CN104353406B - A kind of double-metal hydroxide and preparation method thereof, magnetic dephosphorization adsorbent and preparation method thereof - Google Patents

A kind of double-metal hydroxide and preparation method thereof, magnetic dephosphorization adsorbent and preparation method thereof Download PDF

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CN104353406B
CN104353406B CN201410650699.6A CN201410650699A CN104353406B CN 104353406 B CN104353406 B CN 104353406B CN 201410650699 A CN201410650699 A CN 201410650699A CN 104353406 B CN104353406 B CN 104353406B
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dephosphorization adsorbent
double
sio
metal hydroxide
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CN104353406A (en
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王镜渊
汪国庆
姜宏
李江
徐三强
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Hainan University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character

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Abstract

The invention provides a kind of double-metal hydroxide and preparation method thereof, magnetic dephosphorization adsorbent and preparation method thereof, the adsorbent includes Fe3O4‑SiO2Compound particle and it is wrapped in the Fe3O4‑SiO2The double-metal hydroxide on compound particle surface；The formula of wherein double-metal hydroxide is：[M2+ (1‑x)M'3+ x(OH)2]x+[(A‑)a(A'2‑)b]x‑·nH2O.The magnetic dephosphorization adsorbent includes double-metal hydroxide and Fe3O4‑SiO2Compound particle, wherein, double-metal hydroxide makes adsorbent have dephosphorizing rate higher；Fe3O4‑SiO2Compound particle makes adsorbent to realize Magnetic Isolation by externally-applied magnetic field in liquid phase environment, it is easy to reclaim, and reduces secondary pollution.Test result indicate that：The dephosphorizing rate of such magnetic dephosphorization adsorbent is 45%~91%.The preparation method of the dephosphorization adsorbent is simple, with low cost.

Description

A kind of double-metal hydroxide and preparation method thereof, magnetic dephosphorization adsorbent and its system Preparation Method
Technical field
Invention belongs to technical field of absorbent, is related to a kind of double-metal hydroxide and preparation method thereof, magnetic dephosphorization to inhale Attached dose and preparation method thereof.
Background technology
In recent years, quickly propelling due to population growth, industrialization and modern agriculture, substantial amounts of phosphorus enters enclosed type water body (such as lake, reservoir), causes the eutrophication of water body, causes the aquatiles such as algae excessively to breed, Dissolved Oxygen in Water reduction, Transparency declines, and water quality deteriorates rapidly.Therefore, the phosphorus concentration in control water is to ensure that water body removes an important ring of nutrient laden.
The mode that enters of phosphorus mainly has two aspects：One be it is natural, such as precipitation, ore weathering and plant and animal residues it is corrupt, Erosion of surface soil etc.；Two is artificial, the phosphorous sanitary sewage that such as mankind give off in city, agricultural application chemistry fertilizer Material and excrement of animals.Phosphorus is main in water to be existed in the form of Phos, such as：H2PO4 -、HPO4 2-、PO4 3-。
China's issuing and implementation《Urban wastewater treatment firm pollutant emission standard》(GB18918-2002) regulation in：From From 1 day January in 2006, municipal sewage plant's total phosphorus (refer to dissolving in terms of P, the organophosphor of particle and Phos it is total With) one-level emission standard A be 0.5mg/L, one-level B discharge standards be 1mg/L.
In the minimizing technology of existing phosphorus, chemical precipitation method, bioanalysis and absorption method application it is relatively broad.Chemistry is heavy Shallow lake method is generally used for the removal of the phosphate waste of higher concentration, has the disadvantage that this method has cannot the reclaiming of P elements, chemistry Sludge it is many and cannot reprocess and medicine consuming high.Bioanalysis is relatively more suitable for the removal of phosphorus in urban domestic wastewater, especially It is the dephosphorization of sewage treatment plant, and this method can be used with continuity, but not be suitable for the treatment of high-concentration phosphorus-containing wastewater, and be accounted for Ground, capital construction input are larger, not easy to operate.Absorption method design simple and flexible, operation are easy, are generated without new noxious pollutant.Cause This, absorption method is considered as a kind of promising phosphorus removing method of comparing.But the dephosphorization of dephosphorization adsorbent disclosed in prior art Efficiency is low, limit its extensive use the shortcomings of be difficult to recycling.
The content of the invention
In view of this, it is an object of the invention to provide a kind of double-metal hydroxide and preparation method thereof, magnetic dephosphorization Adsorbent and preparation method thereof, the dephosphorization efficiency of the magnetic dephosphorization adsorbent that the present invention is provided is higher.
The invention provides a kind of double-metal hydroxide, with the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
Preferably, the M2+Including Mg2+、Ca2+Or Zn2+。
Preferably, the M'3+Including Al3+Or Fe3+。
Preferably, the A-Including NO3 -、Cl-Or OH-。
Preferably, the A'2-Including CO3 2-Or SO4 2-。
The invention provides a kind of preparation method of double-metal hydroxide, comprise the following steps：
Divalent metal salt, trivalent metal salt and water are mixed, mixed salt solution is obtained；
It is aged after the mixed salt solution and aqueous slkali are mixed, obtains suspension；
By suspension filtering, thing is precipitated；
The sediment is washed and dried successively, double-metal hydroxide is obtained,
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
Preferably, the divalent metal salt includes ZnCl2、CaCl2、MgCl2、Zn(NO3)2、Ca(NO3)2With Mg (NO3)2In One or more.
Preferably, the trivalent metal salt includes AlCl3·6H2O、FeCl3·6H2O、Al(NO3)3·6H2O and Fe (NO3)3·6H2One or more in O.
The invention provides a kind of magnetic dephosphorization adsorbent, including Fe3O4-SiO2Compound particle and it is wrapped in the Fe3O4- SiO2The double-metal hydroxide on compound particle surface；
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
The invention provides a kind of preparation method of magnetic dephosphorization adsorbent, comprise the following steps：
By Fe3O4-SiO2Compound particle suspension and double-metal hydroxide suspension mix, ultrasonically treated, then carry out Magneto separate, dries, and obtains magnetic dephosphorization adsorbent；
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
The invention provides a kind of double-metal hydroxide and preparation method thereof, magnetic dephosphorization adsorbent and its preparation side Method, the adsorbent includes Fe3O4-SiO2Compound particle and it is wrapped in the Fe3O4-SiO2The bimetallic hydrogen-oxygen on compound particle surface Compound；The double-metal hydroxide has the formula shown in Formulas I：[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-· nH2O Formulas I.The dephosphorization adsorbent that the present invention is provided is by double-metal hydroxide and Fe3O4-SiO2Compound particle two parts are constituted, Wherein, the Main Function of double-metal hydroxide is adsorbent is had dephosphorizing rate higher；Fe3O4-SiO2Magnetic particle is present Main purpose be adsorbent is realized Magnetic Isolation by externally-applied magnetic field in liquid phase environment, it is easy to reclaim, reduce it is secondary Pollution.Test result indicate that, such dephosphorization adsorbent of preparation, due to the difference of composition, the dephosphorization under same specified conditions Rate is 45%~91%.
The preparation method of the dephosphorization adsorbent that the present invention is provided is simple, with low cost.
Brief description of the drawings
Fig. 1 is the dephosphorizing rate that magnetic dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes with pH value；
Fig. 2 is the dephosphorizing rate that magnetic dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes over time；
Fig. 3 is Fe obtained in the embodiment of the present invention 13O4-SiO2The XRD spectra of compound particle；
Fig. 4 is the XRD spectra of magnetic dephosphorization adsorbent prepared by the embodiment of the present invention 1；
Fig. 5 is the TEM figures of magnetic dephosphorization adsorbent prepared by the embodiment of the present invention 1.
