CN101215035A - Method for removing fluorine ion from water by using zirconium oxide carried molecular screen - Google Patents

Method for removing fluorine ion from water by using zirconium oxide carried molecular screen Download PDF

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CN101215035A
CN101215035A CNA2007103024934A CN200710302493A CN101215035A CN 101215035 A CN101215035 A CN 101215035A CN A2007103024934 A CNA2007103024934 A CN A2007103024934A CN 200710302493 A CN200710302493 A CN 200710302493A CN 101215035 A CN101215035 A CN 101215035A
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molecular sieve
water
zirconium oxide
fluorion
oxide carried
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CN101215035B (en
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许昭怡
顾浩
郑寿荣
范杰
刘凤玲
李丽媛
刘景亮
穆容心
邢涛
王家宏
赵瑞东
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Nanjing University
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Nanjing University
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Abstract

The invention discloses application of molecular sieve loading zirconium oxide for removing fluoride ions from water. The invention also discloses a method by employing the molecular sieve loading zirconium oxide to remove the fluoride ions from water, namely absorbing and removing the fluoride ions by modified molecular sieve loading zirconium oxide from polluted water at a temperature of 10-40DEG C under the acidic or alkaline condition. The invention shows remarkable adsorption capacity superior to than of conventional adsorption materials by the time when removing fluorine contaminants from the water by the adsorption method. In addition, the invention has the advantages of simple operation, easy obtaining of materials, low cost and obvious treatment effect, thereby the invention has perfect economic and social benefits for removing the fluoride ions from source water of slightly polluted water.

