CN105642222A - Preparation method and application of magnetic recyclable adsorbent - Google Patents
Preparation method and application of magnetic recyclable adsorbent Download PDFInfo
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- CN105642222A CN105642222A CN201610110906.8A CN201610110906A CN105642222A CN 105642222 A CN105642222 A CN 105642222A CN 201610110906 A CN201610110906 A CN 201610110906A CN 105642222 A CN105642222 A CN 105642222A
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- 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
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a preparation method and an application of a magnetic recyclable adsorbent. Ferric chloride and ferrous chloride react in an ethylenediamine aqueous solution to prepare iron carbonyl, then an organic phytic acid is taken as a phosphorus source, materials after calcination of waste egg shells are taken as a calcium source, ethylenediamine is taken as a pH regulator, citric acid is taken as an activator, carbonate-doped hydroxyapatite-coated iron carbonyl as a precursor of the magnetic recyclable adsorbent is prepared with a water bath synthesis method, the precursor is pre-oxidized at the temperature of 300-350 DEG C after a sol-gel curing process and then calcined at temperature of 450-600 DEG C, and the magnetic recyclable adsorbent is prepared. The adopted raw materials are sourced from domestic waste, the cost is low, and the prepared material is applied to passivation repair of heavy metal ions in soil and treatment of heavy metal ions in water and has low cost and good effect.
Description
[technical field]
The present invention relates in field of Environment ProtectionThe preparation method of the recyclable adsorbent of a kind of magnetic and application thereofSpecifically one has magnetic and with ferroso-ferric oxide for core, the magnetic adsorptive material that carbonate hydroxyapatite is shell of high-carbon acid group doping, it is mainly used in water body and the process field of heavy metal in soil ion, there is cost of material low, preparation condition is gentle, metal biosorption effect is strong, especially metal Cr (VI), Cu (II), Pb (II) have extraordinary adsorption, are applied to sanitary wastewater, industry and mining wastewater treatment and environment heavy metal ion reparation and have a extensive future.
[background technology]
Heavy metal is primarily referred to as hydrargyrum, chromium, lead, cadmium, zinc, cobalt, copper and manganese etc. Heavy metal stains that source is wide, harm is big, and its governing problem is just being increasingly subject to the concern of the public. Adopt Heavymetal Wastewater Treatment by Adsorption, it may be achieved the unification of pollution control and changing waste into resources, meet the requirement of recycling economy and sustainable development. Absorption method is the sewage purification technology of a kind of great application potential, and in actual sewage processing procedure, the selection of adsorbent is key often. Therefore, find efficient adsorbent and become the focus of current research for sewage purification.
Hydroxyapatite [Ca10(OH)2(P04)6] (HAP) be two kinds and have good physicochemical property and biology performance have actual application value widely. HAP molecule is owing to having excellent gap structure and chemism hydroxyl and Ca simultaneously2+The adsorption treatment that structure is widely used in aqueous systems heavy metal, simultaneously as HAP and environment have good harmony, does not easily cause secondary pollution, thus becoming a kind ofNovelEnvironment functional material, is subject to people's strong interest. Abundant raw material source, preparation technology that HAP uses are many and simple and easy, from the 1980s since TSuzuki etc. finds that hydroxyapatite can effectively remove the heavy metal ion in aqueous solution, people are in utilizing synthesizing hydroxylapatite (HAP) and natural apatite (Nap) heavy-metal ion removal, explore, find that apatite race mineral can heavy-metal ion removal, especially lead ion effectively. In recent years, domestic and international many scholars are to HAP'sNovelSynthetic method and it is modifiied, and it applies in pollution control, has carried out positive exploration.
But hydroxyapatite itself is due to hexagonal crystallographic texture, cause crystals be difficult to replaced by metal ion and and metal ion exchanged, cause that absorption property is limited, it is thus desirable to hydroxyapatite is modified, improve adsorbable group number in its specific surface area and molecule and and heavy metal between exchange degree, therefore carbonate doping is the mode having excellence at present most, but the major way of doping carbon acid group is to adopt the inorganic compound containing carbonate to carry out high-temperature calcination sintering at present, therefore, it is difficult to ensure the doping ratio of carbonate in doping process, carbonate is difficult to be entrained in inside hydroxyapatite simultaneously, cause that carbonate doping ratio is low, specific surface area is low, absorption property is limited, a kind of carbon of patent is through the preparation method (ZL201210298413.3) of base apatite superfine nanowire, the synthetic method (CN2015100460298) of a kind of carbonate hydroxyapatite with reproducibility function all adopts DIC acid group to adulterate, and the crystal property of inorganic material itself causes that doping is few, the crystal structure of hydroxyapatite is changed less, it is thus desirable to carry out the doping of height, reduce phosphate content in doping system, realize carbonate doping at high proportion, and make its large-scale application be limited for powdered absorbent owing to being in use difficult to again reclaim, therefore nucleocapsid structure can be adopted, it is the magnetic loading that ferroso-ferric oxide realizes adsorbing material by nuclear structure, but often occur that magnetic material is difficult to prepare, therefore this patent utilizes iron chloride and ferrous chloride to prepare iron carbonyl, forming magnetic core, the nucleocapsid structure adopting ferroso-ferric oxide to be core realizes the non-magnetic problem of sorbent material, by adopting organic phosphorus source and carbon source, utilize the organic phosphorus sources pre-oxidation when uniform temperature, generation has highly active carbonate, realize original position doping, field high-temperature calcination simultaneously realizes the stable of crystal formation and doping process, not only achieve the doping at high proportion of carbonate, adopt biological organic phosphorus sources integrated with carbon source simultaneously, low temperature pre-oxidation high-temperature calcination, realize the preparation of high-carbon acid group doping carbon hydroxyapatite adsorbent, be applied to sanitary wastewater, industry and mining wastewater treatment and environment heavy metal ion reparation and be with a wide range of applications.
