CN102500333B - Magnetic cationic surfactant modified chitosan / hydroxyapatite / zeolite composite and preparation method and application thereof - Google Patents
Magnetic cationic surfactant modified chitosan / hydroxyapatite / zeolite composite and preparation method and application thereof Download PDFInfo
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- 239000004021 humic acid Substances 0.000 abstract description 27
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- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 28
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Abstract
The invention relates to the fields of materials and the water quality purification and pollutant treatment technology. Natural zeolite, hydroxyapatite, ferroferric oxide, chitosan and cationic surfactant are used as basic materials to prepare a magnetic cationic surfactant modified chitosan / hydroxyapatite / zeolite composite which can serve as magnetic organic and inorganic composite adsorbent, and the adsorbent can be used for removing humic acid, cango red and other organic pollutants and copper ions and other heavy metal pollutants in water. The composite serving as the adsorbent is good in adsorption performance, can be gathered through an external magnetic field, and is easy in solid-liquid separation. Process is simple, cost is low, and utilization ratio is high.
Description
Technical field
the present invention relates to Material Field, the purification of water quality and pollutant processing technology field, relate to and utilize natural zeolite, hydroxyapatite, tri-iron tetroxide, shitosan and cationic surfactant prepare a kind of magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition as stock, can be used as magnetic organic/inorganic composite material adsorbent, and this adsorbent is applied to remove humic acid, the Congo red heavy metal contaminants such as organic pollution and copper ion that wait, realize Efficient Development and the utilization of cheap natural resources (shitosan and natural zeolite).
Background technology
In water body, ubiquity a large amount of natural sex organic matters, and such as humic acid etc., natural organic matter is the main precursor of DBPs in drinking water treatment technique.Along with socioeconomic fast development, a large amount of artificial synthetic organic pollutions and heavy metal contaminants have constantly appearred again in water body, such as Congo red and copper ion etc., the existence of these pollutants makes surface water body be subject in various degree pollution.Serious threat of the pollution of water body hydrobiological living safety and the mankind's drinking water safety.
Be to improve the mankind's drinking water quality, must take effective method to reduce the concentration of humic acid concentration and Organic Pollutants in Wastewater and heavy metal contaminants in water.The method that tradition is removed Organic Pollutants In Water mainly contains membrane filter technique, flocculence, advanced oxidation processes, bioanalysis etc.; The method of removing heavy metal contaminants in water mainly contains ion-exchange, membrane separation process and bioanalysis 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 by formed various chemical bonds between surperficial various active groups and adsorbate, pollutant in enrichment water selectively, and then reach the purpose of removing water pollutant.
At present, in absorption method removal water, hardly degraded organic substance and heavy metal contaminants attract wide attention.Natural zeolite is a kind of aluminosilicate mineral with good cation exchange capacity (CEC) and adsorption capacity, is commonly used for cation adsorbent, and is cheap, but natural zeolite is relatively poor to anion and Adsorption of Organic ability.Show according to relevant result of study, with cationic surfactant, zeolite is carried out modification and can greatly improve zeolite to anion and Adsorption of Organic ability.
Hydroxyapatite is a kind of of apatite mineral, is applied to the earliest medical domain, is used for subsequently the reparation of contaminated soil and the improvement of water pollution.Hydroxyapatite has suction-operated preferably to most of heavy metal ion and some organic pollution.
Shitosan is a class natural polymer that is obtained through deacetylation by the chitin that nature extensively exists.Shitosan is considered to effectively to remove a kind of good biological adsorption agent of the heavy metal ion in water.
