CN103191700A - Chitosan/natural zeolite material for removing fluorine in water - Google Patents
Chitosan/natural zeolite material for removing fluorine in water Download PDFInfo
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- CN103191700A CN103191700A CN2013101299340A CN201310129934A CN103191700A CN 103191700 A CN103191700 A CN 103191700A CN 2013101299340 A CN2013101299340 A CN 2013101299340A CN 201310129934 A CN201310129934 A CN 201310129934A CN 103191700 A CN103191700 A CN 103191700A
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Abstract
The invention discloses a chitosan/natural zeolite material for removing fluorine in water. The chitosan/natural zeolite material is a particle which is prepared by enveloping the surface of the natural zeolite by using the chitosan, wherein the mass of the chitosan is 0.1-16.7% of the total mass of the particle, and the average particle size of the particle is 1-2mm. The preparation method of the chitosan/natural zeolite material comprises the following steps of: firstly calcining the screened natural zeolite in a muffle furnace at the temperature of 450-550 DEG C for 1-2 hours, adding glacial acetic acid into deionized water to prepare the glacial acetic acid solution at the concentration of 0.5-10%, and adding the chitosan and the natural zeolite which is pretreated by calcination into the glacial acetic acid solution while stirring to obtain the chitosan/natural zeolite material. The chitosan/natural zeolite material is fast in fluorine removal speed, large in fluorine removal volume, stable in fluorine removal effect, simple and easy in implementation of the preparation process, easy in storage, low in preparation cost, applicable to the in-site fluorine removal for ground water, and suitable for the fluorine removal for the ground water with high Cl- and HCO3- content.
Description
Technical field
The present invention relates to a kind of material for removal water fluorine, relate in particular to a kind of for shitosan/natural zeolite material of removing the water fluorine.
Background technology
Fluorine is the requisite a kind of trace element of human body, takes in the activity that an amount of fluorine can excite osteoblast, makes tooth, bone firm.But, when fluorine content surpasses finite concentration in the human body, then can suppress the activity of osteoblast, cause fluorosis of bone or fluorine dental plaque.When people's long-term drinking fluorine content was lower than the water of 0.5mg/L, the precipitation of fluorine in enamel reduced, and caused the incidence of disease of carious tooth to raise; And long-term drinking fluorine content tarnishes tooth when being higher than the water of 1.5mg/L, patch or brown spot occur at tooth.Except Shanghai, high-fluorine water almost is dispersed throughout each province in China, mainly is distributed in northeast, northwest, North China and area, the Yellow River and Huai He River sea plain, rely the area as the quaint cloth in Inner Mongol, Keshan area, northeast, Ningxia, some areas, Hebei etc., the most serious is Shanxi and the Inner Mongol two provinces.In China 7,700 ten thousand people being arranged approximately is domestic water with the underground water that fluorine content surpasses 1.0mg/L, wherein has 5,000,000 people to drink the water that fluorine content surpasses 5.0mg/L approximately, drinks high-fluorine water and causes fluorine poisoning to become a main endemic disease of country.At present, the method for defluorination mainly contains both at home and abroad: the precipitation method, electrodialysis, electrocoagulation, membrane separation technique, ion-exchange and absorption method etc.Wherein, the precipitation method, electrodialysis, electrocoagulation, membrane separation technique are because processing cost height, shortcoming such as defluorination speed is slow and fluorine removing rate is low have limited its extensive use.Absorption method is most widely used, the more defluorination method of research now.
