CN105642222B - A kind of preparation method and applications of the recyclable adsorbent of magnetic - Google Patents
A kind of preparation method and applications of the recyclable adsorbent of magnetic Download PDFInfo
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- CN105642222B CN105642222B CN201610110906.8A CN201610110906A CN105642222B CN 105642222 B CN105642222 B CN 105642222B CN 201610110906 A CN201610110906 A CN 201610110906A CN 105642222 B CN105642222 B CN 105642222B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01J20/0203—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J20/28009—Magnetic 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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Abstract
The present invention relates to a kind of preparation method and applications of the recyclable adsorbent of magnetic, with iron chloride and frerrous chloride, reaction prepares iron carbonyl in the aqueous solution of ethylenediamine, then using organic phytic acid as phosphorus source, using raw material of the discarded object egg shell after calcining as calcium source, it is pH adjusting agent by ethylenediamine, citric acid is activator, the method synthesized using water-bath, prepare the precursor doped Carbonated hydroxyapatite cladding iron carbonyl of the recyclable adsorbent of magnetic, after the maturing process of collosol and gel, pre-oxidized again under the conditions of 300~350 DEG C, then calcined again under the conditions of 450~600 DEG C, the recyclable adsorbent of magnetic is prepared；The raw material sources that the present invention uses are in domestic refuse, and cost is low, while the materials application prepared is passivated in heavy metal in soil ion and repaired, and heavy metal in water ion processing, low with cost, effect is good.
Description
【Technical field】
The present invention relates to a kind of preparation method and applications of the recyclable adsorbent of magnetic in field of Environment Protection, specifically one
For kind with magnetic and using ferroso-ferric oxide as core, the carbonate hydroxyapatite of high-carbon acid group doping is the magnetic adsorptive material of shell, main
The process field in water body and heavy metal in soil ion is applied, low with cost of material, preparation condition is gentle, to metal
The suction-operated of ion is strong, and especially metal Cr (VI), Cu (II), Pb (II) have extraordinary suction-operated, applied to life
Waste water, industry and mining wastewater treatment and environment heavy metal ion reparation living have a extensive future.
【Background technology】
Heavy metal is primarily referred to as mercury, chromium, lead, cadmium, zinc, cobalt, copper and manganese etc..Heavy metal stains that source is wide, harm is big, and it is controlled
Reason problem is just being increasingly subject to the concern of the public.Using Heavymetal Wastewater Treatment by Adsorption, pollution control and waste resource can be achieved
The unification of change, meet the requirement of recycling economy and sustainable development.Absorption method is a kind of sewage purification skill of great application potential
Art, and in actual sewage processing procedure, the selection of adsorbent is often key.Therefore, find efficient adsorbent and be used for dirt
Water warfare turns into the focus of current research.
Hydroxyapatite [Ca10(OH)2(P04)6] (HAP) is two kinds has good physicochemical property and biology performance, have
Extensive actual application value.HAP molecules are due to excellent gap structure and chemism hydroxyl and Ca simultaneously2+Structure
It is widely used in the adsorption treatment of heavy metal in aqueous systems, simultaneously as HAP has good harmony with environment, does not easily cause
Secondary pollution, so as to turn into a kind of novel environmental functional material, by people's strong interest.Raw material sources that HAP is used are abundant,
Preparation technology is more and simple, finds that hydroxyapatite can effectively remove the aqueous solution from 1980s T Suzuki etc.
In heavy metal ion since, people using synthesizing hydroxylapatite (HAP) and natural apatite (Nap) go removing heavy metals from
Sub- aspect, is explored, it is found that apatite race mineral can effectively heavy-metal ion removal, especially lead ion.In recent years,
Many scholars are modified to HAP novel method for synthesizing and to it both at home and abroad, and it is applied in pollution control, have been carried out actively
Exploration.
