CN103170307A - Magnesium-loaded natural zeolite materials for removing fluorine in water - Google Patents
Magnesium-loaded natural zeolite materials for removing fluorine in water Download PDFInfo
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- CN103170307A CN103170307A CN2013101299209A CN201310129920A CN103170307A CN 103170307 A CN103170307 A CN 103170307A CN 2013101299209 A CN2013101299209 A CN 2013101299209A CN 201310129920 A CN201310129920 A CN 201310129920A CN 103170307 A CN103170307 A CN 103170307A
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Abstract
The invention discloses magnesium-loaded natural zeolite materials for removing fluorine in water. The magnesium-loaded natural zeolite materials are granules formed by wrapping the surface of natural zeolite with magnesium salt, wherein magnesium accounts for 0.1-0.29% of the total mass, and the average grain diameter of the granules is 1-2mm. The magnesium-loaded natural zeolite material is prepared by taking the following steps of: firstly calcining screened natural zeolite at high temperature for 1-2h in a muffle furnace, taking out the zeolite for later use, adding magnesium salt solids to a container, adding deionized water, and preparing a magnesium salt solution with the mass concentration of magnesium being 10%; then adding the natural zeolite at room temperature in a ratio of the natural zeolite to the magnesium salt solution being 1g: 4mL, and stirring and reacting for 3h at the speed of 300r/min; and taking out the modified natural zeolite, washing, drying, and sieving to obtain the magnesium-loaded natural zeolite material. The magnesium-loaded natural zeolite material has the advantages of fast fluorine removal speed, stable fluorine removal effect, simple and practical preparation process, easy storage, low cost and suitability for removal of fluorine in underground water with high Cl<-> and HCO<3-> concentrations.
Description
Technical field
The present invention relates to a kind of material be used to removing removing fluorine in water, relate in particular to a kind of year magnesium natural zeolite material be used to removing removing fluorine in water.
Background technology
Fluorine is the requisite a kind of trace element of human body, takes in the activity that appropriate fluorine can excite osteoblast, makes tooth, bone firm.But, when in human body, fluorine content surpasses finite concentration, can suppress the activity of osteoblast, cause fluorosis of bone or fluorine dental plaque.During lower than the water of 0.5mg/L, the precipitation of fluorine in enamel reduces, and causes the incidence of disease of carious tooth to raise when people's long-term drinking fluorine content; And long-term drinking fluorine content tarnishes tooth during higher than the water of 1.5mg/L, occurs patch or brown spot on tooth.Except Shanghai, high-fluorine water almost is dispersed throughout each province in China, mainly is distributed in northeast, northwest, North China and Huang-Huai-Hai plain regional, cloth as quaint in the Inner Mongol relies the area, Keshan area, northeast, Ningxia, some areas, Hebei etc., the most serious is Shanxi and the Inner Mongol two provinces.Underground water that 7,700 ten thousand people surpass 1.0mg/L take fluorine content is approximately arranged as domestic water in China, wherein approximately have 5,000,000 people to drink the water that fluorine content surpasses 5.0mg/L, drink high-fluorine water and cause 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, the shortcoming such as membrane separation technique is high due to processing cost, defluorination speed is slow, 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, the metal ions such as K, Mg, is comprised 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 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, these ions are exchanged can not cause secondary pollution after getting off.The mechanism of the Adsorption of fluoride 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 fluorinated water, be generally the cation of 1～3 valency.
Zeolite has porous, screening, 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.After adopting some pretreatment, natural zeolite improves the selection switching performance of fluorine ion, and in the process of exchange adsorption fluorine, has adsorbed simultaneously the calcium ion in water, 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 process and disposes trouble.
Cheng Shi etc. have studied in 2006 the first high-temperature activation of analcime, the rear aluminum potassium sulfate solution activation process of using, and under 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%.Natural high-quality zeolite was raw material take Jinzhou in 2008 in the former brooks of pears etc., 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 the shortcomings such as complex process, wastage of material, modification liquid difficult treatment, introducing heavy metal, are not suitable for extensive use.