[summary of the invention]
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation of the recyclable adsorbent of a kind of magnetic and application thereof in field of Environment Protection, particularly there is magnetic and there is the magnetic adsorbent of Coated With Hydroxyapatite ferroso-ferric oxide of high-carbon acid group doping, iron chloride and ferrous chloride is utilized to prepare iron carbonyl, form magnetic core, with garbage Ovum crusta Gallus domesticus for calcium source, with the organic phytic acid of biomass for phosphorus source, by the fixing calcium source of the chelation of phytic acid, utilize the activation reaming effect of citric acid simultaneously, decomposed by phytic acid in preoxidation process and produce carbonate, citric acid decomposes reaming simultaneously, and preparation has the adsorbent of the carbonate hydroxyapatite coated ferriferrous oxide that high-carbon acid group adulterates and specific surface area is big, the nucleocapsid structure adopting ferroso-ferric oxide to be core realizes the non-magnetic problem of sorbent material, employing itself has organic carbon, oxide structure is originated, at aerobic pre-oxidation and high-temperature burning process, the carbonic acid of the carbon dioxide of realization own is to the doping of hydroxyapatite and the fluffy process of reaming, solve the hydroxyapatite adsorbent as sewage disposal, specific surface area its adsorption capacity little is low, conventional carbonate doped hydroxyapatite external carbon acid group source, without hole expandability, and the problem such as poor selectivity, it is applied to sanitary wastewater, industry and mining wastewater treatment and environment heavy metal ion reparation have a extensive future.
It is an object of the invention to be achieved through the following technical solutions:
A kind of recyclable adsorbent of magnetic, specific saturation magnetization is 45��60emu/g, and specific surface area is 250��350g/m2, and carbonate and phosphate radical ratio 1: 3��5.
A kind of preparation method of the recyclable adsorbent of magnetic, its concrete preparation process is:
The preparation of (a) iron carbonyl colloidal sol
Joining in ethylenediamine solution by the aqueous solution of iron chloride and ferrous chloride, the pH being controlled system by ethylenediamine is 8.5��9.0, then reacts 45��60min in 60��80 DEG C, prepares iron carbonyl colloidal sol;
The molar ratio of described iron chloride and ferrous chloride is 2: 1;
Described ferric chloride in aqueous solution molar concentration is 0.1��0.5mol/L;
The preparation of the Coated With Hydroxyapatite iron carbonyl of (b) high doped carbonate
After discarded eggshell is cleaned three times, putting into mass fraction is heat in 5��10% formic acid solutions to 40��60 DEG C of inner membrances sloughing in eggshell, clean with distilled water again, dry, adopting three-roll grinder to carry out crushed into powder, the mean diameter of control powder is 20��50 ��m and prepares pretreatment eggshell powder, then again by pretreated eggshell powder, put in the plant acid solution that mass fraction is 10��30%, stirring reaction 30��45min, then insert again in supersonic reaction device, controlling reaction temperature is 30��45 DEG C, reaction 0.5��2h, after eggshell powder dissolves, add iron carbonyl colloidal sol prepared by above-mentioned steps (a), it is simultaneously introduced ethylenediamine as pH adjusting agent, the pH of control system is 9.8��10.2, after system pH is stable, it is transferred in water-bath synthesis reaction vessel again and reacts, reaction temperature is 150��180 DEG C, response time is 4��6h, it is subsequently adding citric acid solution, the pH of regulation system be 6.5��6.9 then solution after water-bath transfer under normal temperature condition after ultrasonic ripening 2��3h, carry out room temperature concentration of reaction solution, system is made to become viscous liquid, controlling concentrated solution solid content is 75��90%, prepare the Coated With Hydroxyapatite iron carbonyl of high doped carbonate,
Phytic acid has the phosphor-containing structure of excellence, preparation process is possible not only to provide required phosphorus element-containing, phytic acid has Organic substance carbon simultaneously, oxide structure, by the phosphate group absorption chelation to calcium ion in phytic acid in preparation process, calcium ion is made to be enriched in the surface of phytic acid, organic carbon in phytic acid simultaneously, oxide structure forms carbonate in calcination process, it is beneficial to the chanza of hydroxyapatite, particularly in high-temperature burning process, carbon in phytic acid, oxide structure is decomposed to form the carbon dioxide of gaseous state, it is possible not only to improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide generated contacts with hydroxyapatite on molecular structure, therefore activation energy required in doping process is lower, simultaneously gaseous carbon dioxide this as highly active can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore bigger for prepared doped hydroxyapatite specific surface area, carbonate content is with height, to improving prepared absorption property advantageously,
Ethylenediamine acts not only as system pH adjusting agent, makes reaction system pH stable, and in ethylenediamine, the phase decomposes after firing simultaneously, produces ammonia or nitrogen, improves the specific surface area of adsorbent, is beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, Ovum Anas domestica, goose egg. After eggshell calcining, residue composition is single for calcium carbonate, and eggshell wide material sources, and for domestic refuse, the raw material production cost turned waste into wealth is low.
