CN103990428A - Cobalt-aluminum composite oxide defluorination material having rodlike porous structure and preparation method thereof - Google Patents
Cobalt-aluminum composite oxide defluorination material having rodlike porous structure and preparation method thereof Download PDFInfo
- Publication number
- CN103990428A CN103990428A CN201410187603.7A CN201410187603A CN103990428A CN 103990428 A CN103990428 A CN 103990428A CN 201410187603 A CN201410187603 A CN 201410187603A CN 103990428 A CN103990428 A CN 103990428A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- aluminum
- emulsion
- double oxide
- defluorination material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a synthesis method of a rodlike cobalt-aluminum composite oxide defluorination material, and belongs to the technical field of composite metal oxide material preparation. The synthesis method is characterized in that an emulsion method is utilized to be combined with a hydrothermal technology, an aluminum salt and a cobalt salt are used as raw materials, span 80 is used as an emulsifier, a rodlike cobalt-aluminum double-metal hydroxide is generated in rodlike emulsion droplets formed by water and an organic solvent such as aviation kerosene, cyclohexane and n-hexane, and then the cobalt-aluminum composite oxide having a rodlike mesoporous structure is obtained through heat treatment, wherein the size of pores can be controlled at 1-30 nm. The method has the advantages of cheap and easily available raw materials, simple operation, easy control and good repeatability, allows the organic solvent to be recyclable so as to achieve cyclic utilization, and is beneficial for industrialized production. The prepared cobalt-aluminum composite oxide defluorination material has a good adsorption effect on fluorine ions, is suitable for adsorption and defluorination under a condition of the pH of 6.0-9.0, has a wide range of applications, and can be used for treatment of high-concentration fluoride-containing industrial wastewater or groundwater.
Description
Technical field
The present invention relates to a kind of cobalt Al bimetal double oxide defluorination material and preparation method thereof, particularly a kind of bar-shaped loose structure cobalt aluminium double oxide defluorination material and preparation method thereof.
Technical background
Fluorine is one of the widest chemical element that distributes on the earth, and the fluorine element content in the earth's crust accounts for 0.077% of earth's crust total amount.At smelting industry, fluorine-containing mineral are as flux, and the fluoride waste of production discharge, waste gas, waste material etc. have caused very large pollution to water body, air and soil environment around.In addition, the industries such as plating and semiconductor, are also widely used fluorine-containing chemical agent.The industries such as phosphate fertilizer plant, Bricks and Tiles Plant, cement plant, glass factory, coal-fired power plant also can be discharged waste gas containing fluoride in a large number, these mankind's activity heavy damages the Natural Circulation balance of fluorine element, caused zonal fluoride pollution.High fluorine groundwater, at China's widely dispersed, spreads all over 27Ge provinces and cities and autonomous region, and the whole nation approximately has 7,000 ten thousand people to drink the underground water that high fluorine amount exceeds standard.
Fluorine element is to maintain one of indispensable trace element of human normal physiological activity, and appropriate absorption all has facilitation to the metabolism of the conduction of the calcification of human teeth and bone, nervous excitation and enzyme system etc.Yet excessive absorption fluorine element can cause various diseases, as crisp in osteoporosis, arthritis, bone, cancer, infertile, brain damage, senile dementia, thyropathy etc.World Health Organization's regulation in 2011: be limited to 1.5 mg/L on fluoride ion in drinking water content.At present a lot of for the adoptable method of processing of fluoride waste, studying most widely used is absorption method, it has the advantages such as easy and simple to handle, defluorination effect is stable. and wherein the selection of adsorbent is very crucial, and bone black, activated magnesia, activated alumina, zeolite etc. are the adsorbents of the processing fluorine ion polluted source commonly used.In recent years, researcher has been researched and developed a series of efficient de-fluoridation adsorbent materials.For example, document (Ind. Eng. Chem. Res. 2011,50,6871 – 6876) has been reported a kind of layered double hydroxide Mg-Al-CO
3the adsorbent of type has good adsorption effect under acid condition, and saturated extent of adsorption can reach 303.54 mg/g.Chinese patent (CN102389769A) has been reported the compound defluorination material of a kind of calcium aluminium lanthanum base, can be used for the processing of drinking water or high-concentration industrial fluoride waste under pH value 6.5-7.5 condition.Patent (CN102357357B) has been reported the compound defluorination material of a kind of pick aluminium cerium base, has good defluorination effect under neutrallty condition.Chinese patent (CN101229504B) has been announced this compound nanophase defluoridation material of a kind of ferric oxide-alumina, the high fluorine waste water of 20 mg/L can be removed to below 1 mg/L.Patent (CN103349974A) has been announced a kind of spherical hydroxyapatite defluorination material.These sorbent materials or adsorption capacity are little, and preparation technology is comparatively complicated, and cost is higher, or can produce secondary pollution, unstable, the sensitive to pH, and water treatment scope is narrower, for promoting, brings certain difficulty.Therefore, find the defluorination material that synthesis condition is wide, preparation technology is simple, nontoxic, water treatment scope is wide, there is very important Practical significance.
