CN103566904B - A kind of cellulose-chitosan compound and preparation method thereof - Google Patents
A kind of cellulose-chitosan compound and preparation method thereof Download PDFInfo
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- CN103566904B CN103566904B CN201310486515.2A CN201310486515A CN103566904B CN 103566904 B CN103566904 B CN 103566904B CN 201310486515 A CN201310486515 A CN 201310486515A CN 103566904 B CN103566904 B CN 103566904B
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- cellulose
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- ethylenediamine
- shitosan
- potassium rhodanide
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Abstract
The invention discloses a kind of cellulose-chitosan compound and preparation method thereof.This polysaccharide biomass resource utilizing cellulose and shitosan these two kinds source quite to enrich, obtained cellulose-chitosan compound in this novel dicyandiamide solution of ethylenediamine/potassium rhodanide, this compound heavy metal ion Cu
2+, Pb
2+and Cd
2+deng all there is stronger adsorption capacity.Solvent ethylenediamine/potassium rhodanide that the present invention adopts is cheap, and can recycle, and reduces the pollution to environment.
Description
Technical field
The invention belongs to field of polymer composite material, relate to a kind of cellulose-chitosan compound and preparation method thereof.
Background technology
Along with science and technology, economic developing rapidly, the living standard of the people is greatly improved, but fast development has also caused a series of environmental problem, and heavy metal pollution is one of them.Heavy metal can not be degraded by microorganisms, and can enrichment get up to cause water pollution in water body, and harm humans is healthy.As lead directly can injure the brain cell of human body, the especially nervous system of fetus, can cause the congenital feeblemindedness of fetus.At present, the method for the process effluent containing heavy metal ions generally adopted has: chemical precipitation method, active carbon adsorption, ion-exchange, membrane filter method, reverse osmosis method, liquid phase extraction process, and biomass-based absorption method etc.Absorption method wherein based on living beings has many advantages, as biomass material abundance, cheap, and can constantly regenerate with biodegradable.
Cellulose (cellulose) in living beings and chitin (chitin) are the more rich polysaccharide macromolecular materials of occurring in nature content.Cellulose is the main component of plant cell wall, is also a kind of polysaccharide biomass material that occurring in nature distribution is the widest, content is maximum.Next is chitin, and it is extensively present in the shell of shellfish, the cell membrane of fungi and some green algas such as shrimp, crab, insect.To obtaining shitosan (chitosan) after chitin deacetylase base.Research shows that shitosan heavy metal ion has certain absorption affinity, and cellulose-chitosan complex system is stronger compared to shitosan Adsorption of Heavy Metals ability, the heavy metal ion in the more effective removal waste water of energy.But the hydrogen bond network structure of native cellulose and shitosan makes that the strand of cellulose and shitosan is arranged together closely becomes crystal region, so cellulose and shitosan can not by water or most organic solvent dissolutions.Along with going deep into of research, it is found that formic acid, acetic acid, lactic acid equal solvent can dissolve shitosan, but cellulose is easily hydrolyzed in acid condition, can not form compound system with shitosan.According to bibliographical information, available ions liquid B MIMCl (1-butyl-3-methylimidazolium chloride) is as solvent, the mode of microwave pulse dissolving cellulos-shitosan is utilized to obtain the compound of cellulose-shitosan, and for adsorbing Pb
2+, Cu
2+, Zn
2+, Ni
2+etc. contents of many kinds of heavy metal ion.But ionic liquid price is higher, and easily there is cracking in cellulose and shitosan under microwave pulse effect, thus produce adverse influence to the absorption property of compound.
Summary of the invention
The present invention is intended to the polysaccharide biomass resource utilizing cellulose and shitosan these two kinds source quite to enrich, and prepares the compound of cellulose and shitosan in a kind of novel dicyandiamide solution (ethylenediamine/potassium rhodanide), and for removing the Cu in waste water
2+, Pb
2+and Cd
2+etc. heavy metal ion.
The object of the present invention is to provide a kind of cellulose-chitosan compound.
Another object of the present invention is to the preparation method that a kind of cellulose-chitosan compound is provided.
