CN100566818C - A kind of modified chitosan crosslinked resin that is used for removing fluor in water and preparation method thereof - Google Patents
A kind of modified chitosan crosslinked resin that is used for removing fluor in water and preparation method thereof Download PDFInfo
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- CN100566818C CN100566818C CNB200710185294XA CN200710185294A CN100566818C CN 100566818 C CN100566818 C CN 100566818C CN B200710185294X A CNB200710185294X A CN B200710185294XA CN 200710185294 A CN200710185294 A CN 200710185294A CN 100566818 C CN100566818 C CN 100566818C
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Abstract
A kind of modified chitosan crosslinked resin that is used for removing fluor in water is the iron modified chitosan crosslinked resin.Adopting the shitosan of high dehydration acetyl degree 〉=95% is raw material, is that modifier prepares the iron modified chitosan crosslinked resin with iron chloride.This resin is used for the removing fluor in water effect stability, and clearance can reach more than 80%, and is difficult for fragmentation, and regeneration is simple, and is with low cost.Not only can be used for industrial fluorinated water and handle, also be applicable to the processing of high-fluorine drinking water.
Description
Technical field
The present invention relates to resin, specifically belong to a kind of modified chitosan crosslinked resin that is used for removing fluor in water and preparation method thereof.
Background technology
China high fluorine lesion spreads all over 27 provinces, especially northwest, North Chinas and is widely distributed, and the whole nation has 7,700 ten thousand people to drink the underground water that fluorinated volume surpasses 1mg/L approximately, and fluorinated volume surpasses 5.0mg/L in wherein nearly 5,000,000 people's the drinking-water.According to statistics in 2002,1117 in national drinking water type fluorine poisoning lesion county, 117389 in lesion village, about 8,274 ten thousand people of compromised population, existing fluorine dental plaque patient 2,214 ten thousand people, fluorosis of bone patient 1,360,000 people.
Fluorinated water comprises fluorine-containing underground water and fluorine-containing trade effluent.Fluorine-containing underground water is widely distributed in China, and the fluorine in the water is mainly from the sedimentation of rock and ore or atmosphere fluorine.The fluorinated volume fluctuation range of natural water is very big, and low person is below 0.012mg/L, and Gao Zheke reaches 100mg/L.Fluorinated volume in the water is subjected to various natural conditions and artificial factor very big, mainly is subjected to the influence of fluorine content in the acid-base value of water and the regional stratum of flowing through.
The Drinking Water in China national standard is the following 1.0mg/L that is defined as of fluorine poisoning, and desirable fluorine content is 0.5～0.8mg/L.The general high fluorine of China's underground water nearly all greater than 1.0mg/L, therefore causes China's various types of beverages, pure water, drinking water all to carry out 1.0mg/L, is actually the slow poisoning scope that is in.
The method of removing fluor in water mainly contains absorption method, electrocoagulation, hyperfiltration, ion-exchange, chemical precipitation method and coagulation sedimentation etc., and wherein electrocoagulation and chemical precipitation method are applicable to the processing of various amounts of fluoride in drinking water.Form gelatinous precipitate by adding lime, calcium chloride or aluminide etc. with F-.The two is had relatively high expectations to the pH value of water quality in processing procedure, and electrocoagulation also exists the aluminium sheet electrode passivation, problem such as power consumption is big.Though hyperfiltration and ion-exchange can reach the purpose of defluorination, efficient is lower, lacks selectivity.Because the cost of absorption method is lower, and defluorination effect is better, so be the important method that fluoride waste is handled always.Utilize chitosan crosslinked resin to handle waste water, be mainly used in the removal of heavy metal ions in wastewater, still do not have and utilize it to carry out the application of removing fluor in water.
Summary of the invention
The object of the present invention is to provide that a kind of adsorption effect is stable, with low cost, regeneration simply can be used in modified chitosan crosslinked resin of removing fluor in water and preparation method thereof.
A kind of modified chitosan crosslinked resin that is used for removing fluor in water provided by the invention, it is the iron modified chitosan crosslinked resin.