At present, although Defluorination of Formation Mater By Adsorption On Activated Alumina has certain effect, its adsorption capacity is lower, and in adsorption process, aluminium easily runs off, and causes in its water residual concentration too high.Because of the present circumstance, researchers synthesize the composite of the metal oxides such as magnesium, violent, iron and aluminium oxide, are used for improving the Fluoride-Absorption Capacity of aluminium oxide.The present invention intends utilizing microemulsion method to combine with hydro-thermal method, take cobalt nitrate and aluminum nitrate as raw material, prepared cobalt aluminium double oxide, it has, and good dispersion, specific area are large, porous etc. is beneficial to the feature of ionic adsorption, therefore can be used as a kind of simple and defluorination material of function admirable prepared.
Summary of the invention
One of object of the present invention is to overcome the shortcoming existing in prior art, and a kind of bar-shaped loose structure cobalt aluminium double oxide defluorination material is provided.
Two of object of the present invention is to provide the preparation method of this defluorination material.Under the condition that it is 6-9 that the cobalt aluminium double oxide adsorbent that the present invention prepares is applicable at pH, carry out adsorption-defluorination.This adsorbent can be realized regeneration by heat treatment simultaneously.
For achieving the above object, the present invention adopts following technical scheme:
A bar-shaped loose structure cobalt aluminium double oxide defluorination material, is cobalt Al bimetal double oxide material, it is characterized in that this defluorination material is bar-shaped loose structure, diameter 60～80 nm, long 50～200 nm; Aperture is 1～30 nm, and specific area is 38-380 m
2/ g.
A method of preparing above-mentioned bar-shaped loose structure cobalt aluminium double oxide defluorination material, is characterized in that the concrete steps of the method are:
A. the ratio that is 0.1～0.9 by aluminum soluble salt and cobalt salt in cobalt al mole ratio is mixed with mixed aqueous solution, and in this mixed aqueous solution, concentration of metal ions is 0.5～1molL
-1;
B. by emulsifying agent Span-80 with organic solvent by 1g:(18～960) mass volume ratio of ml mixes, and emulsification evenly becomes emulsion;
C. the mixed aqueous solution of step a gained is poured in step b gained emulsion, continued emulsify at a high speed 1 minute, obtain mixed liquor, and regulate pH value to 8～9; Under 500 rpm rotating speeds, continue to stir 30 min, obtain emulsion; Described mixed aqueous solution and the volume ratio of emulsion are 1:2;
D. will after the sealing of step c gained emulsion, react 1～24 h at 100～200 ℃, centrifugation, with deionized water, ethanol washing; Pass through again 300-800 ℃ of calcining, obtain bar-shaped loose structure cobalt aluminium double oxide defluorination material.
Above-mentioned aluminum soluble salt is aluminum nitrate, aluminium chloride, any in aluminum sulfate.
Above-mentioned solubility cobalt salt is cobalt nitrate, cobalt chloride, cobaltous sulfate, any in cobalt acetate.
Above-mentioned organic solvent is aviation kerosine, n-hexane or cyclohexane.
Feature of the present invention is: it is raw material that the cobalt aluminium double oxide defluorination material that this preparation method makes be take aluminium salt and cobalt salt, Span 80 is as emulsifying agent, in the bar-shaped drop forming with oil at water, react and generate bar-shaped cobalt aluminum bimetal hydroxide, through Overheating Treatment, obtain having the mesoporous cobalt aluminium double oxide of club shaped structure.The specific area of this double oxide is 38-380 m
2/ g, pore size is about 1-30 nm.Comparing with traditional adsorbent, is applicable in the wider scope of 6.0-9.0 at reaction pH, and fluoride removing rate can reach 95%, has higher adsorption effect, applied range, and defluorination effect is stable, during reaction, without regulating pH value, has further saved cost.The defluorination that can be used for higher concentration industrial wastewater and underground water.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) shape appearance figure of embodiments of the invention 1 products therefrom under different cobalt al proportions.
