CN102527331B - 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 and its preparation method and application, specifically, is a kind of hydroxyapatite-modified zeolite composite material adsorbent and preparation method thereof and the application in removing organic pollutants and heavy metal.
Background technology
Along with the growth of socioeconomic fast development, population and the quickening of urbanization process, in the surface water bodies such as river, lake and reservoir, a large amount of pollutants has appearred, such as artificial synthetic organic materials and the 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 the mankind's drinking water safety has been arrived in the pollution that surface water body suffers serious threat at present.For drinking water quality and the protection surface water environment that improves the mankind, must take effective method to reduce the concentration of the manually synthetic organic pollution such as natural sex organic matter, dyestuff such as humic acid in water with heavy metal ion such as copper ion and zinc ions.
The method that tradition is removed Organic Pollutants In Water mainly comprises membrane filter technique, flocculence, advanced oxidation processes and bioanalysis etc., and the method that tradition is removed heavy metal ion in 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 adsorbent, huge specific area, or go up formed various chemical bonds between various active groups and adsorbate by surface, organic pollution and heavy metal contaminants in enrichment water selectively, and then reach the purpose of removing organic pollutants and heavy metal contaminants, therefore 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, is commonly used for cation adsorbent, cheap.But zeolite is poor to the adsorption capacity of anionic pollutant and organic pollution.Adopt cationic surfactant to carry out modification to zeolite and can obviously improve the adsorption capacity of zeolite to anionic pollutant and organic pollution.Hydroxyapatite is the main component of human body natural's bone lattice and tooth, and most of heavy metal ion and some organic matter are had and adsorb preferably fixation, can effectively remove heavy-metal pollution thing and some organic pollution in water.
The hydroxyapatite formed as the solvent structure by hydroxyapatite and cationic surfactant modified zeolite-modified zeolite composite is estimated both can effectively remove the organic pollution in water, can effectively remove the heavy-metal pollution thing in water again.But not about the research report of hydroxyapatite-modified zeolite composite material and preparation method thereof, about hydroxyapatite-modified zeolite composite, as the research of adsorbent Adsorption organic pollutants and heavy-metal pollution thing, do not report so far yet.
Chinese patent literature CN100431689C discloses a kind of preparation method who removes the compound adsorbent of nitrogen oxide, zeolite powder is mixed with hydrochloric acid solution, stir and be heated to boiling, cooling, suction filtration, add again the sodium hydroxide solution neutralization, suction filtration, dry, roasting again, make the modified zeolite powder, this powder is mixed and stirs with calcium chloride solution, suction filtration, dry to make and soak the salt zeolite powder, by modification or soak the salt zeolite powder and mix with the calcium hydroxide powder, add the deionized water kneading, extrusion modling is also dried, make compound adsorbent.Chinese patent literature CN102151546A discloses a kind of modified zeolite and its preparation method and application, by natural zeolite, with magnesia, mixed by roasting, cooling making, for the ammonia nitrogen removal preprocessing process of the breeding wastewater of carrying out a biological disposal upon, and as the adsorbent that adsorbs high-strength ammonium nitrogen in breeding wastewater.Chinese patent literature CN101590397B discloses a kind of preparation method and application of modified zeolite adsorbent, quantitatively take several parts of zeolites in conical flask, pipette modifier by the different solid ratio, in uniform temperature, under hunting speed, carry out Separation of Solid and Liquid after the reaction certain hour, water cleans to till can't detect modifier, finally adopt at a certain temperature and dry, make the modified zeolite adsorbent product, described modifier is the halogenated alkyl pyridine, halogen wherein is bromine or chlorine, alkyl carbon atoms is 12-18, product is suitable for the removal of organic substance humic acid etc. in high content of organics source water.But yet there are no report about hydroxyapatite-modified zeolite composite material adsorbent and its preparation method and application.
Summary of the invention
The objective of the invention is for deficiency of the prior art, a kind of hydroxyapatite-modified zeolite composite material adsorbent is provided.
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 is to provide a kind of hydroxyapatite-modified zeolite composite material adsorbent to remove the method for organic pollutants and heavy metal.