Zeolite is the general name of zeolite family mineral, is a kind of moisture alkali metal or the aluminium silicate mineral of alkaline-earth metal, mainly contains Na, Ca and minority Sr, Ba, metal ions such as K, Mg, is made up of silicon-oxy tetrahedron and aluminum-oxygen tetrahedron.The chemical general formula of zeolite can be expressed as: M
xD
y[Al
x+ 2ySin (x+2y) O
2n] mH
2O, in the formula, M is alkali metal or other monovalent cations such as Na, K; D is alkaline-earth metal or other bivalent cations such as Ca, Sr, Ba.The cavity of natural zeolite contains some tradable cations, as K
+, Na
+, Ca
2+, Sr
2+, Ba
2+Deng, after being exchanged, these ions can not cause secondary pollution.The mechanism of the absorption fluorine of natural zeolite can be expressed as:
K
+-Z-Mg
2+-(OH
-)
m-(Cl
-)
2+ (2+m) F
-+ M
N+→ M
N+-Z-Mg
2+-(F
-)
(2+m)+ 2Cl
-+ K
++ m (OH
-) here, Z is zeolitic frameworks; M
N+Be other cation in the fluorinated water, be generally the cation of 1～3 valency.
Zeolite has porous, screening property, acid resistance, ion exchangeable and to the characteristics such as absorption of water.Its cheap and easy to get, nontoxic pollution-free is a kind of comparatively ideal natural sorbing material.Adopt after some preliminary treatment, natural zeolite improves the selection switching performance of fluorine ion, and in the process of exchange absorption fluorine, has adsorbed the calcium in the water, magnesium plasma simultaneously, has reduced hardness of water, has further improved water quality.Studies show that the absorption property of zeolite has the trend of using more excellent and more excellent, what other adsorbent can't be with its analogy.But the natural zeolite adsorption capacity is lower, and the absorption property decay is very fast, needs regeneration and regeneration liquid waste to handle and disposes trouble.
Shitosan is the product of chitin behind the deacetylation of alkali condition lower part, and deacetylated shitosan chemical name is (1,4)-2-amino-2-deoxidation-callose fully.Chitin is that output is only second to cellulosic organic high molecular compound on the earth, extensively is present in the cell membrane of animal shell such as shrimp, crab, pupa and fungi, algae about 10,000,000,000 tons of the year biosynthesis amount of chitin.Containing in the chitosan molecule in a large number can protonated-NH
2, can adsorb F by electrostatic attraction
-Deng anion, but low excessively, the easy loss of its adsorption capacity is not suitable for directly as F in the drinking water
-Adsorbent.A lot of researchs take full advantage of exist on the chitosan molecule chain a large amount of-OH ,-NH
2And the characteristics of N-acetamido, prepare various chitosan derivatives, to improve the defluorination performance.
Cheng Shi etc. have studied the high-temperature activation with analcime elder generation in 2006, the aluminum potassium sulfate solution activation processing is used in the back, and under the optimum condition, the adsorbance of zeolite reaches 420 μ g/g.The adsorption-defluorination performance that Zhan Yuzhong etc. adopted static adsorptive method to study the hydrochloric acid activation clinoptilolite in 2006, after the acid treatment of 1mol/L salt, the zeolite adsorption ability obviously strengthens, and is the fluorinated water of 10mg/L for concentration, and fluoride removing rate is increased to by 40% and surpasses 80%.When concentration of hydrochloric acid was about 4mol/L, fluoride removing rate surpassed 95%.The former brooks of pears etc. were raw material in 2008 with the natural high-quality zeolite in Jinzhou, adopted the method for sulfuric acid activation, lanthanum nitrate dipping to carry out modification, had also obtained good result.But these natural Zeolite modifying researchs have shortcomings such as adsorption capacity is low, complex process, wastage of material, modification liquid difficult treatment, introducing heavy metal, are not suitable for extensive use.
Viswanathan equals to make cross-linked chitosan in 2009, and the maximum adsorption capacity to fluorine under neutrallty condition is 0.052mg/g, and after acid treatment, protonated shitosan maximum adsorption capacity reaches 1.664mg/g.But glutaraldehyde (waits chemical cross-linking agent very big to the toxicity of cell protein, is restricted when being used for drinking water defluorination with the crosslinked chitosan microsphere of its preparation.Yao Ruihua utilized shitosan/rare earth to prepare new defluorinating agent in 2009, but have in its preparation process that rare earth metal is residual, the defluorinating agent particle diameter is unfavorable for underground water original position defluorination for a short time, cost is high has limited its application.