Description

A kind of zirconium oxide carried molecular sieve is removed the method for fluorion in the water
Technical field
The invention belongs to water body molecular sieve and oxide technique field, be specifically related to the application aspect the fluorion in removing water of a kind of molecular sieve carried Zirconium oxide.
Background technology
Along with development of modern industry, the production of fluorine and compound thereof is increasing.The waste water that industries such as the exploitation processing of fluorine-containing ore, Metal smelting, electrolysis of aluminum, coke, glass, electronics, plating, chemical fertilizer, agricultural chemicals, chemical industry produce often contains the fluorochemical of high density, cause environmental pollution after entering water body, caused showing great attention to of people.Fluorine is one of trace element of needed by human, but the fluorine amount of taking the photograph of human body every day will cause endemic fluorosis when surpassing normal need for a long time.Tap water fluorine content height is to cause the most basic, most important factor of endemia fluorosis popular.The long-term drinking water of high fluorine content can cause dental fluorosis and skeletal fluorosis, causes then that gently tooth is rotten, and enamel comes off, and is heavy then cause osteosclerosis or osteoporosis, textured bone, even paralyse, make people's disability.Therefore, the fluoride waste Study on treatment technology is the important topic in domestic and international environmental protection field always.
The defluorination method of report mainly contains the precipitator method, electrocoagulation, reverse osmosis method, ion exchange method and absorption method etc. both at home and abroad at present.Studies show that there is certain limitation respectively in above-mentioned treatment process, undesirable as removal effect, energy consumption is high or mould material vulnerable to pollution etc., and high-efficiency low energy consumption, absorption method easy and simple to handle are one of methods that is most widely used at present.
Adsorption is meant that one or more material molecules are attached to the lip-deep process of another kind of material (generally being solid).Absorption is surface phenomenon, is to be adsorbed dense gather of molecule on the interface.Usually people call sorbent material to sizable materials of specific surface area such as gac, molecular sieve, silica gel, polymeric adsorbents, and the material adsorbed sorbent material calls adsorbate.In recent years, scholars generally believe the sorbent material that utilizes high-specific surface area, remove hazardous and noxious substances in the water by adsorption, are one of effective meanss of water pollution control.
Removing the sorbent material that fluorion is commonly used in the water has activated alumina, gac, bone black and tricalcium phosphate etc., yet the loading capacity of these materials is lower.Absorbent charcoal material with the load aluminium sesquioxide is an example, and the research report is arranged, and it only is 2.549mg/g to the fluorion saturated extent of adsorption, and the adsorptive capacity of common gac is then less than 1mg/g.In addition, the regeneration of absorbent charcoal material is comparatively complicated, has also limited its application.Studies show that in recent years, the hydrous oxide of some metallic element has higher loading capacity and selectivity to fluorion.Simultaneously, some metal ion is loaded on the sorbing material for preparing fluorine on the different carriers and caused people's attention.Molecular sieve is as widely used porous material, has easily characteristics such as modification of the control of regular pore passage structure, skeleton Si/Al ratio and surface properties.Therefore,, both kept molecular sieve pore passage compound with regular structure, steady performance, made full use of the efficient adsorptive power of hydrous zirconium oxide compound again, aspect defluorination, had potential application foreground fluorine at the oxide compound of molecular sieve area load zirconium.Yet the method for utilizing molecular sieve carried Zirconium oxide to remove fluorion in the water is not appeared in the newspapers as yet.
Summary of the invention
The objective of the invention is to overcome existing sorbent material to the low not high problem of selectivity that reaches of fluorion adsorptive capacity, utilize the self-characteristic of metal oxide and molecular sieve, the application aspect the fluorion in removing water of a kind of molecular sieve carried Zirconium oxide is provided.
Another object of the present invention provides the method that the molecular sieve carried Zirconium oxide of a kind of usefulness is removed fluoride ion contaminant in the water.
Purpose of the present invention can reach by following measure:
The application aspect the fluorion in removing water of a kind of zirconium oxide carried molecular sieve.
A kind of zirconium oxide carried molecular sieve is removed the method for fluorion in the water, is that (preferred 10min~12h) removes the fluorion in the polluted water for the acidity of 10~40 ℃ (preferred 25~35 ℃) or meta-alkalescence condition (preferred pH5~8) absorption down with zirconium oxide carried modified molecular screen in temperature.
The starting point concentration of fluorion is 10~200mg/L in the water.The consumption of sorbent material can be regulated as the case may be, and preferred adsorbent and micro-polluted water mass ratio are 1: 400~600.
Wherein use and method described in zirconium oxide carried molecular sieve be zirconium oxide carried modified molecular screen, be specially: it is baking mixed with zirconates again to place ammonium salt solution to soak after the also roasting in molecular sieve, and Zirconium oxide is loaded on the molecular sieve; A kind of method that is more preferably is: place the ammonium salt solution of 0.5~1.5mol/L to soak in molecular sieve and after 450~650 ℃ of following roastings, to be 1~3: 1~3 zirconium nitrate ground and mixed and with the mass ratio of molecular sieve, Zirconium oxide will be loaded on the molecular sieve 100~300 ℃ of following roastings.
Described in the aforesaid method molecular sieve comprise the molecular sieve of common various structures, it is carried out can being used for after the acid exchange is handled the oxide compound of load zirconium, preferred molecular sieve is ZSM-5 or Y molecular sieve, most preferably uses Y molecular sieve; The Si/Al of molecular sieve there is no particular requirement, gets final product greater than 1.The compound of zirconium is common zirconates, and is the most commonly used with zirconium nitrate; Ammonium salt in the acid exchange process requires easily to decompose wash-out, and ammonium nitrate is the most commonly used, and volatile salt etc. also can.
The present invention is a sorbent material with molecular sieve carried Zirconium oxide, and the fluorine contaminant in the water is removed in absorption.The hydrous oxide of metallic element has higher loading capacity and selectivity to fluorion; The skeleton of molecular screen material is by SiO 4Tetrahedron and AlO 4Tetrahedron is formed, Stability Analysis of Structures, and the surface is easy to modify.The present invention is for improving the adsorptive power of molecular sieve for fluorion, its surface is modified, the molecular sieve of oxide compound of zirconium that obtained load is removed the sorbent material of the fluorine pollutant in the water body as absorption, and its adsorption effect to fluorion in the water is significantly improved.