For achieving the above object, the technical scheme that the present invention takes is: a kind of hydroxyapatite-modified zeolite composite material adsorbent, and the preparation method of described adsorbent comprises the following steps:
A, preparation particle size range 20-500 purpose zeolite, be placed in the reactor that fills distilled water or deionized water, stirs and make zeolite 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 are added in the zeolite solution that is suspended state successively, more than adopting the pH value to 8.0 of aqueous slkali regulator solution, after reaction, by Separation of Solid and Liquid, obtain hydroxyapatite-Zeolite composite materials;
C, get step b gained solid and be placed in reactor, press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g, take out the modified system mixture after reaction, centrifugation, analyze the concentration of cationic surfactant in supernatant, the gained solid through cleaning, dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
The method for preparing hydroxyapatite-Zeolite composite materials in 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, more than adopting the pH value to 8.0 of aqueous slkali regulator solution, after reaction, by Separation of Solid and Liquid, obtain hydroxyapatite-Zeolite composite materials; (2) first phosphate is mixed with the zeolite solution of suspended state, and more than adopting the pH value to 8.0 of aqueous slkali adjusting mixed liquor, and drip soluble calcium salt in backward suspension, obtain hydroxyapatite-Zeolite composite materials by Separation of Solid and Liquid after reaction.
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.
In described step a, the ratio of distilled water or deionized water and zeolite is 1-100 mL/g; In described step c, reaction temperature is 15-80 ℃, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60min, and in supernatant, the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach.
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 comprises the following steps:
A, preparation particle size range 20-500 purpose zeolite, be placed in the reactor that fills distilled water or deionized water, stirs and make zeolite 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 are added in the zeolite solution that is suspended state successively, more than adopting the pH value to 8.0 of aqueous slkali regulator solution, after reaction, by Separation of Solid and Liquid, obtain hydroxyapatite-Zeolite composite materials;
C, get step b gained solid and be placed in reactor, press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g, take out the modified system mixture after reaction, centrifugation, analyze the concentration of cationic surfactant in supernatant, the gained solid through cleaning, dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
The method for preparing hydroxyapatite-Zeolite composite materials in 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, more than adopting the pH value to 8.0 of aqueous slkali regulator solution, after reaction, by Separation of Solid and Liquid, obtain hydroxyapatite-Zeolite composite materials; (2) first phosphate is mixed with the zeolite solution of suspended state, and more than adopting the pH value to 8.0 of aqueous slkali adjusting mixed liquor, and drip soluble calcium salt in backward suspension, obtain hydroxyapatite-Zeolite composite materials by Separation of Solid and Liquid after reaction.
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.
In described step a, the ratio of distilled water or deionized water and zeolite is 1-100 mL/g; In described step c, reaction temperature is 15-80 ℃, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60 min, and in supernatant, the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach.
For realizing above-mentioned the 3rd purpose, the technical scheme that the present invention takes is: the application of described adsorbent in Adsorption organic pollutants and heavy metal.
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 comprises the following steps: described hydroxyapatite-modified zeolite composite material adsorbent is joined in the waste water containing organic pollution or heavy metal, vibrate on constant temperature oscillator, can realize the removal to heavy metal in waste water and organic pollution.
The invention has the advantages that:
1, the present invention adopts phosphate, calcium salt, alkali, zeolite and cationic surfactant have prepared a kind of hydroxyapatite-modified zeolite composite material adsorbent as stock, and be applied to the removal of humic acid in water and the organic pollution such as Congo red and the heavy-metal pollution things such as copper ion and zinc ion, Efficient Development and the utilization of cheap natural resources (zeolite) have been realized, and prepared product is suitable for the removal of organic pollutants and heavy-metal pollution thing, it is a kind of multi-functional absorption agent that can be used for simultaneously removing organic pollutants and heavy-metal pollution thing,
2, the present invention can realize nano-grade hydroxy apatite is fixed on the modified zeolite surface, thereby easily reunite this problem while having avoided nano-grade hydroxy apatite to prepare, and be easier to separate and reused from waste liquid compare nano-grade hydroxy apatite-modified zeolite composite application with nano-grade hydroxy apatite after.
The specific embodiment
Below in conjunction with embodiment, the specific embodiment provided by the invention is elaborated.
