CN102527331A - Hydroxyapatite-modified zeolite composite material adsorbent, and preparation method and application thereof - Google Patents
Hydroxyapatite-modified zeolite composite material adsorbent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hydroxyapatite-modified zeolite composite material adsorbent. A preparation method of the adsorbent comprises the following steps of: synthesizing hydroxyapatite in a zeolite system in a suspension state, obtaining a hydroxyapatite-zeolite composite material, then adopting a cationic surfactant to modify the hydroxyapatite-zeolite composite material, preparing the hydroxyapatite-modified zeolite composite material, using the prepared hydroxyapatite-modified zeolite composite material as an absorbent for purifying the water quality and treating organic pollutants and heavy metals in water. The invention has the advantages that high-efficiency development and utilization of low-price natural source (zeolite) are realized, the prepared composite material is a multifunctional absorbent which can be used for removing the organic pollutants and heavy metals in the water simultaneously; the problem of easy agglomeration when nanometer-level hydroxyapatite is prepared is solved, and after being applied, the material of the invention can be easily separated from waste liquid so as to be repeatedly utilized.
Description
Technical field
The present invention relates to a kind of sorbent material, specifically, is a kind of hydroxyapatite-modified zeolite composite material adsorbent and preparation method thereof and the application in organic pollution and the heavy metal in removing water.
Background technology
Along with socioeconomic fast development, Increase of population and quickening of urbanization process; In the surface water bodies such as river, lake and reservoir a large amount of pollutants has appearred, for example artificial synthetic organic materials and heavy-metal pollution things such as copper ion and zinc ion such as natural sex organic matter, dyestuff such as humic acid.Hydrobiological living safety and human drinking water safety have been arrived in the pollution that surface water body suffered serious threat at present.Be to improve human drinking water quality and protection surface water environment, must take effective method to reduce the concentration of artificial synthetic organic pollution such as natural sex organic matter, dyestuff such as humic acid in the water with heavy metal ion such as copper ion and zinc ions.
The method that tradition is removed organic pollution in the water body mainly comprises membrane filter technique, flocculence, advanced oxidation processes and bioanalysis etc., and the method that tradition is removed heavy metal ion in the water mainly comprises chemical precipitation method and membrane filter technique etc.Yet these methods all exist some problems in actual application.The absorption rule relies on pore structure intensive on the adsorbent, huge specific area; Or through formed various chemical bonds between surperficial various active groups and adsorbate; Organic pollution in the water-enriched and heavy metal contaminants selectively; And then reach the purpose of removing organic pollution and heavy metal contaminants in the water, so absorption method enjoys domestic and international researcher's concern in recent years.
Zeolite is a kind of aluminosilicate mineral with good cation exchange capacity (CEC) and adsorption capacity, uses always and makes cation adsorbent, and is cheap.But zeolite is relatively poor to anionic pollutant and organic pollutant adsorption ability.Adopt cationic surfactant that zeolite is carried out modification and then can obviously improve zeolite anionic pollutant and organic pollutant adsorption ability.Hydroxyapatite is the main component of human body natural's bone lattice and tooth, most of heavy metal ion and some organic matter is had adsorb fixation preferably, can effectively remove heavy-metal pollution thing and some organic pollution in the water.
Make up the hydroxyapatite-modified zeolite composite that forms by hydroxyapatite and cationic surfactant modified zeolite as solvent and estimate both can effectively remove the organic pollution in the water, can remove the heavy-metal pollution thing in the water again effectively.But not about the research report of hydroxyapatite-modified zeolite composite material and preparation method thereof, do not report as the research of organic pollution and heavy-metal pollution thing in the adsorbents adsorb removal water so far about hydroxyapatite-modified zeolite composite yet.
Chinese patent document CN100431689C discloses a kind of preparation method who removes the compound adsorbent of nitrogen oxide, and zeolite powder and hydrochloric acid solution are mixed, and stirs and be heated to boiling, cooling; Suction filtration adds the sodium hydroxide solution neutralization again, suction filtration, oven dry; Roasting more promptly makes the modified zeolite powder, and this powder and calcium chloride solution are mixed and stir; Suction filtration, oven dry promptly makes and soaks the salt zeolite powder, with modification or soak the salt zeolite powder and the calcium hydroxide powder mixes; The adding deionized water mixes to be pinched, and compound adsorbent is promptly processed in extrusion modling and oven dry.Chinese patent document CN102151546A discloses a kind of modified zeolite; Mix with magnesia after roasting, cooling make by natural zeolite; Be used for the carrying out a biological disposal upon ammonia nitrogen removal preprocessing process of breeding wastewater, and as the adsorbent of high strength ammonia nitrogen in the absorption breeding wastewater.Chinese patent document CN101590397B discloses a kind of preparation method and application of modified zeolite adsorbent, quantitatively takes by weighing several parts of zeolites in conical flask, pipettes modifier by the different solid ratio; Under uniform temperature, hunting speed, carry out Separation of Solid and Liquid behind the reaction certain hour, water cleans to detecting less than till the modifier; Adopt oven dry at a certain temperature at last; Promptly make the modified zeolite adsorbent product, described modifier is the halogenated alkyl pyridine, and halogen wherein is bromine or chlorine; Alkyl carbon atoms is 12-18, and product is suitable for the removal of organic substance humic acid in the high content of organics source water etc.But about hydroxyapatite-modified zeolite composite material adsorbent and its production and application also do not appear in the newspapers at present.