Method with fluorion in the molecular sieve carried Zirconium oxide removal water specifically may further comprise the steps:
1. at the compound of molecular sieve area load metal zirconium, the molecular sieve of oxide compound of zirconium that reaction has obtained load;
With load the molecular sieve of oxide compound of zirconium be sorbent material, the fluorion in the water is adsorbed, adsorption time is 12h, absorption is at room temperature carried out;
3. fluorinion concentration is measured and is adopted the electrode method to detect ionic concn.
The molecular sieve of above-mentioned finishing, its method of modifying is as follows:
Molecular sieve acid exchange
1. solid mixed grinding, according to the difference of molecular sieve, molecular sieve is different with the adoptable mass ratio of zirconium nitrate; The mass ratio that the present invention preferably adopts is for being 1~2: 1;
2. the ratio control of ammonium salt and molecular sieve is 1: 60~100;
3. filter the hot distilled water washing;
4. repeat said process 1~2 time;
5. sample dries by the fire 6~8h down to constant weight at 80 ℃;
6.450~650 ℃ of following roasting 4~8h, product is standby;
The surface metal load
1. solid mixed grinding, the mass ratio that molecular sieve and zirconium nitrate adopt is 1~2: 1;
2. 100~300 ℃ of roasting 1~3h of grinding product;
3. product of roasting is the sorbent material of removing fluorion in the water.
With above-mentioned load the molecular sieve of Zirconium oxide be sorbent material, the fluorion in the water is carried out adsorption treatment.Absorption can be adopted dynamic successive processes or static intermittent process.The polluted water that the present invention handles is the micro-polluted source water of fluoride ion, and sorbent material and micro-polluted water mass ratio are 1: 400~600, and wherein the starting point concentration scope of fluorion is 10~200mg/L.Adsorption time is 10min~12h, and adsorption effect increases along with the growth of time.Behind the absorption 8h, reach balance substantially.When charge capacity during greater than 3: 1, adsorption effect does not have obvious raising.
When the present invention adopts absorption method to remove fluorine pollutant in the water, show the absorption property that significantly is better than traditional sorbing material (as gac and not modified molecular sieve).In addition, the present invention is simple to operate, and material is easy to get, and is with low cost, obvious processing effect.Therefore, the present invention is used for removing the fluorion of micro-polluted source water, has good economy and environmental benefit.
Embodiment
The molecular sieve that embodiment 1 is zirconium oxide carried
Soaking the Si/Al mol ratios with the ammonium nitrate solution of 1mol/L down at 80 ℃ is 2.45 Y molecular sieve 4h, and (consumption of molecular sieve and ammonium salt is controlled at 1g: 80ml) with magnetic agitation in the actual procedure; Filter the hot distilled water washing; Repeat said process 2 times; Sample is dried by the fire 6~8h down to constant weight at 80 ℃; At 600 ℃ of following roasting 5h, obtain the modified molecular screen that the acid exchange is handled.
With modified molecular screen solid and zirconium nitrate mixed grinding 20~30 minutes, the mass ratio that molecular sieve and zirconium nitrate adopt was 1: 1; With grinding product at 200 ℃ of roasting 2h; Promptly obtain zirconium oxide carried molecular sieve.
The molecular sieve that embodiment 2 is zirconium oxide carried
Soaking the Si/Al mol ratios with the ammonium nitrate solution of 1mol/L down at 80 ℃ is 2.45 Y molecular sieve 3h, and (consumption of molecular sieve and ammonium salt is controlled at 1g: 80ml) with magnetic agitation in the actual procedure; Filter the hot distilled water washing; Repeat said process 1 time; Sample is dried by the fire 6~8h down to constant weight at 80 ℃; At 500 ℃ of following roasting 4h, obtain the modified molecular screen that the acid exchange is handled.
With modified molecular screen solid and zirconium nitrate mixed grinding, the mass ratio that molecular sieve and zirconium nitrate adopt is 1: 2; With grinding product at 200 ℃ of roasting 2h; Promptly obtain zirconium oxide carried molecular sieve.
Embodiment 3
Zirconium oxide carried molecular sieve with embodiment 1 is a sorbent material, the fluorion in the planar water.Adsorb in the closed container (volume is 50ml) at normal temperatures.The fluorion starting point concentration is 100mg/L, and pH=6, the mass ratio of sorbent material and micro-polluted water are 1: 500.298K is absorption 12h down, and maximal absorptive capacity is 23.8mg/g.
In present embodiment and following Comparative Examples or embodiment, adsorptive capacity is meant the quality of the fluorine that every gram sorbent material is adsorbed.
Embodiment 4
Zirconium oxide carried molecular sieve with embodiment 2 is a sorbent material, specifically adsorbs with embodiment 3.The maximal absorptive capacity of sorbent material is 65.6mg/g.
As seen suitably increase the amount of zirconates, can improve the adsorption efficiency of sorbent material fluorion.
Embodiment 5
Zirconium oxide carried molecular sieve with example 1 is a sorbent material, the fluorion in the planar water.Adsorb in closed container, adsorbent mass is 0.1g, and the starting point concentration of fluorion is 200mg/L, and recording maximal absorptive capacity is 36.2mg/g.
As seen, in the low concentration scope, load zirconic molecular sieve the adsorptive power of fluorine contaminant is improved along with the increase of Pollutant levels.
Embodiment 6
With the zirconium oxide carried molecular sieve of example 2 is sorbent material, after 24h is placed in exposure in air, drops into reactor and adsorbs with the method for embodiment 3, and other condition is constant, and recording maximal absorptive capacity is 79.7mg/g.
As seen, after the oxide compound of area load advances sufficient hydrolysis, can improve adsorption efficiency to fluorine contaminant.
Embodiment 7
The zirconium oxide carried molecular sieve of example 2 is a sorbent material, adsorbs 12h under 308K, and other conditions are with example 3, and recording maximal absorptive capacity is 73.3mg/g.
As seen, in certain temperature range, load zirconic molecular sieve the adsorptive power of fluorine contaminant is improved along with the increase of adsorption temp.
Comparative Examples 1
Y molecular sieve with unmodified is a sorbent material, and other conditions record no tangible adsorption effect with example 3.
As seen, the effect of molecular sieve carrier in adsorption process can be ignored.
Comparative Examples 2
Zirconium oxide carried molecular sieve with embodiment 2 is a sorbent material, the fluorion in the planar water.The fluorion starting point concentration is 200mg/L, pH=8, and other conditions are with embodiment 4.Recording adsorptive capacity is 58.7mg/g.
As seen, sorbent material under the condition of meta-alkalescence to the adsorptive power of fluorion and slant acidity condition under quite.