Described pretreatment eggshell powder is 1.27��1.57: 1 with the molar ratio of Ca/P in phytic acid;
The preparation of the recyclable adsorbent of (c) magnetic
The Coated With Hydroxyapatite iron carbonyl of the high doped carbonate that above-mentioned steps (b) is prepared, with under the programming rate of 5��10 DEG C/min, it is warmed up to by room temperature under the aerobic conditions of 300��350 DEG C and carries out pre-oxidation, then with under 20��30 DEG C/min programming rate, it is warming up under 450��600 DEG C of conditions by Pre oxidation to calcine, then, after natural cooling, the recyclable adsorbent of magnetic is prepared.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15��20min, and the calcination time of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate of described high doped carbonate is 75��90min.
Employing first carries out low temperature aerobic pre-oxidation and is then carrying out high-temperature calcination technique, owing to the six-membered ring structure in phytic acid decomposes between 300-350 DEG C, and under aerobic conditions, produce active carbon dioxide gas, it is thus desirable to carry out low temperature aerobic pre-oxidation, the six-membered ring structure being adsorbed in phytate molecule structure is made to decompose, improve carbonate doping activity, decompose the steam of generation to be at high temperature beneficial to and react with hydroxyapatite simultaneously, improve hydroxyl activity in hydroxyapatite molecule, it is beneficial to further carbonate doping process, in high-temperature burning process, the hydroxyapatite making doping carbon acid group is changed completely further, form stable height fluffy high-carbon acid group doped hydroxyapatite structure, improve the absorption property of adsorbent, prepare and there is magnetic texure and high fluffy sorbent material,
Process that the application of the recyclable adsorbent of described magnetic is mainly applied in water sample heavy metal ion and the Passivation Treatment of heavy metal in soil ion, described heavy metal ion is mainly the Cr of high-load (VI), Cu (II), Pb (II) solution or pedotheque;
The recyclable adsorbent of described magnetic processing of heavy metal ion in water sample adopts the method with static adsorption, in processing procedure, the heavy metal ion water sample of high-load adds the recyclable adsorbent of magnetic that mass fraction is 0.5��1%, then the adsorption treatment time is 30��45min, described adsorption treatment temperature is 15��45 DEG C, and in described water sample, concentration of heavy metal ion is 0.5��500mg/L;
The recyclable adsorbent of described magnetic adopts the method to spray powder in the Passivation Treatment of heavy metal in soil ion, in processing procedure, the recyclable adsorbent of magnetic is dispersed in the aqueous solution that mass concentration is 5%, then spraying operation is carried out, and the sprinkling quality of the recyclable adsorbent of magnetic is 0.1��1g/kg in the heavy metal ion soil of high-load, described spraying operation temperature is 15��45 DEG C, and described heavy metal in soil ion concentration is 0.5��500mg/kg.
Compared with prior art, the method have the advantages that
The preparation of the recyclable adsorbent of a kind of magnetic of the present invention and application thereof, with the precursor iron carbonyl of magnetic material ferroso-ferric oxide for raw material, by forming the hydroxyapatite material of high doped carbonate on iron carbonyl surface, prepare and there is excellent absorption property and have magnetic adsorbent, solve conventional absorbtion agent material to be difficult to collect difficulty, recycling, powder body material is difficult to the problems such as separation in the solution simultaneously, it is raw material with domestic refuse eggshell, twice laid, prepare cost of material low simultaneously, and product property is good, meet mass production conditions and sanitary wastewater and restoration of the ecosystem requirement at present, adopt the organic phytic acid of biomass is phosphorus source simultaneously, by the fixing calcium source of the chelation of phytic acid, utilize the activation reaming effect of citric acid simultaneously, preoxidation process is decomposed by phytic acid and produces carbonate and reaming, citric acid decomposes reaming, in conjunction with itself, there is organic carbon, the phytic acid in oxide structure source, at aerobic pre-oxidation and high-temperature burning process, the carbonic acid of the carbon dioxide of realization own is to the doping of hydroxyapatite and the fluffy process of reaming, solve the hydroxyapatite adsorbent as sewage disposal, specific surface area its adsorption capacity little is low, conventional carbonate doped hydroxyapatite external carbon acid group source, without hole expandability, and the problem such as poor selectivity, utilize the particularity of six-membered ring structure in phytic acid simultaneously, in calcination process, employing first carries out low temperature aerobic pre-oxidation and is then carrying out high-temperature calcination technique, the six-membered ring structure in phytic acid is made to carry out aerobic breakdown between 300-350 DEG C, produce active carbon dioxide gas, improve carbonate doping activity, decompose the steam of generation to be at high temperature beneficial to and react with hydroxyapatite simultaneously, improve hydroxyl activity in hydroxyapatite molecule, it is beneficial to further carbonate doping process, in high-temperature burning process, the hydroxyapatite making doping carbon acid group is changed completely further, form stable height fluffy high-carbon acid group doped hydroxyapatite structure, improve the absorption property of adsorbent,Therefore the magnetic recyclable adsorbent specific surface area prepared by the present invention is big, adsorption capacity is big, reaction condition gentleness is controlled, post processing is simple, products collection efficiency is high, the feature that production cost is low, is applied to sanitary wastewater, industry and mining wastewater treatment and environment heavy metal ion reparation and is with a wide range of applications.