Summary of the invention
The objective of the invention is provides a kind of hydroxyapatite-modified zeolite composite material adsorbent to deficiency of the prior art.
One purpose more of the present invention is that the preparation method of a kind of hydroxyapatite-modified zeolite composite material adsorbent is provided.
Another purpose of the present invention is that the application of a kind of hydroxyapatite-modified zeolite composite material adsorbent is provided.
The 4th purpose of the present invention be, provides a kind of hydroxyapatite-modified zeolite composite material adsorbent to remove the method for organic pollution and heavy metal in the water.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is: a kind of hydroxyapatite-modified zeolite composite material adsorbent, and described preparation of adsorbent method may further comprise the steps:
A, preparation particle size range 20-500 purpose zeolite place in the reactor that fills distilled water or deionized water, stir to make zeolite be in suspended state;
B, according to required soluble phosphate, calcium salt and the aqueous slkali of the required proportioning of hydroxyapatite synthetic chemistry equation preparation synthesizing hydroxylapatite; And phosphate and calcium salt soln added in the zeolite solution that is suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid;
C, get step b gained solid and place reactor; Press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g; The modified system mixture is taken out in the reaction back; Centrifugation, the concentration of cationic surfactant in the clear liquid analytically, the gained solid through clean, oven dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
The method for preparing hydroxyapatite-Zeolite composite materials among the described step b is selected from any one of following two kinds of methods: (1) joins phosphate and calcium salt soln in the zeolite solution of suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid; (2) earlier phosphate is mixed with the zeolite solution of suspended state, and adopt aqueous slkali to regulate more than the pH value to 8.0 of mixed liquor, then in suspension, drip soluble calcium salt, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid.
Described soluble phosphate is ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium dihydrogen phosphate; Calcium salt is calcium nitrate or calcium chloride; Aqueous slkali is NaOH, potassium hydroxide or ammoniacal liquor; The concentration of soluble phosphate, calcium salt, aqueous slkali is 0.1-5 mol/L; Described cationic surfactant is halogenated alkyl pyridine or quaternary cationic surfactant, and halogen wherein is bromine or chlorine, and alkyl carbon atoms is 12-18, and the cationic surfactant solution concentration is 5-50 mmol/L.
The ratio of distilled water or deionized water and zeolite is 1-100 mL/g among the described step a; Reaction temperature is 15-80 ℃ among the described step c, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60min, and the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach in the supernatant.
For realizing above-mentioned second purpose, the technical scheme that the present invention takes is: the preparation method of a kind of hydroxyapatite-modified zeolite composite material adsorbent, and described preparation method may further comprise the steps:
A, preparation particle size range 20-500 purpose zeolite place in the reactor that fills distilled water or deionized water, stir to make zeolite be in suspended state;
B, according to required soluble phosphate, calcium salt and the aqueous slkali of the required proportioning of hydroxyapatite synthetic chemistry equation preparation synthesizing hydroxylapatite; And phosphate and calcium salt soln added in the zeolite solution that is suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid;
C, get step b gained solid and place reactor; Press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g; The modified system mixture is taken out in the reaction back; Centrifugation, the concentration of cationic surfactant in the clear liquid analytically, the gained solid through clean, oven dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
The method for preparing hydroxyapatite-Zeolite composite materials among the described step b is selected from any one of following two kinds of methods: (1) joins phosphate and calcium salt soln in the zeolite solution of suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid; (2) earlier phosphate is mixed with the zeolite solution of suspended state, and adopt aqueous slkali to regulate more than the pH value to 8.0 of mixed liquor, then in suspension, drip soluble calcium salt, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid.
Described soluble phosphate is ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium dihydrogen phosphate; Calcium salt is calcium nitrate or calcium chloride; Aqueous slkali is NaOH, potassium hydroxide or ammoniacal liquor; The concentration of soluble phosphate, calcium salt, aqueous slkali is 0.1-5 mol/L; Described cationic surfactant is halogenated alkyl pyridine or quaternary cationic surfactant, and halogen wherein is bromine or chlorine, and alkyl carbon atoms is 12-18, and the cationic surfactant solution concentration is 5-50 mmol/L.
The ratio of distilled water or deionized water and zeolite is 1-100 mL/g among the described step a; Reaction temperature is 15-80 ℃ among the described step c, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60 min, and the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach in the supernatant.
For realizing above-mentioned the 3rd purpose, the technical scheme that the present invention takes is: described adsorbent is removed the application in the organic pollution and heavy metal in the water in absorption.
For realizing above-mentioned the 4th purpose; The technical scheme that the present invention takes is: the method for heavy metal and organic pollution in a kind of hydroxyapatite-modified zeolite composite material adsorbent removal water; Described method may further comprise the steps: described hydroxyapatite-modified zeolite composite material adsorbent is joined in the waste water that contains organic pollution or heavy metal; Vibrate on the constant temperature oscillator, can realize removal heavy metal in the waste water and organic pollution.