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 running water or distilled water or washed with de-ionized water post-drying a period of time; Get that cooled zeolite carries out fragmentation, the processing of grinding, sieve, the zeolite made in certain particle size range is standby.
Take a certain amount of soluble phosphate, calcium salt and alkali, be mixed with certain density phosphate, calcium salt and aqueous slkali by distilled water or deionized water standby.
Take a certain amount of cationic surfactant, by distilled water or deionized water, be mixed with certain density cationic surfactant solution for standby.
It should be noted 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 is prepared by any method in following two kinds of methods:
It should be noted that, 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 ℃.In the hydroxyapatite-Zeolite composite materials prepared, the mass ratio of hydroxyapatite and zeolite is 1:(0.01 ~ 100), be preferably 1:1.
(3) preparation of hydroxyapatite-modified zeolite composite
Take respectively a certain amount of standby hydroxyapatite-Zeolite composite materials and be placed in 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, and the concentration of cationic surfactant in supernatant is analyzed in centrifugation, thereby determines the unit load amount of hydroxyapatite-Zeolite composite materials to cationic surfactant.The gained solid through cleaning, dry, broken, after sieving the particle in certain particle size range is standby, obtain hydroxyapatite-modified zeolite composite.
It should be noted 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 ℃, and 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 in supernatant, the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach, and baking temperature is 40 ℃-110 ℃.
(4) removal of hydroxyapatite-modified zeolite composite to organic pollution and heavy metal contaminants
Taking a certain amount of hydroxyapatite of preparation-modified zeolite composite material adsorbent 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, then be placed on the water-bath constant temperature oscillator of uniform temperature and vibrated, measure humic acid in supernatant after reaction a period of time, Congo red, the concentration of copper ion and zinc ion, according to humic acid in water before and after absorption, Congo red, the concentration difference of copper ion and zinc ion determines that hydroxyapatite-modified zeolite composite material adsorbent is to humic acid in water, Congo red, the unit adsorbance of copper ion and zinc ion.
It should be noted that, aqueous solution humic acid concentration range is 10-250 mg/L, and 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 water-bath constant temperature 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, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 200 mesh sieves standby; 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; The brocide that compound concentration is 25 mmol/L (CPB) solution for standby.
(2) get the standby natural zeolite of 20 g, be placed in the distilled water reactor that fills 100 mL, stir and make natural zeolite in suspended state, then add respectively successively Ca (the NO of 100 mL
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.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, then solid is placed under 105 ℃ after drying and ground 200 mesh sieves.Take the NaCl solution that 20g solid and 200mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take 10 g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 150 mL concentration with pipette is that 25 mmol/L brocide solution and hydroxyapatite-Zeolite composite materials fully mix and be placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.After 48 h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt ultraviolet spectrophotometry (measuring wavelength is 259 nm) to analyze CPB concentration in supernatant, according to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 235 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-CPB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 96.7 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.010 g, being placed in 25 mL concentration is the Congo red solution of 50 mg/L, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 20 hours, and oscillation rate is 150 rpm.Then adopt visible spectrophotometry to measure residual Congo red concentration in solution, calculate this adsorbent Congo red unit adsorbance is reached to 91.4 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 33.8 mg/ (g hydroxyapatite-CPB modified zeolite composite).
embodiment 3
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 200 mesh sieves standby; 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; The softex kw that compound concentration is 25 mmol/L (HTAB) solution for standby.
(2) get the standby natural zeolite of 20 g, be placed in the distilled water reactor that fills 100 mL, stir and make natural zeolite in suspended state, then add respectively successively Ca (the NO of 100 mL
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.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, solid ground 200 mesh sieves after being placed under 105 ℃ and drying.Take the NaCl solution that 20g solid and 200mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take 10 g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 150 mL concentration with pipette is that 25 mmol/L softex kw solution and hydroxyapatite-Zeolite composite materials fully mix and be placed on 40 ℃ of constant temperature waters oscillators and vibrate with 150 rpm.After 48h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt total organic carbon analyzer to analyze HTAB concentration in supernatant, according to HTAB calibration curve calculated equilibrium concentration, the adsorbance that obtains HTAB is 212 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-HTAB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 91.6 (mg humic acid)/(g hydroxyapatite-HTAB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 7.0.Solution is placed in to vibration 24 h on water-bath constant temperature oscillator, and oscillation rate is 150 rpm.Then adopt the Congo red concentration in solution after the visible spectrophotometry assaying reaction, and calculate this adsorbent to Congo red unit adsorbance reach 99.0 mg Congo red/(g hydroxyapatite-HTAB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 40.9 mg/ (g hydroxyapatite-HTAB modified zeolite composite).
embodiment 4
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 200 mesh sieves standby; 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; The brocide that compound concentration is 25 mmol/L (CPB) solution for standby.
