CN1954906A - Compound metal oxide de-fluorine sorbent - Google Patents
Compound metal oxide de-fluorine sorbent Download PDFInfo
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- CN1954906A CN1954906A CN 200510116751 CN200510116751A CN1954906A CN 1954906 A CN1954906 A CN 1954906A CN 200510116751 CN200510116751 CN 200510116751 CN 200510116751 A CN200510116751 A CN 200510116751A CN 1954906 A CN1954906 A CN 1954906A
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Abstract
A complex metal oxide used as an adsorbent for removing fluorine from water is prepared from the transition metal chosen from Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, aluminum and RE metal chosen from Ce and La in the mole ratio of (0.5-1.5): (2-6): (0.5-1.5) through dissolving them in water to become aqueous solution, dropping alkali solution to make its pH=9.0-9.5, laying aside, centrifugal washing and separating by deionized water, drying, and grinding.
Description
Technical field
The invention belongs to the sorbing material technical field, particularly a kind of composite metal oxide de-fluoridation adsorbent.
Background technology
The fluorine disease that causes by drinking high-fluorine water is one of the endemic disease the most widely that distributes in the world.China is except that Shanghai City, and all the other each province autonomous regions and municipality directly under the Central Government have all found drinking-water property fluorine disease.Therefore, for the fluorine content in the drinking water strict demand is arranged in the world, the safe level of fluorine is 0.6-1.5mg/L in World Health Organization's regulation drinking water, the maximum permissible concentration of fluorine is 1mg/L in China's Drinking Water, and the highest permission concentration of emission of inorganic fluorine compounds is 10mg/L in the industrial wastewater.In numerous drinking water defluorination methods, absorption method is considered to the most promising method.And the key of absorption method then is adsorbent.At present, the de-fluoridation adsorbent that domestic and international application is maximum is an activated alumina, but this adsorbent optimal adsorption pH is 5, and adsorption capacity (saturated adsorption capacity is generally 10-20mg/g) on the low side, causes the stripping of aluminium easily, and problem is more in actual applications.Therefore, the research and development that are used for substituting the new adsorbent of activated alumina are subjected to international showing great attention to.The trend of current defluorination research is except conventional materials such as activated alumina, bone carbon are improved the research, more pays attention to development, the screening defluorination effect is good, the defluorination material of applied range and stable performance.
In recent years, some studies show that polyvalent metal compounds such as rare earth, iron, manganese have the ability of high adsorpting anion.Jiao Zhongzhi, Zhang Yu, Yang Min etc. are in " rare earth cerium base inorganic adsorbent is to the absorption property of fluorine " (Environmental Chemistry, V21, No.4,2002.7) in the literary composition, reported a kind of Ce-Fe de-fluoridation adsorbent, adsorption test to fluorine shows that its applicable pH range is 3-5, and (the normal pH scope of drinking water is 6.5-8.5) its absorption property is relatively poor when pH is near neutral.
Summary of the invention
The objective of the invention is to, the present ubiquitous adsorption capacity of de-fluoridation adsorbent is little at solving, problems such as applicable pH range is narrow, a kind of composite metal oxide de-fluoridation adsorbent is provided, it is the composite metal oxide de-fluoridation adsorbent of transition metal (comprising Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn etc.)-Al-terres rares (comprising Ce, La etc.), it is to the adsorption capacity height of fluorine, and pH is applied widely.
Technical scheme of the present invention is as follows:
Composite metal oxide de-fluoridation adsorbent provided by the invention contains transition metal, Al and rare earth metal; The mol ratio of described transition metal, Al and rare earth metal is 0.5-1.5: 2-6: 0.5-1.5;
Described transition metal Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn.
Described rare earth metal Ce or La.
Described Fe: Al: the mol ratio of rare earth metal also can be 1.0: 4.0: 1.0.