Summary of the invention
The purpose of this invention is to provide that a kind of defluorination speed is fast, the defluorination capacity is big, defluorination effect is stable, preparation process is simple, preserve easily and the cheap shitosan/natural zeolite material that is used for removing the water fluorine.
The objective of the invention is to be achieved through the following technical solutions:
Of the present invention for shitosan/natural zeolite material of removing the water fluorine, this material is for being wrapped in the particle on natural zeolite surface by shitosan, and wherein shitosan accounts for 0.1～16.7% of particle gross mass, and the average grain diameter of this particle is 1～2mm.
This material prepares by following steps:
A. will screen good natural zeolite adopts temperature to be 450～550 ℃ in Muffle furnace to calcine 1～2h, take out standby;
B. glacial acetic acid is joined in the container, add deionized water, be mixed with concentration and be 0.5～10% glacial acetic acid solution;
C. under the room temperature, add shitosan while stirring in described glacial acetic acid solution, stir 5～30min, obtaining solubility is the thick chitosan solution of 0.001～0.05mg/L;
D. under the room temperature, add the natural zeolite of process calcining pretreatment while stirring to described chitosan solution, stir 5～30min, obtain shitosan/natural zeolite material;
E. shifting shitosan/natural zeolite material that the d step makes puts into evaporating dish and dries;
F. broken, sieve.
As seen from the above technical solution provided by the invention, shitosan/natural zeolite the material that is used for removing the water fluorine that the embodiment of the invention provides, had the big and shitosan defluorination advantage capacious of natural zeolite specific area concurrently, has good defluorination performance, except having the performance that defluorination speed is fast, the defluorination capacity is big, defluorination effect is stable, it is simple also to have preparation process, preserves easily and cheap advantage.This material can be used for underground water original position defluorination, is applicable to high Cl
-, high HCO
3 -The underground water defluorination.
Description of drawings
Fig. 1 is that shitosan in the embodiment of the invention/natural zeolite material defluorination effect is with the variation diagram of pH value;
Fig. 2 is that shitosan in the embodiment of the invention/natural zeolite material defluorination effect is with the variation diagram of adsorption time;
Fig. 3 is that shitosan in the embodiment of the invention/natural zeolite material defluorination effect is with the variation diagram of mixing speed;
Fig. 4 be in the embodiment of the invention initial zeolite consumption to the influence of shitosan/natural zeolite material defluorination effect;
Fig. 5 is that shitosan in the embodiment of the invention/natural zeolite material defluorination effect is with the variation diagram of chlorine ion concentration;
Fig. 6 is that shitosan in the embodiment of the invention/natural zeolite material defluorination effect is with the variation diagram of bicarbonate ion concentration;
Fig. 7 is the SEM scintigram (1000 times) after the high-temperature calcination of natural zeolite process in the embodiment of the invention;
Fig. 8 is the SEM scintigram (1000 times) of shitosan in the embodiment of the invention/natural zeolite material.
The specific embodiment
To be described in further detail the embodiment of the invention below.
Of the present invention for shitosan/natural zeolite material of removing the water fluorine, its preferable specific embodiment is:
This material is for being wrapped in the particle on natural zeolite surface by shitosan, wherein shitosan accounts for 0.1～16.7% of particle gross mass, and the average grain diameter of this particle is 1～2mm.
Described shitosan accounts for 0.5～6.55% of total amount.
Described shitosan accounts for 6% of total amount.
This material prepares by following steps:
A. will screen good natural zeolite adopts temperature to be 450～550 ℃ in Muffle furnace to calcine 1～2h, take out standby;
B. glacial acetic acid is joined in the container, add deionized water, be mixed with concentration and be 0.5～10% glacial acetic acid solution;
C. under the room temperature, add shitosan while stirring in described glacial acetic acid solution, stir 5～30min, obtaining solubility is the thick chitosan solution of 0.001～0.05mg/L;
D. under the room temperature, add the natural zeolite of process calcining pretreatment while stirring to described chitosan solution, stir 5～30min, obtain shitosan/natural zeolite material;
