CN102161781B - Modified chitosan material capable of absorbing heavy metal ions and preparation method thereof - Google Patents
Modified chitosan material capable of absorbing heavy metal ions and preparation method thereof Download PDFInfo
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- CN102161781B CN102161781B CN2011100423182A CN201110042318A CN102161781B CN 102161781 B CN102161781 B CN 102161781B CN 2011100423182 A CN2011100423182 A CN 2011100423182A CN 201110042318 A CN201110042318 A CN 201110042318A CN 102161781 B CN102161781 B CN 102161781B
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Abstract
The invention discloses a modified chitosan material capable of absorbing heavy metal ions and a preparation method thereof. The modified chitosan material is prepared by a method comprising: dissolving the chitosan and sodium alga acid in water respectively to prepare chitosan solution at a concentration of 1.5 mass percent and sodium alga acid solution at a concentration of 2 mass percent; mixing the chitosan solution and sodium alga acid solution uniformly according to a mass ratio of the chitosan and the sodium alga acid of (8-10):1 under a room temperature condition, and dripping calcium chloride solution at a concentration of 1.5 mass percent according to a solid to liquid ratio of the sodium alga acid to the calcium chloride solution of 1:37 with stirring; fully stirring after dripping is finished; regulating the pH value of the solution to 7.2+-0.2 till solid floccules appear; standing till solid gel appears; and filtering, and drying the gel at 35 DEG C to obtain the modified chitosan material.
Description
Technical field:
The present invention relates to material of a kind of Adsorption of Heavy Metal Ions and preparation method thereof, be specifically related to modified chitosan material of a kind of good to heavy metal ion adsorbed performance in the seawater medium, good stability and preparation method thereof.
Background technology:
Chitosan has another name called chitin, glycosaminoglycan, chitose etc., is a kind of natural polymer straight-chain polysaccharide, is chitin hydrolysis and slough the verivate that generates behind the part ethanoyl under alkaline condition.Occurring in nature, chitin are that the nature reserves are only second to cellulosic second largest organic resource, thereby the chitosan source is abundant.Chitosan can form similar cancellated cage type molecule by hydrogen bond and ionic linkage, and heavy metal ion is had stronger adsorptive power, receives much concern as the heavy metal sorbing material in recent years.Chitosan is as the waste of sea-food processing industry, though abundant as the sorbent material source, high adsorption capacity influenced greatly by the pH value, and selectivity ratios is relatively poor.Mostly the study on the modification of the heavy metal of chitosan absorption at present is at the fresh water medium, the study on the modification (preparation and the performance that comprise modified absorbing material) of Shang Weijian chitosan absorption heavy metal in polyhalide water body (like seawater).
Sodium-alginate is the sodium salt of a kind of polyanionic polysaccharide (Lalgine) of from the sea-tangle of phaeophyta or sargassun, extracting, is a kind of in the Lalgine verivate, also claims sodium alginate or seaweed gel and seaweed gel sometimes.But it is very big that some physico-chemical properties of sodium-alginate are influenced by the pH value.The pH value is lower than at 6 o'clock and separates out Lalgine, and is water insoluble; The pH value is higher than at 11 o'clock and condenses again.Viscosity is 7 o'clock maximums in the pH value, but significantly descends with the rising of temperature.
The develop rapidly of mariculture industry has brought bigger income for the human lives, but the heavy metal contamination of seawater self makes heavy metals exceeding standard in the sea-food of sea farming, and mariculture industry has received bigger influence.Research shows that the amino in chitosan and its molecule of verivate thereof can form the stable chelated key with amino adjacent hydroxyl and many heavy metals; Many materials there is the chelating adsorption, thereby has good economic benefits and environmental benefit in the environmental improvement field as environmentally friendly sorbing material.
Summary of the invention:
The object of the present invention is to provide a kind of can be in briny environment Adsorption of Heavy Metal Ions, and adsorptive power is strong, absorption stability better, be convenient to use, environmentally friendly sorbing material-modified chitosan material and preparation method thereof.