A kind of preparation method who is used for the modified chitosan crosslinked resin of removing fluor in water provided by the invention comprises the steps:
(1) shitosan and acetic acid are mixed according to mass ratio 1: 23～25, be mixed with shitosan acetic acid colloidal sol, shitosan acetic acid colloidal sol mixes according to volume ratio 1: 3～5 with atoleine;
(2) get iron chloride by shitosan and iron chloride mass ratio 1: 10～13, be mixed with the 0.2mol/L ferric chloride solution with deionized water, add in the above-mentioned reaction system, stir, add the concentration that is equivalent to 1.5～2.5 times of chitosan masses again and be 50% glutaraldehyde solution, continue to stir, be warming up to 40 ℃, reaction 1h is behind sig water adjusting pH value to 9～10, be warming up to 60～70 ℃ of reaction 3～5h down again, cooling back suction filtration;
(3) wash 2～3 times with benzinum, acetone, ethanol successively, wash with water at last to neutrality, vacuum filtration, drying promptly makes the iron modified chitosan crosslinked resin.
Shitosan is the shitosan of dehydration acetyl degree 〉=95% in described (1) step.Make adsorption effect stable, regeneration is simple, must guarantee that the dehydration acetyl degree of shitosan reaches 95% at least, and dehydration acetyl degree is high more, and adsorption effect is stable more, but cost is just high more.Therefore selecting high dehydration acetyl degree is that 95% shitosan is prepared comparatively economical as raw material.
Shitosan and acetic acid mass ratio are preferably 1: 24 in described (1) step.Its bead yield rate is reached more than 90%, and the bead-like resin smooth surface, the sphere diameter narrow distribution range.
Shitosan acetic acid colloidal sol and atoleine volume ratio are preferably 1: 3 in described (1) step.
Shitosan and iron chloride mass ratio are preferably 1: 12 in described (2) step.
Concentration is 1.5 times that the addition of 50% glutaraldehyde solution is preferably chitosan mass in described (2) step.
Mixing speed 160～220r/min in described (2) step is preferably 180～200r/min.In this scope, speed is fast more, and the chitosan crosslinked resin of preparation is more little, and specific area is big more, helps absorption; Surpass this scope excessive velocities, easily make the chitosan crosslinked resin fragmentation, be unfavorable for preparation.
The application of chitosan crosslinked resin removing fluor in water:
Fluorinated water is prepared voluntarily, and concentration is 2.0mg/L, pH=7.Adopt above-mentioned chitosan crosslinked resin to handle fluorinated water, test temperature is a room temperature, use amount is pressed the chitosan crosslinked resin quality: fluorine-containing gross mass=chitosan crosslinked resin with fluorinated water mixed back place 10～13 hour (adsorption-defluorination) at 5000: 1, filter then, measure content of fluoride ion in the filtrate.The result shows that chitosan crosslinked resin can reach more than 80% the clearance of fluorine ion.Chitosan crosslinked resin after the absorption is regenerated with variable concentrations ammoniacal liquor, is used further to defluorination, the result as shown in Figure 1: employing 0.2mol/L ammoniacal liquor is regenerated to this resin, and effect is best.
Get the 0.2mol/L ammoniacal liquor regenerating resin of above-mentioned absorption, with the double regeneration of 0.2mol/L ammoniacal liquor, be used further to defluorination, the clearance of fluorine ion still can reach more than 80%.
Advantage compared with prior art of the present invention and beneficial effect:
It is raw material that the present invention adopts the shitosan of high dehydration acetyl degree 〉=95%, is the modified chitosan crosslinked resin of modifier preparation with iron chloride, the removing fluor in water effect stability, and resin is difficult for broken, and regeneration is simple, and is with low cost.Not only can be used for industrial fluorinated water and handle, also be applicable to the processing of high-fluorine drinking water.
Description of drawings
Fluorine curve map in Fig. 1 variable concentrations ammoniacal liquor regenerating resin adsorbed water
The specific embodiment
Embodiment 1: the preparation of resin
Getting shitosan 1g, acetic acid 25ml respectively mixes, be mixed with shitosan acetic acid colloidal sol, with the 0.2mol/L ferric chloride solution of 75ml atoleine and 3.7ml, add in the above-mentioned reaction system and stir, mixing speed 160～220r/min, add the 1.5ml glutaraldehyde solution again, be warming up to 40 ℃, reaction 1h is behind sig water adjusting pH value to 9～10, be warming up to 60～70 ℃ of reaction 4h down again, cooling back suction filtration.Wash 3 times with benzinum, acetone, ethanol successively, wash with water at last to neutrality, vacuum filtration, drying promptly makes 1.72g iron modified chitosan crosslinked resin.