The invention has the advantages that:
1, the present invention adopts phosphate, calcium salt, alkali, zeolite and cationic surfactant to prepare a kind of hydroxyapatite-modified zeolite composite material adsorbent as stock; And be applied to the removal of humic acid in the water and organic pollution such as Congo red and heavy-metal pollution things such as copper ion and zinc ion; Realized the efficient development and utilization of cheap natural resources (zeolite); And prepared product is suitable for the removal of organic pollution and heavy-metal pollution thing in the water, is a kind of multi-functional absorption agent that can be used for removing simultaneously organic pollution and heavy-metal pollution thing in the water;
2, the present invention can realize nano-grade hydroxy apatite is fixed on the modified zeolite surface; Thereby reunite easily this problem when having avoided nano-grade hydroxy apatite to prepare, and compare to be easier to from waste liquid, separate after nano-grade hydroxy apatite-modified zeolite composite is used with nano-grade hydroxy apatite and reuse.
The specific embodiment
Below in conjunction with embodiment the specific embodiment provided by the invention is elaborated.
The preparation method and the application thereof of embodiment 1 hydroxyapatite-modified zeolite composite material adsorbent
(1) preparation of material
Screen a certain amount of zeolite, with drying a period of time after running water or distilled water or the washed with de-ionized water; Get that cooled zeolite carries out fragmentation, the processing of grinding, sieve, the zeolite that makes in the certain grain size scope is subsequent use.
Take by weighing a certain amount of soluble phosphate, calcium salt and alkali, it is subsequent use to be mixed with certain density phosphate, calcium salt and aqueous slkali with distilled water or deionized water.
Take by weighing a certain amount of cationic surfactant, be mixed with certain density cationic surfactant solution for standby with distilled water or deionized water.
Need to prove that described zeolite particle diameter is the 20-500 order; Soluble phosphate is ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium dihydrogen phosphate; Calcium salt is calcium nitrate or calcium chloride; Aqueous slkali is by preparations such as NaOH, potassium hydroxide or ammoniacal liquor; The concentration of soluble phosphate, calcium salt, aqueous slkali is 0.1 mol/L-5 mol/L.
Described cationic surfactant is halogenated alkyl pyridine or quaternary cationic surfactant, and halogen wherein is bromine or chlorine, and alkyl carbon atoms is 12-18.The cationic surfactant solution concentration is 5 mmol/L-50 mmol/L.
(2) preparation of hydroxyapatite-Zeolite composite materials
Hydroxyapatite-Zeolite composite materials prepares through any method in following two kinds of methods:
Need to prove, at first distilled water or deionized water and zeolite are mixed according to the ratio of 1-100 mL/g; Certain proportioning is the required proportioning of hydroxyapatite synthetic chemistry equation; Duration of oscillation is 24h-96h, and bake out temperature is 60-150 ℃.The mass ratio of hydroxyapatite and zeolite is 1 in the hydroxyapatite-Zeolite composite materials for preparing: (0.01 ~ 100) is preferably 1:1.
(3) preparation of hydroxyapatite-modified zeolite composite
Take by weighing a certain amount of subsequent use hydroxyapatite-Zeolite composite materials respectively and place reactor, pipette cationic surfactant solution by certain solid-to-liquid ratio and put into the reactor that fills hydroxyapatite-Zeolite composite materials and fully mix with hydroxyapatite-Zeolite composite materials.Reaction a period of time is taken out the modified system mixture, centrifugation, and the concentration of cationic surfactant in the clear liquid analytically, thus confirm the unit load amount of hydroxyapatite-Zeolite composite materials to cationic surfactant.The gained solid through clean, oven dry, broken, after sieving the particle in the certain grain size scope is subsequent use, promptly get hydroxyapatite-modified zeolite composite.
Need to prove that cationic surfactant solution is mixed according to the liquid-solid ratio of 8-80 mL/g with hydroxyapatite-Zeolite composite materials, and reaction temperature is 15-80 ℃, hunting speed is 50-500 rpm; Duration of oscillation is 1 h-96 h.
Centrifugation rate is 500 rpm-5000 rpm, and centrifugation time is 5min-60min, and the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach in the supernatant, and baking temperature is 40 ℃-110 ℃.
(4) hydroxyapatite-modified zeolite composite is to the removal of organic pollution and heavy metal contaminants
Taking by weighing a certain amount of hydroxyapatite-modified zeolite composite material adsorbent of preparation according to the method described above joins in the humic acid or Congo red or copper ion or zinc ion solution of finite concentration scope; Be placed on then on the constant temperature water bath oscillator of uniform temperature and vibrate; Measure the concentration of humic acid in the supernatant, Congo red, copper ion and zinc ion after reaction a period of time, confirm the unit adsorbance of hydroxyapatite-modified zeolite composite material adsorbent humic acid in the water, Congo red, copper ion and zinc ion according to the concentration difference of humic acid in the water before and after the absorption, Congo red, copper ion and zinc ion.
Need to prove that aqueous solution humic acid concentration range is 10-250 mg/L, Congo red concentration range is 10-250 mg/L, and copper ion concentration is 10-300 mg/L, and zinc ion concentration is 10-300 mg/L; The pH value of solution is 4.00-12.00; The oscillation rate of constant temperature water bath oscillator is 60-600 rpm, and duration of oscillation is 1-96 h, and reaction temperature is 15-60 ℃.The alkali of regulating the pH value is NaOH, potassium hydroxide, and acid is hydrochloric acid, sulfuric acid or nitric acid, and the pH value of solution adjustable range is 4.00-12.00.