The modified chitosan material of Adsorption of Heavy Metal Ions of the present invention, through following method preparation, this method may further comprise the steps:
Chitosan and sodium-alginate is soluble in water respectively, be mixed with massfraction and be 1.5% chitosan solution and 2% sodium alginate soln, under the room temperature condition; Mass ratio according to chitosan and sodium-alginate is 8～10: 1, and chitosan solution and sodium alginate soln are mixed, and adds massfraction again and be 1.5% calcium chloride solution; Its add-on is 1: 37 for the solid-to-liquid ratio by sodium-alginate and calcium chloride solution, stirs while dripping, and is added dropwise to complete and fully stirs; Regulator solution pH value is 7.2 ± 0.2, wait to occur the solid floss after, leave standstill to solid gel and after-filtration occurs; 35 ℃ of oven dry of gel obtain the modified chitosan material.
The mass ratio of described chitosan and sodium-alginate is preferably 10: 1.
The present invention utilizes chitosan and sodium-alginate to carry out the crosslinked modified chitosan material for preparing by a certain percentage; (massfraction of NaCl is about 23% to this modified chitosan material at simulated seawater; The pH value is about 7.5) to heavy metal ion as: the absorption property of Cd, Cu, Pb and Zn is good; Stability is strong; Simultaneously the chitosan material after the modification can exist with colloidal solid so that comparatively stable porous is cotton-shaped in massfraction is 23% NaCl solution, thereby the modified chitosan material after the Adsorption of Heavy Metal Ions is easy to from water body, reclaim and handle.Thereby modified chitosan material of the present invention heavy metal contamination improvement field in mudflat aquaculture seawater and cage culture seawater has broad application prospects.And modified chitosan material prepn reaction conditions of the present invention is gentle, preparation is simple, only needs commercially available chitosan, sodium-alginate and calcium chloride in the preparation process, need not to use organic reagent; Chitosan and sodium-alginate all are the environmental protection polymers simultaneously; The source is abundant, and price economy is nontoxic, harmless; Have good bio-compatibility, and biodegradable.
Description of drawings:
Fig. 1 is the electronic microscope photos shape appearance figure of former chitosan A and modified chitosan C;
Fig. 2 is the former chitosan A absorption synoptic diagram of counterweight Metal Ions Cd, Cu, Pb and Zn respectively;
Fig. 3 is the modified chitosan B absorption synoptic diagram of counterweight Metal Ions Cd, Cu, Pb and Zn respectively;
Fig. 4 is the modified chitosan C absorption synoptic diagram of counterweight Metal Ions Cd, Cu, Pb and Zn respectively;
Fig. 5 is the desorption efficiency synoptic diagram of former chitosan A the heavy metal ion Cd, Cu, Pb and the Zn that adsorb respectively;
Fig. 6 is the desorption efficiency synoptic diagram of modified chitosan B the heavy metal ion Cd, Cu, Pb and the Zn that adsorb respectively;
Fig. 7 is the desorption efficiency synoptic diagram of modified chitosan C the heavy metal ion Cd, Cu, Pb and the Zn that adsorb respectively.
Embodiment:
Below be to further specify to of the present invention, rather than limitation of the present invention.
The chitosan that relates in following examples and the Comparative Examples is available from Chemical Reagent Co., Ltd., Sinopharm Group, and its article No. is 69047438; Sodium-alginate is available from Aladdin, and its article No. is 1127954.
Comparative Examples:
Get the 30g chitosan and be dissolved in the 2L water, filter, 35 ℃ of oven dry of filter residue obtain former chitosan A.
Embodiment 1:
Under the room temperature condition, get 24g chitosan and 3g sodium-alginate respectively and be dissolved in 1.6L and the 150mL water, again sodium alginate soln is joined in the chitosan solution, after mixing; The massfraction that slowly adds 111mL is 1.5% calcium chloride solution, stirs while dripping, and is added dropwise to complete and fully stirs; Dilute NaOH solution regulator solution pH value is 7.2 ± 0.2, wait to occur the solid floss after, leave standstill to solid gel and occur; Filter then, 35 ℃ of oven dry of gel obtain modified chitosan B.