E. shifting shitosan/natural zeolite material that the d step makes puts into evaporating dish and dries;
F. broken, sieve.
Preferably, this material prepares by following steps:
A. will screen good natural zeolite adopts temperature to be 450～550 ℃ in Muffle furnace to calcine 1.2～1.8h, take out standby;
B. glacial acetic acid is joined in the container, add deionized water, be mixed with concentration and be 0.5～4% glacial acetic acid solution;
C. under the room temperature, add shitosan while stirring in described glacial acetic acid solution, stir 10～20min, obtaining solubility is the thick chitosan solution of 0.01～0.05mg/L;
D. under the room temperature, add the natural zeolite of process calcining pretreatment while stirring to described chitosan solution, stir 10～20min, obtain shitosan/natural zeolite material;
E. shifting shitosan/natural zeolite material that the d step makes puts into evaporating dish and dries;
F. broken, sieve.
Preferred, described material prepares by following steps:
A. will screen good natural zeolite adopts temperature to be 450～550 ℃ in Muffle furnace to calcine 1.5h, take out standby;
B. glacial acetic acid is joined in the container, add deionized water, be mixed with concentration and be 2% glacial acetic acid solution;
C. under the room temperature, add shitosan while stirring in described glacial acetic acid solution, stir 15min, obtaining solubility is the thick chitosan solution of 0.05mg/L;
D. under the room temperature, add the natural zeolite of process calcining pretreatment while stirring to described chitosan solution, stir 15min, obtain shitosan/natural zeolite material;
E. shifting shitosan/natural zeolite material that the d step makes puts into evaporating dish and dries;
F. broken, sieve.
The temperature of described baking step is 40～105 ℃.
Described natural zeolite is selected clinoptilolite or analcime for use, and its particle diameter is 0.1～2mm.
It is 80～95% shitosan that described shitosan is selected deacetylation for use.
Embodiment one
In the 50mL glass beaker, adding 14mL concentration is 2.0% glacial acetic acid solution, accurately taking by weighing the 0.7g shitosan adds in the beaker, be stirred to dissolving fully with glass bar, take by weighing 10g again and add in this beaker through the natural zeolite after calcining, stir 15min under the room temperature, be transferred in the evaporating dish, dry under 40～105 ℃ of conditions, broken back obtains the shitosan that particle diameter is 1～2mm/natural zeolite granular materials with screening.
Adopt this material processed fluorinated water, when initial fluorine concentration was 2mg/L, the pH value was 6.0(Fig. 1), the speed with 100r/min under the room temperature condition stirs (Fig. 3) absorption 50min(Fig. 2) reach capacity.When adopting the 0.1g/250mL adsorbent (Fig. 4), the fluoride ion removing rate can reach 61%, and water outlet fluorine concentration is 0.78mg/L, reaches drinking water sanitary standard.Defluorinating agent is to F
-The good accords with Langmuir adsorption isotherm of adsorption process, derive to such an extent that the saturated adsorption capacity of adsorbent is 10.63mg/g by Langmuir.
Embodiment two
At first, adopt and analyze pure NaF preparation, purity is 98%.Take by weighing 2.210g benchmark NaF(in advance prior to 105～110 ℃ of dry 2h, perhaps in 500～650 ℃ of dry about 40min, cooling in the drier), change in the 1000mL volumetric flask, be diluted to graticule, shake up.Be stored in the polyethylene bottle every milliliter of fluorine-containing (F of this solution
-) 1000 μ g.Pipette this stock solution 2mL, 5mL, 10mL more respectively in the 1000mL volumetric flask, constant volume shakes up, and namely gets the F that concentration is 2mg/L, 5mg/L and 10mg/L
-Solution.
Secondly, in fluorinated water, add an amount of sodium chloride and sodium acid carbonate preparation Cl
-, HCO
3 -Concentration is respectively 100,200,400,600,800 and the water sample of 1000mg/L, and regulating pH is 6.0.