But hydroxyapatite is in itself due to hexagonal crystallographic texture, cause crystals be difficult to by metal ion replace with
And and metal ion exchanged, cause absorption property limited, it is therefore desirable to be modified to hydroxyapatite, improve its specific surface area
And adsorbable group number and exchange degree between heavy metal in molecule；Therefore carbonate doping be at present most have it is excellent
Mode, but at present doping carbonate major way be using containing carbonate inorganic compound carry out high-temperature calcination sintering,
Therefore, it is difficult to ensure the doping ratio of carbonate during adulterating, while carbonate is difficult to be entrained in inside hydroxyapatite, leads
Cause carbonate doping ratio is low, and specific surface area is low, and absorption property is limited, a kind of system of the carbon of patent through base apatite superfine nanowire
Preparation Method (ZL 201210298413.3), a kind of synthetic method (CN with the carbonate hydroxyapatite for reducing sexual function
2015100460298) it is doped using DIC acid group, and the crystal property of inorganic material in itself causes doping few,
Crystal structure change to hydroxyapatite is less, it is therefore desirable to carries out the doping of height, reduces phosphate radical in doping system and contain
Amount, realize that carbonate adulterates at high proportion；And make its big due to being difficult to reclaim again in use for powdered absorbent
Sizable application is limited, therefore can use core shell structure, is the magnetic that ferroso-ferric oxide realizes sorbing material by nuclear structure
Load, but often magnetic material occur and be difficult to prepare, therefore this patent prepares iron carbonyl using iron chloride and frerrous chloride, forms magnetic
Property core, uses ferroso-ferric oxide to realize the non-magnetic problem of sorbent material for the core shell structure of core；By using organic phosphorus
Source and carbon source, using pre-oxidation of the organic phosphorus sources under the conditions of certain temperature, carbonate of the generation with high activity, realize in situ
Doping, while the stabilization and doping process of crystal formation are realized in field high-temperature calcination, not only realize the doping at high proportion of carbonate, together
Shi Caiyong biological organic phosphorus sources are integrated with carbon source, low temperature pre-oxidation high-temperature calcination, realize high-carbon acid group doped carbon hydroxy-apatite
The preparation of stone adsorbent, have applied to sanitary wastewater, industry and mining wastewater treatment and the reparation of environment heavy metal ion extensive
Application prospect.
【The content of the invention】
It is an object of the invention to overcome the deficiencies of the prior art and provide the recyclable adsorbent of a kind of magnetic in field of Environment Protection
Preparation and its application, particularly with magnetic and with high-carbon acid group doping Coated With Hydroxyapatite ferroso-ferric oxide magnetic
Property adsorbent；Iron carbonyl is prepared using iron chloride and frerrous chloride, magnetic core is formed, using discarded object egg shell as calcium source, with life
The organic phytic acid of material is phosphorus source, and calcium source is fixed by the chelation of phytic acid, while is acted on using the activation reaming of citric acid,
In preoxidation process by phytic acid decompose produce carbonate, while citric acid decompose reaming, prepare have high-carbon acid group doping and
The adsorbent of the big carbonate hydroxyapatite coated ferriferrous oxide of specific surface area；Use ferroso-ferric oxide real for the core shell structure of core
The non-magnetic problem of existing sorbent material, using itself having organic carbon, oxide structure source, in aerobic pre-oxidation and high-temperature calcination
Process, doping and reaming fluffy process of the carbonic acid of carbon dioxide to hydroxyapatite itself is realized, solves hydroxyapatite
As the adsorbent of sewage disposal, its small adsorption capacity of specific surface area is low, conventional carbonate doped hydroxyapatite external carbon
Acid group source, no hole expandability, and the problems such as poor selectivity, applied to sanitary wastewater, industry and mining wastewater treatment and an environment huge sum of money
Category ion reparation has a extensive future.