The technical solution used in the present invention is:
A kind of cellulose-chitosan compound, its preparation method comprises the following steps:
1) be dissolved in ethylenediamine by potassium rhodanide, wherein the weight ratio of potassium rhodanide and ethylenediamine is (1 ︰ 4) ~ (3 ︰ 7), dissolves completely, obtains the ethylenediamine solution of potassium rhodanide;
2) ethylenediamine solution of potassium rhodanide is divided into two parts, adds cellulose powder and Chitosan powder respectively, respectively the dispersion of obtained cellulose solution and chitosan-containing, wherein the mass concentration of cellulose and shitosan is independently 1 ~ 5%;
3) by the dispersion of cellulose solution and chitosan-containing in mass ratio (1 ~ 4): 1 mixes, and utilizes dry-jet wet spinning technique, the compound of obtained cellulose-shitosan, then dry.
Further, step 2) in, before adding cellulose powder and Chitosan powder, first the ethylenediamine solution of potassium rhodanide is cooled to-10 DEG C ~-20 DEG C.
Further, the coagulating bath of the technique of dry-jet wet spinning described in step 3) is selected from methyl alcohol, acetone and water.
Further, drying described in step 3) comprises vacuum freezedrying, room temperature and naturally dries or 50 DEG C of oven dry.
The invention has the beneficial effects as follows:
Cellulose-chitosan compound heavy metal ion Cu prepared by the present invention
2+, Pb
2+and Cd
2+deng all, there is stronger adsorption capacity, significantly improve effective utilization of cellulose and these two kinds of biomass resources of shitosan.
In the present invention, the preparation flow of cellulose-chitosan compound is simple, and ethylenediamine/potassium rhodanide solvent is cheap, and cost is low, and can recycle, and reduces the pollution to environment, inexpensive, the easy and environmental protection of visible the present invention.
Detailed description of the invention
A kind of cellulose-chitosan compound, its preparation method comprises the following steps:
1) be dissolved in ethylenediamine by potassium rhodanide, wherein the weight ratio of potassium rhodanide and ethylenediamine is (1 ︰ 4) ~ (3 ︰ 7), dissolves completely, obtains the ethylenediamine solution of potassium rhodanide;
2) ethylenediamine solution of potassium rhodanide is divided into two parts, adds cellulose powder and Chitosan powder respectively, respectively the dispersion of obtained cellulose solution and chitosan-containing, wherein the mass concentration of cellulose and shitosan is independently 1 ~ 5%;
3) by the dispersion of cellulose solution and chitosan-containing in mass ratio (1 ~ 4): 1 mixes, and utilizes dry-jet wet spinning technique, the compound of obtained cellulose-shitosan, then dry.
Step 2) in, before adding cellulose powder and Chitosan powder, first the ethylenediamine solution of potassium rhodanide is cooled to-10 DEG C ~-20 DEG C, with the solubility of the ethylenediamine solution improving potassium rhodanide to cellulose and shitosan.
The technique of dry-jet wet spinning described in step 3) particular methanol, acetone or water are as coagulating bath.
Described in step 3), dry preferably vacuum freezedrying, room temperature are dried or 50 DEG C of oven dry naturally.
Below in conjunction with specific embodiment, the invention will be further described, but be not limited thereto.
embodiment 1:
1) be dissolved in ethylenediamine by potassium rhodanide, wherein the weight ratio of potassium rhodanide and ethylenediamine is 1 ︰ 4, dissolves completely;
2) ethylenediamine solution of potassium rhodanide is divided into two parts, and is refrigerated to-10 DEG C, then add cellulose powder and Chitosan powder respectively, respectively the dispersion of obtained cellulose solution and chitosan-containing, wherein the mass concentration of cellulose and shitosan is 1%.