For adsorbent, grain diameter more small specific surface is long-pending larger, and adsorption capacity is just higher.The time that is suspended in after but the adsorbent that particle diameter is less is finished using in processed waste water system is just more of a specified duration, more is difficult to separate fast reclaim.The pollutant of magnetic adsorptive material in both can Adsorption water also can directly be separated magnetic adsorptive material fast by the effect of externally-applied magnetic field from the waste water system, thereby realizes combining of sorbing material high adsorption and Magnetic Isolation characteristic.The magnetic organic/inorganic composite material adsorbent that is prepared from as stock by natural zeolite, hydroxyapatite, tri-iron tetroxide, shitosan and cationic surfactant will be both organic matter and heavy metal in can Adsorption waste water, the effect that can cross again externally-applied magnetic field is separated it rapidly from waste water.But still do not adopt so far natural zeolite, hydroxyapatite, tri-iron tetroxide, shitosan and cationic surfactant to prepare the relevant report of magnetic organic/inorganic composite material adsorbent as stock, also do not remove the research report of water pollutant about this adsorbent.
Summary of the invention
The purpose of this invention is to provide a kind of natural zeolite, hydroxyapatite, tri-iron tetroxide, shitosan and cationic surfactant of utilizing and prepare composite as stock, it is a kind of magnetic organic/inorganic composite material adsorbent, and be applied to the removal of humic acid in water and the heavy metal such as the organic matter such as Congo red and copper ion, to realize the Efficient Development utilization of cheap natural resources.This scheme technique is simple, with low cost, and the absorption property of product is good.
Technical solution of the present invention is, prepares the method for magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition, and step comprises:
(1) preparation of chitosan magnetic/hydroxyapatite/zeolite: natural zeolite, hydroxyapatite and tri-iron tetroxide and water are stirred fully mix and be in suspended state; The mass ratio of natural zeolite, hydroxyapatite and tri-iron tetroxide is 1: (0.5～2.5): (0.5～2.5) is preferably 1: (0.5～1.5): (0.5～2.5); The particle diameter of natural zeolite, hydroxyapatite and tri-iron tetroxide is 150～300 orders;
Adding chitosan solution chitosan concentration to the reaction system is 0.004～0.012g/ml, fully mixes; Drip again alkaline solution, until obvious floccule appears in reactant liquor pH＞7 (being preferably 7.5～11), continue to stir 10～30min; Precipitation is got in centrifugation, washing to neutral and 90～110 ℃ under oven dry, ground 150～300 mesh sieves, obtain chitosan magnetic/hydroxyapatite/zeolite;
The chitosan solution that adds is prepared by the acid solution of mass concentration 0.5%～10%, and wherein shitosan content is 0.005～0.1g/ml, preferred 0.01～0.05g/ml;
The alkaline solution that adds is NaOH or KOH solution, and concentration is 0.5～5mol/L;
(2) modification: get the chitosan magnetic/hydroxyapatite of step (1) preparation/zeolite, liquid-solid ratio by 1～200mL/g (is preferably 1～20mL/g) and adds cationic surfactant solution, vibration 5～96h, hunting speed is 100～500rpm; 15～60 ℃ of temperature; Obtain magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition, i.e. magnetic organic/inorganic composite material adsorbent;
Described cationic surfactant solution concentration is 5～100mmol/L, is preferably 10～50mmol/L; Cationic surfactant is preferably brocide or softex kw.
Solid is got in the mixed liquor centrifugation of vibration after modification, and washing, and is dry under 50～60 ℃.
Magnetic cationic surfactant modified chitosan/hydroxyapatite that processing obtains through above-mentioned steps/zeolite composition, the cationic surfactant load capacity is 60～160mmol/kg.
Determine by the following method the load capacity of cationic surfactant in step (2): when cationic surfactant is brocide or softex kw, get the mixed liquor of vibration after modification in 500rpm～4000rpm centrifugation, centrifugation time is 5min～60min; Adopt ultraviolet-visible spectrophotometry or total organic carbon analytic approach to analyze the concentration of cationic surfactant in supernatant, the load capacity of quantitative analysis cationic surfactant.Adopt at last distilled water to clean, there is no Br until adopt liquor argenti nitratis ophthalmicus to detect in upper the cleaning
-Till, solid is placed in carries out air blast oven dry under 50 ℃ of conditions, namely make magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition adsorbent after cooling.