Specific embodiment
The invention provides a kind of double-metal hydroxide, with the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
In the present invention, the M2+Preferably include Mg2+、Ca2+Or Zn2+；
The M'3+Preferably include Al3+Or Fe3+；
The A-To bear univalent anion, NO is preferably included3 -、Cl-Or OH-, more preferably including Cl-Or OH-；
The A'2-To bear dianion, CO is preferably included3 2-Or SO4 2-, more preferably CO3 2-；
0.25<n<1.42, preferably 0.67<n<1.17, more preferably n=0.67, n=0.88, n=0.93, n= 0.95th, n=1.10 or n=1.17；
a>0, preferred 0.05<a<0.13, preferred a=0.05, a=0.09, a=0.11 or a=0.13；
b>0, preferred 0.10<b<0.14, preferred b=0.10, b=0.11, b=0.12 or b=0.14；
0<x<1, preferred 0.1<x<0.9, preferred 0.2<x<0.8, most preferably x=0.33；
In the present invention, described a, b and x meet a+2b=x relational expressions.
Specifically, working as M2+It is Ca2+, M'3+It is Al3+, A-It is Cl-, A'2-It is CO3 2-, a=0.05, b=0.14, x are 0.33, During n=0.88, the double-metal hydroxide is specially：[Ca0.67Al0.33(OH)2][Cl0.05(CO3)0.14]·0.88H2O；
Work as M2+It is Ca2+, M'3+It is Fe3+, A-It is Cl-, A'2-It is CO3 2-, a=0.11, b=0.11, x are 0.33, n=0.95 When, the double-metal hydroxide is specially：[Ca0.67Fe0.33(OH)2][Cl0.11(CO3)0.11]·0.95H2O；
Work as M2+It is Mg2+, M'3+It is Al3+, A-It is Cl-, A'2-It is CO3 2-, a=0.09, b=0.12, x are 0.33, n=1.17 When, the double-metal hydroxide is specially：[Mg0.67Al0.33(OH)2][Cl0.09(CO3)0.12]·1.17H2O；
Work as M2+It is Mg2+, M'3+It is Fe3+, A-It is Cl-, A'2-It is CO3 2-, a=0.13, b=0.10, x are 0.33, n=1.10 When, the double-metal hydroxide is specially：[Mg0.67Fe0.33(OH)2][Cl0.13(CO3)0.10]·1.10H2O；
Work as M2+It is Zn2+, M'3+It is Al3+, A-It is Cl-, A'2-It is CO3 2-, a=0.09, b=0.12, x are 0.33, n=0.67 When, the double-metal hydroxide is specially：[Zn0.67Al0.33(OH)2][Cl0.09(CO3)0.12]·0.67H2O；
Work as M2+It is Zn2+, M'3+It is Fe3+, A-It is Cl-, A'2-It is CO3 2-, a=0.11, b=0.11, x are 0.33, n=0.93 When, the double-metal hydroxide is specially：[Zn0.67Fe0.33(OH)2][Cl0.11(CO3)0.11]·0.93H2O。
The invention provides a kind of preparation method of double-metal hydroxide, comprise the following steps：
Divalent metal salt, trivalent metal salt and water are mixed, mixed salt solution is obtained；
It is aged after the mixed salt solution and aqueous slkali are mixed, obtains suspension；
The suspension is filtered, thing is precipitated；
The sediment is washed and dried successively, double-metal hydroxide is obtained,
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
The present invention mixes divalent metal salt, trivalent metal salt and water, obtains mixed salt solution.The present invention is to described The order by merging of divalent metal salt, trivalent metal salt and water does not have special limitation, preferably by the divalent metal salt and trivalent Slaine is added sequentially in water.
In the present invention, the divalent metal salt preferably includes ZnCl2、CaCl2、MgCl2、Zn(NO3)2、Ca(NO3)2With Mg(NO3)2In one or more；More preferably include CaCl2、MgCl2And ZnCl2In one or more.
In the present invention, the trivalent metal salt preferably includes AlCl3·6H2O、FeCl3·6H2O、Al(NO3)3·6H2O With Fe (NO3)3·6H2One or more in O, more preferably including AlCl3·6H2O and/or FeCl3·6H2O。
In the present invention, the water is preferably deionized water.
In the present invention, the amount ratio preferably 1~3 of the material of the divalent metal salt and trivalent metal salt:1, more preferably It is 2:1；The amount of the material of the trivalent metal salt and the volume ratio of water are preferably 1mol:(65~80) mL, more preferably 1mol: (67~75) mL, most preferably 1mol:70mL.
After obtaining mixed salt solution, the present invention is aged after mixing the mixed salt solution and aqueous slkali, obtains To suspension.Preferably be added to the mixed salt solution in the aqueous slkali by the present invention；The present invention is preferably with 0.8mL/ Be added to mixed salt solution in the aqueous slkali by the drop rate of min~1.2mL/min, more preferably 0.9mL/min ~1.1mL/min, most preferably 1mL/min；Mixed salt solution is preferably added to alkali by the present invention under conditions of stirring In solution；The temperature of the stirring is preferably 15 DEG C~35 DEG C, more preferably 20 DEG C~30 DEG C；The speed of the stirring is preferably 280r/min~320r/min, more preferably 290r/min~310r/min.
In the present invention, the aqueous slkali is preferably NaOH solution；The molar concentration of the NaOH solution is preferably 1.5mol/L~2.5mol/L, more preferably 1.8mol/L~2.2mol/L, most preferably 2mol/L；The aqueous slkali neutral and alkali The amount ratio preferably 6~8 of the material of material and trivalent metal salt:1, more preferably 6.5~7.5:1, most preferably 7:1.
In the present invention, the temperature that the mixed salt solution and aqueous slkali are aged after mixing is preferably 65 DEG C~75 DEG C, more preferably 68 DEG C~72 DEG C, most preferably 70 DEG C；The time being aged after the mixed salt solution and aqueous slkali mixing Preferably 20h~30h, more preferably 22h~27h, most preferably 24h.
After obtaining suspension, suspension filtering is precipitated thing by the present invention.Method of the present invention to the filtering There is no special limitation, using filtering technique scheme well known to those skilled in the art.
After being precipitated thing, the sediment is washed and dried by the present invention successively, obtains double-metal hydroxide, The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I.
Sediment is washed present invention preferably employs deionized water.In the present invention, the number of times of the washing is preferred It is 3 times~5 times.In the present invention, the drying preferably using vacuum drying or is spray-dried；The present invention is to the spray drying Method there is no special limitation, using spray drying well known to those skilled in the art；The import of the spray drying Temperature is preferably 150 DEG C~170 DEG C, most preferably more preferably 155 DEG C~165 DEG C, 160 DEG C；The outlet of the spray drying Temperature is preferably 75 DEG C~85 DEG C, most preferably more preferably 78 DEG C~82 DEG C, 80 DEG C；The vacuum drying temperature is preferably 55 DEG C~65 DEG C, most preferably more preferably 58 DEG C~63 DEG C, 60 DEG C；The vacuum drying time is preferably 10h~15h, More preferably 11h~14h, most preferably 12h.
The present invention is entered using inductive coupling plasma emission spectrograph (ICP-OES) to the double-metal hydroxide for obtaining Row detection, testing result shows：Double-metal hydroxide prepared by the present invention has the formula shown in Formulas I.
Present invention also offers a kind of magnetic dephosphorization adsorbent, including Fe3O4-SiO2Compound particle and it is wrapped in described Fe3O4-SiO2The double-metal hydroxide on compound particle surface；
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
In the present invention, the Fe3O4-SiO2The mass ratio of compound particle and double-metal hydroxide is 1~3:5, it is more excellent Elect 1.5~2.5 as:5, most preferably 2:5.
In the present invention, the species one of the double-metal hydroxide and double-metal hydroxide described in above-mentioned technical proposal Cause, will not be repeated here.