(2) get the standby natural zeolite of 20 g, be placed in the distilled water reactor that fills 100 mL, stir and make natural zeolite in suspended state, then add respectively successively Ca (the NO of 50 mL
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.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, solid ground 200 mesh sieves after being placed under 105 ℃ and drying.Take the NaCl solution that 20g solid and 200mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take 1.5 g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 24 mL concentration with pipette is that 25 mmol/L brocide solution and hydroxyapatite-Zeolite composite materials fully mix and be placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.After reaction 48h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt ultraviolet spectrophotometry (measuring wavelength is 259 nm) to analyze CPB concentration in supernatant, according to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 251 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-CPB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 91.9 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt visible spectrophotometry to measure residual Congo red concentration in solution, calculate this adsorbent Congo red unit adsorbance is reached to 99.4 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 29.5 mg/ (g hydroxyapatite-CPB modified zeolite composite).
embodiment 5
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 200 mesh sieves standby; 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; The brocide that compound concentration is 25 mmol/L (CPB) solution for standby.
(2) get the standby natural zeolite of 5 g, be placed in the distilled water reactor that fills 100 mL, stir and make natural zeolite in suspended state, then add respectively successively Ca (the NO of 50 mL
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.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, solid ground 200 mesh sieves after being placed under 105 ℃ and drying.Take the NaCl solution that 10g solid and 100mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, gained solid note is hydroxyapatite-Zeolite composite materials.
(3) take 1.5 g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 24 mL concentration with pipette is that 25 mmol/L brocide solution and hydroxyapatite-Zeolite composite materials fully mix, being placed in 40 ℃ of water bath with thermostatic control oscillators take 150 rpm and vibrates after 48 h and carry out centrifugation (centrifugal speed is 3000 rpm), adopt ultraviolet spectrophotometry (measuring wavelength is 259 nm) to analyze CPB concentration in supernatant, according to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 105 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-CPB modified zeolite composite after cooling.
(4) take 0.025 adsorbent prepared according to the method described above, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 88.1 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt visible spectrophotometry to measure residual Congo red concentration in solution, calculate this adsorbent Congo red unit adsorbance is reached to 68.4 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 40.0 mg/ (g hydroxyapatite-CPB modified zeolite composite).
embodiment 6
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 200 mesh sieves standby; 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; The brocide that compound concentration is 25 mmol/L (CPB) solution for standby.
(2) get the standby natural zeolite of 15 g, be placed in the distilled water reactor that fills 15 mL, stir and make natural zeolite in suspended state, then add (the NH of 150 mL
4)
2hPO
4solution, and adopt the pH value to 9.0 of NaOH solution conditioned reaction liquid, drip again the Ca (NO of 150 mL in the continuous stirring situation
3)
2solution.Continue, after reaction 72 h, mixture is carried out to centrifugation, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0.The gained solid is joined in the NaCl solution that the concentration of 250 mL is 1 mol/L, and centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and ground 200 mesh sieves after oven dry, the gained solid is nano-grade hydroxy apatite-Zeolite composite materials.
(3) take 10 g nano-grade hydroxy apatite-Zeolite composite materials in conical flask, pipetting 120 mL concentration with pipette is that 25 mmol/L brocide solution and nano-grade hydroxy apatite-Zeolite composite materials fully mix and be placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.After reaction 48h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt ultraviolet spectrophotometry (measuring wavelength is 259 nm) to analyze CPB concentration in supernatant, according to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 251 mmol/ (kg nano-grade hydroxy apatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make nano-grade hydroxy apatite-CPB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 95.6 (mg humic acid)/(g nano-grade hydroxy apatite-CPB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt visible spectrophotometry to measure residual Congo red concentration in solution, calculate this adsorbent Congo red unit adsorbance is reached to 98.6 (mg is Congo red)/(g nano-grade hydroxy apatite-CPB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, be placed in 25 mL concentration and be respectively 20,50 and 100 mg/L copper ions (Cu (II)) solution, the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 19.9,49.1 and 70.9 mg/ (g nano-grade hydroxy apatite-CPB modified zeolite composite).