can measure by the following method magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition to the Adsorption effect of pollutant: take magnetic cationic surfactant modified chitosan/hydroxyapatite that 0.005～0.500g prepares/zeolite composition, join in the solution of humic acid that concentration is 1mg/L～250mg/L or Congo red or copper ion, after pH value (5～10) with acid or aqueous slkali regulator solution, be placed on 15 ℃～60 ℃ water-bath constant temperature oscillators and vibrated 1～48 hour, the concentration of humic acid or Congo red or copper ion in the separation determination supernatant, concentration difference according to humic acid or Congo red or copper ion in water before and after absorption, determine that this adsorbent is to the adsorption effect of humic acid in water or Congo red or copper ion.
Magnetic cationic surfactant modified chitosan/the hydroxyapatite for preparing by said method/zeolite composition, it is a kind of magnetic organic/inorganic composite material adsorbent, can be used as the water body adsorbent, can remove organic matter in water (as humic acid and Congo red etc.) and heavy metal ion (as copper ion etc.).More than humic acid and Congo red adsorbance reach 80mg/kg, more than cupric ion adsorption reaches 27mg/kg.
This compound is as adsorbent, and absorption property is good; And after absorption, by externally-applied magnetic field, this compound is assembled, easily Separation of Solid and Liquid.
the present invention adopts shitosan, natural zeolite, hydroxyapatite, tri-iron tetroxide and cationic surfactant prepare a kind of magnetic organic/inorganic composite material adsorbent as raw material, be used for the removal of water humic acid and the heavy metal contaminants such as the organic pollution such as Congo red and copper ion in conjunction with adsorption technology, Efficient Development and the utilization of cheap natural resources (natural zeolite and shitosan) have been realized, and dissolubility organic pollution in the product that makes water suitable for drinking, anionic dye and smelting and processing of metals industry heavy metal in waste water removal of pollutants in dyeing waste water, has utilization rate high, the advantage such as with low cost.This scheme technique is simple, with low cost, and the absorption property of product is good.
Description of drawings
Fig. 1 is the not photo before Separation of Solid and Liquid of adsorbent and Congo red mixing suspension;
Fig. 2 is the photo after adsorbent and Congo red mixing suspension pass through the externally-applied magnetic field Separation of Solid and Liquid.
The specific embodiment
The present invention is described in further detail and completely below in conjunction with embodiment.
Embodiment 1
(1) got natural zeolite, hydroxyapatite, the tri-iron tetroxide of 200 mesh sieves standby; Be that the chitosan solution of 0.02g/ml is standby with the concentration acetic acid solutions concentration that is 2wt%; Compound concentration is that brocide (CPB) storing solution of 25mmol/L is standby.
(2) take respectively 5g natural zeolite, 5g hydroxyapatite and 10g tri-iron tetroxide, be placed in the distilled water reactor that fills 200mL, stirring fully mixes natural zeolite, hydroxyapatite and tri-iron tetroxide and is in suspended state; The chitosan solution that takes 200mL is with after suspended solid fully mixes, and dripping concentration in the reactant liquor is the sodium hydroxide solution of 2.0mol/L, until reactant liquor occurs continuing to stir 15min after obvious cotton-shaped object (this moment pH approximately 8～11); Then centrifugation adopts distilled water repeatedly to rinse solid, until the pH of supernatant is close to till 7.0, solid is placed under 105 ℃ after oven dry, grinds after 200 mesh sieves standbyly, and the gained solid is designated as chitosan magnetic/hydroxyapatite/zeolite.