In the present invention, the Fe3O4-SiO2Compound particle is preferably obtained by following preparation method：
It is aged after mixed molysite and alkali source are mixed, is precipitated thing, will be aged the sediment for obtaining carries out Magneto separate, washes Wash, it is soluble in water, obtain suspension；
The suspension is mixed with nitric acid, colloidal sol is obtained；
By the colloidal sol, ammoniacal liquor and silicate solutions hybrid reaction, product is obtained；
The product is carried out into Magneto separate, washing and is dried, obtain Fe3O4-SiO2Compound particle.
The present invention is aged after mixing mixed molysite and alkali source, is precipitated thing.In the present invention, the mixed molysite bag Include divalence source of iron and ferric iron source；The divalence source of iron preferably includes ferrous nitrate and/or frerrous chloride；The ferric iron source is excellent Choosing includes ferric nitrate and/or iron chloride；More preferably include ferrous nitrate and ferric nitrate, frerrous chloride and iron chloride；The divalence The mol ratio of source of iron and ferric iron source is preferably 1~3:1, more preferably 1.5~2.5:1, most preferably 2:1.In the present invention, The alkali source is preferably ammoniacal liquor；The mass fraction of the alkali source is preferably 4%~6%, more preferably 4.5%~5.5%, optimal Elect 5% as；The amount of the material of the alkali source and divalence source of iron is than being preferably (0.25~0.3):(0.014~0.017), more preferably It is (0.26~0.29):(0.015~0.0165), most preferably 0.27:0.016.
The present invention is mixed mixed molysite and alkali source preferably under conditions of stirring；Mixed molysite and alkali source stirring are mixed Temperature during conjunction is preferably 15 DEG C~35 DEG C, more preferably 20 DEG C~30 DEG C；Stirring when mixed molysite and alkali source stirring mixing Speed is preferably 480r/min~520r/min, more preferably 490r/min~510r/min.In the present invention, the mixing iron Salt is preferably added in the alkali source with the drop rate of 0.8mL/min~1.2mL/min, and more preferably 0.9mL/min~ 1.1mL/min, most preferably 1.0mL/min.In the present invention, the temperature that the mixed molysite and alkali source are aged after mixing is preferred It is 15 DEG C~35 DEG C, more preferably 20 DEG C~30 DEG C；The mixed molysite and alkali source mixing after be aged time be preferably 2h~ 4h, more preferably 2.5h~3.5h, most preferably 3h.
After being precipitated thing, the sediment is carried out Magneto separate, washing by the present invention, soluble in water, obtains suspension.This Invention does not have special limitation to the method for the Magneto separate, using the technical scheme of Magneto separate well known to those skilled in the art .The present invention by alternately washing 4 times of sediment deionized water and ethanol, using externally-applied magnetic field by sediment the magnetic from solution Property is separated.Then it is Magneto separate gained sediment is soluble in water, obtain suspension.In the present invention, the divalent iron salt The amount of material and the volume ratio of water be preferably 0.032mol:(100~120) mL, more preferably 0.032mol:(105~115) ML, most preferably 0.032mol:110mL.
After obtaining suspension, the present invention mixes the nitric acid of the suspension and certain concentration, obtains colloidal sol.In the present invention In, the amount ratio preferably 0.032 of the material of the divalent iron salt and nitric acid:0.07~0.12, more preferably 0.032mol:0.08 ~0.10.
After obtaining colloidal sol, the present invention reacts after mixing the colloidal sol, ammoniacal liquor and silicate solutions, obtains product. The present invention preferably before reactions to acetic acid is added in the colloidal sol, adjusts the pH value of colloidal sol in order that above-mentioned colloidal sol is more stable Save is 1~2.In the present invention, the molar concentration of the acetic acid is preferably 1.5mol/L~2.5mol/L, more preferably 1mol/ L.Order by merging of the present invention to the colloidal sol, ammoniacal liquor and silicate solutions does not have special limitation, preferably adds the ammoniacal liquor Enter in the colloidal sol, then be added thereto to silicate solutions.In the present invention, the material of the ammoniacal liquor, nitric acid and silicate Amount than be preferably (25~30):(0.8~1.2):(0.2~0.7), more preferably (26~28):(0.9~1.1):(0.3~ 0.55), most preferably 27:1:0.4.In the present invention, the silicate solutions are sodium silicate solution.
After obtaining product, the product is carried out Magneto separate, washing and dried by the present invention, obtains Fe3O4- SiO2Compound particle.The present invention does not have special limitation to the method for the Magneto separate, using well known to those skilled in the art Magnetic separation technique scheme.The present invention replaces washing reaction and produces under the conditions of capable of magnetic separating, using deionized water and ethanol Thing；The alternating washing times of preferred pair product of the present invention are 3 times~5 times；After completing to wash by product Magneto separate out, do It is dry, obtain final product Fe3O4-SiO2Compound particle.In the present invention, Fe3O4-SiO2The dried forms of compound particle are true at being preferably 60 DEG C Sky is dried.
Fe prepared by the present invention3O4-SiO2Compound particle has superparamagnetism；The Fe3O4-SiO2The particle diameter of compound particle Preferably 0.3 μm~2 μm, more preferably 0.4 μm~1 μm, most preferably 0.5 μm~0.8 μm.
Present invention also offers a kind of preparation method of magnetic dephosphorization adsorbent, comprise the following steps：
By Fe3O4-SiO2Compound particle suspension and double-metal hydroxide suspension mix, ultrasonically treated, then carry out Magneto separate, dries, and obtains magnetic dephosphorization adsorbent；
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is bivalent metal ion；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
The present invention is by Fe3O4-SiO2Compound particle suspension and double-metal hydroxide suspension mix.In the present invention, The Fe3O4-SiO2Solvent in compound particle suspension is preferably deionized water；The Fe3O4-SiO2Compound particle suspension Middle Fe3O4-SiO2The mass ratio of compound particle and solvent is preferably 8~12:300, more preferably 9~11:300, most preferably 10:300。
In the present invention, the Fe3O4-SiO2Fe in compound particle suspension3O4-SiO2Compound particle and above-mentioned technical side Fe described in case3O4-SiO2The source of compound particle is consistent, will not be repeated here.
In the present invention, the solvent in the double-metal hydroxide suspension is preferably deionized water；The bimetallic The mass ratio of double-metal hydroxide and solvent is preferably 3~5 in hydroxide suspension liquid:300, more preferably 3.5~4.5: 300, most preferably 4:300.
Complete Fe3O4-SiO2After compound particle suspension and the mixing of double-metal hydroxide suspension, the present invention is to obtaining Mixing suspension carry out it is ultrasonically treated.The present invention carries out Fe preferably under conditions of stirring3O4-SiO2Compound particle suspension It is ultrasonically treated with double-metal hydroxide suspension.In the present invention, the Fe3O4-SiO2Compound particle suspension and double gold Speed preferably 280r/min~320r/min, more preferably 290r/min that category hydroxide suspension liquid is stirred when ultrasonically treated ~310r/min, most preferably 300r/min.In the present invention, the Fe3O4-SiO2Compound particle suspension and bimetallic hydrogen The oxide suspension ultrasonically treated time is preferably 4h~6h, most preferably more preferably 4.5h~5.5h, 5h.
Complete it is suspension mixed it is ultrasonically treated after, the present invention carries out Magneto separate to the ultrasonic mixing suspension that obtains. In the present invention, the temperature that ultrasonic mixing suspension carries out Magneto separate is preferably 22 DEG C~31 DEG C, more preferably 25 DEG C~29 DEG C, most Preferably 28 DEG C；Ultrasonic mixing suspension carries out the time preferably 5min~10min of Magneto separate, and more preferably 6min~ 9min, most preferably 8min.The present invention does not have special limitation to the method that ultrasonic mixing suspension carries out Magneto separate, using this Magnetic separation technique scheme known to art personnel.
After completing the Magneto separate of ultrasonic mixing suspension, the Magneto separate product that the present invention will be obtained is dried, and is removed Phosphorus adsorbent.In the present invention, the dried forms of mixing suspension Magneto separate product are preferably vacuum drying, vacuum drying temperature Degree is preferably 55 DEG C~65 DEG C, most preferably more preferably 58 DEG C~63 DEG C, 60 DEG C；The Magneto separate product vacuum dry time is excellent Elect 22h~26h, most preferably more preferably 23h~25h, 24h as.