The preparation method of composite metal oxide de-fluoridation adsorbent provided by the invention comprises the steps:
1) will contain the compound of transition metal, aluminium and rare earth metal, be that the ratio dissolving of 0.8-1.2: 3.5-4.5: 0.6-1.0 forms the aqueous solution in the mol ratio of contained transition metal, aluminium and rare earth metal, at room temperature, and stirring and evenly mixing;
The described transistion metal compound that contains is its nitrate, chloride or sulfate;
Described aluminum contained compound is aluminum sulfate, aluminum nitrate or aluminium chloride;
The described compound that contains rare earth metal is cerium chloride, cerous nitrate, cerous sulfate, lanthanum chloride, lanthanum nitrate or lanthanum sulfate;
2) under stirring state, in above-mentioned solution, drip aqueous slkali (can be NaOH, ammonia, sodium carbonate, sodium acid carbonate etc.), be 9.0-9.5 until pH value of solution, leave standstill; Separate with the deionized water centrifuge washing, be neutral until water outlet pH;
3) product after the washing is dried to constant weight at 90-120 ℃, at 250-500 ℃ of following roasting 1-3 hour, grinds again, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
The mol ratio of transition metal described in the step 1), aluminium and rare earth metal is 1.0: 4.0: 1.0.
Composite metal oxide de-fluoridation adsorbent of the present invention is based on metal oxide to anionic specific absorption property.It is generally acknowledged that metal oxide electrolysis meeting in solution produces metal ion, when suitable pH the mineral surfaces hydroxylating taking place forms a series of metal hydroxide and polyhydroxy hydrous metal oxides, the existence of surface hydroxyl functional group makes it to have powerful affinity, by the exchange interaction of effect such as covalent bond chemisorbed, Electrostatic Absorption and ion-exchange absorption performance hydroxyl, absorption, fixing fluoride; Under neutrallty condition when (pH=7), can be higher than other sorbing material far away up to 179mg/g to the saturated extent of adsorption of fluorine in the water, comprise the Ce-Fe sorbing material of having reported.
The specific embodiment
Embodiment 1
With zinc sulfate, aluminum sulfate, lanthanum chloride is Zn: Al: La=0.5 in molar ratio: 4: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dropping sodium solution in above-mentioned solution, to pH value of solution be 9.0; Left standstill 24 hours;
Separate with the deionized water centrifuge washing, approaching neutral until water outlet pH; Product after the washing is dried to constant weight at 120 ℃, 250 ℃ of following roastings 3 hours, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), is 47mg/g (being the fluorine of this composite metal oxide de-fluoridation adsorbent absorption of every gram 47mg) to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Embodiment 2
With iron chloride, aluminum sulfate, lanthanum nitrate dissolving is Fe: Al: La=1 in molar ratio: 4: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, in above-mentioned solution, drip sodium carbonate liquor, be 9.0 until pH value of solution; Left standstill 24 hours;
Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight at 90 ℃, 500 ℃ of following roastings 3 hours, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), when the fluorine ion equilibrium concentration is 25mg/L in the water, is 75mg/g to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Embodiment 3
With manganese nitrate, aluminum nitrate, cerous nitrate is Mn: Al: La=1.5 in molar ratio: 4: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dripping molal weight concentration in above-mentioned solution is ammonia solution, is 9.5 until the pH of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight at 100 ℃, 400 ℃ of following roastings 2 hours, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), is 47mg/g to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Embodiment 4
With copper sulphate, aluminum nitrate, cerium chloride is Cu: Al: Ce=1 in molar ratio: 2: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dripping molal weight concentration in above-mentioned solution is sodium bicarbonate solution, is 9.5 until pH value of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH.Product after the washing is dried to constant weight at 110 ℃, 300 ℃ of following roastings 1.5 hours, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), is 63mg/g to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Embodiment 5
