that 1- butyl -3- methylimidazole villaumite-LiBr-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 6.0h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 12.0wt%, and LiBr content is 3.0wt%, and DMF content is 85.0wt%；
(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 60g, makes its concentration 3.0wt%, in temperature 70 C, dispersion revolving speed
High shear sulfonation is carried out under 12000rpm handles 80min；
(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 -0.09MPa, and temperature is
It is 40 DEG C, time 9.0h, dry after the completion up to target product.
4. a kind of method that 1- butyl -3- methylimidazole villaumite-LiBr-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, 35 DEG C of temperature, time 7.0h vacuum
Drying to moisture content is less than 2.0wt%；
(2) 1- butyl -3- methylimidazole villaumite-LiBr-DMF composite solvent system is prepared, solvent group becomes: 1- butyl -3- first
The content of base imidazoles villaumite is 14.5wt%, and LiBr content is 3.5wt%, and DMF content is 82.0wt%；
(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 50g, makes its concentration 4.0wt%, in temperature 45 C, dispersion revolving speed
High shear sulfonation is carried out under 10000rpm handles 130min；
(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 30 DEG C, time 7.0h, it is dry after the completion up to target product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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