The present invention is tested obtained dephosphorization adsorbent using X-ray diffraction (XRD) and transmission electron microscope (TEM), is surveyed Test result shows：The magnetic dephosphorization adsorbent that the present invention is provided is with Fe3O4-SiO2Compound particle is inner core, bimetal hydroxide Thing is the labyrinth of outer layer, and the present invention utilizes Fe3O4-SiO2The magnetic that compound particle possesses so that magnetic dephosphorization adsorbent Can be easy to be separated from liquid phase after dephosphorization.
The present invention carries out phosphorus removal property test to the dephosphorization adsorbent for providing, and detailed process is：
The phosphorus-rich water of 10mg/L is prepared, the pH value that phosphorus-rich water is adjusted with the HCl and NaOH of 1mol/L is 4.0~9.0, is taken The phosphorus-rich water that 0.5L is prepared is placed in the conical flask of 1L, is added thereto to 0.25g dephosphorization adsorbents, and absorption is vibrated at 30 DEG C, Time is 1h~24h, after vibration adsorption equilibrium, dephosphorization adsorbent is separated as externally-applied magnetic field with the strong magnet of N52, is taken after filtering Supernatant, the content to the phosphorus in supernatant is measured, and the calculating of adsorbance is carried out using formula 1, and dephosphorizing rate is carried out using formula 2 Calculating：
Formula 1；
In formula 1, q is adsorption capacity, and unit is mg/g；
C0It is the mass concentration of phosphorus in phosphorus-rich water before absorption, unit is mg/L；
CeIt is the mass concentration of phosphorus in water after absorption, unit is mg/L；
V is the volume of phosphorus-rich water, and unit is L；
M is the quality of dephosphorization adsorbent, and unit is g；
Formula 2；
In formula 2, C0It is the mass concentration of phosphorus before absorption, unit is mg/L；
CeIt is the mass concentration of phosphorus after absorption, unit is mg/L.
Test result shows：The dephosphorization adsorbent that the present invention is provided is 4.4,6.4,8.4 in pH value, after absorption 10h, dephosphorization Rate is 38%~94%, and for same kind of adsorbent, dephosphorizing rate is reduced with the rising of pH value；In the feelings that pH is 6.4 The relation of different adsorbents adsorption time under the same conditions and dephosphorizing rate is have studied under condition：With the increase of adsorption time, Its dephosphorizing rate gradually increases, and reaches maximum material removal rate in 4h, the maximum dephosphorizing rate of all kinds of adsorbents between 45%~91% it Between, hereafter, increasing over time, clearance change is little, shows that adsorbent reaches adsorption equilibrium.
In order to further illustrate the present invention, with reference to embodiment to the present invention provide a kind of double-metal hydroxide and Its preparation method, magnetic dephosphorization adsorbent and preparation method thereof are described in detail, but they can not be interpreted as to this hair The restriction of bright protection domain.
Embodiment 1
Step 1：The preparation of particles with superparamagnetism and its is immobilized in SiO2Matrix, is designated as Fe3O4-SiO2Compound particle：
Step 11：By 8.64g FeCl3·6H2O and 3.18g FeCl2·4H2O be dissolved at 20 DEG C 110mL go from In sub- water, now two kinds of mol ratios of molysite are 2:1, as source of iron；
Step 12：The ammoniacal liquor deionized water that 20mL mass fractions are 25% is diluted to 100mL, as alkali source；
Step 13：Under 25 DEG C of room temperature, the stirring condition of 500r/min, by mixed molysite solution with the speed of 1mL/min Be added dropwise in above-mentioned ammonia spirit, after be aged 3h at room temperature, gained is then precipitated into Magneto separate, handed over ethanol and deionized water For Magneto separate again after washing 4 times, it is dissolved in the deionized water of 130mL, obtains suspension；
Step 14：Step 13 gained suspension is mixed with the nitric acid of 130mL 0.66mol/L, it is then molten to what is obtained again The acetic acid of 6mL 1mol/L is added in glue, by pH value regulation to 1.3；
Step 15：The ammoniacal liquor (25%) of 88mL is added in the deionized water of 80mL, the ammoniacal liquor after gained is diluted Solution is added slowly in the product obtained by back, lasting stirring, and it is 70 DEG C to keep mixing temperature with water-bath, and mixing is equal After even, the sodium silicate solution for preparing is added dropwise over thereto, and (mol ratio is NH4OH:HNO3:Na2O·3SiO2=27:1: 0.4)
Step 16：Final reaction gained sediment is separated by Magnetic Isolation from mixed solution, is then spent Ionized water and ethanol are obtained final product and contain Fe to its alternately washing 4 time3O4-SiO2The suspension of compound particle.
Step 17：Vacuum drying treatment is carried out in 60 DEG C, Fe is obtained3O4-SiO2Compound particle.
Step 2：It is prepared by the co-precipitation of LDHs：
Step 21：It is 2 to prepare mol ratio:1 mixed salt solution, weighs the CaCl of 8.8792g2With 9.6572g's AlCl3·6H2O is dissolved in the deionized water of 70mL, is sufficiently mixed；
Step 22：Prepare the NaOH aqueous slkalis of 2mol/L；
Step 23：It is 2 by above-mentioned mol ratio under the conditions of room temperature, the strong agitation of 300r/min:1 mixed metal salt Solution is added in the NaOH solution of the 2mol/L of 150mL with the speed of 1mL/min；
Step 24：24h is aged at 70 DEG C, suspension is obtained；
Step 25：Filtering, the precipitation that will be obtained clean 4 times with deionized water, after be vacuum dried 12h at 60 DEG C, it is prepared Calcium aluminum bimetal hydroxide (LDHs)；
Step 3：LDHs modifies Fe3O4-SiO2Compound particle：
Step 31：The above-mentioned made LDHs of 10g are scattered in the deionized water of 300mL, LDHs suspension is configured to；
By the above-mentioned made Fe of 4g3O4-SiO2Compound particle is scattered in the deionized water of 300mL, is configured to Fe3O4-SiO2 Compound particle suspension；
Step 32：Two kinds of suspension are mixed under conditions of stirring, 5h, magnetic is stirred under conditions of ultrasonic wave thereafter Separate, then in 24h is vacuum dried at 60 DEG C, obtain Fe3O4-SiO2[the Ca of compound particle modification0.67Al0.33(OH)2] [Cl0.05(CO3)0.14]·0.88H2O magnetic dephosphorization adsorbents.
The method of testing according to above-mentioned technical proposal of the invention carries out the test of dephosphorizing rate to the dephosphorization adsorbent for obtaining, As depicted in figs. 1 and 2, Fig. 1 is magnetic dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 as pH value changes to test result Dephosphorizing rate, wherein,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 1,The dephosphorization absorption obtained in embodiment 2 The dephosphorizing rate of agent,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 3,The dephosphorization adsorbent obtained in embodiment 4 Dephosphorizing rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 5,The dephosphorization adsorbent obtained in embodiment 6 Dephosphorizing rate.Fig. 2 is the dephosphorizing rate that magnetic dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes over time, wherein The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 1；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 2；For The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 3；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 4；It is reality Apply the dephosphorizing rate of dephosphorization adsorbent obtained in example 5；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 6.Can be with from Fig. 1 Find out, dephosphorization adsorbent obtained in the embodiment of the present invention 1 when it is 4.4,6.4,8.4 to simulate solution containing phosphate initial pH value, dephosphorization Rate is respectively 88%, 82%, 78%；Figure it is seen that dephosphorization adsorbent obtained in the embodiment of the present invention 1, at room temperature, 500mL concentration is taken for 10mg/L phosphorus-rich waters, pH is 6.4, adsorbent dosage is 0.25g, and with the increase of adsorption time, it is removed Phosphorus rate gradually increases, and maximum material removal rate 82% is reached in 4h, and adsorbent reaches adsorption equilibrium afterwards, and clearance is stablized relatively.