(7) take adsorbent prepared according to the method described above by 0.025 g, be placed in 25 mL concentration and be respectively 20,40 and 80 mg/L zinc ion solution, the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of zinc ion in solution, calculate this adsorbent the unit adsorbance of Zn (II) is respectively to 19.7,39.7 and 51.6 mg/ (g nano-grade hydroxy apatite-CPB modified zeolite composite).
embodiment 7
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 200 mesh sieves standby; 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; The softex kw that compound concentration is 25 mmol/L (HTAB) solution for standby.
(2) get the standby natural zeolite of 15 g, be placed in the distilled water reactor that fills 150 mL, stir and make natural zeolite in suspended state, then add (the NH of 150 mL
4)
2hPO
4solution, and adopt the pH value to 9.0 of NaOH solution conditioned reaction liquid, drip again the Ca (NO of 150 ml in the situation of continuous stirring
3)
2solution.Continue, after reaction 72 h, mixed liquor is carried out to centrifugation, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0.Solid is placed under 105 ℃ again and ground 200 mesh sieves after oven dry, the gained solid is nano-grade hydroxy apatite-Zeolite composite materials.
(3) take 1.0 g nano-grade hydroxy apatite-Zeolite composite materials in conical flask, pipetting 16mL concentration with pipette is that 25 mmol/L softex kw solution and nano-grade hydroxy apatite-zeolite fully mix and be placed on 40 ℃ of constant temperature waters oscillators and vibrate with 150 rpm.After reaction 48h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt total organic carbon analyzer to analyze HTAB concentration in supernatant, according to HTAB calibration curve calculated equilibrium concentration, the adsorbance that obtains HTAB is 253 mmol/ (kg nano-grade hydroxy apatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make nano-grade hydroxy apatite-HTAB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 95.8 (mg humic acid)/(g nano-grade hydroxy apatite-HTAB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 7.0.Solution is placed in to vibration 24 h on water-bath constant temperature oscillator, and oscillation rate is 150 rpm.Then adopt the Congo red concentration in solution after the visible spectrophotometer assaying reaction, 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 adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 50.0 mg/ (g nano-grade hydroxy apatite-HTAB modified zeolite composite).
(7) take adsorbent prepared according to the method described above by 0.050 g, be placed in 25 mL concentration and be respectively 50 mg/L zinc ion solution, the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of zinc ion in solution, calculate this adsorbent the unit adsorbance of Zn (II) is reached to 24.9 mg/ (g nano-grade hydroxy apatite-CPB modified zeolite composite).
embodiment 8
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 20 mesh sieves standby; 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; The brocide that compound concentration is 50 mmol/L (CPB) solution for standby.
(2) get the standby natural zeolite of 20g, be placed in the distilled water reactor that fills 100mL, stir and make natural zeolite in suspended state, then add respectively successively the CaCl of 100 mL
2na with 100 mL
2hPO
4, and the pH value to 9.0 of employing KOH solution conditioned reaction liquid.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, then solid is placed under 105 ℃ after drying and ground 200 mesh sieves.Take the NaCl solution that 20g solid and 200mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take 10 g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 80 mL concentration with pipette is that 50 mmol/L brocide solution and hydroxyapatite-Zeolite composite materials fully mix and be placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.After reacting 48 h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt ultraviolet spectrophotometry (measuring wavelength is 259 nm) to analyze CPB concentration in supernatant, according to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 228 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-CPB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.050 g, being placed in 50 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 96.5 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt visible spectrophotometry to measure residual Congo red concentration in solution, calculate this adsorbent Congo red unit adsorbance is reached to 90.1 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 60 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 38.1 mg/ (g hydroxyapatite-CPB modified zeolite composite).
embodiment 9
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 400 mesh sieves standby; 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; The softex kw that compound concentration is 50 mmol/L (HTAB) solution for standby.