[accompanying drawing explanation]
Fig. 1For the present inventionThe preparation method of the recyclable adsorbent of a kind of magnetic and application thereofThe stereoscan photograph of adsorbent;
Fig. 2For the present inventionThe preparation method of the recyclable adsorbent of a kind of magnetic and application thereofThe XRD of adsorbentFigureSpectrum;
Fig. 3For the present inventionThe preparation method of the recyclable adsorbent of a kind of magnetic and application thereofThe FT-IR of adsorbentFigureSpectrum;
[detailed description of the invention]
The present invention presented belowThe preparation method of the recyclable adsorbent of a kind of magnetic and application thereofDetailed description of the invention.
Embodiment 1
A kind of recyclable adsorbent of magnetic, specific saturation magnetization is 45��60emu/g, and specific surface area is 250��350g/m2, and carbonate and phosphate radical ratio 1: 3.
A kind of preparation method of the recyclable adsorbent of magnetic, its concrete preparation process is:
The preparation of (a) iron carbonyl colloidal sol
Joining in ethylenediamine solution by the aqueous solution of iron chloride and ferrous chloride, the pH being controlled system by ethylenediamine is 8.5��9.0, then reacts 45��60min in 60��80 DEG C, prepares iron carbonyl colloidal sol;
The molar ratio of described iron chloride and ferrous chloride is 2: 1;
Described ferric chloride in aqueous solution molar concentration is 0.1mol/L;
The preparation of the Coated With Hydroxyapatite iron carbonyl of (b) high doped carbonate
After discarded eggshell is cleaned three times, putting into mass fraction is heat in 5% formic acid solution to 40��60 DEG C of inner membrances sloughing in eggshell, clean with distilled water again, dry, adopting three-roll grinder to carry out crushed into powder, the mean diameter of control powder is 20��50 ��m and prepares pretreatment eggshell powder, then again by pretreated eggshell powder, put in the plant acid solution that mass fraction is 10%, stirring reaction 30��45min, then insert again in supersonic reaction device, controlling reaction temperature is 30��45 DEG C, reaction 0.5��2h, after eggshell powder dissolves, add iron carbonyl colloidal sol prepared by above-mentioned steps (a), it is simultaneously introduced ethylenediamine as pH adjusting agent, the pH of control system is 9.8��10.2, after system pH is stable, it is transferred in water-bath synthesis reaction vessel again and reacts, reaction temperature is 150��180 DEG C, response time is 4��6h, it is subsequently adding citric acid solution, the pH of regulation system be 6.5��6.9 then solution after water-bath transfer under normal temperature condition after ultrasonic ripening 2��3h, carry out room temperature concentration of reaction solution, system is made to become viscous liquid, controlling concentrated solution solid content is 75%, prepare the Coated With Hydroxyapatite iron carbonyl of high doped carbonate,
Phytic acid has the phosphor-containing structure of excellence, preparation process is possible not only to provide required phosphorus element-containing, phytic acid has Organic substance carbon simultaneously, oxide structure, by the phosphate group absorption chelation to calcium ion in phytic acid in preparation process, calcium ion is made to be enriched in the surface of phytic acid, organic carbon in phytic acid simultaneously, oxide structure forms carbonate in calcination process, it is beneficial to the chanza of hydroxyapatite, particularly in high-temperature burning process, carbon in phytic acid, oxide structure is decomposed to form the carbon dioxide of gaseous state, it is possible not only to improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide generated contacts with hydroxyapatite on molecular structure, therefore activation energy required in doping process is lower, simultaneously gaseous carbon dioxide this as highly active can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore bigger for prepared doped hydroxyapatite specific surface area, carbonate content is with height, to improving prepared absorption property advantageously,
Ethylenediamine acts not only as system pH adjusting agent, makes reaction system pH stable, and in ethylenediamine, the phase decomposes after firing simultaneously, produces ammonia or nitrogen, improves the specific surface area of adsorbent, is beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, Ovum Anas domestica, goose egg. After eggshell calcining, residue composition is single for calcium carbonate, and eggshell wide material sources, and for domestic refuse, the raw material production cost turned waste into wealth is low.