Embodiment 2
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 200 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 2 mol/L, 1.2 mol/L and 1.6 mol/L
3)
2, (NH
4)
2HPO
4And NH
3H
2O solution; Compound concentration is brocide (CPB) solution for standby of 25 mmol/L.
(2) get the subsequent use natural zeolite of 20 g, place in the distilled water reactor that fills 100 mL, stirring makes natural zeolite be in suspended state, adds the Ca (NO of 100 mL more successively respectively
3)
2(NH with 100 mL
4)
2HPO
4, and adopt NH
3H
2The pH value to 9.0 of O solution conditioned reaction liquid.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0, place 105 ℃ to grind 200 mesh sieves after the oven dry down solid again until the pH of supernatant.The NaCl solution that takes by weighing 20g solid and 200mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take by weighing 10 g hydroxyapatite-Zeolite composite materials in conical flask, using pipette to pipette 150 mL concentration is that 25 mmol/L brocide solution and the abundant mixing of hydroxyapatite-Zeolite composite materials are placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.Behind 48 h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically CPB concentration in the clear liquid of ultraviolet spectrophotometry (measuring wavelength is 259 nm); According to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 235 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-CPB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 96.7 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take by weighing the adsorbent that 0.010 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 50 mg/L, in advance the pH value of solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 20 hours, and oscillation rate is 150 rpm.Adopt visible spectrophotometry to measure residual Congo red concentration in the solution then, calculate this adsorbent Congo red unit adsorbance is reached 91.4 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 33.8 mg/ (g hydroxyapatite-CPB modified zeolite composite).
Embodiment 3
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 200 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 2 mol/L, 1.2 mol/L and 1.6 mol/L
3)
2, (NH
4)
2HPO
4And NH
3H
2O solution; Compound concentration is softex kw (HTAB) solution for standby of 25 mmol/L.
(2) get the subsequent use natural zeolite of 20 g, place in the distilled water reactor that fills 100 mL, stirring makes natural zeolite be in suspended state, adds the Ca (NO of 100 mL more successively respectively
3)
2(NH with 100 mL
4)
2HPO
4, and adopt NH
3H
2The pH value of O solution conditioned reaction liquid is 9.0.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant, solid places 105 ℃ to grind 200 mesh sieves after the oven dry down.The NaCl solution that takes by weighing 20g solid and 200mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take by weighing 10 g hydroxyapatite-Zeolite composite materials in conical flask, using pipette to pipette 150 mL concentration is that 25 mmol/L softex kw solution and the abundant mixing of hydroxyapatite-Zeolite composite materials are placed on 40 ℃ of constant temperature waters oscillators and vibrate with 150 rpm.Behind the 48h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically HTAB concentration in the clear liquid of total organic carbon analyzer; According to HTAB calibration curve calculated equilibrium concentration, the adsorbance that obtains HTAB is 212 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-HTAB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 91.6 (mg humic acid)/(g hydroxyapatite-HTAB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, is 7.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed vibration 24 h on the constant temperature water bath oscillator, and oscillation rate is 150 rpm.Adopt the Congo red concentration in the solution behind the visible spectrophotometry assaying reaction then, and calculate this adsorbent to Congo red unit adsorbance reach 99.0 mg Congo red/(g hydroxyapatite-HTAB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 40.9 mg/ (g hydroxyapatite-HTAB modified zeolite composite).
Embodiment 4
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 200 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 2 mol/L, 1.2 mol/L and 1.6 mol/L
3)
2, (NH
4)
2HPO
4And NH
3H
2O solution; Compound concentration is brocide (CPB) solution for standby of 25 mmol/L.
(2) get the subsequent use natural zeolite of 20 g, place in the distilled water reactor that fills 100 mL, stirring makes natural zeolite be in suspended state, adds the Ca (NO of 50 mL more successively respectively
3)
2(NH with 50 mL
4)
2HPO
4, and adopt NH
3H
2The pH value of O solution conditioned reaction liquid is 9.0.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant, solid places 105 ℃ to grind 200 mesh sieves after the oven dry down.The NaCl solution that takes by weighing 20g solid and 200mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take by weighing 1.5 g hydroxyapatite-Zeolite composite materials in conical flask, using pipette to pipette 24 mL concentration is that 25 mmol/L brocide solution and the abundant mixing of hydroxyapatite-Zeolite composite materials are placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.Behind the reaction 48h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically CPB concentration in the clear liquid of ultraviolet spectrophotometry (measuring wavelength is 259 nm); According to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 251 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-CPB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 91.9 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, in advance the pH value of solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt visible spectrophotometry to measure residual Congo red concentration in the solution then, calculate this adsorbent Congo red unit adsorbance is reached 99.4 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 29.5 mg/ (g hydroxyapatite-CPB modified zeolite composite).
Embodiment 5
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 200 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 2 mol/L, 1.2 mol/L and 1.6 mol/L
3)
2, (NH
4)
2HPO
4And NH
3H
2O solution; Compound concentration is brocide (CPB) solution for standby of 25 mmol/L.