The present invention is according to method of testing described in above-mentioned technical proposal to the Fe that obtains3O4-SiO2Compound particle and magnetic dephosphorization Adsorbent carries out XRD tests, and test result distinguishes Fig. 3 and as shown in figure 4, wherein, Fig. 3 is obtained in the embodiment of the present invention 1 Fe3O4-SiO2The XRD spectra of compound particle, Fig. 4 is the XRD spectra of magnetic dephosphorization adsorbent prepared by the embodiment of the present invention 1；Figure 3 compare with Fig. 4 can be seen that：The characteristic diffraction peak for having CaAl-LDHs in Fig. 4 occurs, and shows the successful conjunction of dephosphorization adsorbent Into.
The present invention carries out TEM tests according to method of testing described in above-mentioned technical proposal to the dephosphorization adsorbent for obtaining, and tests Result is as shown in figure 5, Fig. 5 is the TEM figures of magnetic dephosphorization adsorbent prepared by the embodiment of the present invention 1.As can be seen from Figure 5：This The internal color deeper portion of the dephosphorization adsorbent that embodiment is provided is Fe3O4-SiO2Compound particle, outer layer color is relatively shallower Part is double-metal hydroxide, therefore, magnetic dephosphorization adsorbent possesses with Fe3O4-SiO2Compound particle makees inner core, bimetallic Hydroxide is the clad type structure of outer layer.
Embodiment 2
Step 1：The preparation of particles with superparamagnetism and its is immobilized in SiO2Matrix, is designated as Fe3O4-SiO2Compound particle：
Step 11：By 8.64g FeCl3·6H2O and 3.18g FeCl2·4H2O be dissolved at 20 DEG C 110mL go from In sub- water, now two kinds of mol ratios of molysite are 2:1, as source of iron；
Step 12：The ammoniacal liquor deionized water that 20mL mass fractions are 25% is diluted to 100mL, this is alkali source；
Step 13：Under 25 DEG C of room temperature, the stirring condition of 500r/min, by mixed molysite solution with the speed of 1mL/min Be added dropwise in above-mentioned ammonia spirit, after be aged 3h at room temperature, gained is then precipitated into Magneto separate, handed over ethanol and deionized water For Magneto separate again after washing 4 times, it is dissolved in the deionized water of 130mL；
Step 14：By back gained suspension and 130mL concentration for the nitric acid of 0.66mol/L mixes, then again to must To colloidal sol in add the acetic acid of 6mL1mol/L, by pH value regulation to 1.3；
Step 15：The ammoniacal liquor (25%) of 88mL is added in the deionized water of 80mL, the ammoniacal liquor after gained is diluted Solution is added slowly in the product obtained by back, lasting stirring, and it is 70 DEG C to keep mixing temperature with water-bath, and mixing is equal After even, the sodium silicate solution for preparing is added dropwise over thereto, and (mol ratio is NH4OH:HNO3:Na2O·3SiO2=27:1: 0.4)
Step 16：Final reaction gained sediment is separated by Magnetic Isolation from mixed solution, is then spent Ionized water and ethanol are obtained final product and contain Fe to its alternately washing 4 time3O4-SiO2The suspension of compound particle.
Step 17：Vacuum drying treatment is carried out in 60 DEG C, Fe is obtained3O4-SiO2Compound particle.
Step 2：It is prepared by the co-precipitation of LDHs：
Step 21：It is 2 to prepare mol ratio:1 mixed salt solution, weighs the CaCl of 8.8792g2With 10.8116g's FeCl3·6H2O is dissolved in the deionized water of 70mL, is sufficiently mixed；
Step 22：Prepare the NaOH aqueous slkalis of 2mol/L；
Step 23：It is 2 by above-mentioned mol ratio under the conditions of room temperature, the strong agitation of 300r/min:1 mixed metal salt Solution is added in the NaOH solution of the 2mol/L of 150mL with the speed of 1mL/min；
Step 24：24h is aged at 70 DEG C, suspension is obtained；
Step 25：Filtering, the precipitation that will be obtained clean 4 times with deionized water, after be vacuum dried 12h at 60 DEG C, it is prepared Calcium iron double metal hydroxide (LDHs).
Step 3：LDHs modifies Fe3O4-SiO2Compound particle：
Step 31：The above-mentioned made LDHs of 10g are scattered in the deionized water of 300mL, LDHs suspension is configured to, by 4g Above-mentioned made Fe3O4-SiO2Compound particle is scattered in the deionized water of 300mL, is configured to Fe3O4-SiO2Compound particle suspends Liquid；
Step 32：Two kinds of suspension are mixed under conditions of stirring, 5h, magnetic is stirred under conditions of ultrasonic wave thereafter Separate, then in 24h is vacuum dried at 60 DEG C, obtain Fe3O4-SiO2[the Ca of compound particle modification0.67Fe0.33(OH)2][Cl0.11 (CO3)0.11]·0.95H2O magnetic dephosphorization adsorbents.
The method of testing according to above-mentioned technical proposal of the invention carries out the test of dephosphorizing rate to the dephosphorization adsorbent for obtaining, As depicted in figs. 1 and 2, Fig. 1 is dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 with removing that pH value changes to test result Phosphorus rate, whereinThe dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 1,The dephosphorization adsorbent obtained in embodiment 2 Dephosphorizing rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 3,Dephosphorization adsorbent removes obtained in embodiment 4 Phosphorus rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 5,The dephosphorization of dephosphorization adsorbent obtained in embodiment 6 Rate.Fig. 2 is the dephosphorizing rate that dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes over time, whereinIt is embodiment 1 The dephosphorizing rate of obtained dephosphorization adsorbent；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 2；For embodiment 3 is made The dephosphorizing rate of the dephosphorization adsorbent for obtaining；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 4；For embodiment 5 is obtained Dephosphorization adsorbent dephosphorizing rate；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 6.It will be seen from figure 1 that this hair When it is 4.4,6.4,8.4 to simulate solution containing phosphate initial pH value, dephosphorizing rate is respectively dephosphorization adsorbent obtained in bright embodiment 2 94%th, 90%, 81%；Figure it is seen that dephosphorization adsorbent obtained in the embodiment of the present invention 2, at room temperature, takes 500mL dense It is 10mg/L phosphorus-rich waters to spend, and pH is 6.4, and adsorbent dosage is 0.25g, and with the increase of adsorption time, its dephosphorizing rate is gradually Increase, in 4h, interior speedup is very fast and up to maximum material removal rate 90%, adsorbent reaches adsorption equilibrium afterwards, and clearance is relatively steady It is fixed.
Embodiment 3
Step 1：The preparation of particles with superparamagnetism and its is immobilized in SiO2Matrix, is designated as Fe3O4-SiO2Compound particle：
Step 11：By 8.64g FeCl3·6H2O and 3.18g FeCl2·4H2O be dissolved at 20 DEG C 110mL go from In sub- water, now two kinds of mol ratios of molysite are 2:1, as source of iron；
Step 12：The ammoniacal liquor deionized water of 20mL25% is diluted to 100mL, this is alkali source；
Step 13：Under 25 DEG C of room temperature, the stirring condition of 500r/min, by mixed molysite solution with the speed of 1mL/min Be added dropwise in above-mentioned ammonia spirit, after be aged 3h at room temperature, gained is then precipitated into Magneto separate, handed over ethanol and deionized water For Magneto separate again after washing 4 times, it is dissolved in the deionized water of 130mL；
Step 14：By back gained suspension and 130mL concentration for the nitric acid of 0.66mol/L mixes, then again to must To colloidal sol in add the acetic acid of 6mL1mol/L, by pH value regulation to 1.4；
Step 15：The ammoniacal liquor (25%) of 88mL is added in the deionized water of 80mL, the ammoniacal liquor after gained is diluted Solution is added slowly in the product obtained by back, lasting stirring, and it is 70 DEG C to keep mixing temperature with water-bath, and mixing is equal After even, the sodium silicate solution for preparing is added dropwise over thereto, and (mol ratio is NH4OH:HNO3:Na2O·3SiO2=27:1: 0.4)
Step 16：Final reaction gained sediment is separated by Magnetic Isolation from mixed solution, is then spent Ionized water and ethanol are obtained final product and contain Fe to its alternately washing 4 time3O4-SiO2The suspension of compound particle.