At last, get the above-mentioned solution of anion that contains of 250mL in the 500mL plastic cup, add the 0.5g adsorbent, be positioned on six mixers, speed with 100r/min stirs 50min, leave standstill and get upper strata liquid after a period of time in right amount in the 100mL volumetric flask, add 25mL total ionic strength adjustment buffer degree and regulate cushioning liquid, constant volume.Again solution is poured in the 100mL plastic beaker, with the F in the fluoride ion electrode mensuration solution
-Concentration.F
-Concentration is that the operation of 5mg/L and 10mg/L is the same.
By Fig. 5 and Fig. 6 anion Cl as can be seen
-, HCO
3 -Existence, all to shitosan/natural zeolite material defluorination effect is influential, but Cl
-, HCO
3 -Influence less, so can utilize shitosan/high Cl of natural zeolite material processed
-, HCO
3 -The underground water of concentration.
The above; only for the preferable specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (9)
1. shitosan/natural zeolite the material that is used for removing the water fluorine is characterized in that, this material is for being wrapped in the particle on natural zeolite surface by shitosan, and wherein shitosan accounts for 0.1～16.7% of particle gross mass, and the average grain diameter of this particle is 1～2mm.
2. according to claim 1 for shitosan/natural zeolite material of removing the water fluorine, it is characterized in that described shitosan accounts for 0.5～6.55% of total amount.
3. according to claim 2 for shitosan/natural zeolite material of removing the water fluorine, it is characterized in that described shitosan accounts for 6% of total amount.
4. according to claim 1 for shitosan/natural zeolite material of removing the water fluorine, it is characterized in that this material prepares by following steps:
A. will screen good natural zeolite adopts temperature to be 450～550 ℃ in Muffle furnace to calcine 1～2h, take out standby;
B. glacial acetic acid is joined in the container, add deionized water, be mixed with concentration and be 0.5～10% glacial acetic acid solution;
C. under the room temperature, add shitosan while stirring in described glacial acetic acid solution, stir 5～30min, obtaining solubility is the thick chitosan solution of 0.001～0.05mg/L;
D. under the room temperature, add the natural zeolite of process calcining pretreatment while stirring to described chitosan solution, stir 5～30min, obtain shitosan/natural zeolite material;
E. shifting shitosan/natural zeolite material that the d step makes puts into evaporating dish and dries;
F. broken, sieve.
5. according to claim 4 for shitosan/natural zeolite material of removing the water fluorine, it is characterized in that this material prepares by following steps:
A. will screen good natural zeolite adopts temperature to be 450～550 ℃ in Muffle furnace to calcine 1.2～1.8h, take out standby;
B. glacial acetic acid is joined in the container, add deionized water, be mixed with concentration and be 0.5～4% glacial acetic acid solution;
C. under the room temperature, add shitosan while stirring in described glacial acetic acid solution, stir 10～20min, obtaining solubility is the thick chitosan solution of 0.01～0.05mg/L;
D. under the room temperature, add the natural zeolite of process calcining pretreatment while stirring to described chitosan solution, stir 10～20min, obtain shitosan/natural zeolite material;
E. shifting shitosan/natural zeolite material that the d step makes puts into evaporating dish and dries;
F. broken, sieve.
6. according to claim 5 for shitosan/natural zeolite material of removing the water fluorine, it is characterized in that described material prepares by following steps:
A. will screen good natural zeolite adopts temperature to be 450～550 ℃ in Muffle furnace to calcine 1.5h, take out standby;
B. glacial acetic acid is joined in the container, add deionized water, be mixed with concentration and be 2% glacial acetic acid solution;
C. under the room temperature, add shitosan while stirring in described glacial acetic acid solution, stir 15min, obtaining solubility is the thick chitosan solution of 0.05mg/L;
D. under the room temperature, add the natural zeolite of process calcining pretreatment while stirring to described chitosan solution, stir 15min, obtain shitosan/natural zeolite material;
E. shifting shitosan/natural zeolite material that the d step makes puts into evaporating dish and dries;
F. broken, sieve.
7. according to each described shitosan/natural zeolite material for removal water fluorine in the claim 4～6, it is characterized in that the temperature of described baking step is 40～105 ℃.
8. according to each described shitosan/natural zeolite material for removal water fluorine in the claim 4～6, it is characterized in that described natural zeolite is selected clinoptilolite or analcime for use, its particle diameter is 0.1～2mm.