(2) get the subsequent use natural zeolite of 5 g, place in the distilled water reactor that fills 100 mL, stirring makes natural zeolite be in suspended state, adds the Ca (NO of 50 mL more successively respectively
3)
2(NH with 50 mL
4)
2HPO
4After fully mixing, adopt NH
3H
2The pH value of O solution conditioned reaction liquid is 9.0.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant, solid places 105 ℃ to grind 200 mesh sieves after the oven dry down.The NaCl solution that takes by weighing 10g solid and 100mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, gained solid note is hydroxyapatite-Zeolite composite materials.
(3) take by weighing 1.5 g hydroxyapatite-Zeolite composite materials in conical flask; Using pipette to pipette 24 mL concentration is 25 mmol/L brocide solution and the abundant mixing of hydroxyapatite-Zeolite composite materials; Place 40 ℃ of water bath with thermostatic control oscillators to vibrate and centrifugalize (centrifugal speed is 3000 rpm) behind 48 h with 150 rpm; Adopt analytically CPB concentration in the clear liquid of ultraviolet spectrophotometry (measuring wavelength is 259 nm); According to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 105 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-CPB modified zeolite composite after the cooling.
(4) take by weighing 0.025 according to the method described above the preparation adsorbent, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 88.1 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, in advance the pH value of solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt visible spectrophotometry to measure residual Congo red concentration in the solution then, calculate this adsorbent Congo red unit adsorbance is reached 68.4 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 40.0 mg/ (g hydroxyapatite-CPB modified zeolite composite).
Embodiment 6
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 200 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 1 mol/L, 0.6 mol/L and 0.8 mol/L
3)
2, (NH
4)
2HPO
4With NaOH solution; Compound concentration is brocide (CPB) solution for standby of 25 mmol/L.
(2) get the subsequent use natural zeolite of 15 g, place in the distilled water reactor that fills 15 mL, stirring makes natural zeolite be in suspended state, adds (the NH of 150 mL again
4)
2HPO
4Solution, and adopt the pH value to 9.0 of NaOH solution conditioned reaction liquid, drip the Ca (NO of 150 mL under the continuous stirring situation again
3)
2Solution.Continue behind reaction 72 h mixture to be centrifugalized, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant.The concentration that the gained solid is joined 250 mL is in the NaCl solution of 1 mol/L, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, place 105 ℃ to grind 200 mesh sieves after the oven dry down solid again, the gained solid is nano-grade hydroxy apatite-Zeolite composite materials.
(3) take by weighing 10 g nano-grade hydroxy apatite-Zeolite composite materials in conical flask, using pipette to pipette 120 mL concentration is that 25 mmol/L brocide solution and the abundant mixing of nano-grade hydroxy apatite-Zeolite composite materials are placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.Behind the reaction 48h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically CPB concentration in the clear liquid of ultraviolet spectrophotometry (measuring wavelength is 259 nm); According to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 251 mmol/ (kg nano-grade hydroxy apatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make nano-grade hydroxy apatite-CPB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 95.6 (mg humic acid)/(g nano-grade hydroxy apatite-CPB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, in advance the pH value of solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt visible spectrophotometry to measure residual Congo red concentration in the solution then, calculate this adsorbent Congo red unit adsorbance is reached 98.6 (mg is Congo red)/(g nano-grade hydroxy apatite-CPB modified zeolite composite).
(6) taking by weighing the adsorbent that 0.025 g prepares according to the method described above, place 25 mL concentration to be respectively 20,50 and 100 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 19.9,49.1 and 70.9 mg/ (g nano-grade hydroxy apatite-CPB modified zeolite composite).
(7) taking by weighing the adsorbent that 0.025 g prepares according to the method described above, place 25 mL concentration to be respectively 20,40 and 80 mg/L zinc ion solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of zinc ion in the solution then, calculate this adsorbent the unit adsorbance of Zn (II) is respectively 19.7,39.7 and 51.6 mg/ (g nano-grade hydroxy apatite-CPB modified zeolite composite).
Embodiment 7
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 200 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 1 mol/L, 0.6 mol/L and 0.8 mol/L
3)
2, (NH
4)
2HPO
4With NaOH solution; Compound concentration is softex kw (HTAB) solution for standby of 25 mmol/L.
(2) get the subsequent use natural zeolite of 15 g, place in the distilled water reactor that fills 150 mL, stirring makes natural zeolite be in suspended state, adds (the NH of 150 mL again
4)
2HPO
4Solution, and adopt the pH value to 9.0 of NaOH solution conditioned reaction liquid, drip the Ca (NO of 150 ml under the situation of continuous stirring again
3)
2Solution.Continue behind reaction 72 h mixed liquor to be centrifugalized, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant.Place 105 ℃ to grind 200 mesh sieves after the oven dry down solid again, the gained solid is nano-grade hydroxy apatite-Zeolite composite materials.