Chinese patent (publication number CN102145239) discloses a kind of water and has purified the preparation method who uses zeolite filler.After pulverizing take natural zeolite as raw material, process through multiple tracks solution modifications such as persalt, alum, NaOH, ferric trichlorides, obtain a kind of material that can remove the polluters such as removing fluorine in water, arsenic, ammonia nitrogen, heavy metal simultaneously.But the method operation is loaded down with trivial details, and the modification liquid utilization is incomplete, and the liquid waste processing difficulty is not suitable for extensive utilization.
Chinese patent (publication number CN101088604) discloses a kind of process of preparing filter material for reducing fluoride content and improving water quality.At first natural zeolite being pulverized, is secondly high-temperature calcination a period of time, then soaks with concentrated hydrochloric acid, then soaks with inorganic salts, then use soaking with sodium hydroxide, then process with alum, carries out at last acid-base balance, the dry finished product that just makes.The method technique is too complicated, has used a large amount of high concentration soda acids, environment is had adverse effect, therefore be unsuitable for being widely used.
Summary of the invention
The purpose of this invention is to provide that a kind of defluorination speed is fast, defluorination effect is stable, preparation process is simple, easily preserve and removing fluorine in water is removed in cheap being used for carries magnesium natural zeolite material.
The objective of the invention is to be achieved through the following technical solutions:
Year magnesium natural zeolite material be used to removing removing fluorine in water of the present invention, this material is for being wrapped in the particle on natural zeolite surface by magnesium salts, and wherein magnesium accounts for 0.1～0.29% of 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 and adopt high-temperature calcination 1～2h in Muffle furnace, take out standby;
B. the magnesium salts solid is joined in container, add deionized water, be mixed with magnesia amount concentration and be 10% magnesium salt solution;
C. under room temperature, add natural zeolite, stirring reaction 3h under the speed of 300r/min in the ratio of natural zeolite: magnesium salt solution=1g:4mL;
D. take out the natural zeolite after modification, with deionized water rinsing 3～5 times, obtain carrying a magnesium natural zeolite material;
E. the magnesium natural zeolite material that carries that steps d is made is dried in evaporating dish;
F. sieve.
As seen from the above technical solution provided by the invention, year magnesium natural zeolite material that is used for going removing fluorine in water that the embodiment of the present invention provides, had the large and fireballing advantage of magnesia defluorination of natural zeolite specific area concurrently, good Fluoride-Absorption Capacity is arranged, has the performance that defluorination speed is fast, defluorination effect is stable, and preparation process is simple, easily preserves and cheap advantage.This material is not only applicable to drinking water defluorination and also can be used for underground water original position defluorination, is applicable to high Cl
-, HCO
3 -Removal of Fluorine From Underground Water.
Description of drawings
Fig. 1 carries magnesium natural zeolite material defluorination effect with the variation diagram of pH value in the embodiment of the present invention;
Fig. 2 carries magnesium natural zeolite material defluorination effect with the variation diagram of adsorption time in the embodiment of the present invention;
Fig. 3 carries magnesium natural zeolite material defluorination effect with the variation diagram of mixing speed in the embodiment of the present invention;
Fig. 4 carries magnesium natural zeolite material defluorination effect with the variation diagram of chlorine ion concentration in the embodiment of the present invention;
Fig. 5 carries magnesium natural zeolite material defluorination effect with the variation diagram of bicarbonate ion concentration in the embodiment of the present invention;
Fig. 6 is the SEM scintigram (1000 times) after the high-temperature calcination of natural zeolite process in the embodiment of the present invention;
Fig. 7 carries the SEM scintigram (1000 times) of magnesium natural zeolite material in the embodiment of the present invention.
The specific embodiment
The below will be described in further detail the embodiment of the present invention.