(3) take 10g magnetic CPB/ shitosan/hydroxyapatite/zeolite in conical flask, after pipetting 80mL concentration and be 25mmol/L brocide storing solution and the abundant mixing of chitosan magnetic/hydroxyapatite/zeolite with pipette, be placed in 40 ℃ of water bath with thermostatic control oscillators with 150rpm vibration 2d after with the speed centrifugation of 3000rpm, adopt ultraviolet spectrophotometry (the mensuration wavelength is 259nm) to analyze CPB concentration in supernatant, according to calculated equilibrium concentration on the CPB calibration curve, the adsorbance that obtains CPB is 86mmol/ (kg chitosan magnetic/hydroxyapatite/zeolite).Adopt at last distilled water to clean, there is no Br until adopt liquor argenti nitratis ophthalmicus to detect in upper the cleaning
-Till, solid is placed in carries out air blast oven dry under 50 ℃ of conditions, namely make magnetic CPB modification of chitosan/hydroxyapatite/zeolite after cooling, be designated as magnetic CPB/ shitosan/hydroxyapatite/zeolite.
(4) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0100g said method preparation/zeolite adsorbents, being placed in 25mL concentration is the Congo red solution of 50.0mg/L, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm, and Congo red adsorbance reaches 110 (mg is Congo red)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
As depicted in figs. 1 and 2, magnetic CPB/ shitosan/hydroxyapatite/zeolite adsorbents joins in Congo red solution, and after vibration, liquid is dark suspension russet (Fig. 1); After externally-applied magnetic field was separated, magnetic CPB/ shitosan/hydroxyapatite/zeolite adsorbents was assembled, and liquid becomes clear (Fig. 2).
(5) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100.0mg/L humic acid solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate the humic acid adsorbance and reach 94.3 (mg humic acid)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
(6) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100mg/L copper ion (Cu (II)) solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 6.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.The adsorbance that calculates copper ion reaches 30.6mg Cu (II)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
Embodiment 2
(1) got natural zeolite, hydroxyapatite, the tri-iron tetroxide of 200 mesh sieves standby; Be that 2% acetic acid solutions concentration is that the chitosan solution of 0.02g/ml is standby with concentration; Compound concentration is that softex kw (HTAB) storing solution of 25mmol/L is standby.
(2) take respectively 1g natural zeolite, 1g hydroxyapatite and 0.5g tri-iron tetroxide, be placed in the distilled water reactor that fills 15mL, stirring fully mixes natural zeolite, hydroxyapatite and tri-iron tetroxide and is in suspended state; The chitosan solution that takes 12.5mL is with after the suspended state mixture fully mixes, and dripping concentration in the reactant liquor is the sodium hydroxide solution of 2.0mol/L, until reactant liquor occurs continuing to stir 15min after obvious cotton-shaped object (this moment pH approximately 8～11); Then centrifugation adopts distilled water repeatedly to rinse solid, until the pH of supernatant is close to till 7.0, solid is placed under 105 ℃ after oven dry, and standby after grinding, the gained solid is designated as chitosan magnetic/hydroxyapatite/zeolite.
(3) take 0.5g chitosan magnetic/hydroxyapatite/zeolite in conical flask, after pipetting 5mL concentration and be 25mmol/L softex kw storing solution and the abundant mixing of chitosan magnetic/hydroxyapatite/zeolite with pipette, be placed in 40 ℃ of water bath with thermostatic control oscillators with 150rpm vibration 24hr after with the centrifugation of 4000rpm speed, adopt the total organic carbon method to analyze HTAB concentration in supernatant, calculate residual HTAB concentration in solution according to the HTAB calibration curve, the adsorbance that calculates HTAB is 133mmol/ (kg shell chitosan magnetic/hydroxyapatite/zeolite).Adopt at last distilled water to clean, there is no Br until adopt liquor argenti nitratis ophthalmicus to detect in supernatant
-Till, solid is placed in carries out air blast oven dry under 50 ℃ of conditions, namely make magnetic HTAB modification of chitosan/hydroxyapatite/zeolite after cooling, be designated as magnetic HTAB/ shitosan/hydroxyapatite/zeolite.
(4) take the magnetic HTAB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100mg/L humic acid solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate the humic acid adsorbance and reach 92.8 (mg humic acid)/(g magnetic HTAB/ shitosan/hydroxyapatite/zeolite).