Described pretreatment eggshell powder is 1.27: 1 with the molar ratio of Ca/P in phytic acid;
The preparation of the recyclable adsorbent of (c) magnetic
The Coated With Hydroxyapatite iron carbonyl of the high doped carbonate that above-mentioned steps (b) is prepared, with under the programming rate of 5��10 DEG C/min, it is warmed up to by room temperature under the aerobic conditions of 300��350 DEG C and carries out pre-oxidation, then with under 20��30 DEG C/min programming rate, it is warming up under 450��600 DEG C of conditions by Pre oxidation to calcine, then, after natural cooling, the recyclable adsorbent of magnetic is prepared.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15��20min, and the calcination time of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate of described high doped carbonate is 75��90min.
Employing first carries out low temperature aerobic pre-oxidation and is then carrying out high-temperature calcination technique, owing to the six-membered ring structure in phytic acid decomposes between 300-350 DEG C, and under aerobic conditions, produce active carbon dioxide gas, it is thus desirable to carry out low temperature aerobic pre-oxidation, the six-membered ring structure being adsorbed in phytate molecule structure is made to decompose, improve carbonate doping activity, decompose the steam of generation to be at high temperature beneficial to and react with hydroxyapatite simultaneously, improve hydroxyl activity in hydroxyapatite molecule, it is beneficial to further carbonate doping process, in high-temperature burning process, the hydroxyapatite making doping carbon acid group is changed completely further, form stable height fluffy high-carbon acid group doped hydroxyapatite structure, improve the absorption property of adsorbent, prepare and there is magnetic texure and high fluffy sorbent material,
Fig. 1Corresponding is the electromicroscopic photograph of the recyclable adsorbent of magnetic prepared in embodiment 1, and the stereoscan photograph of adsorbent is saidBright suctionAttached dose has reasonable gap structure and particle aggregation, and surface has the microcellular structure of excellence;
Fig. 2The XRD of the corresponding recyclable adsorbent of the magnetic prepared by embodiment 1FigureSpectrum;FigureSpectrum detects carbonate hydroxyapatite (CHAP) and ferroso-ferric oxide (Fe respectively3O4) characteristic absorption peak, therefore illustrate synthesize successfully carbonate hydroxyapatite and ferroso-ferric oxide;Fig. 3The FT-IR of adsorbent for the preparation of embodiment 1 correspondenceFigureSpectrum;FigureIn spectrum, sample characteristic absworption peak substantially conforms to CHAP and Fe-HAP infrared signatureFigureSpectrum.Fig. 3In it can be seen that at 3572.32cm-1��3420.90cm-1And 1634.74cm-1OH occurs-Stretching vibration peak, 1459.21cm-1And 1414.85cm-1For CO in crystal structure3 2-Two division peaks, 1037.75cm-1��961.55cm-1And 605.67cm-1��567.09cm-1Respectively PO4 3-V1��v2And v3��v4Vibration absorption peak, 572.12cm-1For Fe3O4The position of characteristic peak of HAP and CHAP flexible for Fe-O, the therefore prepared carbonate hydroxyapatite in material is successfully prepared. CO simultaneously3 2-Characteristic absorption peak 1459.21cm-1And 1414.85cm-1Area S1 and PO4 3-Characteristic absorption peak 1037.75cm-1Area S2 ratio be 1: 4.96, hence it is demonstrated that carbonate doping enters in sample, and CO3 -2It is 1: 4.15 in hydroxyapatite doping, CO in sample3 -2With PO4 3-Ratio be 1: 4.96, simultaneously Fe3O4Also it is wrapped in the sample.
Embodiment 2
A kind of recyclable adsorbent of magnetic, specific saturation magnetization is 45��60emu/g, and specific surface area is 250��350g/m2, and carbonate and phosphate radical ratio 1: 4.