Embodiment 2:
Under the room temperature condition, get 30g chitosan and 3g sodium-alginate respectively and be dissolved in 2L and the 150mL water, again sodium alginate soln is joined in the chitosan solution, after mixing; The massfraction that slowly adds 111mL is 1.5% calcium chloride solution, stirs while dripping, and is added dropwise to complete and fully stirs; Dilute NaOH solution regulator solution pH value is 7.2, wait to occur the solid floss after, leave standstill to solid gel and occur; Filter then, 35 ℃ of oven dry of gel obtain modified chitosan C.
The effect experiment:
One, former chitosan A and modified chitosan C are carried out electron-microscope scanning, its result is as shown in Figure 1, and as can be seen from Figure 1, more former chitosan A is tight for modified chitosan C crosslinking degree, and demonstrates vesicular structure, is beneficial to the absorption to heavy metal ion.
Two, modified chitosan B and C being placed massfraction respectively is 23% NaCl solution; Modified chitosan B and C can exist in the NaCl solution with colloidal form so that stable porous is cotton-shaped, so are convenient to the recovery and the processing of the modified chitosan material after the Adsorption of Heavy Metal Ions.
Three, adsorption experiment:
The massfraction of getting nearly 40mL respectively is that 23% sodium chloride solution is in the 50mL centrifuge tube; The heavy metal mark liquid (Cd, Cu, Pb and Zn) that adds the different amounts of different sorts respectively; Make the every heavy metal species ion starting point concentration gradient in the solution be all 0.125mmol/L, 0.375mmol/L, 0.750mmol/L, 1.500mmol/L, 2.500mmol/L; 5 concentration gradients of 4 heavy metal species, totally 20 centrifuge tubes.
Take by weighing the former chitosan A of 1g respectively in above-mentioned centrifuge tube, dilute NaOH solution regulates separately that the pH value is 7.5 ± 0.2, is settled to 40mL with high purity water, and making the solution salinity is 23%.Cyclotron oscillation 5h reaches adsorption equilibrium on vibrator, and is centrifugal, gets residue in 40 ℃ of oven dry, obtains the chitosan material A-J after the adsorption equilibrium, and wherein A-J comprises the chitosan material after the adsorption equilibrium under the different heavy metal ion different concns.
According to the method described above; Change former chitosan A into modified chitosan B and modified chitosan C respectively; Carry out adsorption experiment; Obtain modified chitosan material B-J and C-J after the adsorption equilibrium respectively, these modified chitosan materials comprise the modified chitosan material after the adsorption equilibrium under the different heavy metal ion different concns.
Respectively A-J, B-J and C-J series are cleared up with nitric acid, AAS measures.
The present invention is with heavy metal ion in above-mentioned protoconch glycan A, modified chitosan B and the C adsorbing seawater simulation medium; Add flowing of slight cyclotron oscillation simulated seawater again; The result is like Fig. 2, shown in 3 and 4: on the one hand; The result shows that in the starting point concentration scope of 0.125mmol/L～2.500mmol/L, modified chitosan is 38.4%～65.6% to the adsorption rate of Cd in the high salinity solution; Adsorption rate to Cu in the solution is 57.3%～98.4%; Adsorption rate to Pb in the solution is 26.5%～54.6%; Adsorption rate to Zn in the solution is 45.3%～83.4%.Chitosan and modified chitosan (B and C) are bigger to the less Cu loading capacity of ionic radius, and be less to the Pb loading capacity that ionic radius is bigger.On the other hand, the result shows that at each starting point concentration, modified chitosan is big to the more former chitosan of the adsorptive capacity of heavy metal, and adsorption rate all increases.With regard to Cd, the adsorption rate of modified chitosan improves 4.0%～19%; With regard to Cu, the adsorption rate of modified chitosan improves 4.5%～14.4%; With regard to Pb, the adsorption rate of modified chitosan improves 2.8%～9.9%; With regard to Zn, the adsorption rate of modified chitosan improves 2.4%～27.9% respectively.