(5) take the magnetic HTAB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is the Congo red solution of 100mg/L, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate Congo red adsorbance and reach 90.2 (mg is Congo red)/(g magnetic HTAB/ shitosan/hydroxyapatite/zeolite).
(6) take the magnetic HTAB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100mg/L copper ion (Cu (II)) solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 6.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.The adsorbance that calculates copper ion reaches 29.2mg Cu (II)/(g magnetic HTAB/ shitosan/hydroxyapatite/zeolite).
Embodiment 3
(1) got natural zeolite, hydroxyapatite, the tri-iron tetroxide of 200 mesh sieves standby; Be that 2% acetic acid solutions concentration is that the chitosan solution of 0.02g/ml is standby with concentration; Compound concentration is that the brocide storing solution of 25mmol/L is standby.
(2) take respectively 0.6g natural zeolite, 0.6g hydroxyapatite and 0.8g tri-iron tetroxide, be placed in the distilled water reactor that fills 20mL, stirring fully mixes natural zeolite, hydroxyapatite and tri-iron tetroxide and is in suspended state; The chitosan solution that takes 20mL is with after the suspended state mixture fully mixes, and dripping concentration in the reactant liquor is the sodium hydroxide solution of 2.0mol/L, until reactant liquor obvious cotton-shaped object appears and after (this moment pH approximately 8～11) continue to stir 15min; Then centrifugation adopts distilled water repeatedly to rinse solid, until the pH of supernatant is close to till 7.0, solid is placed under 105 ℃ after oven dry, grinds after 200 mesh sieves standbyly, and the gained solid is chitosan magnetic/hydroxyapatite/zeolite.
(3) take 0.5g chitosan magnetic/hydroxyapatite/zeolite in conical flask, after pipetting 5mL concentration and be 25mmol/L brocide (CPB) storing solution and the abundant mixing of chitosan magnetic/hydroxyapatite/zeolite with pipette, be placed in 40 ℃ of water bath with thermostatic control oscillators with 150rpm vibration 48hr after with the speed centrifugation of 4000rpm, adopt ultraviolet spectrophotometry (the mensuration wavelength is 259nm) to analyze CPB concentration in supernatant, according to calculated equilibrium concentration on the CPB calibration curve, the adsorbance that obtains CPB is 129mmol/ (kg shell chitosan magnetic/hydroxyapatite/zeolite).Adopt at last distilled water to clean, there is no Br until adopt liquor argenti nitratis ophthalmicus to detect in supernatant
-Till, solid is placed in carries out air blast oven dry under 50 ℃ of conditions, namely make magnetic CPB modification of chitosan/hydroxyapatite/zeolite after cooling, be designated as magnetic CPB/ shitosan/hydroxyapatite/zeolite.
(4) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100mg/L humic acid solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.The adsorbance that calculates humic acid reaches 92.5 (mg humic acid)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
(5) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is the Congo red solution of 100mg/L, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate Congo red adsorbance and reach 90.9 (mg is Congo red)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
(6) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100mg/L copper ion (Cu (II)) solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 6.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.The adsorbance that calculates copper ion reaches 36.0mg Cu (II)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
Embodiment 4
(1) got natural zeolite, hydroxyapatite, the tri-iron tetroxide of 200 mesh sieves standby; Be that 2% acetic acid solutions concentration is that the chitosan solution of 0.02g/ml is standby with concentration; Compound concentration is that the brocide storing solution of 25mmol/L is standby.
(2) take respectively 1.2g natural zeolite, 0.8g hydroxyapatite and 2g tri-iron tetroxide, be placed in the distilled water reactor that fills 40mL, stirring fully mixes natural zeolite, hydroxyapatite and tri-iron tetroxide and is in suspended state; The chitosan solution that takes 40mL is with after the suspended state mixture fully mixes, and dripping concentration in the reactant liquor is the sodium hydroxide solution of 2.0mol/L, until reactant liquor obvious cotton-shaped object appears and after (this moment pH approximately 8～11) continue to stir 15min; Then centrifugation adopts distilled water repeatedly to rinse solid, until the pH of supernatant is close to till 7.0, solid is placed under 105 ℃ after oven dry, grinds after 200 mesh sieves standbyly, and the gained solid is chitosan magnetic/hydroxyapatite/zeolite.