A kind of preparation method of the recyclable adsorbent of magnetic, its concrete preparation process is:
The preparation of (a) iron carbonyl colloidal sol
Joining in ethylenediamine solution by the aqueous solution of iron chloride and ferrous chloride, the pH being controlled system by ethylenediamine is 8.5��9.0, then reacts 45��60min in 60��80 DEG C, prepares iron carbonyl colloidal sol;
The molar ratio of described iron chloride and ferrous chloride is 2: 1;
Described ferric chloride in aqueous solution molar concentration is 0.3mol/L;
The preparation of the Coated With Hydroxyapatite iron carbonyl of (b) high doped carbonate
After discarded eggshell is cleaned three times, putting into mass fraction is heat in 8% formic acid solution to 40��60 DEG C of inner membrances sloughing in eggshell, clean with distilled water again, dry, adopting three-roll grinder to carry out crushed into powder, the mean diameter of control powder is 20��50 ��m and prepares pretreatment eggshell powder, then again by pretreated eggshell powder, put in the plant acid solution that mass fraction is 20%, stirring reaction 30��45min, then insert again in supersonic reaction device, controlling reaction temperature is 30��45 DEG C, reaction 0.5��2h, after eggshell powder dissolves, add iron carbonyl colloidal sol prepared by above-mentioned steps (a), it is simultaneously introduced ethylenediamine as pH adjusting agent, the pH of control system is 9.8��10.2, after system pH is stable, it is transferred in water-bath synthesis reaction vessel again and reacts, reaction temperature is 150��180 DEG C, response time is 4��6h, it is subsequently adding citric acid solution, the pH of regulation system be 6.5��6.9 then solution after water-bath transfer under normal temperature condition after ultrasonic ripening 2��3h, carry out room temperature concentration of reaction solution, system is made to become viscous liquid, controlling concentrated solution solid content is 75��90%, prepare the Coated With Hydroxyapatite iron carbonyl of high doped carbonate,
Phytic acid has the phosphor-containing structure of excellence, preparation process is possible not only to provide required phosphorus element-containing, phytic acid has Organic substance carbon simultaneously, oxide structure, by the phosphate group absorption chelation to calcium ion in phytic acid in preparation process, calcium ion is made to be enriched in the surface of phytic acid, organic carbon in phytic acid simultaneously, oxide structure forms carbonate in calcination process, it is beneficial to the chanza of hydroxyapatite, particularly in high-temperature burning process, carbon in phytic acid, oxide structure is decomposed to form the carbon dioxide of gaseous state, it is possible not only to improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide generated contacts with hydroxyapatite on molecular structure, therefore activation energy required in doping process is lower, simultaneously gaseous carbon dioxide this as highly active can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore bigger for prepared doped hydroxyapatite specific surface area, carbonate content is with height, to improving prepared absorption property advantageously,
Ethylenediamine acts not only as system pH adjusting agent, makes reaction system pH stable, and in ethylenediamine, the phase decomposes after firing simultaneously, produces ammonia or nitrogen, improves the specific surface area of adsorbent, is beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, Ovum Anas domestica, goose egg. After eggshell calcining, residue composition is single for calcium carbonate, and eggshell wide material sources, and for domestic refuse, the raw material production cost turned waste into wealth is low.
Described pretreatment eggshell powder is 1.47: 1 with the molar ratio of Ca/P in phytic acid;
The preparation of the recyclable adsorbent of (c) magnetic
The Coated With Hydroxyapatite iron carbonyl of the high doped carbonate that above-mentioned steps (b) is prepared, with under the programming rate of 5��10 DEG C/min, it is warmed up to by room temperature under the aerobic conditions of 300��350 DEG C and carries out pre-oxidation, then with under 20��30 DEG C/min programming rate, it is warming up under 450��600 DEG C of conditions by Pre oxidation to calcine, then, after natural cooling, the recyclable adsorbent of magnetic is prepared.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15��20min, and the calcination time of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate of described high doped carbonate is 75��90min.
Employing first carries out low temperature aerobic pre-oxidation and is then carrying out high-temperature calcination technique, owing to the six-membered ring structure in phytic acid decomposes between 300-350 DEG C, and under aerobic conditions, produce active carbon dioxide gas, it is thus desirable to carry out low temperature aerobic pre-oxidation, the six-membered ring structure being adsorbed in phytate molecule structure is made to decompose, improve carbonate doping activity, decompose the steam of generation to be at high temperature beneficial to and react with hydroxyapatite simultaneously, improve hydroxyl activity in hydroxyapatite molecule, it is beneficial to further carbonate doping process, in high-temperature burning process, the hydroxyapatite making doping carbon acid group is changed completely further, form stable height fluffy high-carbon acid group doped hydroxyapatite structure, improve the absorption property of adsorbent, prepare and there is magnetic texure and high fluffy sorbent material,
Embodiment 3
A kind of recyclable adsorbent of magnetic, specific saturation magnetization is 45��60emu/g, and specific surface area is 250��350g/m2, and carbonate and phosphate radical ratio 1: 5.