Year magnesium natural zeolite material be used to removing removing fluorine in water of the present invention, its better specific embodiment is:
This material is for being wrapped in the particle on natural zeolite surface by magnesium salts, wherein magnesium accounts for 0.1～0.29% of 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 and adopt high-temperature calcination 1～2h in Muffle furnace, take out standby;
B. the magnesium salts solid is joined in container, add deionized water, be mixed with magnesia amount concentration and be 10% magnesium salt solution;
C. under room temperature, add natural zeolite, stirring reaction 3h under the speed of 300r/min in the ratio of natural zeolite: magnesium salt solution=1g:4mL;
D. take out the natural zeolite after modification, with deionized water rinsing 3～5 times, obtain carrying a magnesium natural zeolite material;
E. the magnesium natural zeolite material that carries that steps d is made is dried in evaporating dish;
F. sieve.
The temperature that described high-temperature calcination is adopted is 450～550 ℃.
The temperature of described baking step is 40～105 ℃.
Described natural zeolite is selected clinoptilolite or analcime, and its particle diameter is 0.1～2mm.
Described magnesium salts is selected magnesium chloride or magnesium sulfate.
Embodiment one
Compound concentration is 10% magnesium chloride solution in beaker, in the 250mL conical flask, add the just magnesium chloride solution of preparation of 80mL, control pH in 7.0 left and right, accurately taking 20g active natural zeolite adds in conical flask, the temperature that oscillator is set is 25 ℃, rotating speed is 300r/min, begin timing after temperature and rotating speed all reach setting value, reaction 3h takes out conical flask, with washed with de-ionized water natural zeolite 3～5 times, be transferred in evaporating dish, dry under 40～105 ℃ of conditions, screening obtains year magnesium natural zeolite granular materials that particle diameter is 1～2mm.
Adopt this material processed fluorinated water, when initial fluorine concentration was 2mg/L, the pH value was 7.0(Fig. 1), the speed with 300r/min under room temperature condition stirs (Fig. 3) absorption 1.5h(Fig. 2) reach capacity.Under optimum reaction condition, 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
-Adsorption process well meet Langmuir and Freundlich adsorption isotherm, derive to such an extent that the saturated adsorption capacity of adsorbent is 0.52mg/g by Langmuir, by the D-R models fitting as can be known, adsorbent is physical absorption to the adsorption process of fluorine.
Embodiment two
At first, adopt and analyze pure NaF preparation, purity is 98%.Take 2.210g benchmark sodium fluoride (in advance prior to 105～110 ℃ of dry 2h, perhaps in the about 40min of 500～650 ℃ of dryings, cooling in drier), change in the 1000mL volumetric flask, be diluted to graticule, shake up.Be stored in polyethylene bottle every milliliter of fluorine-containing (F of this solution
-) 1000 μ g.Pipette respectively this stock solution 2mL, 5mL, 10mL in the 1000mL volumetric flask, constant volume shakes up again, and namely gets the F that concentration is 2mg/L, 5mg/L and 10mg/L
-Solution.
Secondly, add appropriate sodium chloride and sodium acid carbonate preparation Cl in fluorinated water
-, HCO
3 -Concentration is respectively 100,200,400,600,800 and the water sample of 1000mg/L, and regulating pH is 7.0.
At last, get the above-mentioned solution of anion that contains of 250mL in the 500mL plastic cup, add the 5g adsorbent, be positioned on six mixers, speed with 300r/min stirs 1.5h, get upper strata liquid after standing a period of time in right amount in the 100mL volumetric flask, add 25mL total ionic strength adjustment buffer degree to regulate cushioning liquid, constant volume.Again solution is poured in the 100mL plastic beaker, with the F-concentration in fluoride ion electrode mensuration solution.F-concentration is that the operation of 5mg/L and 10mg/L is the same.
Can find out anion Cl by Fig. 4 and Fig. 5
-, HCO
3 -Existence, all influential to carrying magnesium natural zeolite material defluorination effect, but Cl
-, HCO
3 -Impact less, carry the high Cl of magnesium natural zeolite material processed therefore can utilize
-, HCO
3 -The underground water of concentration.