Step 17：Vacuum drying treatment is carried out in 60 DEG C, Fe is obtained3O4-SiO2Compound particle.
Step 2：It is prepared by the co-precipitation of LDHs：
Step 21：It is 2 to prepare mol ratio:1 mixed salt solution, weighs the MgCl of 16.264g2With 9.6572g's AlCl3·6H2O is dissolved in the deionized water of 70mL, is sufficiently mixed；
Step 22：Prepare the NaOH aqueous slkalis of 2mol/L；
Step 23：It is 2 by above-mentioned mol ratio under room temperature, the stirring condition of 300r/min:1 mixed salt solution It is added in the NaOH solution of the 2mol/L of 150mL with the speed of 1mL/min；
Step 24：24h is aged at 70 DEG C, suspension is obtained；
Step 25：Filtering, the precipitation that will be obtained clean 4 times with deionized water, after be vacuum dried 12h at 60 DEG C, it is prepared Magnalium double-metal hydroxide (LDHs) powder；
Step 3：LDHs modifies Fe3O4-SiO2Compound particle：
Step 31：The above-mentioned made LDHs of 10g are scattered in the deionized water of 300mL, LDHs suspension is configured to, by 4g Above-mentioned made Fe3O4-SiO2Compound particle is scattered in the deionized water of 300mL, is configured to Fe3O4-SiO2Compound particle suspends Liquid；
Step 32：Two kinds of suspension are mixed under conditions of stirring, 5h, magnetic is stirred under conditions of ultrasonic wave thereafter Separate, then in 24h is vacuum dried at 60 DEG C, obtain Fe3O4-SiO2[the Mg of compound particle modification0.67Al0.33(OH)2] [Cl0.09(CO3)0.12]·1.17H2O magnetic dephosphorization adsorbents.
The method of testing according to above-mentioned technical proposal of the invention carries out the test of dephosphorizing rate to the dephosphorization adsorbent for obtaining, As depicted in figs. 1 and 2, Fig. 1 is dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 with removing that pH value changes to test result Phosphorus rate, whereinThe dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 1,The dephosphorization adsorbent obtained in embodiment 2 Dephosphorizing rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 3,Dephosphorization adsorbent removes obtained in embodiment 4 Phosphorus rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 5,The dephosphorization of dephosphorization adsorbent obtained in embodiment 6 Rate.Fig. 2 is the dephosphorizing rate that dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes over time, whereinIt is embodiment 1 The dephosphorizing rate of obtained dephosphorization adsorbent；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 2；For embodiment 3 is made The dephosphorizing rate of the dephosphorization adsorbent for obtaining；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 4；For embodiment 5 is obtained Dephosphorization adsorbent dephosphorizing rate；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 6.It will be seen from figure 1 that this hair When it is 4.4,6.4,8.4 to simulate solution containing phosphate initial pH value, dephosphorizing rate is respectively dephosphorization adsorbent obtained in bright embodiment 3 53%th, 45%, 38%；Figure it is seen that dephosphorization adsorbent obtained in the embodiment of the present invention 3, at room temperature, takes 500mL dense It is 10mg/L phosphorus-rich waters to spend, and pH is 6.4, and adsorbent dosage is 0.25g, and with the increase of adsorption time, its dephosphorizing rate is gradually Increase, in 4h, interior speedup is very fast and up to maximum material removal rate 44%, adsorbent reaches adsorption equilibrium afterwards, and clearance is relatively steady It is fixed.
Embodiment 4
Step 1：The preparation of particles with superparamagnetism and its is immobilized in SiO2Matrix, is designated as Fe3O4-SiO2Compound particle：
Step 11：By 8.64g FeCl3·6H2O and 3.18g FeCl2·4H2O be dissolved at 20 DEG C 110mL go from In sub- water, now two kinds of mol ratios of molysite are 2:1, as source of iron；
Step 12：The ammoniacal liquor deionized water of 20mL 25% is diluted to 100mL, this is alkali source；
Step 13：Under 25 DEG C of room temperature, the stirring condition of 500r/min, by mixed molysite solution with the speed of 1mL/min Be added dropwise in above-mentioned ammonia spirit, after be aged 3h at room temperature, gained is then precipitated into Magneto separate, handed over ethanol and deionized water For Magneto separate again after washing 4 times, it is dissolved in the deionized water of 130mL；
Step 14：By back gained suspension and 130mL concentration for the nitric acid of 0.66mol/L mixes, then again to must To colloidal sol in add the acetic acid of 6mL1mol/L, by pH value regulation to 1.4；
Step 15：The ammoniacal liquor (25%) of 88mL is added in the deionized water of 80mL, the ammoniacal liquor after gained is diluted Solution is added slowly in the product obtained by back, lasting stirring, and it is 70 DEG C to keep mixing temperature with water-bath, and mixing is equal After even, the sodium silicate solution for preparing is added dropwise over thereto, and (mol ratio is NH4OH:HNO3:Na2O·3SiO2=27:1: 0.4)
Step 16：Final reaction gained sediment is separated by Magnetic Isolation from mixed solution, is then spent Ionized water and ethanol are obtained final product and contain Fe to its alternately washing 4 time3O4-SiO2The suspension of compound particle.
Step 17：Vacuum drying treatment is carried out in 60 DEG C, Fe is obtained3O4-SiO2Compound particle.
Step 2：It is prepared by the co-precipitation of LDHs：
Step 21：It is 2 to prepare mol ratio:1 mixed salt solution, weighs the MgCl of 16.264g2With 10.8116g's FeCl3·6H2O is dissolved in the deionized water of 70mL, is sufficiently mixed；
Step 22：Prepare the NaOH aqueous slkalis of 2mol/L；
Step 23：It is 2 by above-mentioned mol ratio under room temperature, the stirring condition of 300r/min:1 mixed salt solution It is added in the NaOH solution of the 2mol/L of 150mL with the speed of 1mL/min；
Step 24：24h is aged at 70 DEG C, suspension is obtained；
Step 25：Filtering, the precipitation that will be obtained clean 4 times with deionized water, after be vacuum dried 12h at 60 DEG C, it is prepared Magnesium iron double metal hydroxide (LDHs) powder；
Step 3：LDHs modifies Fe3O4-SiO2Compound particle：
Step 31：The above-mentioned made LDHs of 10g are scattered in the deionized water of 300mL, LDHs suspension is configured to, by 4g Above-mentioned made Fe3O4-SiO2Compound particle is scattered in the deionized water of 300mL, is configured to Fe3O4-SiO2Compound particle suspends Liquid；
Step 32：Two kinds of suspension are mixed under conditions of stirring, 5h, magnetic is stirred under conditions of ultrasonic wave thereafter Separate, then in 24h is vacuum dried at 60 DEG C, obtain Fe3O4-SiO2[the Mg of compound particle modification0.67Fe0.33(OH)2] [Cl0.13(CO3)0.10]·1.10H2O magnetic dephosphorization adsorbents.