(3) take by weighing 1.0 g nano-grade hydroxy apatite-Zeolite composite materials in conical flask, using pipette to pipette 16mL concentration is that 25 mmol/L softex kw solution and the abundant mixing of nano-grade hydroxy apatite-zeolite are placed on 40 ℃ of constant temperature waters oscillators and vibrate with 150 rpm.Behind the reaction 48h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically HTAB concentration in the clear liquid of total organic carbon analyzer; According to HTAB calibration curve calculated equilibrium concentration, the adsorbance that obtains HTAB is 253 mmol/ (kg nano-grade hydroxy apatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make nano-grade hydroxy apatite-HTAB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 95.8 (mg humic acid)/(g nano-grade hydroxy apatite-HTAB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, is 7.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed vibration 24 h on the constant temperature water bath oscillator, and oscillation rate is 150 rpm.Adopt the Congo red concentration in the solution behind the visible spectrophotometer assaying reaction then, and calculate this adsorbent to Congo red unit adsorbance reach 99.1 mg Congo red/(g nano-grade hydroxy apatite-HTAB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 50.0 mg/ (g nano-grade hydroxy apatite-HTAB modified zeolite composite).
(7) taking by weighing the adsorbent that 0.050 g prepares according to the method described above, place 25 mL concentration to be respectively 50 mg/L zinc ion solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of zinc ion in the solution then, calculate this adsorbent the unit adsorbance of Zn (II) is reached 24.9 mg/ (g nano-grade hydroxy apatite-CPB modified zeolite composite).
Embodiment 8
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 20 mesh sieves are subsequent use; Compound concentration is respectively the CaCl of 2 mol/L, 1.2 mol/L and 1.6 mol/L
2, Na
2HPO
4With KOH solution; Compound concentration is brocide (CPB) solution for standby of 50 mmol/L.
(2) get the subsequent use natural zeolite of 20g, place in the distilled water reactor that fills 100mL, stirring makes natural zeolite be in suspended state, adds the CaCl of 100 mL more successively respectively
2Na with 100 mL
2HPO
4, and the pH value to 9.0 of employing KOH solution conditioned reaction liquid.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0, place 105 ℃ to grind 200 mesh sieves after the oven dry down solid again until the pH of supernatant.The NaCl solution that takes by weighing 20g solid and 200mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take by weighing 10 g hydroxyapatite-Zeolite composite materials in conical flask, using pipette to pipette 80 mL concentration is that 50 mmol/L brocide solution and the abundant mixing of hydroxyapatite-Zeolite composite materials are placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.After reacting 48 h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically CPB concentration in the clear liquid of ultraviolet spectrophotometry (measuring wavelength is 259 nm); According to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 228 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-CPB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.050 g prepares according to the method described above, placing 50 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 96.5 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, in advance the pH value of solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt visible spectrophotometry to measure residual Congo red concentration in the solution then, calculate this adsorbent Congo red unit adsorbance is reached 90.1 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 60 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 38.1 mg/ (g hydroxyapatite-CPB modified zeolite composite).
Embodiment 9
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 400 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 2 mol/L, 1.2 mol/L and 1.6 mol/L
3)
2, NaH
2PO
4And NH
3H
2O solution; Compound concentration is softex kw (HTAB) solution for standby of 50 mmol/L.
(2) get the subsequent use natural zeolite of 20 g, place in the distilled water reactor that fills 100 mL, stirring makes natural zeolite be in suspended state, adds the Ca (NO of 100 mL more successively respectively
3)
2NaH with 100 mL
2PO
4, and adopt NH
3H
2The pH value of O solution conditioned reaction liquid is 9.0.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant, solid places 105 ℃ to grind 200 mesh sieves after the oven dry down.The NaCl solution that takes by weighing 20g solid and 200mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take by weighing 1.0g hydroxyapatite-Zeolite composite materials in conical flask, using pipette to pipette 12 mL concentration is that 50 mmol/L softex kw solution and the abundant mixing of hydroxyapatite-Zeolite composite materials are placed on 40 ℃ of constant temperature waters oscillators and vibrate with 150 rpm.Behind the 48h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically HTAB concentration in the clear liquid of total organic carbon analyzer; According to HTAB calibration curve calculated equilibrium concentration, the adsorbance that obtains HTAB is 217 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-HTAB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 92.8 (mg humic acid)/(g hydroxyapatite-HTAB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, is 7.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed vibration 24 h on the constant temperature water bath oscillator, and oscillation rate is 150 rpm.Adopt the Congo red concentration in the solution behind the visible spectrophotometry assaying reaction then, and calculate this adsorbent to Congo red unit adsorbance reach 99.6 mg Congo red/(g hydroxyapatite-HTAB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 38.7 mg/ (g hydroxyapatite-HTAB modified zeolite composite).
Embodiment 10
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 100 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 2 mol/L, 1.2 mol/L and 1.6 mol/L
3)
2, K
2HPO
4With KOH solution; Compound concentration is brocide (CPB) solution for standby of 5 mmol/L.