The above; only for the better specific embodiment of the present invention, but protection scope of the present invention is not limited to this, 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 are within all should being encompassed in 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 (6)
1. a year magnesium natural zeolite material that is used for going removing fluorine in water, is characterized in that, this material is for being wrapped in the particle on natural zeolite surface by magnesium salts, and wherein magnesium accounts for 0.1～0.29% of gross mass, and the average grain diameter of this particle is 1～2mm.
2. year magnesium natural zeolite material be used to removing removing fluorine in water according to claim 1, is characterized in that, this material prepares by following steps:
A. will screen good natural zeolite and adopt high-temperature calcination 1～2h in Muffle furnace, take out standby;
B. the magnesium salts solid is joined in container, add deionized water, be mixed with magnesia amount concentration and be 10% magnesium salt solution;
C. under room temperature, add natural zeolite, stirring reaction 3h under the speed of 300r/min in the ratio of natural zeolite: magnesium salt solution=1g:4mL;
D. take out the natural zeolite after modification, with deionized water rinsing 3～5 times, obtain carrying a magnesium natural zeolite material;
E. the magnesium natural zeolite material that carries that steps d is made is dried in evaporating dish;
F. sieve.
3. what being used for described according to claim 2 removed removing fluorine in water carries magnesium natural zeolite material, it is characterized in that, the temperature that described high-temperature calcination is adopted is 450～550 ℃.
4. what being used for described according to claim 2 removed removing fluorine in water carries magnesium natural zeolite material, it is characterized in that, the temperature of described baking step is 40～105 ℃.
5. what being used for described according to claim 2 removed removing fluorine in water carries magnesium natural zeolite material, it is characterized in that, described natural zeolite is selected clinoptilolite or analcime, and its particle diameter is 0.1～2mm.
6. what being used for described according to claim 2 removed removing fluorine in water carries magnesium natural zeolite material, it is characterized in that, described magnesium salts is selected magnesium chloride or magnesium sulfate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837785A (en) * | 2017-10-25 | 2018-03-27 | 马鞍山拓锐金属表面技术有限公司 | A kind of preparation method of composite molecular screen defluorinating agent |
| CN108996691A (en) * | 2018-06-15 | 2018-12-14 | 江苏龙腾工程设计股份有限公司 | A kind of aluminium sludge compounded mix and preparation method thereof for artificial swamp |
| CN113477211A (en) * | 2021-07-15 | 2021-10-08 | 厦门理工学院 | Rare earth composite salt-alkali modified zeolite and preparation method thereof |
| CN113694879A (en) * | 2021-08-27 | 2021-11-26 | 国能神东煤炭集团有限责任公司 | Preparation and regeneration method of modified defluorination stone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069831A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院生态环境研究中心 | Method for preparing sulfate akaganeite adsorbent for de-arsenation |
-
2013
- 2013-04-15 CN CN2013101299209A patent/CN103170307A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069831A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院生态环境研究中心 | Method for preparing sulfate akaganeite adsorbent for de-arsenation |
Non-Patent Citations (2)
| Title |
|---|
| 陈水飞等: "载镁活化天然沸石处理高氟水实验研究", 《环境工程》 * |
| 陈飞水: "改性天然沸石处理高氟地下水实验研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837785A (en) * | 2017-10-25 | 2018-03-27 | 马鞍山拓锐金属表面技术有限公司 | A kind of preparation method of composite molecular screen defluorinating agent |
| CN108996691A (en) * | 2018-06-15 | 2018-12-14 | 江苏龙腾工程设计股份有限公司 | A kind of aluminium sludge compounded mix and preparation method thereof for artificial swamp |
| CN113477211A (en) * | 2021-07-15 | 2021-10-08 | 厦门理工学院 | Rare earth composite salt-alkali modified zeolite and preparation method thereof |
| CN113694879A (en) * | 2021-08-27 | 2021-11-26 | 国能神东煤炭集团有限责任公司 | Preparation and regeneration method of modified defluorination stone |
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Application publication date: 20130626 |