The method of testing according to above-mentioned technical proposal of the invention carries out the test of dephosphorizing rate to the dephosphorization adsorbent for obtaining, As depicted in figs. 1 and 2, Fig. 1 is dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 with removing that pH value changes to test result Phosphorus rate, whereinThe dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 1,The dephosphorization adsorbent obtained in embodiment 2 Dephosphorizing rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 3,Dephosphorization adsorbent removes obtained in embodiment 4 Phosphorus rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 5,The dephosphorization of dephosphorization adsorbent obtained in embodiment 6 Rate.Fig. 2 is the dephosphorizing rate that dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes over time, whereinIt is embodiment 1 The dephosphorizing rate of obtained dephosphorization adsorbent；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 2；For embodiment 3 is made The dephosphorizing rate of the dephosphorization adsorbent for obtaining；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 4；For embodiment 5 is obtained Dephosphorization adsorbent dephosphorizing rate；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 6.It will be seen from figure 1 that this hair When it is 4.4,6.4,8.4 to simulate solution containing phosphate initial pH value, dephosphorizing rate is respectively dephosphorization adsorbent obtained in bright embodiment 4 80%th, 67%, 53%；Figure it is seen that dephosphorization adsorbent obtained in the embodiment of the present invention 4, at room temperature, takes 500mL dense It is 10mg/L phosphorus-rich waters to spend, and pH is 6.4, and adsorbent dosage is 0.25g, and with the increase of adsorption time, its dephosphorizing rate is gradually Increase, in 4h, interior speedup is very fast and up to maximum material removal rate 67%, adsorbent reaches adsorption equilibrium afterwards, and clearance is relatively steady It is fixed.
Embodiment 5
Step 1：The preparation of particles with superparamagnetism and its is immobilized in SiO2Matrix, is designated as Fe3O4-SiO2Compound particle：
Step 11：By 8.64gFeCl3·6H2O and 3.18gFeCl2·4H2O is dissolved in the deionization of 110mL at 20 DEG C In water, now two kinds of mol ratios of molysite are 2:1, as source of iron；
Step 12：The ammoniacal liquor deionized water of 20mL25% is diluted to 100mL, this is alkali source；
Step 13：Under 25 DEG C of room temperature, the stirring condition of 500r/min, by mixed molysite solution with the speed of 1mL/min Be added dropwise in above-mentioned ammonia spirit, after be aged 3h at room temperature, gained is then precipitated into Magneto separate, handed over ethanol and deionized water For Magneto separate again after washing 4 times, it is dissolved in the deionized water of 130mL；
Step 14：By back gained suspension and 130mL concentration for the nitric acid of 0.66mol/L mixes, then again to must To colloidal sol in add the acetic acid of 6mL1mol/L, by pH value regulation to 1.4；
Step 15：The ammoniacal liquor (25%) of 88mL is added in the deionized water of 80mL, the ammoniacal liquor after gained is diluted Solution is added slowly in the product obtained by back, lasting stirring, and it is 70 DEG C to keep mixing temperature with water-bath, and mixing is equal After even, the sodium silicate solution for preparing is added dropwise over thereto, and (mol ratio is NH4OH:HNO3:Na2O·3SiO2=27:1: 0.4)
Step 16：Final reaction gained sediment is separated by Magnetic Isolation from mixed solution, is then spent Ionized water and ethanol are obtained final product and contain Fe to its alternately washing 4 time3O4-SiO2The suspension of compound particle.
Step 17：Vacuum drying treatment is carried out in 60 DEG C, Fe is obtained3O4-SiO2Compound particle.
Step 2：It is prepared by the co-precipitation of LDHs：
Step 21：It is 2 to prepare mol ratio:1 mixed salt solution, weighs the ZnCl of 10.9056g2With 9.6572g's AlCl3·6H2O is dissolved in the deionized water of 70mL, is sufficiently mixed；
Step 22：Prepare the NaOH aqueous slkalis of 2mol/L；
Step 23：It is 2 by above-mentioned mol ratio under room temperature, the stirring condition of 300r/min:1 mixed salt solution It is added in the NaOH solution of the 2mol/L of 150mL with the speed of 1mL/min；
Step 24：24h is aged at 70 DEG C, suspension is obtained；
Step 25：Filtering, the precipitation that will be obtained clean 4 times with deionized water, after be vacuum dried 12h at 60 DEG C, it is prepared Zinc-aluminium double-metal hydroxide (LDHs) powder；
Step 3：LDHs modifies Fe3O4-SiO2Compound particle：
Step 31：The above-mentioned made LDHs of 10g are scattered in the deionized water of 300mL, LDHs suspension is configured to, by 4g Above-mentioned made Fe3O4-SiO2Compound particle is scattered in the deionized water of 300mL, is configured to Fe3O4-SiO2Compound particle suspends Liquid；
Step 32：Two kinds of suspension are mixed under conditions of stirring, 5h, magnetic is stirred under conditions of ultrasonic wave thereafter Separate, then in 24h is vacuum dried at 60 DEG C, obtain Fe3O4-SiO2[the Zn of compound particle modification0.67Al0.33(OH)2] [Cl0.09(CO3)0.12]·0.67H2O magnetic dephosphorization adsorbents.
The method of testing according to above-mentioned technical proposal of the invention carries out the test of dephosphorizing rate to the dephosphorization adsorbent for obtaining, As depicted in figs. 1 and 2, Fig. 1 is dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 with removing that pH value changes to test result Phosphorus rate, whereinThe dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 1,The dephosphorization adsorbent obtained in embodiment 2 Dephosphorizing rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 3,Dephosphorization adsorbent removes obtained in embodiment 4 Phosphorus rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 5,The dephosphorization of dephosphorization adsorbent obtained in embodiment 6 Rate.Fig. 2 is the dephosphorizing rate that dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes over time, whereinIt is embodiment 1 The dephosphorizing rate of obtained dephosphorization adsorbent；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 2；For embodiment 3 is made The dephosphorizing rate of the dephosphorization adsorbent for obtaining；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 4；For embodiment 5 is obtained Dephosphorization adsorbent dephosphorizing rate；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 6.It will be seen from figure 1 that this hair When it is 4.4,6.4,8.4 to simulate solution containing phosphate initial pH value, dephosphorizing rate is respectively dephosphorization adsorbent obtained in bright embodiment 5 82%th, 63%, 47%；Figure it is seen that dephosphorization adsorbent obtained in the embodiment of the present invention 5, at room temperature, takes 500mL dense It is 10mg/L phosphorus-rich waters to spend, and pH is 6.4, and adsorbent dosage is 0.25g, and with the increase of adsorption time, its dephosphorizing rate is gradually Increase, in 4h, interior speedup is very fast and up to maximum material removal rate 63%, adsorbent reaches adsorption equilibrium afterwards, and clearance is relatively steady It is fixed.
Embodiment 6
Step 1：The preparation of particles with superparamagnetism and its is immobilized in SiO2Matrix, is designated as Fe3O4-SiO2Compound particle：
Step 11：By 8.64g FeCl3·6H2O and 3.18g FeCl2·4H2O be dissolved at 20 DEG C 110mL go from In sub- water, now two kinds of mol ratios of molysite are 2:1, as source of iron；
Step 12：The ammoniacal liquor deionized water of 20mL25% is diluted to 100mL, this is alkali source；
Step 13：Under 25 DEG C of room temperature, the stirring condition of 500r/min, by mixed molysite solution with the speed of 1mL/min Be added dropwise in above-mentioned ammonia spirit, after be aged 3h at room temperature, gained is then precipitated into Magneto separate, handed over ethanol and deionized water For Magneto separate again after washing 4 times, it is dissolved in the deionized water of 130mL；
Step 14：By back gained suspension and 130mL concentration for the nitric acid of 0.66mol/L mixes, then again to must To colloidal sol in add the acetic acid of 6mL1mol/L, by pH value regulation to 1.4；
Step 15：The ammoniacal liquor (25%) of 88mL is added in the deionized water of 80mL, the ammoniacal liquor after gained is diluted Solution is added slowly in the product obtained by back, lasting stirring, and it is 70 DEG C to keep mixing temperature with water-bath, and mixing is equal After even, the sodium silicate solution for preparing is added dropwise over thereto, and (mol ratio is NH4OH:HNO3:Na2O·3SiO2=27:1: 0.4)
Step 16：Final reaction gained sediment is separated by Magnetic Isolation from mixed solution, is then spent Ionized water and ethanol are obtained final product and contain Fe to its alternately washing 4 time3O4-SiO2The suspension of compound particle.