(2) get the subsequent use natural zeolite of 20 g, place in the distilled water reactor that fills 100 mL, stirring makes natural zeolite be in suspended state, adds the Ca (NO of 50 mL more successively respectively
3)
2K with 50 mL
2HPO
4, and the pH value of employing KOH solution conditioned reaction liquid is 9.0.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant, solid places 105 ℃ to grind 200 mesh sieves after the oven dry down.The NaCl solution that takes by weighing 20g solid and 200mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take by weighing 1.0 g hydroxyapatite-Zeolite composite materials in conical flask, using pipette to pipette 80 mL concentration is that 5 mmol/L brocide solution and the abundant mixing of hydroxyapatite-Zeolite composite materials are placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.Behind the 48h mixed liquor is centrifugalized (centrifugal speed is 3000 rpm); Adopt analytically CPB concentration in the clear liquid of ultraviolet spectrophotometry (measuring wavelength is 259 nm); According to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 248 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-CPB modified zeolite composite after the cooling.
(4) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 90.8 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, in advance the pH value of solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt visible spectrophotometry to measure residual Congo red concentration in the solution then, calculate this adsorbent Congo red unit adsorbance is reached 99.0 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 30.5 mg/ (g hydroxyapatite-CPB modified zeolite composite).
Embodiment 11
(1) get natural zeolite, adopt the distilled water cleaning many times after, air blast is air-dry, broken, grind, mistake 500 mesh sieves are subsequent use; Compound concentration is respectively the Ca (NO of 2 mol/L, 1.2 mol/L and 1.6 mol/L
3)
2, KH
2PO
4And NH
3H
2O solution; Compound concentration is brocide (CPB) solution for standby of 25 mmol/L.
(2) get the subsequent use natural zeolite of 5 g, place in the distilled water reactor that fills 100 mL, stirring makes natural zeolite be in suspended state, adds the Ca (NO of 50 mL more successively respectively
3)
2KH with 50 mL
2PO
4After fully mixing, adopt NH
3H
2The pH value of O solution conditioned reaction liquid is 9.0.Centrifugalize after reacting 72 h, adopt distilled water to wash solid repeatedly, approach till 7.0 until the pH of supernatant, solid places 105 ℃ to grind 200 mesh sieves after the oven dry down.The NaCl solution that takes by weighing 10g solid and 100mL concentration and be 1mol/L places reactor in the lump, centrifugalizes behind the reaction 24h, adopts distilled water to wash solid repeatedly, in supernatant, adopts liquor argenti nitratis ophthalmicus to detect less than Cl
-Till, again solid being placed 105 ℃ of oven dry down, gained solid note is hydroxyapatite-Zeolite composite materials.
(3) take by weighing 1.5 g hydroxyapatite-Zeolite composite materials in conical flask; Using pipette to pipette 24 mL concentration is 25 mmol/L brocide solution and the abundant mixing of hydroxyapatite-Zeolite composite materials; Place 40 ℃ of water bath with thermostatic control oscillators to vibrate and centrifugalize (centrifugal speed is 3000 rpm) behind 48 h with 150 rpm; Adopt analytically CPB concentration in the clear liquid of ultraviolet spectrophotometry (measuring wavelength is 259 nm); According to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 110 mmol/ (kg hydroxyapatite-Zeolite composite materials).Adopt distilled water to clean the solid of gained at last, in cleaning supernatant, adopt liquor argenti nitratis ophthalmicus to detect less than Br
-Till, be put in again and carry out air blast oven dry (bake out temperature is 50 ℃) in the beaker, promptly make hydroxyapatite-CPB modified zeolite composite after the cooling.
(4) take by weighing 0.025 according to the method described above the preparation adsorbent, placing 25 mL concentration is 100 mg/L humic acid solution, in advance the pH value of humic acid solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt humic acid concentration residual in the determined by ultraviolet spectrophotometry solution then, calculate this adsorbent humic acid unit's adsorbance is reached 89.5 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is the Congo red solution of 100 mg/L, in advance the pH value of solution is adjusted to 7.0 with sodium hydroxide solution and hydrochloric acid solution.Reactant liquor is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt visible spectrophotometry to measure residual Congo red concentration in the solution then, calculate this adsorbent Congo red unit adsorbance is reached 67.6 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take by weighing the adsorbent that 0.025 g prepares according to the method described above, placing 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, is 6.0 with the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution.Solution is placed on the constant temperature water bath oscillator vibration 24 hours, and oscillation rate is 150 rpm.Adopt behind the atomic absorption spectrophotometry light method assaying reaction concentration of copper ion in the solution then, calculate this adsorbent the unit adsorbance of Cu (II) is reached 39.2 mg/ (g hydroxyapatite-CPB modified zeolite composite).
The beneficial effect that the present invention brought is:
(1) the present invention adopts phosphate, calcium salt, alkali, zeolite and cationic surfactant to prepare a kind of hydroxyapatite-modified zeolite composite material adsorbent as stock; And be applied to the removal of humic acid in the water and organic pollution such as Congo red and heavy-metal pollution things such as copper ion and zinc ion; Realized the efficient development and utilization of cheap natural resources (zeolite); And prepared product is suitable for the removal of organic pollution and heavy-metal pollution thing in the water, is a kind of multi-functional absorption agent that can be used for removing simultaneously organic pollution and heavy-metal pollution thing in the water.