Fig. 2 is X-ray powder diffraction (XRD) figure of embodiments of the invention 1 products therefrom under different cobalt al proportions.
Fig. 3 is the comparison diagram of cobalt aluminium double oxide defluorination material defluorination effect under different pH of obtaining of embodiments of the invention 1.
The specific embodiment
Embodiment mono-: concrete steps are as follows:
A. the cobalt nitrate that takes 2 mmol is dissolved in 18 mL deionized waters, stirs it is dissolved completely, and the aluminum nitrate that takes 18 mmol is dissolved in above-mentioned solution;
B. in an other beaker, take the Span 80 of 0.5 g, measure the aviation kerosine of 54 ml, use high-speed emulsifying machine emulsification even;
C. the aqueous solution of step a gained is poured in the organic mixed solvent of step b gained, continued emulsify at a high speed 1 minute;
D. pour step c gained mixed solution into 126 mL 0.94 mol/L
in solution, under 500 rpm rotating speeds, continue to stir 30 min;
E. after reacting completely, steps d gained emulsion is transferred in the stainless steel autoclave that the liner of 100 mL volumes is polytetrafluoroethylene (PTFE), autoclave sealing is placed in baking oven, standing 12 h of constant temperature at 120 ℃, naturally cool to room temperature, centrifugal, with deionized water, ethanol washing for several times.
F. the sample of step e gained is dried, 500 ℃ of calcinings obtain required cobalt aluminium double oxide material.
Fluorine ion initial concentration is the solution of 8 mg/L, the cobalt aluminium double oxide defluorination material dosage making by this embodiment is 1.0 g/L, in pH value, be 8, after adsorption equilibrium, fluoride ion removing rate reaches 96.0%, fluorinion concentration is 0.32 mg/L, has reached drinking water standard, illustrates that this cobalt aluminium double oxide defluorination material has good Fluoride-Absorption Capacity.
Fig. 1 has provided transmission electron microscope (TEM) shape appearance figure of gained cobalt aluminium double oxide defluorinating agent under different cobalt al proportions.Fig. 2 has provided X-ray powder diffraction (XRD) figure of products therefrom under different cobalt al proportions.Fig. 3 has provided the defluorination effect of cobalt aluminium double oxide defluorination material under condition of different pH, and initial concentration is 8mg/L.
Embodiment bis-: concrete steps are as follows:
A. the cobalt nitrate that takes 4 mmol is dissolved in 18 mL deionized waters, stirs it is dissolved completely, and the aluminium chloride that takes 16 mmol is dissolved in above-mentioned solution;
B. in an other beaker, take the Span 80 of 0.35 g, measure the aviation kerosine of 72 ml, use high-speed emulsifying machine emulsification even;
C. the aqueous solution of step a gained is poured in the organic mixed solvent of step b gained, continued emulsify at a high speed 1 minute;
D. pour step c gained mixed solution into 126 mL 1.0 mol/L
in solution, under 500 rpm rotating speeds, continue to stir 30 min;
E. after reacting completely, steps d gained emulsion is transferred in the stainless steel autoclave that the liner of 100 mL volumes is polytetrafluoroethylene (PTFE), autoclave sealing is placed in baking oven, standing 12 h of constant temperature at 150 ℃, naturally cool to room temperature, centrifugal, with deionized water, ethanol washing for several times.
F. the sample of step e gained is dried, 400 ℃ of calcinings obtain required cobalt aluminium double oxide material.
Fluorine ion initial concentration is the solution of 8 mg/L, and the cobalt aluminium double oxide defluorination material dosage making by this embodiment is 1.0 g/L, in pH value, is 8, and after adsorption equilibrium, fluoride ion removing rate reaches 71.6%, and fluorinion concentration is 2.27 mg/L.
Embodiment tri-: concrete steps are as follows:
A. the cobalt nitrate that takes 6 mmol is dissolved in 18 mL deionized waters, stirs it is dissolved completely, and the aluminium chloride that takes 14 mmol is dissolved in above-mentioned solution;
B. in an other beaker, take the Span 80 of 0.5 g, measure the n-hexane of 36 ml, use high-speed emulsifying machine emulsification even;
C. the aqueous solution of step a gained is poured in the organic mixed solvent of step b gained, continued emulsify at a high speed 1 minute;
D. pour step c gained mixed solution into 126 mL 0.94 mol/L
in solution, under 500 rpm rotating speeds, continue to stir 30 min;
E. after reacting completely, steps d gained emulsion is transferred in the stainless steel autoclave that the liner of 100 mL volumes is polytetrafluoroethylene (PTFE), autoclave sealing is placed in baking oven, standing 12 h of constant temperature at 100 ℃, naturally cool to room temperature, centrifugal, with deionized water, ethanol washing for several times.