3) by the dispersion of cellulose solution and chitosan-containing in mass ratio 2 ︰ 1 mix, utilize dry-jet wet spinning technique, using water as coagulating bath, the compound of obtained cellulose-shitosan, then 50 DEG C of oven dry.
embodiment 2:
1) be dissolved in ethylenediamine by potassium rhodanide, wherein the weight ratio of potassium rhodanide and ethylenediamine is 3 ︰ 7, dissolves completely;
2) ethylenediamine solution of potassium rhodanide is divided into two parts, and is refrigerated to-19 DEG C, then add cellulose powder and Chitosan powder respectively, respectively the dispersion of obtained cellulose solution and chitosan-containing, wherein the mass concentration of cellulose and shitosan is 4.8%.
3) by the dispersion of cellulose solution and chitosan-containing in mass ratio 1 ︰ 1 mix, utilize dry-jet wet spinning technique, using methyl alcohol as coagulating bath, the compound of obtained cellulose-shitosan, then vacuum freezedrying.
embodiment 3:
1) be dissolved in ethylenediamine by potassium rhodanide, wherein the weight ratio of potassium rhodanide and ethylenediamine is 1 ︰ 3, dissolves completely;
2) ethylenediamine solution of potassium rhodanide is divided into two parts, and is refrigerated to-19 DEG C, then add cellulose powder and Chitosan powder respectively, respectively the dispersion of obtained cellulose solution and chitosan-containing, wherein the mass concentration of cellulose and shitosan is 4%.
3) by the dispersion of cellulose solution and chitosan-containing in mass ratio 4 ︰ 1 mix, utilize dry-jet wet spinning technique, using methyl alcohol as coagulating bath, the compound of obtained cellulose-shitosan, then room temperature is dried naturally.
Further effect detection is done to the cellulose-chitosan compound prepared in embodiment below.
heavy metal ion adsorbed experiment
The cellulose-chitosan compound of preparation in above-described embodiment 2 is carried out heavy metal ion adsorbed detection.
1) Cu is prepared respectively
2+, Cd
2+, Pb
2+heavy metal ion solution, its initial concentration is 200 mg/L, measures the concentration of heavy metal ion solution before absorption with Atomic Absorption Spectrometer (ComntrAA700, Germany).
2) the cellulose-chitosan compound 20mg taking in embodiment 2 preparation joins 10mL concentration respectively and is 200 mg/L(pH5) Pb
2+, Cd
2+, Cu
2+in heavy metal ion solution, each group is tested and is all at room temperature placed 24 hours, measures the concentration of the rear heavy metal ion solution of absorption with Atomic Absorption Spectrometer (ComntrAA700, Germany).
3) each group of dimension element/chitosan complexes is calculated to Pb
2+, Cd
2+, Cu
2+adsorbance, result of calculation is as shown in table 1.
In order to compare prepared by cellulose-chitosan compound prepared by the present invention and existing additive method the adsorption capacity of cellulose-chitosan compound heavy metal ion, choose the ability of cellulose-chitosan compound Adsorption of Heavy Metal Ions prepared by existing two kinds of additive methods as a control group (see table 1), the cellulose-chitosan compound of two groups of control groups cited in table 1 all adopts ［ Bmim ］ Cl ionic liquid as solvent in preparation process, wherein the cellulose-chitosan compound of control group 1 is derived from Sun. X, Peng. B, Ji. W, Chen. Ji, Li. D. Chitosan (Chitin)/cellulose composite biosorbents prepared using ionic liquid for heavy metal ions adsorption. AIChE Journal, 2009, 55, 2062 – 2069, the cellulose-chitosan compound of control group 2 is derived from Liu. Z, Wang. H, Liu. C, Jiang. Y, Yu. G, Mu. X, Wang. X. Magnetic cellulose-chitosan hydrogels prepared from ionic liquids as reusable adsorbent for removal of heavy metal ions. Chem. Commun, 2012, 48, 7350-7352.
Can know from the data of table 1, the cellulose-chitosan compound of embodiment 2 is to Pb
2+, Cd
2+, Cu
2+adsorbance respectively at about 32.39 mg/g, 31.02mg/g, 33.89mg/g.Compared with the cellulose-chitosan compound prepared with additive method, the cellulose-chitosan compound of embodiment is to Pb
2+the adsorbance of ion all higher than control group 1 and 2, to Cu
2+the adsorbance of ion is lower than control group 2 but higher than control group 1, and the present invention is to Cd
2+ion also has higher adsorbance.Above-mentioned experimental result illustrates that cellulose-chitosan compound prepared by the present invention is to Pb
2+, Cu
2+, Cd
2+all there is higher adsorption capacity.