(2) get the standby natural zeolite of 20 g, be placed in the distilled water reactor that fills 100 mL, stir and make natural zeolite in suspended state, then add respectively successively Ca (the NO of 100 mL
3)
2naH with 100 mL
2pO
4, and adopt NH
3h
2the pH value of O solution conditioned reaction liquid is 9.0.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, solid ground 200 mesh sieves after being placed under 105 ℃ and drying.Take the NaCl solution that 20g solid and 200mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take 1.0g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 12 mL concentration with pipette is that 50 mmol/L softex kw solution and hydroxyapatite-Zeolite composite materials fully mix and be placed on 40 ℃ of constant temperature waters oscillators and vibrate with 150 rpm.After 48h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt total organic carbon analyzer to analyze HTAB concentration in supernatant, according to HTAB calibration curve calculated equilibrium concentration, the adsorbance that obtains HTAB is 217 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-HTAB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 92.8 (mg humic acid)/(g hydroxyapatite-HTAB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 7.0.Solution is placed in to vibration 24 h on water-bath constant temperature oscillator, and oscillation rate is 150 rpm.Then adopt the Congo red concentration in solution after the visible spectrophotometry assaying reaction, and calculate this adsorbent to Congo red unit adsorbance reach 99.6 mg Congo red/(g hydroxyapatite-HTAB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 38.7 mg/ (g hydroxyapatite-HTAB modified zeolite composite).
embodiment 10
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 100 mesh sieves standby; 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; The brocide that compound concentration is 5 mmol/L (CPB) solution for standby.
(2) get the standby natural zeolite of 20 g, be placed in the distilled water reactor that fills 100 mL, stir and make natural zeolite in suspended state, then add respectively successively Ca (the NO of 50 mL
3)
2k with 50 mL
2hPO
4, and the pH value of employing KOH solution conditioned reaction liquid is 9.0.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, solid ground 200 mesh sieves after being placed under 105 ℃ and drying.Take the NaCl solution that 20g solid and 200mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, the gained solid is designated as hydroxyapatite-Zeolite composite materials.
(3) take 1.0 g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 80 mL concentration with pipette is that 5 mmol/L brocide solution and hydroxyapatite-Zeolite composite materials fully mix and be placed on 40 ℃ of water bath with thermostatic control oscillators and vibrate with 150 rpm.After 48h, mixed liquor is carried out to centrifugation (centrifugal speed is 3000 rpm), adopt ultraviolet spectrophotometry (measuring wavelength is 259 nm) to analyze CPB concentration in supernatant, according to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 248 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-CPB modified zeolite composite after cooling.
(4) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 90.8 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt visible spectrophotometry to measure residual Congo red concentration in solution, calculate this adsorbent Congo red unit adsorbance is reached to 99.0 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 30.5 mg/ (g hydroxyapatite-CPB modified zeolite composite).
embodiment 11
(1) get natural zeolite, after adopting distilled water to clean for several times, air blast is air-dry, broken, grind, 500 mesh sieves standby; 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; The brocide that compound concentration is 25 mmol/L (CPB) solution for standby.
(2) get the standby natural zeolite of 5 g, be placed in the distilled water reactor that fills 100 mL, stir and make natural zeolite in suspended state, then add respectively successively Ca (the NO of 50 mL
3)
2kH with 50 mL
2pO
4after fully mixing, adopt NH
3h
2the pH value of O solution conditioned reaction liquid is 9.0.React centrifugation after 72 h, adopt distilled water repeatedly to rinse solid, until the pH of supernatant is close to 7.0, solid ground 200 mesh sieves after being placed under 105 ℃ and drying.Take the NaCl solution that 10g solid and 100mL concentration are 1mol/L and be placed in the lump reactor, centrifugation after reaction 24h, adopt distilled water repeatedly to rinse solid, until adopt liquor argenti nitratis ophthalmicus to can't detect Cl in supernatant
-till, then solid is placed under 105 ℃ and dries, gained solid note is hydroxyapatite-Zeolite composite materials.