The purpose of the present invention is achieved through the following technical solutions：
A kind of recyclable adsorbent of magnetic, specific saturation magnetization are 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 specific preparation process are：
(a) preparation of hydroxyl ferrum collosol
The aqueous solution of iron chloride and frerrous chloride is added in ethylenediamine solution, the pH by ethylenediamine control system is
8.5~9.0,45~60min is then reacted in 60~80 DEG C, hydroxyl ferrum collosol is prepared；
Described iron chloride and the molar ratio of frerrous chloride are 2: 1；
Described ferric chloride in aqueous solution molar concentration is 0.1~0.5mol/L；
(b) preparation of the Coated With Hydroxyapatite iron carbonyl of high doped carbonate
After the cleaning three times of discarded eggshell, it is de- to be heated to 40~60 DEG C in 5~10% formic acid solutions to be put into mass fraction
Inner membrance in shell breaking, then cleaned with distilled water, dry, crushed into powder is carried out using three-roll grinder, control the flat of powder
Equal particle diameter is 20~50 μm and pretreatment eggshell powder is prepared；Then again by pretreated eggshell powder, input quality point
Number is in 10~30% plant acid solution, 30~45min of stirring reaction, then inserts in supersonic reaction device again, control reaction
Temperature is 30~45 DEG C, reacts 0.5~2h, and after the dissolving of eggshell powder, the iron carbonyl for adding above-mentioned steps (a) preparation is molten
Glue, while ethylenediamine is added as pH adjusting agent, the pH of control system is 9.8~10.2, after system pH is stable, then is transferred to
To be reacted in water-bath synthesis reaction vessel, reaction temperature is 150~180 DEG C, and the reaction time is 4~6h, then adds citric acid solution,
The pH of regulation system is that the solution after 6.5~6.9 and then water-bath is transferred under normal temperature condition after 2~3h of ultrasound curing,
Normal temperature concentration of reaction solution is carried out, making system, it is 75~90% to control concentration fluid solid content, and height is prepared into viscous liquid
Adulterate the Coated With Hydroxyapatite iron carbonyl of carbonate；
Phytic acid has excellent phosphor-containing structure, and required phosphorus element-containing can be not only provided in preparation process, is planted simultaneously
Acid has organic matter carbon, oxide structure, by absorption chelation of the phosphate group in phytic acid to calcium ion in preparation process, makes
Calcium ion is enriched in the surface of phytic acid, while organic matter carbon, oxide structure form carbonate in calcination process in phytic acid, beneficial to hydroxyl
The chanza of base apatite, especially in high-temperature burning process, carbon, oxide structure in phytic acid are decomposed to form gaseous dioxy
Change carbon, can not only improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide of generation exists
Contacted on molecular structure with hydroxyapatite, therefore the activation energy needed for during doping is lower, while gaseous carbon dioxide sheet
As high activity can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore for prepared doping
Hydroxyapatite specific surface area is bigger, and 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, while in ethylenediamine after firing
Phase decomposes, and produces ammonia or nitrogen, improves the specific surface area of adsorbent, beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, duck's egg, goose egg.Residue composition is single after eggshell calcining
For calcium carbonate, and eggshell wide material sources, it is domestic refuse, the raw material production cost to turn waste into wealth is low.
Described pretreatment eggshell powder and Ca/P in phytic acid molar ratio are 1.27~1.57: 1；
(c) preparation of the recyclable adsorbent of magnetic
The Coated With Hydroxyapatite iron carbonyl for the high doped carbonate that above-mentioned steps (b) are prepared, with 5~10
DEG C/min programming rate under, be warming up under 300~350 DEG C of aerobic conditions and pre-oxidized by normal temperature, then with 20~30
DEG C/min programming rates under, be warming up under the conditions of 450~600 DEG C and calcined by Pre oxidation, then after natural cooling, is prepared into
To the recyclable adsorbent of magnetic.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15~20min, institute
During the calcining of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate for the high doped carbonate stated
Between be 75~90min.
