CN109054075A - A kind of preparation method of micro-structure and the controllable porous cellulose microballoon of size - Google Patents
A kind of preparation method of micro-structure and the controllable porous cellulose microballoon of size Download PDFInfo
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- CN109054075A CN109054075A CN201810635846.0A CN201810635846A CN109054075A CN 109054075 A CN109054075 A CN 109054075A CN 201810635846 A CN201810635846 A CN 201810635846A CN 109054075 A CN109054075 A CN 109054075A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
- C08J2201/0545—Precipitating the polymer by adding a non-solvent or a different solvent from an aqueous solvent-based polymer composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- Polymers & Plastics (AREA)
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- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention provides a kind of preparation methods of the controllable porous cellulose microballoon of micro-structure and size, belong to technical field of polymer materials.It solves the problems, such as that the prior art is costly there is preparing.This micro-structure and the preparation method of the controllable porous cellulose microballoon of size are the following steps are included: A, stock: preparing discarded cotton, urea and sodium hydroxide mixed solution, coagulating bath；B, it prepares cellulose solution: discarded cotton is shredded, then the discarded cotton shredded is put into urea and sodium hydroxide mixed solution, obtains cellulose solution；C, it forms: by cellulose solution cryogenic freezing, then the cellulose solution after freezing being shaken and be centrifuged through machinery, is then injected cellulose solution in coagulating bath, cellulose solution forms solid cellulose microsphere under the action of coagulating bath；D, it cleans: cellulose microsphere is washed with deionized water.It is low that this preparation method prepares expense.
Description
Technical field
The invention belongs to natural macromolecular material field, it is related to a kind of micro-structure and the controllable porous cellulose microballoon of size
Preparation method.
Background technique
Currently, water environment pollution has become the key subjects that countries in the world the Implement of sustainable development is faced, and weaves and print
The organic pollutant wastewaters such as the dyestuff that dye industry is discharged are one of them important pollution sources.According to incompletely statistics, the whole world
Dyestuff total output is more than 70 ten thousand tons, and main woven dyeing industry is consumed.And about 10% in the dyeing process of textile
~15% dyestuff is directly discharged to natural water.
Therefore, developing effective printing and dyeing industrial waste water processing technique is a highly important research topic.Industry at present
On generally use the organic contaminations such as physical-chemical processes and Biochemical method dyestuff such as absorption, ion exchange, film filtering, catalysis oxidation
Object.Wherein, absorption method is that a kind of application is more mature and effective pollutant effluents processing technique, is particularly suitable for difficult biochemistry
The decolorization of the dyeing waste water of degradation.
Cellulose is most abundant and reproducible natural polymer on the earth, as the function of raw material development environment close friend
Material is always a branch in materialogy field.It was noticed that containing a large amount of hydrophilies on linear fibre element molecular structure
Hydroxyl, expansion easy to moisture absorption have high affinity with the dye molecule of various structures type, such as direct dyes, insoluble azo
Dyestuff, reducing dye, sulfur dye and reactive dye etc..That is, cellulosic molecule is to dye molecule with more wide in range
Adsorption capacity, a plurality of types of dyestuffs may be implemented from liquid phase and be quickly transferred to cellulosic material surface and inside.
Currently, the hot spot that cellulose spherical adsorbent has become for Cellulose-based Adsorbents research, is widely used
In various aspects such as Food Science, separation engineering, biomedicine, biochemical industry environmental protections.
The preparation process of ball shaped cellulose is generally divided into dissolution, balling-up and solidification three phases, specifically: first by fiber
Solution (or molten condition) is made in element or derivatives thereof, is subsequently dispersed in specific dispersion liquid or decentralized medium and forms drop, connects
Get off and drop is solidified using different curing methods by balling-up according to cellulosic material property and SOLUTION PROPERTIES.However, traditional system
Preparation Method is directed to the course of dissolution of cellulose, and requires using organic solvent, prepare it is costly, at subsequent purification
Reason difficulty is big, different degrees of can all bring a negative impact to environment, be unfavorable for industrialized large-scale production.