Four, stability experiment:
Getting 2g respectively is the condition of the 0.750mmol/L former chitosan A that is issued to adsorption equilibrium in the 40mL massfraction is 23% sodium chloride solution at the starting point concentration of heavy metal ion Cd, Cu, Pb and Zn, and adjust pH is 7.5 ± 0.2.Cyclotron oscillation on vibrator.Took out at first day, the 5th day, the tenth day, the 15 day respectively, centrifugal, remove supernatant, 40 ℃ of oven dry obtain the chitosan A-D after the desorb
1d, A-D
5d, A-D
10d, A-D
15d
Get respectively 2g the starting point concentration of heavy metal ion Cd, Cu, Pb and Zn be the condition of 0.750mmol/L be issued to adsorption equilibrium modified chitosan B and C respectively according to the working method of above-mentioned former chitosan A, obtain the modified chitosan B-D after the desorb
1d, B-D
5d, B-D
10d, B-D
15dC-D
1d, C-D
5d, C-D
10d, C-D
15d
A-D, B-D and C-D series are cleared up with nitric acid respectively, and AAS measures, with the desorption efficiency in the sea water simulation medium after the former chitosan A of computes, modified chitosan B and the C adsorption equilibrium.
The present invention investigates counterweight metal adsorption stability in the sea water simulation medium with the desorption efficiency of above-mentioned former chitosan A, modified chitosan B and C; Its result is like Fig. 5, shown in 6 and 7: on the one hand; The result shows that heavy metal Cd, Cu, Pb and Zn desorption efficiency increased in the sorbing material with interior increase along with desorption time in preceding 10 days in the polyhalide water body medium; And after the 15th day desorption efficiency reduce rapidly, heavy metal ion is chitosan material absorption again.On the other hand, the result shows that with regard to Cd, Cu, Pb and Zn, the last heavy metal desorption efficiency of the more former chitosan A of desorption efficiency of the last absorption of modified chitosan B and C heavy metal is low, and (for Cd, modified chitosan C compares former chitosan A low 10%～48%; For Cu, low 0～30%; For Pb, low 7%～37%; For Zn, low 0～39%), modified chitosan counterweight metal adsorption stability is better.Take all factors into consideration adsorptive power and stability and economic angle (the sodium-alginate price is more expensive), modified chitosan C is best to the absorption property of Cd, Cu and Zn in the polyhalide water body medium.Be chitosan and sodium-alginate are suitable for heavy metal ion in the breeding seawater class polyhalide water body in the crosslinked modified chitosan that obtains of 10: 1 ratio of mass ratio absorption and removal.
Claims (3)
1. a method for preparing the modified chitosan material of Adsorption of Heavy Metal Ions is characterized in that this method may further comprise the steps: chitosan and sodium-alginate is soluble in water respectively; Being mixed with massfraction and being 1.5% chitosan solution and 2% sodium alginate soln, under the room temperature condition, is 8～10: 1 according to the mass ratio of chitosan and sodium-alginate; Chitosan solution and sodium alginate soln are mixed, add massfraction again and be 1.5% calcium chloride solution, its add-on is 1 for the solid-to-liquid ratio by sodium-alginate and calcium chloride solution: 37g/ml; Stir while dripping, be added dropwise to complete and fully stir, regulator solution pH value is 7.2 ± 0.2; After waiting to occur the solid floss; Leave standstill to solid gel and after-filtration occurs, 35 ℃ of oven dry of gel obtain the modified chitosan material.
2. the method for the modified chitosan material of preparation Adsorption of Heavy Metal Ions according to claim 1 is characterized in that, the mass ratio of described chitosan and sodium-alginate is 10: 1.
3. modified chitosan material for preparing according to the method for the modified chitosan material of the described preparation Adsorption of Heavy Metal Ions of claim 1.
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Application publication date: 20110824 Assignee: GDZC FOODS AND COSMETICS SAFETY TESTING CENTER CO., LTD. Assignor: China Guangzhou Analysis &. Test Center Contract record no.: 2015440000342 Denomination of invention: Modified chitosan material capable of absorbing heavy metal ions and preparation method thereof Granted publication date: 20120711 License type: Exclusive License Record date: 20150626 |
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Address after: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee after: Institute of testing and analysis, Guangdong Academy of Sciences (Guangzhou analysis and testing center, China) Address before: 510070 Building No. 34, compound 100, martyrs Road, Guangzhou, Guangdong Patentee before: GUANGDONG INSTITUTE OF ANALYSIS (CHINA NATIONAL ANALYTICAL CENTER, GUANGZHOU) |