9. according to each describedly is characterized in that for shitosan/natural zeolite material of removing the water fluorine in the claim 4～6, it is 80～95% shitosan that described shitosan is selected deacetylation for use.
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|---|---|---|---|---|
| CN104014315A (en) * | 2014-06-06 | 2014-09-03 | 黄淮学院 | Sulfydryl-phenyl thiosemicarbazide chitosan modified zeolite as well as preparation and applications thereof |
| CN104874374A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Sealed calcium carbide furnace tail gas adsorbent and preparation method thereof |
| CN104874364A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Active modified zeolite composite adsorption material and preparation method thereof |
| CN104874373A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Modified zeolite-calcium oxide adsorbent and preparation method thereof |
| CN104874372A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Multifunctional adsorbent and preparation method thereof |
| CN104888722A (en) * | 2015-05-12 | 2015-09-09 | 安徽鑫昆净化设备有限公司 | Flue gas demercuration adsorbent and preparation method therefor |
| CN104888723A (en) * | 2015-05-12 | 2015-09-09 | 安徽鑫昆净化设备有限公司 | Adsorbent for industrial silicon furnace and preparation method for adsorbent |
| CN106006890A (en) * | 2016-06-24 | 2016-10-12 | 佛山科学技术学院 | Preparation method of chitosan coagulant |
| CN115090266A (en) * | 2022-06-21 | 2022-09-23 | 郑州大学 | Fluorine adsorbent, preparation method and adsorption method thereof |
| CN116212824A (en) * | 2022-11-16 | 2023-06-06 | 云南驰宏锌锗股份有限公司 | Defluorination material for zinc hydrometallurgy and preparation method thereof |
| CN116237023A (en) * | 2023-05-11 | 2023-06-09 | 清有生态科技(上海)有限公司 | Chitosan-based defluorinating agent and preparation method thereof |
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| CN104014315A (en) * | 2014-06-06 | 2014-09-03 | 黄淮学院 | Sulfydryl-phenyl thiosemicarbazide chitosan modified zeolite as well as preparation and applications thereof |
| CN104014315B (en) * | 2014-06-06 | 2016-04-06 | 黄淮学院 | A kind of chitin modified zeolite of sulfydryl phenylthiosemicarbazide and preparation and application thereof |
| CN104888723A (en) * | 2015-05-12 | 2015-09-09 | 安徽鑫昆净化设备有限公司 | Adsorbent for industrial silicon furnace and preparation method for adsorbent |
| CN104874373A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Modified zeolite-calcium oxide adsorbent and preparation method thereof |
| CN104874372A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Multifunctional adsorbent and preparation method thereof |
| CN104888722A (en) * | 2015-05-12 | 2015-09-09 | 安徽鑫昆净化设备有限公司 | Flue gas demercuration adsorbent and preparation method therefor |
| CN104874364A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Active modified zeolite composite adsorption material and preparation method thereof |
| CN104874374A (en) * | 2015-05-12 | 2015-09-02 | 安徽鑫昆净化设备有限公司 | Sealed calcium carbide furnace tail gas adsorbent and preparation method thereof |
| CN106006890A (en) * | 2016-06-24 | 2016-10-12 | 佛山科学技术学院 | Preparation method of chitosan coagulant |
| CN115090266A (en) * | 2022-06-21 | 2022-09-23 | 郑州大学 | Fluorine adsorbent, preparation method and adsorption method thereof |
| CN115090266B (en) * | 2022-06-21 | 2023-11-03 | 郑州大学 | Fluorine adsorbent, preparation method and adsorption method thereof |
| CN116212824A (en) * | 2022-11-16 | 2023-06-06 | 云南驰宏锌锗股份有限公司 | Defluorination material for zinc hydrometallurgy and preparation method thereof |
| CN116237023A (en) * | 2023-05-11 | 2023-06-09 | 清有生态科技(上海)有限公司 | Chitosan-based defluorinating agent and preparation method thereof |
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Application publication date: 20130710 |