A kind of preparation method of the recyclable adsorbent of magnetic, its concrete preparation process is:
The preparation of (a) iron carbonyl colloidal sol
Joining in ethylenediamine solution by the aqueous solution of iron chloride and ferrous chloride, the pH being controlled system by ethylenediamine is 8.5��9.0, then reacts 45��60min in 60��80 DEG C, prepares iron carbonyl colloidal sol;
The molar ratio of described iron chloride and ferrous chloride is 2: 1;
Described ferric chloride in aqueous solution molar concentration is 0.5mol/L;
The preparation of the Coated With Hydroxyapatite iron carbonyl of (b) high doped carbonate
After discarded eggshell is cleaned three times, putting into mass fraction is heat in 5��10% formic acid solutions to 40��60 DEG C of inner membrances sloughing in eggshell, clean with distilled water again, dry, adopting three-roll grinder to carry out crushed into powder, the mean diameter of control powder is 20��50 ��m and prepares pretreatment eggshell powder, then again by pretreated eggshell powder, put in the plant acid solution that mass fraction is 10��30%, stirring reaction 30��45min, then insert again in supersonic reaction device, controlling reaction temperature is 30��45 DEG C, reaction 0.5��2h, after eggshell powder dissolves, add iron carbonyl colloidal sol prepared by above-mentioned steps (a), it is simultaneously introduced ethylenediamine as pH adjusting agent, the pH of control system is 9.8��10.2, after system pH is stable, it is transferred in water-bath synthesis reaction vessel again and reacts, reaction temperature is 150��180 DEG C, response time is 4��6h, it is subsequently adding citric acid solution, the pH of regulation system be 6.5��6.9 then solution after water-bath transfer under normal temperature condition after ultrasonic ripening 2��3h, carry out room temperature concentration of reaction solution, system is made to become viscous liquid, controlling concentrated solution solid content is 75��90%, prepare the Coated With Hydroxyapatite iron carbonyl of high doped carbonate,
Phytic acid has the phosphor-containing structure of excellence, preparation process is possible not only to provide required phosphorus element-containing, phytic acid has Organic substance carbon simultaneously, oxide structure, by the phosphate group absorption chelation to calcium ion in phytic acid in preparation process, calcium ion is made to be enriched in the surface of phytic acid, organic carbon in phytic acid simultaneously, oxide structure forms carbonate in calcination process, it is beneficial to the chanza of hydroxyapatite, particularly in high-temperature burning process, carbon in phytic acid, oxide structure is decomposed to form the carbon dioxide of gaseous state, it is possible not only to improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide generated contacts with hydroxyapatite on molecular structure, therefore activation energy required in doping process is lower, simultaneously gaseous carbon dioxide this as highly active can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore bigger for prepared doped hydroxyapatite specific surface area, carbonate content is with height, to improving prepared absorption property advantageously,
Ethylenediamine acts not only as system pH adjusting agent, makes reaction system pH stable, and in ethylenediamine, the phase decomposes after firing simultaneously, produces ammonia or nitrogen, improves the specific surface area of adsorbent, is beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, Ovum Anas domestica, goose egg. After eggshell calcining, residue composition is single for calcium carbonate, and eggshell wide material sources, and for domestic refuse, the raw material production cost turned waste into wealth is low.
Described pretreatment eggshell powder is 1.57: 1 with the molar ratio of Ca/P in phytic acid;
The preparation of the recyclable adsorbent of (c) magnetic
The Coated With Hydroxyapatite iron carbonyl of the high doped carbonate that above-mentioned steps (b) is prepared, with under the programming rate of 5��10 DEG C/min, it is warmed up to by room temperature under the aerobic conditions of 300��350 DEG C and carries out pre-oxidation, then with under 20��30 DEG C/min programming rate, it is warming up under 450��600 DEG C of conditions by Pre oxidation to calcine, then, after natural cooling, the recyclable adsorbent of magnetic is prepared.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15��20min, and the calcination time of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate of described high doped carbonate is 75��90min.
Employing first carries out low temperature aerobic pre-oxidation and is then carrying out high-temperature calcination technique, owing to the six-membered ring structure in phytic acid decomposes between 300-350 DEG C, and under aerobic conditions, produce active carbon dioxide gas, it is thus desirable to carry out low temperature aerobic pre-oxidation, the six-membered ring structure being adsorbed in phytate molecule structure is made to decompose, improve carbonate doping activity, decompose the steam of generation to be at high temperature beneficial to and react with hydroxyapatite simultaneously, improve hydroxyl activity in hydroxyapatite molecule, it is beneficial to further carbonate doping process, in high-temperature burning process, the hydroxyapatite making doping carbon acid group is changed completely further, form stable height fluffy high-carbon acid group doped hydroxyapatite structure, improve the absorption property of adsorbent, prepare and there is magnetic texure and high fluffy sorbent material,
Embodiment 4
The process that the application of the recyclable adsorbent of described magnetic is mainly applied in water sample heavy metal ion, described heavy metal ion is mainly the Cr of high-load (VI), Cu (II), Pb (II) solution or pedotheque;
The recyclable adsorbent of described magnetic processing of heavy metal ion in water sample adopts the method with static adsorption, in processing procedure, the heavy metal ion water sample of high-load adds the recyclable adsorbent of magnetic that mass fraction is 0.5��1%, then the adsorption treatment time is 30��45min, described adsorption treatment temperature is 15��45 DEG C, and in described water sample, concentration of heavy metal ion is 0.5��500mg/L;
Embodiment 5
The application of the recyclable adsorbent of described magnetic is mainly applied to the Passivation Treatment of heavy metal in soil ion, and described heavy metal ion is mainly the Cr of high-load (VI), Cu (II), Pb (II) solution or pedotheque;
The recyclable adsorbent of described magnetic adopts the method to spray powder in the Passivation Treatment of heavy metal in soil ion, in processing procedure, the recyclable adsorbent of magnetic is dispersed in the aqueous solution that mass concentration is 5%, then spraying operation is carried out, and the sprinkling quality of the recyclable adsorbent of magnetic is 0.1��1g/kg in the heavy metal ion soil of high-load, described spraying operation temperature is 15��45 DEG C, and described heavy metal in soil ion concentration is 0.5��500mg/kg.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, without departing from the inventive concept of the premise; can also making some improvements and modifications, these improvements and modifications also should be regarded as in protection scope of the present invention.