(3) take 1.5 g hydroxyapatite-Zeolite composite materials in conical flask, pipetting 24 mL concentration with pipette is that 25 mmol/L brocide solution and hydroxyapatite-Zeolite composite materials fully mix, being placed in 40 ℃ of water bath with thermostatic control oscillators take 150 rpm and vibrates after 48 h and carry out centrifugation (centrifugal speed is 3000 rpm), adopt ultraviolet spectrophotometry (measuring wavelength is 259 nm) to analyze CPB concentration in supernatant, according to CPB calibration curve calculated equilibrium concentration, the adsorbance that obtains CPB is 110 mmol/ (kg hydroxyapatite-Zeolite composite materials).Finally adopt distilled water to clean the solid of gained, until clean in supernatant, adopt liquor argenti nitratis ophthalmicus to can't detect Br
-till, then be put in beaker and carry out air blast oven dry (bake out temperature is 50 ℃), make hydroxyapatite-CPB modified zeolite composite after cooling.
(4) take 0.025 adsorbent prepared according to the method described above, being placed in 25 mL concentration is 100 mg/L humic acid solution, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of humic acid solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt humic acid concentration residual in determined by ultraviolet spectrophotometry solution, calculate this adsorbent humic acid unit's adsorbance is reached to 89.5 (mg humic acid)/(g hydroxyapatite-CPB modified zeolite composite).
(5) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is the Congo red solution of 100 mg/L, with sodium hydroxide solution and hydrochloric acid solution, in advance the pH value of solution is adjusted to 7.0.Reactant liquor is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt visible spectrophotometry to measure residual Congo red concentration in solution, calculate this adsorbent Congo red unit adsorbance is reached to 67.6 (mg is Congo red)/(g hydroxyapatite-CPB modified zeolite composite).
(6) take adsorbent prepared according to the method described above by 0.025 g, being placed in 25 mL concentration is 50 mg/L copper ions (Cu (II)) solution, and the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution of take is 6.0.Solution is placed on water-bath constant temperature oscillator and vibrates 24 hours, and oscillation rate is 150 rpm.Then adopt after atomic absorption spectrophotometry light method assaying reaction the concentration of copper ion in solution, calculate this adsorbent the unit adsorbance of Cu (II) is reached to 39.2 mg/ (g hydroxyapatite-CPB modified zeolite composite).
The beneficial effect that the present invention brings is:
(1) the present invention adopts phosphate, calcium salt, alkali, zeolite and cationic surfactant have prepared a kind of hydroxyapatite-modified zeolite composite material adsorbent as stock, and be applied to the removal of humic acid in water and the organic pollution such as Congo red and the heavy-metal pollution things such as copper ion and zinc ion, Efficient Development and the utilization of cheap natural resources (zeolite) have been realized, and prepared product is suitable for the removal of organic pollutants and heavy-metal pollution thing, it is a kind of multi-functional absorption agent that can be used for simultaneously removing organic pollutants and heavy-metal pollution thing.
(2) for adsorbent, grain diameter more small specific surface is long-pending larger, and adsorption capacity is just higher.Nano-grade hydroxy apatite has very strong adsorption capacity to the heavy-metal pollution thing in water, but easily reunites when prepared by nano-grade hydroxy apatite, and is difficult to separate and reused from waste liquid after application.The present invention can realize nano-grade hydroxy apatite is fixed on the modified zeolite surface, thereby easily reunite this problem while having avoided nano-grade hydroxy apatite to prepare, and be easier to separate and reused from waste liquid compare nano-grade hydroxy apatite-modified zeolite composite application with nano-grade hydroxy apatite after.
The above is only the preferred embodiment of the present invention; it 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 supplement, these improvement and supplement and also should be considered as protection scope of the present invention.
Claims (10)
1. hydroxyapatite-modified zeolite composite material adsorbent, is characterized in that, the preparation method of described adsorbent comprises the following steps:
A, preparation particle size range 20-500 purpose zeolite, be placed in the reactor that fills distilled water or deionized water, stirs and make zeolite 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 are added in the zeolite solution that is suspended state successively, more than adopting the pH value to 8.0 of aqueous slkali regulator solution, after reaction, by Separation of Solid and Liquid, obtain hydroxyapatite-Zeolite composite materials;
C, get step b gained solid and be placed in reactor, press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g, take out the modified system mixture after reaction, centrifugation, analyze the concentration of cationic surfactant in supernatant, the gained solid through cleaning, dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
2. adsorbent according to claim 1, it is characterized in that, prepare the another kind of method of hydroxyapatite-Zeolite composite materials in described step b for first phosphate is mixed with the zeolite solution of suspended state, and more than adopting the pH value to 8.0 of aqueous slkali adjusting mixed liquor, and drip soluble calcium salt in backward suspension, obtain hydroxyapatite-Zeolite composite materials by Separation of Solid and Liquid after reaction.