(3) take 1.5g chitosan magnetic/hydroxyapatite/zeolite in conical flask, after pipetting 12mL concentration and be 25mmol/L brocide (CPB) storing solution and the abundant mixing of chitosan magnetic/hydroxyapatite/zeolite with pipette, be placed in 40 ℃ of water bath with thermostatic control oscillators with 150rpm vibration 48hr after with the speed centrifugation of 4000rpm, adopt ultraviolet spectrophotometry (the mensuration wavelength is 259nm) to analyze CPB concentration in supernatant, according to calculated equilibrium concentration on the CPB calibration curve, the adsorbance that obtains CPB is 90.9mmol/ (kg shell chitosan magnetic/hydroxyapatite/zeolite).Adopt at last distilled water to clean, there is no Br until adopt liquor argenti nitratis ophthalmicus to detect in supernatant
-Till, solid is placed in carries out air blast oven dry under 50 ℃ of conditions, namely make magnetic CPB modification of chitosan/hydroxyapatite/zeolite after cooling, be designated as magnetic CPB/ shitosan/hydroxyapatite/zeolite.
(4) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, be placed in 25mL concentration and be respectively 50,100 and 150mg/L humic acid solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate experiment condition magnetic CPB/ shitosan/hydroxyapatite/zeolite adsorbents the adsorbance of humic acid is reached respectively 46.2,77.4 and 97.0 (mg humic acid)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
(5) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is the Congo red solution of 100mg/L, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate Congo red adsorbance and reach 88.7 (mg is Congo red)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
(6) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100mg/L Cu (II) solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 6.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.The adsorbance that calculates copper ion reaches 27.1 (mg Cu (II))/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
Embodiment 5
(1) got natural zeolite, hydroxyapatite, the tri-iron tetroxide of 200 mesh sieves standby; Be that 2% acetic acid solutions concentration is that the chitosan solution of 0.02g/ml is standby with concentration; Compound concentration is that the brocide storing solution of 25mmol/L is standby.
(2) take respectively 0.8g natural zeolite, 1.2g hydroxyapatite and 2g tri-iron tetroxide, be placed in the distilled water reactor that fills 40mL, stirring fully mixes natural zeolite, hydroxyapatite and tri-iron tetroxide and is in suspended state; The chitosan solution that takes 40mL is with after the suspended state mixture fully mixes, and dripping concentration in the reactant liquor is the sodium hydroxide solution of 2.0mol/L, until reactant liquor obvious cotton-shaped object appears and after (this moment pH approximately 8～11) continue to stir 15min; Then centrifugation adopts distilled water repeatedly to rinse solid, until the pH of supernatant is close to till 7.0, solid is placed under 105 ℃ after oven dry, grinds after 200 mesh sieves standbyly, and the gained solid is chitosan magnetic/hydroxyapatite/zeolite.
(3) take 1.5g chitosan magnetic/hydroxyapatite/zeolite in conical flask, after pipetting 12mL concentration and be 25mmol/L brocide (CPB) storing solution and the abundant mixing of chitosan magnetic/hydroxyapatite/zeolite with pipette, be placed in 40 ℃ of water bath with thermostatic control oscillators with 150rpm vibration 48hr after with the speed centrifugation of 4000rpm, adopt ultraviolet spectrophotometry (the mensuration wavelength is 259nm) to analyze CPB concentration in supernatant, according to calculated equilibrium concentration on the CPB calibration curve, the adsorbance that obtains CPB is 63.1mmol/ (kg shell chitosan magnetic/hydroxyapatite/zeolite).Adopt at last distilled water to clean, there is no Br until adopt liquor argenti nitratis ophthalmicus to detect in supernatant
-Till, solid is placed in carries out air blast oven dry under 50 ℃ of conditions, namely make magnetic CPB modification of chitosan/hydroxyapatite/zeolite after cooling, be designated as magnetic CPB/ shitosan/hydroxyapatite/zeolite.