With ferric nitrate, aluminium chloride, cerous sulfate is Fe: Al: Ce=1 in molar ratio: 6: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dropping sodium solution in above-mentioned solution is 9.5 until pH value of solution, leaves standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH.Product after the washing is dried to constant weight at 95 ℃, 450 ℃ of following roastings 1 hour, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), is 63mg/g to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Embodiment 6
With manganese sulfate, aluminum sulfate, cerous sulfate is Mn: Al: Ce=1 in molar ratio: 4: 1 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dropping sodium solution in above-mentioned solution is 9.5 until pH value of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH; Product after the washing is dried to constant weight at 120 ℃, 250 ℃ of following roastings 3 hours, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), is 110mg/g to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Embodiment 7
Nickelous sulfate, aluminum nitrate, cerous sulfate are pressed a mole mass concentration Ni: Al: Ce=1: 4: the 0.5 formation aqueous solution that is dissolved in the water, at room temperature, stirring and evenly mixing;
Under stirring state, dropping sodium solution in above-mentioned solution is 9.5 until pH value of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH.Product after the washing is dried to constant weight at 120 ℃, 250 ℃ of following roastings 3 hours, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), is 40mg/g to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Embodiment 8
With iron chloride, aluminum nitrate, cerous sulfate is Fe: Al: Ce=1 in molar ratio: 4: 1.5 ratio dissolving forms the aqueous solution, at room temperature, and stirring and evenly mixing;
Under stirring state, dropping sodium solution in above-mentioned solution is 9.5 until pH value of solution; Left standstill 24 hours; Separate with the deionized water centrifuge washing, closely neutral until water outlet pH.Product after the washing is dried to constant weight at 110 ℃, 400 ℃ of following roastings 2.5 hours, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
It (when water fluorine ion equilibrium concentration is 25mg/L, in the time of pH=7), is 85mg/g to the adsorbance of fluorine that this composite metal oxide de-fluoridation adsorbent is used for handling fluorine-containing water.
Claims (5)
1, a kind of composite metal oxide de-fluoridation adsorbent is characterized in that, contains transition metal, Al and rare earth metal; The mol ratio of described transition metal, Al and rare earth metal is 0.5-1.5: 2-6: 0.5-1.5; Described transition metal is Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn; Described rare earth metal is Ce or La.
2, by the described composite metal oxide de-fluoridation adsorbent of claim 1, it is characterized in that described transition metal: Al: the mol ratio of rare earth metal is 1.0: 4.0: 1.0.
3, the preparation method of the described composite metal oxide de-fluoridation adsorbent of a kind of claim 1 is characterized in that, comprises the steps:
1) will contain the compound of transition metal, aluminium and rare earth metal, be that the ratio dissolving of 0.5-1.5: 2-6: 0.5-1.5 forms the aqueous solution in the mol ratio of contained transition metal, aluminium and rare earth metal, at room temperature, and stirring and evenly mixing;
The described compound that contains transition metal is nitrate, chloride or the sulfate that contains transition metal; Described transition metal is Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn;
The described compound that contains aluminium is aluminum sulfate, aluminum nitrate or aluminium chloride;
The described compound that contains rare earth metal is cerium chloride, cerous nitrate, cerous sulfate, lanthanum chloride, lanthanum nitrate or lanthanum sulfate;
2) under stirring state, in above-mentioned solution, drip aqueous slkali, be 9.0-9.5 until pH value of solution, leave standstill; Separate with the deionized water centrifuge washing, be neutral until water outlet pH;
3) product after the washing is dried to constant weight at 90-120 ℃, at 250-500 ℃ of following roasting 1-3 hour, grinds again, promptly makes composite metal oxide de-fluoridation adsorbent of the present invention.
4, by the preparation method of the described composite metal oxide de-fluoridation adsorbent of claim 3, it is characterized in that the mol ratio of transition metal described in the step 1), aluminium and rare earth metal is 1.0: 4.0: 1.0.
5, by the preparation method of the described composite metal oxide de-fluoridation adsorbent of claim 3, it is characterized in that described aqueous slkali is NaOH, ammonia, sodium carbonate or sodium acid carbonate.
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