F. the sample of step e gained is dried, 300 ℃ of calcinings obtain required cobalt aluminium double oxide material.
Fluorine ion initial concentration is the solution of 8 mg/L, and the cobalt aluminium double oxide defluorination material dosage making by this embodiment is 1.0 g/L, in pH value, is 8, and after adsorption equilibrium, fluoride ion removing rate reaches 69.0%, and fluorinion concentration is 2.48 mg/L.
Embodiment tetra-: concrete steps are as follows:
A. the cobalt nitrate that takes 8 mmol is dissolved in 18 mL deionized waters, stirs it is dissolved completely, and the aluminium chloride that takes 12 mmol is dissolved in above-mentioned solution;
B. in an other beaker, take the Span80 of 0.8 g, measure the n-hexane of 54 ml, use high-speed emulsifying machine emulsification even;
C. the aqueous solution of step a gained is poured in the organic mixed solvent of step b gained, continued emulsify at a high speed 1 minute;
D. pour step c gained mixed solution into 126 mL 0.5 mol/L
in solution, under 500 rpm rotating speeds, continue to stir 30 min;
E. after reacting completely, steps d gained emulsion is transferred in the stainless steel autoclave that the liner of 100 mL volumes is polytetrafluoroethylene (PTFE), autoclave sealing is placed in baking oven, standing 12 h of constant temperature at 200 ℃, naturally cool to room temperature, centrifugal, with deionized water, ethanol washing for several times.
F. the sample of step e gained is dried, 500 ℃ of calcinings obtain required cobalt aluminium double oxide material.
Fluorine ion initial concentration is the solution of 8 mg/L, and the cobalt aluminium double oxide defluorination material dosage making by this embodiment is 1.0 g/L, in pH value, is 8, and after adsorption equilibrium, fluoride ion removing rate reaches 69.4%, and fluorinion concentration is 2.45 mg/L.
Claims (5)
1. a bar-shaped loose structure cobalt aluminium double oxide defluorination material, is cobalt Al bimetal double oxide material, it is characterized in that this defluorination material is bar-shaped loose structure, diameter 60～80 nm, long 50～200 nm; Aperture is 1～30 nm, and specific area is 38-380 m
2/ g.
2. a method of preparing bar-shaped loose structure cobalt aluminium double oxide defluorination material according to claim 1, is characterized in that the concrete steps of the method are:
A. the ratio that is 0.1～0.9 by aluminum soluble salt and cobalt salt in cobalt al mole ratio is mixed with mixed aqueous solution, and in this mixed aqueous solution, concentration of metal ions is 0.5～1molL
-1;
B. by emulsifying agent Span-80 with organic solvent by 1g:(18～960) mass volume ratio of ml mixes, and emulsification evenly becomes emulsion;
C. the mixed aqueous solution of step a gained is poured in step b gained emulsion, continued emulsify at a high speed 1 minute, obtain mixed liquor, and regulate pH value to 8～9; Under 500 rpm rotating speeds, continue to stir 30 min, obtain emulsion; Described mixed aqueous solution and the volume ratio of emulsion are 1:2;
D. will after the sealing of step c gained emulsion, react 1～24 h at 100～200 ℃, centrifugation, with deionized water, ethanol washing; Pass through again 300-800 ℃ of calcining, obtain bar-shaped loose structure cobalt aluminium double oxide defluorination material.
3. method according to claim 2, is characterized in that described aluminum soluble salt is aluminum nitrate, aluminium chloride, any in aluminum sulfate.
4. method according to claim 2, is characterized in that described solubility cobalt salt is cobalt nitrate, cobalt chloride, cobaltous sulfate, any in cobalt acetate.