Claims (8)
1. the recyclable adsorbent of magnetic, it is characterised in that specific saturation magnetization is 45��60emu/g, specific surface area is 250��350g/m2, and carbonate and phosphate radical ratio 1:3��5.
2. the preparation method of the recyclable adsorbent of magnetic, it is characterised in that its concrete preparation process is:
The preparation of (a) iron carbonyl colloidal sol
Joining in ethylenediamine solution by the aqueous solution of iron chloride and ferrous chloride, the pH being controlled system by ethylenediamine is 8.5��9.0, then reacts 45��60min in 60��80 DEG C, prepares iron carbonyl colloidal sol;
The preparation of the Coated With Hydroxyapatite iron carbonyl of (b) high doped carbonate
After discarded eggshell is cleaned three times, putting into mass fraction is heat in 5��10% formic acid solutions to 40��60 DEG C of inner membrances sloughing in eggshell, clean with distilled water again, dry, adopting three-roll grinder to carry out crushed into powder, the mean diameter of control powder is 20��50 ��m and prepares pretreatment eggshell powder, then again by pretreated eggshell powder, put in the plant acid solution that mass fraction is 10��30%, stirring reaction 30��45min, then insert again in supersonic reaction device, controlling reaction temperature is 30��45 DEG C, reaction 0.5��2h, after eggshell powder dissolves, add iron carbonyl colloidal sol prepared by above-mentioned steps (a), it is simultaneously introduced ethylenediamine as pH adjusting agent, the pH of control system is 9.8��10.2, after system pH is stable, it is transferred in water-bath synthesis reaction vessel again and reacts, reaction temperature is 150��180 DEG C, response time is 4��6h, it is subsequently adding citric acid solution, the pH of regulation system be 6.5��6.9 then solution after water-bath transfer under normal temperature condition after ultrasonic ripening 2��3h, carry out room temperature concentration of reaction solution, system is made to become viscous liquid, controlling concentrated solution solid content is 75��90%, prepare the Coated With Hydroxyapatite iron carbonyl of high doped carbonate,
The preparation of the recyclable adsorbent of (c) magnetic
The Coated With Hydroxyapatite iron carbonyl of the high doped carbonate that above-mentioned steps (b) is prepared, with under the programming rate of 5��10 DEG C/min, it is warmed up to by room temperature under the aerobic conditions of 300��350 DEG C and carries out pre-oxidation, then with under 20��30 DEG C/min programming rate, it is warming up under 450��600 DEG C of conditions by Pre oxidation to calcine, then, after natural cooling, the recyclable adsorbent of magnetic is prepared.
3. the molar ratio of the preparation method of the recyclable adsorbent of a kind of magnetic as claimed in claim 2, it is characterised in that in step (a), described iron chloride and ferrous chloride is 2:1.
4. the preparation method of the recyclable adsorbent of a kind of magnetic as claimed in claim 2, it is characterised in that in step (a), described ferric chloride in aqueous solution molar concentration is 0.1��0.5mol/L.
5. the preparation method of the recyclable adsorbent of a kind of magnetic as claimed in claim 2, it is characterized in that, in step (a), in step (b), described pretreatment eggshell powder is 1.27��1.57:1 with the molar ratio of Ca/P in phytic acid.
6. the preparation method of the recyclable adsorbent of a kind of magnetic as claimed in claim 2, it is characterized in that, in step (a), in step (c), the preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15��20min, and the calcination time of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate of described high doped carbonate is 75��90min.
7. the recyclable adsorbent of a kind of magnetic application in the process of heavy metal ion in water sample as claimed in claim 1, it is characterized in that, it concretely comprises the following steps: adopt the method with static adsorption, in processing procedure, the heavy metal ion water sample of high-load adds the recyclable adsorbent of magnetic that mass fraction is 0.5��1%, then the adsorption treatment time is 30��45min, and described adsorption treatment temperature is 15��45 DEG C, and in described water sample, concentration of heavy metal ion is 0.5��500mg/L;
Described heavy metal ion is mainly the Cr (VI) of high-load, Cu (II), Pb (II) solution or pedotheque.
8. the recyclable adsorbent of a kind of magnetic as claimed in claim 1 is in the application of the Passivation Treatment of heavy metal in soil ion, it is characterized in that, it concretely comprises the following steps: adopt the method with static adsorption, in processing procedure, adopt the method to spray powder, in processing procedure, the recyclable adsorbent of magnetic is dispersed in the aqueous solution that mass concentration is 5%, then spraying operation is carried out, and the sprinkling quality of the recyclable adsorbent of magnetic is 0.1��1g/kg in the heavy metal ion soil of high-load, described spraying operation temperature is 15��45 DEG C, described heavy metal in soil ion concentration is 0.5��500mg/kg,
Described heavy metal ion is mainly the Cr (VI) of high-load, Cu (II), Pb (II) solution or pedotheque.
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