Claims (10)

1. zirconium oxide carried molecular sieve application aspect the fluorion in removing water.
2. a zirconium oxide carried molecular sieve is removed the method for fluorion in the water, it is characterized in that be that fluorion in the polluted water is removed in absorption under 10~40 ℃ acidity or the meta-alkalescence condition with zirconium oxide carried modified molecular screen in temperature.
3. method according to claim 2 is characterized in that described zirconium oxide carried modified molecular screen is: place ammonium salt solution to soak in molecular sieve and roasting after baking mixed with zirconates again, Zirconium oxide is loaded on the molecular sieve.
4. method according to claim 3, it is characterized in that described zirconium oxide carried modified molecular screen is: place the ammonium salt solution of 0.5~1.5mol/L to soak in molecular sieve and after 450~650 ℃ of following roastings, to be 1~3: 1~3 zirconium nitrate ground and mixed and with the mass ratio of molecular sieve, Zirconium oxide will be loaded on the molecular sieve 100~300 ℃ of following roastings.
5. according to claim 3 or 4 described methods, it is characterized in that described molecular sieve is ZSM-5 molecular sieve or Y molecular sieve.
6. according to claim 3 or 4 described methods, it is characterized in that described ammonium salt is ammonium nitrate or volatile salt.
7. method according to claim 2 is characterized in that adsorption process carries out under the condition of pH5~8.
8. method according to claim 2 is characterized in that adsorption time is 10min~12h, and temperature is 25~35 ℃.
9. method according to claim 2, the concentration that it is characterized in that fluoride ion contaminant in the water is 10~200mg/L.
10. method according to claim 2, the mass ratio that it is characterized in that sorbent material and polluted water is 1: 400~600.
CN2007103024934A 2007-12-28 2007-12-28 Method for removing fluorine ion from water by using zirconium oxide carried molecular screen Expired - Fee Related CN101215035B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101773816A (en) * 2010-03-05 2010-07-14 广东药学院 Preparation method of zirconium-loaded zeolite used for removing fluorine
CN101811020A (en) * 2010-03-22 2010-08-25 南昌航空大学 Method for preparing Fe3O4@ZrO(OH)2 magnetic nano-adsorbing material for high-efficient fluoride removal from drinking water
CN101966445A (en) * 2010-08-30 2011-02-09 南昌航空大学 Magnetism-based nanocomposite for simultaneously removing arsenic and fluorine and application method thereof
CN102001722A (en) * 2010-11-04 2011-04-06 南京大学 Method for removing phosphate from water by using zirconia-modified mesoporous silicon material
CN102335585A (en) * 2011-09-09 2012-02-01 陕西科技大学 Method for preparing zirconium-modified attapulgite clay adsorbent and method for removing fluorine from water by using adsorbent
CN102952946A (en) * 2012-11-20 2013-03-06 东北大学 Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by using zirconium-containing adsorbent

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101773816A (en) * 2010-03-05 2010-07-14 广东药学院 Preparation method of zirconium-loaded zeolite used for removing fluorine
CN101773816B (en) * 2010-03-05 2012-11-14 广东药学院 Preparation method of zirconium-loaded zeolite used for removing fluorine
CN101811020A (en) * 2010-03-22 2010-08-25 南昌航空大学 Method for preparing Fe3O4@ZrO(OH)2 magnetic nano-adsorbing material for high-efficient fluoride removal from drinking water
CN101966445A (en) * 2010-08-30 2011-02-09 南昌航空大学 Magnetism-based nanocomposite for simultaneously removing arsenic and fluorine and application method thereof
CN102001722A (en) * 2010-11-04 2011-04-06 南京大学 Method for removing phosphate from water by using zirconia-modified mesoporous silicon material
CN102001722B (en) * 2010-11-04 2012-06-13 南京大学 Method for removing phosphate from water by using zirconia-modified mesoporous silicon material
CN102335585A (en) * 2011-09-09 2012-02-01 陕西科技大学 Method for preparing zirconium-modified attapulgite clay adsorbent and method for removing fluorine from water by using adsorbent
CN102335585B (en) * 2011-09-09 2013-04-10 陕西科技大学 Method for preparing zirconium-modified attapulgite clay adsorbent and method for removing fluorine from water by using adsorbent
CN102952946A (en) * 2012-11-20 2013-03-06 东北大学 Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by using zirconium-containing adsorbent

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