CN101215035B - 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 PDFInfo
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- CN101215035B CN101215035B CN2007103024934A CN200710302493A CN101215035B CN 101215035 B CN101215035 B CN 101215035B CN 2007103024934 A CN2007103024934 A CN 2007103024934A CN 200710302493 A CN200710302493 A CN 200710302493A CN 101215035 B CN101215035 B CN 101215035B
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- 238000000034 method Methods 0.000 title claims abstract description 34
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 68
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 239000000356 contaminant Substances 0.000 claims abstract description 11
- 239000003463 adsorbent Substances 0.000 claims description 28
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- -1 fluoride ions Chemical class 0.000 abstract 4
- 230000002378 acidificating effect Effects 0.000 abstract 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 208000004042 dental fluorosis Diseases 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
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- 231100000719 pollutant Toxicity 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 206010016818 Fluorosis Diseases 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 206010033799 Paralysis Diseases 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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
Technical field
The invention belongs to water body molecular sieve and oxide technique field, be specifically related to the application aspect the fluorine ion 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 smelt, aluminium electroloysis, coke, glass, electronics, plating, chemical fertilizer, agricultural chemicals, chemical industry produce often contains the fluoride of high concentration, 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.Drinking water fluorinated volume height is the most basic, a most important factor that causes endemia fluorosis popular.The long-term drinking high-fluorine water can cause fluorine dental plaque and fluorosis of bone, 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 precipitation method, electrocoagulation, hyperfiltration, ion-exchange and absorption method etc. both at home and abroad at present.Studies show that there is certain limitation respectively in above-mentioned processing method, undesirable as removal effect, energy consumption is high or membrane 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.
Suction-operated 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 interfacial phenomenon, is to be adsorbed dense gather of molecule on the interface.Usually people call adsorbent to sizable materials of specific area such as active carbon, molecular sieve, silica gel, polymeric adsorbents, and the material adsorbed adsorbent calls adsorbate.In recent years, scholars generally believe the adsorbent that utilizes high-specific surface area, remove poisonous and harmful substance in the water by suction-operated, are one of effective methods of water pollution control.
Removing the adsorbent that fluorine ion is commonly used in the water has activated alumina, active carbon, bone black and tricalcium phosphate etc., yet the adsorption capacity of these materials is lower.Absorbent charcoal material with the load alundum (Al is an example, and the research report is arranged, and it only is 2.549mg/g to the fluorine ion saturated extent of adsorption, and the adsorbance of common active carbon 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 adsorption capacity and selectivity to fluorine ion.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 nature.Therefore,, both kept molecular sieve pore passage compound with regular structure, steady performance, made full use of the efficient adsorption capacity of hydrous zirconium oxide again, aspect defluorination, had potential application foreground fluorine at the oxide of molecular sieve area load zirconium.Yet the method for utilizing molecular sieve carried Zirconium oxide to remove fluorine ion in the water is not appeared in the newspapers as yet.
Summary of the invention
The objective of the invention is to overcome existing adsorbent to the low not high problem of selectivity that reaches of fluorine ion adsorbance, utilize the self-characteristic of metal oxide and molecular sieve, the application aspect the fluorine ion 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 fluorine ion 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 fluorine ion in the water, is that (preferred 10min～12h) removes the fluorine ion in the contaminant 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 initial concentration of fluorine ion is 10～200mg/L in the water.The consumption of adsorbent 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 said 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 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 ammonium carbonate etc. also can.
The present invention is an adsorbent 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 adsorption capacity and selectivity to fluorine ion; 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 adsorption capacity of molecular sieve for fluorine ion, its surface is modified, the molecular sieve of oxide of zirconium that obtained load is removed the adsorbent of the fluorine pollutant in the water body as absorption, and its adsorption effect to fluorine ion in the water is significantly improved.
Method with fluorine ion 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 of zirconium that reaction has obtained load;
With load the molecular sieve of oxide of zirconium be adsorbent, the fluorine ion 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 ion concentration.
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 proportion 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 adsorbent of removing fluorine ion in the water.
With above-mentioned load the molecular sieve of Zirconium oxide be adsorbent, the fluorine ion in the water is carried out adsorption treatment.Absorption can be adopted dynamic continuous process or static batch process.The contaminant water that the present invention handles is the micro-polluted source water of fluoride ion, and adsorbent and micro-polluted water mass ratio are 1: 400～600, and wherein the initial concentration scope of fluorine ion 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 load 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 active carbon 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 fluorine ion of micro-polluted source water, has good economy and environmental benefit.
The specific 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 real process; 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 real process; 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 an adsorbent, the fluorine ion in the adsorbed water.Adsorb in the closed container (volume is 50ml) at normal temperatures.The fluorine ion initial concentration is 100mg/L, and pH=6, the mass ratio of adsorbent 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, adsorbance is meant the quality of the fluorine that every gram adsorbent is adsorbed.
Embodiment 4
Zirconium oxide carried molecular sieve with embodiment 2 is an adsorbent, specifically adsorbs with embodiment 3.The maximal absorptive capacity of adsorbent is 65.6mg/g.
As seen suitably increase the amount of zirconates, can improve the adsorption efficiency of adsorbent fluorine ion.
Embodiment 5
Zirconium oxide carried molecular sieve with example 1 is an adsorbent, the fluorine ion in the adsorbed water.Adsorb in closed container, adsorbent mass is 0.1g, and the initial concentration of fluorine ion is 200mg/L, and recording maximal absorptive capacity is 36.2mg/g.
As seen, in the low concentration scope, load zirconic molecular sieve the adsorption capacity 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 adsorbent, 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 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 an adsorbent, 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 adsorption capacity of fluorine contaminant is improved along with the increase of adsorption temp.
Comparative Examples 1
Y molecular sieve with unmodified is an adsorbent, 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 an adsorbent, the fluorine ion in the adsorbed water.The fluorine ion initial concentration is 200mg/L, pH=8, and other conditions are with embodiment 4.Recording adsorbance is 58.7mg/g.
As seen, adsorbent under the condition of meta-alkalescence to the adsorption capacity of fluorine ion and slant acidity condition under quite.
Claims (5)
1. a zirconium oxide carried molecular sieve is removed the method for fluorine ion in the water, it is characterized in that be that fluorine ion in the contaminant water is removed in absorption under 10～40 ℃ acidity or the meta-alkalescence condition with zirconium oxide carried modified molecular screen in temperature;
Wherein said 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; Described molecular sieve is ZSM-5 molecular sieve or Y molecular sieve; Described ammonium salt is ammonium nitrate or ammonium carbonate.
2. method according to claim 1 is characterized in that adsorption process carries out under the condition of pH5～8.
3. method according to claim 1 is characterized in that adsorption time is 10min～12h, and temperature is 25～35 ℃.
4. method according to claim 1, the concentration that it is characterized in that fluoride ion contaminant in the water is 10～200mg/L.
5. method according to claim 1, the mass ratio that it is characterized in that adsorbent and contaminant water is 1: 400～600.
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| CN101773816B (en) * | 2010-03-05 | 2012-11-14 | 广东药学院 | Preparation method of zirconium-loaded zeolite used for removing fluorine |
| CN101811020B (en) * | 2010-03-22 | 2012-01-04 | 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 |
| 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 |
| 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 |
| CN102952946B (en) * | 2012-11-20 | 2014-05-14 | 东北大学 | Method for removing fluorine in bastnaesite sulfuric acid leaching liquid by using zirconium-containing adsorbent |
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