5. method according to claim 2, is characterized in that described organic solvent is aviation kerosine, n-hexane or cyclohexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410187603.7A CN103990428A (en) | 2014-05-06 | 2014-05-06 | Cobalt-aluminum composite oxide defluorination material having rodlike porous structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410187603.7A CN103990428A (en) | 2014-05-06 | 2014-05-06 | Cobalt-aluminum composite oxide defluorination material having rodlike porous structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103990428A true CN103990428A (en) | 2014-08-20 |
Family
ID=51304907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410187603.7A Pending CN103990428A (en) | 2014-05-06 | 2014-05-06 | Cobalt-aluminum composite oxide defluorination material having rodlike porous structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103990428A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1251117A1 (en) * | 2000-07-27 | 2002-10-23 | Jemco Inc. | Method of treating fluorine compound and treated substance |
| CN101229504A (en) * | 2007-07-05 | 2008-07-30 | 中国科学院生态环境研究中心 | Preparing and applications of ferric oxide-alumina compound nanophase defluoridation material |
| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
-
2014
- 2014-05-06 CN CN201410187603.7A patent/CN103990428A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1251117A1 (en) * | 2000-07-27 | 2002-10-23 | Jemco Inc. | Method of treating fluorine compound and treated substance |
| CN101229504A (en) * | 2007-07-05 | 2008-07-30 | 中国科学院生态环境研究中心 | Preparing and applications of ferric oxide-alumina compound nanophase defluoridation material |
| CN101670267A (en) * | 2009-10-26 | 2010-03-17 | 北京林业大学 | Composite metal oxide de-fluoridation adsorbent and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 申杉杉 等: "介孔型铝酸镍纳米棒的制备及其催化氢化裂解甲苯性能", 《物理化学学报》, vol. 27, no. 7, 31 December 2011 (2011-12-31), pages 1743 - 1750 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Loiola et al. | Structural analysis of zeolite NaA synthesized by a cost-effective hydrothermal method using kaolin and its use as water softener | |
| Granados-Correa et al. | Chromium (VI) adsorption on boehmite | |
| Das et al. | Defluoridation of drinking water using activated titanium rich bauxite | |
| CN104383873B (en) | Method for preparing composite adsorbent by using low-grade attapulgite clay | |
| CN100434364C (en) | 4A zeolite synthesized from kaolin by low-temperature alkali fusion method | |
| Wu et al. | Adsorption of chromium (VI) from aqueous solution by a mesoporous aluminosilicate synthesized from microcline | |
| Shao et al. | Behavior and mechanism of fluoride removal from aqueous solutions by using synthesized CaSO4· 2H2O nanorods | |
| Weiwei et al. | Removal of Cu2+ from aqueous solutions using Na-A zeolite from oil shale ash | |
| Zhou et al. | Synthesis of high-quality NaP1 zeolite from municipal solid waste incineration fly ash by microwave-assisted hydrothermal method and its adsorption capacity | |
| CN104258804B (en) | A kind of method of comprehensive utilization of gangue | |
| CN102649590B (en) | Method for preparing mesoporous material NiAl2O4 without specific surface active agent | |
| Feng et al. | Fabrication of mesoporous magnesium oxide nanosheets using magnesium powder and their excellent adsorption of Ni (II) | |
| CN106115751B (en) | A kind of method that utilization two-part acid reaction method extracts aluminum oxide | |
| CN106215846B (en) | A kind of magnalium silicon composite adsorbing material and its preparation method and application | |
| CN101531375A (en) | Method for synthesizing bimodal silicon-aluminum mesoporous material | |
| CN106799202A (en) | A kind of molecular sieve for for gas separate and its preparation and application | |
| CN106268614B (en) | A kind of preparation method of magnesium-hydroxyapatite adsorbent | |
| CN105618050A (en) | Visible-light responded compound catalyst for degrading organic pollutants in salt-containing wastewater and preparation method of visible-light responded compound catalyst | |
| CN103787354B (en) | One utilizes coal ash for manufacturing for the application of Cr (VI) ion in MCM-41 molecular sieve adsorption solution | |
| CN105664842B (en) | A kind of fluorine removal Ca-base adsorbent and its application | |
| CN103071452B (en) | Method for preparing lanthanum or cerium pillared montmorillonite fluorine removal agent | |
| CN104307462B (en) | The method that one step water-boiling method prepares mesoporous magnesia | |
| CN105498683A (en) | Preparation method of modified clay mineral material for purification of fluorine-containing sewage | |
| Wang et al. | Synthesis and characterization of zeolite A obtained from coal gangue for the adsorption of F–in wastewater | |
| CN103537253B (en) | A kind of method of hydroxyapatite preparation mesoporous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140820 |