The adsorption capacity of cellulose-chitosan compound heavy metal ion prepared by table 1 different solvents system
Claims (3)
1. a preparation method for cellulose-chitosan compound, comprises the following steps:
1) be dissolved in ethylenediamine by potassium rhodanide, wherein the weight ratio of potassium rhodanide and ethylenediamine is (1 ︰ 4) ~ (3 ︰ 7), dissolves completely, obtains the ethylenediamine solution of potassium rhodanide;
2) ethylenediamine solution of potassium rhodanide is cooled to-10 DEG C ~-20 DEG C, be divided into two parts, add cellulose powder and Chitosan powder respectively, respectively the dispersion of obtained cellulose solution and chitosan-containing, wherein the mass concentration of cellulose and shitosan is independently 1 ~ 5%;
3) by the dispersion of cellulose solution and chitosan-containing in mass ratio (1 ~ 4): 1 mixes, and utilizes dry-jet wet spinning technique, the compound of obtained cellulose-shitosan, then dry.
2. the preparation method of a kind of cellulose-chitosan compound according to claim 1, is characterized in that: the coagulating bath of the technique of dry-jet wet spinning described in step 3) is selected from methyl alcohol, acetone and water.
3. the preparation method of a kind of cellulose-chitosan compound according to claim 1, is characterized in that: drying described in step 3) comprises vacuum freezedrying, room temperature and naturally dries or 50 DEG C of oven dry.
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| US11118308B2 (en) | 2013-03-15 | 2021-09-14 | Ip2Ipo Innovations Limited | Treatment of lignocellulosic biomass with ionic liquid |
| GB201520453D0 (en) * | 2015-11-20 | 2016-01-06 | Imp Innovations Ltd | Process |
| CN106861628B (en) * | 2017-01-22 | 2020-09-15 | 青岛科技大学 | Preparation of carboxymethyl chitosan-shell particle composite fiber and use method for adsorbing paralytic shellfish toxin |
| CN112641704A (en) * | 2020-12-31 | 2021-04-13 | 重庆知翔科技有限公司 | Moisturizing composition and preparation method thereof |
| CN115155538A (en) * | 2022-08-12 | 2022-10-11 | 扬州工业职业技术学院 | Process for extracting heavy metal ions in sewage |
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| CN1467248A (en) * | 2002-06-19 | 2004-01-14 | 独立行政法人农业生物资源研究所 | Biodegradable biopolymers, method for their preparation and functional materials constituted by these biopolymers |
| CN101274268A (en) * | 2007-12-29 | 2008-10-01 | 中国科学院长春应用化学研究所 | Biological adsorbing agent with adsorption capacity of heavy metal ion, and producing method and application thereof |
| CN101864089A (en) * | 2010-06-10 | 2010-10-20 | 武汉大学 | Method for preparing cellulose/chitin blending film |
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Patent Citations (3)
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| CN1467248A (en) * | 2002-06-19 | 2004-01-14 | 独立行政法人农业生物资源研究所 | Biodegradable biopolymers, method for their preparation and functional materials constituted by these biopolymers |
| CN101274268A (en) * | 2007-12-29 | 2008-10-01 | 中国科学院长春应用化学研究所 | Biological adsorbing agent with adsorption capacity of heavy metal ion, and producing method and application thereof |
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Address after: 510000 Zhujiang Road 1-2, Chaotian Industrial Zone, Shilou Town, Panyu District, Guangzhou, Guangdong Province Patentee after: Guangzhou fiber product detects research institute Address before: 510220, No. 35, No. two, Cao Fang Wai, Binjiang Road, Haizhuqu District, Guangdong, Guangzhou Patentee before: Guangzhou Fibre Product Testing Institute |