Step 17：Vacuum drying treatment is carried out in 60 DEG C, Fe is obtained3O4-SiO2Compound particle.
Step 2：It is prepared by the co-precipitation of LDHs：
Step 21：It is 2 to prepare mol ratio:1 mixed salt solution, weighs the ZnCl of 10.9056g2With 10.8116g FeCl3·6H2O is dissolved in the deionized water of 70mL, is sufficiently mixed；
Step 22：Prepare the NaOH aqueous slkalis of 2mol/L；
Step 23：It is 2 by above-mentioned mol ratio under room temperature, the stirring condition of 300r/min:1 mixed salt solution It is added in the NaOH solution of the 2mol/L of 150mL with the speed of 1mL/min；
Step 24：24h is aged at 70 DEG C, suspension is obtained；
Step 25：Filtering, the precipitation that will be obtained clean 4 times with deionized water, after be vacuum dried 12h at 60 DEG C, it is prepared Zinc-iron double-metal hydroxide (LDHs) powder；
Step 3：LDHs modifies Fe3O4-SiO2Compound particle：
Step 31：The above-mentioned made LDHs of 10g are scattered in the deionized water of 300mL, LDHs suspension is configured to, by 4g Above-mentioned made Fe3O4-SiO2Compound particle is scattered in the deionized water of 300mL, is configured to Fe3O4-SiO2Compound particle suspends Liquid；
Step 32：Two kinds of suspension are mixed under conditions of stirring, 5h, magnetic is stirred under conditions of ultrasonic wave thereafter Separate, then in 24h is vacuum dried at 60 DEG C, obtain Fe3O4-SiO2[the Zn of compound particle modification0.67Fe0.33(OH)2] [Cl0.11(CO3)0.11]·0.93H2O magnetic dephosphorization adsorbents.
The method of testing according to above-mentioned technical proposal of the invention carries out the test of dephosphorizing rate to the dephosphorization adsorbent for obtaining, As depicted in figs. 1 and 2, Fig. 1 is dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 with removing that pH value changes to test result Phosphorus rate, whereinThe dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 1,The dephosphorization adsorbent obtained in embodiment 2 Dephosphorizing rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 3,Dephosphorization adsorbent removes obtained in embodiment 4 Phosphorus rate,The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 5,The dephosphorization of dephosphorization adsorbent obtained in embodiment 6 Rate.Fig. 2 is the dephosphorizing rate that dephosphorization adsorbent obtained in the embodiment of the present invention 1~6 changes over time, whereinIt is embodiment 1 The dephosphorizing rate of obtained dephosphorization adsorbent；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 2；For embodiment 3 is made The dephosphorizing rate of the dephosphorization adsorbent for obtaining；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 4；For embodiment 5 is obtained Dephosphorization adsorbent dephosphorizing rate；The dephosphorizing rate of dephosphorization adsorbent obtained in embodiment 6.It will be seen from figure 1 that this hair When it is 4.4,6.4,8.4 to simulate solution containing phosphate initial pH value, dephosphorizing rate is respectively dephosphorization adsorbent obtained in bright embodiment 6 79%th, 68%, 55%；Figure it is seen that dephosphorization adsorbent obtained in the embodiment of the present invention 6, at room temperature, takes 500mL dense It is 10mg/L phosphorus-rich waters to spend, and pH is 6.4, and adsorbent dosage is 0.25g, and with the increase of adsorption time, its dephosphorizing rate is gradually Increase, in 4h, interior speedup is very fast and up to maximum material removal rate 68%, adsorbent reaches adsorption equilibrium afterwards, and clearance is relatively steady It is fixed.
Comparative example
By 8.64g FeCl3·6H2O and 3.18g FeCl2·4H2In the deionized water that O is dissolved in 110mL at 25 DEG C, The ammoniacal liquor deionized water of 20mL 25% is diluted to 100mL, under 25 DEG C of room temperature, the stirring condition of 500r/min, will be mixed Iron salt solutions are added dropwise in above-mentioned ammonia spirit with the speed of 1mL/min, after be aged 3h at room temperature, gained is then precipitated into magnetic Separate, replace Magneto separate again after washing 4 times with deionized water with ethanol, vacuum drying, obtains dephosphorization adsorbent at 60 DEG C.Should Adsorbent dephosphorization efficiency under the same conditions is only 28%.
As seen from the above embodiment, inhaled as the magnetic dephosphorization of clad the invention provides a kind of double-metal hydroxide Attached dose of the preparation method adsorbent includes Fe3O4-SiO2Compound particle and it is wrapped in the Fe3O4-SiO2Compound particle surface Double-metal hydroxide；The double-metal hydroxide has the formula shown in Formulas I：[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a (A'2-)b]x-·nH2O.The dephosphorization adsorbent that the present invention is provided includes the double-metal hydroxide with formula shown in Formulas I so that Dephosphorization adsorbent has dephosphorizing rate higher.In addition, the Fe in the dephosphorization adsorbent of present invention offer3O4-SiO2Compound particle is Particles with superparamagnetism so that adsorbent can from liquid phase Magnetic Isolation, it is easy to reclaim, non-secondary pollution.Test result indicate that： At room temperature, 500mL concentration is 10mg/L phosphorus-rich waters, and pH is 6.4, and adsorbent dosage is 0.25g, and after absorption 10h, the present invention is carried The dephosphorizing rate of the dephosphorization adsorbent of confession is 45%~91%.
The preparation method route of the dephosphorization adsorbent that the present invention is provided is simple, with low cost.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (8)

1. a kind of magnetic dephosphorization adsorbent, including Fe3O4-SiO2Compound particle and it is wrapped in the Fe3O4-SiO2Compound particle table The double-metal hydroxide in face；
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is Ca2+；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
2. magnetic dephosphorization adsorbent according to claim 1, it is characterised in that the M'3+Including Al3+Or Fe3+。
3. magnetic dephosphorization adsorbent according to claim 1, it is characterised in that the A-Including NO3 -、Cl-Or OH-。
4. magnetic dephosphorization adsorbent according to claim 1, it is characterised in that the A'2-Including CO3 2-Or SO4 2-。
5. magnetic dephosphorization adsorbent according to claim 1, it is characterised in that the preparation side of the double-metal hydroxide Method, comprises the following steps：
Divalent metal salt, trivalent metal salt and water are mixed, mixed salt solution is obtained；
It is aged after the mixed salt solution and aqueous slkali are mixed, obtains suspension；
By suspension filtering, thing is precipitated；
The sediment is washed and dried successively, double-metal hydroxide is obtained,
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is Ca2+；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
6. magnetic dephosphorization adsorbent according to claim 5, it is characterised in that the divalent metal salt includes CaCl2And Ca (NO3)2In one or more.
7. magnetic dephosphorization adsorbent according to claim 5, it is characterised in that the trivalent metal salt includes AlCl3· 6H2O、FeCl3·6H2O、Al(NO3)3·6H2O and Fe (NO3)3·6H2One or more in O.
8. a kind of preparation method of magnetic dephosphorization adsorbent, comprises the following steps：
By Fe3O4-SiO2Compound particle suspension and double-metal hydroxide suspension mix, ultrasonically treated, then carry out magnetic point From, dry, obtain magnetic dephosphorization adsorbent；
The double-metal hydroxide has the formula shown in Formulas I：
[M2+ (1-x)M'3+ x(OH)2]x+[(A-)a(A'2-)b]x-·nH2O Formulas I；
In Formulas I, M2+It is Ca2+；
M'3+It is trivalent metal ion；
A-To bear univalent anion；
A'2-To bear dianion；
a>0, b>0,0<x<1；
0.25<n<1.42。
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