In addition, current material, which is only confined in aqueous solution, adsorbs pollutant in terms of ball shaped cellulose absorption property,
Seldom it is related to the absorption to pollutant in organic solvent.
Summary of the invention
It is a kind of using cellulose fibre as original the purpose of the present invention is in view of the above-mentioned problems existing in the prior art, providing
Material, forms the new method of porous cellulose microballoon by coagulating bath.This method is using water as medium, and preparation process environmental protection is without dirt
Dye, and, form stable uniform according to this method formation porous cellulose microspherulite diameter, strong operability.
Object of the invention can be realized by the following technical scheme:
A kind of preparation method of micro-structure and the controllable porous cellulose microballoon of size, method includes the following steps:
A, it stocks up: preparing discarded cotton, urea and sodium hydroxide mixed solution, coagulating bath；
B, it prepares cellulose solution: discarded cotton is shredded, the discarded cotton shredded is then put into urea and hydroxide
In sodium mixed solution, cellulose solution is obtained；
C, it forms: by cellulose solution cryogenic freezing, then the cellulose solution after freezing being shaken and be centrifuged through machinery,
Then cellulose solution is injected in coagulating bath, cellulose solution forms solid cellulose microsphere under the action of coagulating bath；
D, it cleans: cellulose microsphere is washed with deionized water.
Lignin in discarded cotton, hemicellulose can be effectively removed under the action of urea and sodium hydroxide mixed solution
Element, remaining starch and pectin etc..
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, the cellulose solution
Concentration be 3%~4%.
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, by peristaltic pump and more
Root syringe needle, which instills cellulose solution in coagulating bath, to be solidified.
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, the coagulating bath is sulfuric acid
With the mixed solution of sodium sulphate.
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, sulfuric acid in the coagulating bath
Concentration be 0.5~2.5mol/L-1。
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, sulfuric acid in the coagulating bath
The mass ratio of sodium and sulfuric acid is 1:10.
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, the temperature of the coagulating bath
It is 0~45 DEG C.
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, the cellulose microsphere
Shape be spherical shape, specific surface area be 45~100m2/ g, 2~4mm of partial size.
In the preparation method of the controllable porous cellulose microballoon of above-mentioned micro-structure and size, the mechanical concussion is
Mechanical stirring or magnetic agitation, meanwhile, blender is placed on bumper together with the container equipped with cellulose solution and is shaken
It swings.
Compared with prior art, the present invention has the positive effect that:
(1) porous cellulose microballoon is prepared as raw material using discarded cotton, not only reduces manufacturing cost, and ring
It protects pollution-free.
(2) decentralized medium is not only reduced costs only with aqueous solution without organic solute, and has been truly realized green
Color is pollution-free.
(3) the porous cellulose Microsphere Size distribution prepared is uniform, and performance inconsistency is small to be not necessarily to subsequent processing, and yield
It can achieve 80% or more.
(4) the porous cellulose microballoon of different size difference micro-structures can be prepared by change condition.
(5) raw material sources of the invention are extensive, and room temperature can produce, and required equipment is simple and is common apparatus,
It is convenient for industrialization large-scale production.
Specific embodiment
Embodiment one
It by discarded drying cotton, weighs 3g sample and shreds, be immersed in urea/sodium hydroxide mixed solution that quality is 97g
In, cryogenic freezing 2h, mechanical concussion 0.5h, is centrifuged with the speed of 2000 turns/min, supernatant is then utilized wriggling after taking-up
Pump and 14G syringe needle instill 1mol/L-1Sulfuric acid, 4g sodium sulphate, 25 DEG C of coagulating bath, are finally washed with deionized water.
Absorbency Test: weighing a certain amount of porous cellulose microballoon, be put into 10ml sample bottle, and a certain concentration is added
Methylene blue solution its concentration is surveyed with ultraviolet spectrometer to filter after the velocity fluctuation 6h of 120 turns/min at 25 DEG C, lead to
It crosses standard curve and calculates adsorption rate.The mass ratio of sodium sulphate and sulfuric acid is 1:10 in coagulating bath
The shape of the cellulose microsphere finally obtained is spherical shape, specific surface area 45m2/ g, partial size 2mm.