Embodiment 2: adopt chitosan crosslinked resin to handle fluorinated water
Chitosan crosslinked resin adopts the product of embodiment 1, and test ambient temperature is 25 ℃, and fluorinated water pH=6.8, fluorinated water select preparation voluntarily, and concentration is 2.0mg/L.
Get the iron modified chitosan crosslinked resin 0.5g that embodiment 1 prepares and mix back 12h with the 50ml fluorinated water, filter then, measure that content of fluoride ion is 0.186mg/L in the filtrate.Analysis result shows that chitosan crosslinked resin can reach more than 80% the clearance of fluorine ion.
Embodiment 3: chitosan crosslinked resin regeneration and removing fluor in water effect thereof
The chitosan crosslinked resin of getting among the embodiment 2 after the absorption is regenerated with variable concentrations ammoniacal liquor, is used further to defluorination, the result as shown in Figure 1: employing 0.2mol/L ammoniacal liquor is regenerated to this resin, and effect is best.
Get the 0.2mol/L ammoniacal liquor regenerating resin of above-mentioned absorption, with the double regeneration of 0.2mol/L ammoniacal liquor, be used further to defluorination, the clearance of fluorine ion still can reach more than 80%, and content of fluoride ion is respectively in the mensuration filtrate: 0.187mg/L and 0.187mg/L.
Claims (8)
1, a kind of preparation method who is used for the modified chitosan crosslinked resin of removing fluor in water is characterized in that comprising the steps:
(1) shitosan and acetic acid are mixed according to mass ratio 1: 23～25, be mixed with shitosan acetic acid colloidal sol, shitosan acetic acid colloidal sol mixes according to volume ratio 1: 3～5 with atoleine;
(2) get iron chloride by shitosan and iron chloride mass ratio 1: 10～13, be mixed with the 0.2mol/L ferric chloride solution with deionized water, add in the reaction system of above-mentioned steps (1), stir, add the concentration that is equivalent to 1.5～2.5 times of chitosan masses again and be 50% glutaraldehyde solution, continue to stir, be warming up to 40 ℃, reaction 1h is behind sig water adjusting pH value to 9～10, be warming up to 60～70 ℃ of reaction 3～5h down again, cooling back suction filtration;
(3) wash 2～3 times with benzinum, acetone, ethanol successively, wash with water at last to neutrality, vacuum filtration, drying promptly makes the iron modified chitosan crosslinked resin.
2, the preparation method of modified chitosan crosslinked resin as claimed in claim 1 is characterized in that shitosan is the shitosan of dehydration acetyl degree 〉=95% in described (1) step.
3, the preparation method of modified chitosan crosslinked resin as claimed in claim 1 is characterized in that shitosan and acetic acid mass ratio are 1: 24 in described (1) step.
4, the preparation method of modified chitosan crosslinked resin as claimed in claim 1 is characterized in that shitosan acetic acid colloidal sol and atoleine volume ratio are 1: 3 in described (1) step.
5, the preparation method of modified chitosan crosslinked resin as claimed in claim 1 is characterized in that shitosan and iron chloride mass ratio are 1: 12 in described (2) step.
6, the preparation method of modified chitosan crosslinked resin as claimed in claim 1 is characterized in that concentration in described (2) step is that the addition of 50% glutaraldehyde solution is 1.5 times of chitosan mass.
7, the preparation method of modified chitosan crosslinked resin as claimed in claim 1 is characterized in that mixing speed 160～220r/min in described (2) step.
8, the iron modified chitosan crosslinked resin that makes of method according to claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973618A (en) * | 2010-08-27 | 2011-02-16 | 浙江大学 | Method for removing and recycling hexavalent chromium ions by using chitosan-iron complex |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731594A (en) * | 2016-03-29 | 2016-07-06 | 苏州蔻美新材料有限公司 | Fluoride adsorption resin and preparation method thereof |
| CN106749756A (en) * | 2016-10-28 | 2017-05-31 | 江苏梅兰化工有限公司 | A kind of preparation method of praseodymium modification of chitosan defluorinate polymeric adsorbent |
| CN106853362B (en) * | 2017-01-11 | 2019-04-02 | 福州大学 | A kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine |
| CN108587811A (en) * | 2018-05-07 | 2018-09-28 | 安徽索亚装饰材料有限公司 | A kind of production method of skin carving cuticle removers |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973618A (en) * | 2010-08-27 | 2011-02-16 | 浙江大学 | Method for removing and recycling hexavalent chromium ions by using chitosan-iron complex |
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