(4) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, be placed in 25mL concentration and be respectively 50,100 and 150mg/L humic acid solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate experiment condition magnetic CPB/ shitosan/hydroxyapatite/zeolite adsorbents the adsorbance of humic acid is reached respectively 46.2,77.5 and 811 (mg humic acid)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
(5) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is the Congo red solution of 100mg/L, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 7.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.Calculate Congo red adsorbance and reach 88.6 (mg is Congo red)/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
(6) take the magnetic CPB/ shitosan/hydroxyapatite of 0.0250g said method preparation/zeolite adsorbents, being placed in 25mL concentration is 100mg/L Cu (II) solution, take the pH of sodium hydroxide solution and hydrochloric acid solution regulator solution as 6.0.Solution is placed on water-bath constant temperature oscillator vibrated 24 hours, oscillation rate is 150rpm.The adsorbance that calculates copper ion reaches 32.6 (mg Cu (II))/(g magnetic CPB/ shitosan/hydroxyapatite/zeolite).
Claims (10)
1. the preparation method of magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition, is characterized in that, comprises the following steps:
(1) natural zeolite, hydroxyapatite and tri-iron tetroxide and water are stirred fully mix and be in suspended state; The mass ratio of natural zeolite, hydroxyapatite and tri-iron tetroxide is 1:(0.5～2.5): (0.5～2.5); Adding chitosan solution chitosan concentration to the reaction system is 0.004～0.012g/mL, fully mixes; Drip again alkaline solution, until reactant liquor pH〉7, obvious floccule appears, continue to stir 10～30min; Precipitation is got in centrifugation, and washing was ground 150～300 mesh sieves to neutral and oven dry, obtained chitosan magnetic/hydroxyapatite/zeolite;
(2) get the chitosan magnetic/hydroxyapatite of step (1) preparation/zeolite, adding concentration by the liquid-solid ratio of 1～200mL/g is 5～100mmol/L cationic surfactant solution, vibration 5～96h; Obtain magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition.
2. the preparation method of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 1/zeolite composition, it is characterized in that, the mass ratio of the described natural zeolite of step (1), hydroxyapatite and tri-iron tetroxide is 1:(0.5～1.5): (0.5～2.5).
3. the preparation method of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 1/zeolite composition, is characterized in that, in step (1), the particle diameter of natural zeolite, hydroxyapatite and tri-iron tetroxide is 150～300 orders.
4. the preparation method of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 1/zeolite composition, it is characterized in that, in step (1), the chitosan solution that adds is prepared by the acid solution of mass concentration 0.5%～10%, and wherein shitosan content is 0.005～0.1g/mL.
5. the preparation method of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 1/zeolite composition, is characterized in that, alkaline solution described in step (1) is NaOH or KOH solution, and concentration is 0.5～5mol/L.
6. the preparation method of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 1/zeolite composition, it is characterized in that, the described cationic surfactant solution concentration of step (2) is 10～50mmol/L, and cationic surfactant is brocide or softex kw.
7. the preparation method of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 1/zeolite composition, is characterized in that, in step (2), hunting speed is 100～500rpm, 15～60 ℃ of temperature.
8. the preparation method of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 1/zeolite composition, is characterized in that, the liquid-solid ratio 1～20mL/g described in step (2).
9. magnetic cationic surfactant modified chitosan/hydroxyapatite/zeolite composition, is characterized in that, by the described method preparation of claim 1～8 any one, the cationic surfactant load capacity is 60～160mmol/kg.
10. the application of the described magnetic cationic surfactant modified chitosan/hydroxyapatite of claim 9/zeolite composition aspect the preparation adsorbent is characterized in that, is used for organic matter and the heavy metal contaminants of adsorbed water.
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