Embodiment two
It by discarded drying cotton, weighs 4g sample and shreds, be immersed in urea/sodium hydroxide mixed solution that quality is 96g
In, cryogenic freezing 2h, mechanical concussion 0.5h, is centrifuged with the speed of 2000 turns/min, supernatant is then utilized wriggling after taking-up
Pump and 14G syringe needle instill 1mol/L-1Sulfuric acid, 4g sodium sulphate, 25 DEG C of coagulating bath, are finally washed with deionized water.
The shape of the cellulose microsphere finally obtained is spherical shape, specific surface area 100m2/ g, partial size 4mm.
Embodiment three
It by discarded drying cotton, weighs 3g sample and shreds, be immersed in urea/sodium hydroxide mixed solution that quality is 97g
In, cryogenic freezing 2h, mechanical concussion 0.5h, is centrifuged with the speed of 2000 turns/min, supernatant is then utilized wriggling after taking-up
Pump and 25G syringe needle instill 1mol/L-1Sulfuric acid, 4g sodium sulphate, 25 DEG C of coagulating bath, are finally washed with deionized water.
The shape of the cellulose microsphere finally obtained is spherical shape, specific surface area 54m2/ g, partial size 3mm.
Example IV
It by discarded drying cotton, weighs 3g sample and shreds, be immersed in urea/sodium hydroxide mixed solution that quality is 97g
In, cryogenic freezing 2h, mechanical concussion 0.5h, is centrifuged with the speed of 2000 turns/min, supernatant is then utilized wriggling after taking-up
Pump and 14G syringe needle instill 2mol/L-1Sulfuric acid, 4g sodium sulphate, 25 DEG C of coagulating bath, are finally washed with deionized water.
The shape of the cellulose microsphere finally obtained is spherical shape, specific surface area 60m2/ g, partial size 2mm.
Embodiment five
It by discarded drying cotton, weighs 3g sample and shreds, be immersed in urea/sodium hydroxide mixed solution that quality is 97g
In, cryogenic freezing 2h, mechanical concussion 0.5h, is centrifuged with the speed of 2000 turns/min, supernatant is then utilized wriggling after taking-up
Pump and 14G syringe needle instill 1mol/L-1Sulfuric acid, 8g sodium sulphate, 25 DEG C of coagulating bath, are finally washed with deionized water.
The shape of the cellulose microsphere finally obtained is spherical shape, specific surface area 71m2/ g, partial size 4mm.
Embodiment six
It by discarded drying cotton, weighs 3g sample and shreds, be immersed in urea/sodium hydroxide mixed solution that quality is 97g
In, cryogenic freezing 2h, mechanical concussion 0.5h, is centrifuged with the speed of 2000 turns/min, supernatant is then utilized wriggling after taking-up
Pump and 14G syringe needle instill 1mol/L-1Sulfuric acid, 4g sodium sulphate, 35 DEG C of coagulating bath, are finally washed with deionized water.
The shape of the cellulose microsphere finally obtained is spherical shape, specific surface area 66m2/ g, partial size 3mm.
Claims (9)
1. the preparation method of a kind of micro-structure and the controllable porous cellulose microballoon of size, method includes the following steps:
A, it stocks up: preparing discarded cotton, urea and sodium hydroxide mixed solution, coagulating bath；
B, it prepares cellulose solution: discarded cotton is shredded, the discarded cotton shredded is then put into urea and sodium hydroxide mixes
It closes in solution, obtains cellulose solution；
C, it forms: by cellulose solution cryogenic freezing, then the cellulose solution after freezing being shaken and be centrifuged through machinery, then
Cellulose solution is injected in coagulating bath, cellulose solution forms solid cellulose microsphere under the action of coagulating bath；
D, it cleans: cellulose microsphere is washed with deionized water.
2. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In the concentration of the cellulose solution is 3%~4%.
3. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In cellulose solution is instilled in coagulating bath by peristaltic pump and a plurality of needles head and is solidified.
4. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In the coagulating bath is the mixed solution of sulfuric acid and sodium sulphate.
5. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In the molar concentration of sulfuric acid is 0.5~2.5mol/L in the coagulating bath-1。
6. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In the mass ratio of sodium sulphate and sulfuric acid is 1:10 in the coagulating bath.
7. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In the temperature of the coagulating bath is 0~45 DEG C.
8. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In the shape of the cellulose microsphere is spherical shape, and specific surface area is 45~100m2/ g, 2~4mm of partial size.
9. the preparation method of micro-structure according to claim 1 and the controllable porous cellulose microballoon of size, feature exist
In, the described mechanical concussion be mechanical stirring or magnetic agitation, meanwhile, by blender together with the container that cellulose solution is housed
It is placed on bumper and is shaken.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810635846.0A CN109054075A (en) | 2018-06-20 | 2018-06-20 | A kind of preparation method of micro-structure and the controllable porous cellulose microballoon of size |
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| CN201810635846.0A CN109054075A (en) | 2018-06-20 | 2018-06-20 | A kind of preparation method of micro-structure and the controllable porous cellulose microballoon of size |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109837774A (en) * | 2019-02-27 | 2019-06-04 | 温州优巴信息技术有限公司 | An a kind of one-step dyeing method of the cotton blended fabric for the dyeing that porous cellulose is microsphere modified |
| CN112742314A (en) * | 2020-12-01 | 2021-05-04 | 浙江理工大学 | Preparation method of sea urchin-like cellulose microspheres |
| CN115975261A (en) * | 2021-10-15 | 2023-04-18 | 中国科学院化学研究所 | Cellulose-based microsphere based on metal salt and preparation method and application thereof |
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| JPH0457836A (en) * | 1990-06-27 | 1992-02-25 | Fukui Kagaku Kogyo Kk | Spherical porous cellulose particle comprising chitin or deacetylated chitin and cellulose, and preparation thereof |
| CN104327286A (en) * | 2014-11-20 | 2015-02-04 | 武汉工程大学 | Preparation method of cellulose peaberry |
| CN105713600A (en) * | 2016-03-21 | 2016-06-29 | 南京林业大学 | Preparing method of natural cellulose fluorescent microsphere |
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2018
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Patent Citations (3)
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|---|---|---|---|---|
| JPH0457836A (en) * | 1990-06-27 | 1992-02-25 | Fukui Kagaku Kogyo Kk | Spherical porous cellulose particle comprising chitin or deacetylated chitin and cellulose, and preparation thereof |
| CN104327286A (en) * | 2014-11-20 | 2015-02-04 | 武汉工程大学 | Preparation method of cellulose peaberry |
| CN105713600A (en) * | 2016-03-21 | 2016-06-29 | 南京林业大学 | Preparing method of natural cellulose fluorescent microsphere |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109837774A (en) * | 2019-02-27 | 2019-06-04 | 温州优巴信息技术有限公司 | An a kind of one-step dyeing method of the cotton blended fabric for the dyeing that porous cellulose is microsphere modified |
| CN109837774B (en) * | 2019-02-27 | 2021-09-14 | 淮安嘉德纺织有限公司 | One-step dyeing method of porous cellulose microsphere modified dyed cotton blended fabric |
| CN112742314A (en) * | 2020-12-01 | 2021-05-04 | 浙江理工大学 | Preparation method of sea urchin-like cellulose microspheres |
| CN112742314B (en) * | 2020-12-01 | 2023-03-14 | 浙江理工大学 | Preparation method of sea urchin-like cellulose microspheres |
| CN115975261A (en) * | 2021-10-15 | 2023-04-18 | 中国科学院化学研究所 | Cellulose-based microsphere based on metal salt and preparation method and application thereof |
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Application publication date: 20181221 |