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, in described step a, the ratio of distilled water or deionized water and zeolite is 1-100mL/g; In described step c, reaction temperature is 15-80 ℃, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60min, and in supernatant, the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach.
5. the preparation method of hydroxyapatite-modified zeolite composite material adsorbent, is characterized in that, described preparation method comprises the following steps:
A, preparation particle size range 20-500 purpose zeolite, be placed in the reactor that fills distilled water or deionized water, stirs and make zeolite 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 are added in the zeolite solution that is suspended state successively, more than adopting the pH value to 8.0 of aqueous slkali regulator solution, after reaction, by Separation of Solid and Liquid, obtain hydroxyapatite-Zeolite composite materials;
C, get step b gained solid and be placed in reactor, press the liquid-solid ratio mixed-cation surfactant solution of 8-80 mL/g, take out the modified system mixture after reaction, centrifugation, analyze the concentration of cationic surfactant in supernatant, the gained solid through cleaning, dry, broken, be hydroxyapatite-modified zeolite composite material adsorbent after sieving.
6. preparation method according to claim 5, it is characterized in that, prepare the another kind of method of hydroxyapatite-Zeolite composite materials in described step b for first phosphate is mixed with the zeolite solution of suspended state, and more than adopting the pH value to 8.0 of aqueous slkali adjusting mixed liquor, and drip soluble calcium salt in backward suspension, obtain hydroxyapatite-Zeolite composite materials by Separation of Solid and Liquid after reaction.
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, in described step a, the ratio of distilled water or deionized water and zeolite is 1-100mL/g; In described step c, reaction temperature is 15-80 ℃, and centrifugation rate is 500-5000 rpm, and centrifugation time is 5-60min, and in supernatant, the analytical method of cationic surfactant is ultraviolet spectrophotometry or total organic carbon analytic approach.
9. according to the application of the arbitrary described adsorbent of claim 1-4 in Adsorption organic pollutants and heavy metal.
10. a hydroxyapatite-modified zeolite composite material adsorbent is removed the method for organic pollutants and heavy metal, it is characterized in that, described method comprises the following steps: the arbitrary described hydroxyapatite of claim 1-4-modified zeolite composite material adsorbent is joined in the waste water containing organic pollution or heavy metal, vibrate on constant temperature oscillator, can realize the removal to heavy metal in waste water and organic pollution.
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| ES2500042B1 (en) * | 2013-02-26 | 2015-07-06 | Consejo Superior De Investigaciones Científicas (Csic) | Composite material of stilbite-nanohydroxyapatite, preparation and use procedure for the removal of fluoride from water |
| CN107258812A (en) * | 2017-06-22 | 2017-10-20 | 安徽省德邦瓷业有限公司 | A kind of preparation method of composite modified zeolite with carrying silver for domestic ceramics glaze slip |
| CN107213866A (en) * | 2017-06-26 | 2017-09-29 | 泉州师范学院 | A kind of preparation method and application for being used to go the zinc oxide modified zeolite adsorbing material of anionic pollutant in water removal |
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| CN108217889A (en) * | 2018-02-07 | 2018-06-29 | 宁波高新区斯汀环保科技有限公司 | A kind of hydroxyapatite inorganic agent of modification and its preparation method and application |
| CN112607889A (en) * | 2018-09-15 | 2021-04-06 | 南京霄祥工程技术有限公司 | Treatment method of fermentation wastewater |
| CN109692655B (en) * | 2019-01-14 | 2021-08-06 | 昆明理工大学 | Preparation method and application of modified natural apatite adsorption material |
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| CN111533188B (en) * | 2020-04-22 | 2022-07-12 | 北京泷涛环境修复有限公司 | Repairing agent for heavy metal polluted underground water, preparation method and application method |
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