(2) for adsorbent, grain diameter small specific surface more is long-pending big more, and adsorption capacity is just high more.Nano-grade hydroxy apatite has very strong adsorption capacity to the heavy-metal pollution thing in the water, but reunites easily when nano-grade hydroxy apatite prepares, and is difficult to from waste liquid, separate after using and reuses.The present invention can realize nano-grade hydroxy apatite is fixed on the modified zeolite surface; Thereby reunite easily this problem when having avoided nano-grade hydroxy apatite to prepare, and compare to be easier to from waste liquid, separate after nano-grade hydroxy apatite-modified zeolite composite is used with nano-grade hydroxy apatite and reuse.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the inventive method; Can also make some improvement and replenish, these improvement and replenish and also should be regarded as protection scope of the present invention.
Claims (10)
1. hydroxyapatite-modified zeolite composite material adsorbent is characterized in that, described preparation of adsorbent method may further comprise the steps:
A, preparation particle size range 20-500 purpose zeolite place in the reactor that fills distilled water or deionized water, stir to make zeolite be in suspended state;
B, according to required soluble phosphate, calcium salt and the aqueous slkali of the required proportioning of hydroxyapatite synthetic chemistry equation preparation synthesizing hydroxylapatite; And phosphate and calcium salt soln added in the zeolite solution that is suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid;
C, get step b gained solid and place reactor; Press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g; The modified system mixture is taken out in the reaction back; Centrifugation, the concentration of cationic surfactant in the clear liquid analytically, the gained solid through clean, oven dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
2. adsorbent according to claim 1; It is characterized in that; The method for preparing hydroxyapatite-Zeolite composite materials among the described step b is selected from any one of following two kinds of methods: (1) joins phosphate and calcium salt soln in the zeolite solution of suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid; (2) earlier phosphate is mixed with the zeolite solution of suspended state, and adopt aqueous slkali to regulate more than the pH value to 8.0 of mixed liquor, then in suspension, drip soluble calcium salt, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid.
3. adsorbent according to claim 1 is characterized in that, described soluble phosphate is ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium dihydrogen phosphate; Calcium salt is calcium nitrate or calcium chloride; Aqueous slkali is NaOH, potassium hydroxide or ammoniacal liquor; The concentration of soluble phosphate, calcium salt, aqueous slkali is 0.1-5 mol/L; Described cationic surfactant is halogenated alkyl pyridine or quaternary cationic surfactant, and halogen wherein is bromine or chlorine, and alkyl carbon atoms is 12-18, and the cationic surfactant solution concentration is 5-50 mmol/L.
4. adsorbent according to claim 1 is characterized in that, the ratio of distilled water or deionized water and zeolite is 1-100mL/g among the described step a; Reaction temperature is 15-80 ℃ among the described step c, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60min, and the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach in the supernatant.
5. the preparation method of hydroxyapatite-modified zeolite composite material adsorbent is characterized in that, described preparation method may further comprise the steps:
A, preparation particle size range 20-500 purpose zeolite place in the reactor that fills distilled water or deionized water, stir to make zeolite be in suspended state;
B, according to required soluble phosphate, calcium salt and the aqueous slkali of the required proportioning of hydroxyapatite synthetic chemistry equation preparation synthesizing hydroxylapatite; And phosphate and calcium salt soln added in the zeolite solution that is suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid;
C, get step b gained solid and place reactor; Press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g; The modified system mixture is taken out in the reaction back; Centrifugation, the concentration of cationic surfactant in the clear liquid analytically, the gained solid through clean, oven dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
6. preparation method according to claim 5; It is characterized in that; The method for preparing hydroxyapatite-Zeolite composite materials among the described step b is selected from any one of following two kinds of methods: (1) joins phosphate and calcium salt soln in the zeolite solution of suspended state successively; Adopt more than the pH value to 8.0 of aqueous slkali regulator solution, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid; (2) earlier phosphate is mixed with the zeolite solution of suspended state, and adopt aqueous slkali to regulate more than the pH value to 8.0 of mixed liquor, then in suspension, drip soluble calcium salt, the reaction back obtains hydroxyapatite-Zeolite composite materials through Separation of Solid and Liquid.
7. preparation method according to claim 5 is characterized in that, described soluble phosphate is ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium dihydrogen phosphate; Calcium salt is calcium nitrate or calcium chloride; Aqueous slkali is NaOH, potassium hydroxide or ammoniacal liquor; The concentration of soluble phosphate, calcium salt, aqueous slkali is 0.1-5 mol/L; Described cationic surfactant is halogenated alkyl pyridine or quaternary cationic surfactant, and halogen wherein is bromine or chlorine, and alkyl carbon atoms is 12-18, and the cationic surfactant solution concentration is 5-50 mmol/L.
8. preparation method according to claim 5 is characterized in that, the ratio of distilled water or deionized water and zeolite is 1-100mL/g among the described step a; Reaction temperature is 15-80 ℃ among the described step c, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60min, and the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach in the supernatant.
9. remove the application in the organic pollution and heavy metal in the water according to the arbitrary described adsorbent of claim 1-4 in absorption.
10. a hydroxyapatite-modified zeolite composite material adsorbent is removed the method for organic pollution and heavy metal in the water; It is characterized in that; Described method may further comprise the steps: the arbitrary described hydroxyapatite of claim 1-4-modified zeolite composite material adsorbent is joined in the waste water that contains organic pollution or heavy metal; Vibrate on the constant temperature oscillator, can realize removal heavy metal in the waste water and organic pollution.
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