High-temperature calcination technique then is being carried out using the aerobic pre-oxidation of low temperature is first carried out, due to the six-membered ring structure in phytic acid
Decomposed between 300-350 DEG C, and active carbon dioxide gas is produced under aerobic conditions, it is therefore desirable to which carrying out low temperature has
Oxygen pre-oxidizes, and decomposes six-membered ring structure of the absorption in phytate molecule structure, improves carbonate doping activity, while decompose production
Raw steam is beneficial to react with hydroxyapatite at high temperature, hydroxyl activity in hydroxyapatite molecule is improved, beneficial to further
Carbonate adulterates process, in high-temperature burning process, the hydroxyapatite of doping carbonate is further changed completely, is formed steady
Fixed high fluffy high-carbon acid group doped hydroxyapatite structure, improves the absorption property of adsorbent, is prepared with magnetic junction
Structure and high fluffy sorbent material；
The application of the recyclable adsorbent of described magnetic is mainly to be applied to the processing of heavy metal ion and soil in water sample
The Passivation Treatment of middle heavy metal ion, described heavy metal ion are mainly the Cr (VI), Cu (II), Pb (II) solution of high content
Or pedotheque；
The processing of heavy metal ion in water sample of the recyclable adsorbent of described magnetic uses the method with Static Adsorption, place
During reason, the recyclable adsorbent of magnetic that mass fraction is 0.5~1% is added in the heavy metal ion water sample of high content,
Then the adsorption treatment time is 30~45min, and described adsorption treatment temperature is 15~45 DEG C, in described water sample heavy metal from
Sub- concentration is 0.5~500mg/L；
The recyclable adsorbent of described magnetic is used in the Passivation Treatment of heavy metal in soil ion to spray the side of pulvis
Method, in processing procedure, the recyclable adsorbent of magnetic is dispersed in the aqueous solution that mass concentration is 5%, then carries out spraying operation,
And the sprinkling quality of the recyclable adsorbent of magnetic is 0.1~1g/kg in the heavy metal ion soil of high content, described sprinkling
Processing temperature is 15~45 DEG C, and described heavy metal in soil ion concentration is 0.5~500mg/kg.
Compared with prior art, the positive effect of the present invention is：
The present invention a kind of preparation and its application of the recyclable adsorbent of magnetic, with the precursor of magnetic material ferroso-ferric oxide
Iron carbonyl is raw material, and by forming the hydroxyapatite material of high doped carbonate in hydroxyl iron surface, being prepared has
Excellent absorption property and the magnetic adsorbent of tool, solve conventional absorbtion agent material and be difficult to collect difficult, recycling, simultaneously
The problems such as powder body material is difficult to separate in the solution；With domestic refuse eggshell be raw material, twice laid, while preparing raw material into
This is low, and product property is good, meets mass production conditions and current sanitary wastewater and restoration of the ecosystem requirement；Use simultaneously
The organic phytic acid of biomass is phosphorus source, and calcium source is fixed by the chelation of phytic acid, while is acted on using the activation reaming of citric acid,
Decomposed in preoxidation process by phytic acid and produce carbonate and reaming, citric acid decomposes reaming, had with reference to itself organic
Carbon, the phytic acid in oxide structure source, in aerobic pre-oxidation and high-temperature burning process, realize the carbonic acid of carbon dioxide itself to hydroxyl phosphorus
The fluffy process of doping and reaming of lime stone, solve adsorbent of the hydroxyapatite as sewage disposal, its small suction of specific surface area
Attached capacity is low, the additional carbonate source of conventional carbonate doped hydroxyapatite, no hole expandability, and the problems such as poor selectivity；
Simultaneously using the particularity of six-membered ring structure in phytic acid, in calcination process, using first carrying out, the aerobic pre-oxidation of low temperature is right
High-temperature calcination technique is being carried out afterwards, the six-membered ring structure in phytic acid is carried out aerobic breakdown between 300-350 DEG C, is producing activity
Carbon dioxide, carbonate doping activity is improved, while steam caused by decomposition is at high temperature beneficial to anti-with hydroxyapatite
Should, hydroxyl activity in hydroxyapatite molecule is improved, process is adulterated beneficial to further carbonate, in high-temperature burning process, makes
The hydroxyapatite for adulterating carbonate further changes the high fluffy high-carbon acid group doped hydroxyapatite knot for completely, forming stabilization
Structure, improve the absorption property of adsorbent；Therefore the recyclable adsorbent specific surface area of magnetic prepared by the present invention is big, adsorption capacity
Greatly, the characteristics of reaction condition is gently controllable, and post processing is simple, and products collection efficiency is high, and production cost is low, applied to sanitary wastewater, work
Mining industry wastewater treatment and environment heavy metal ion reparation are with a wide range of applications.
【Brief description of the drawings】
Fig. 1 is that a kind of ESEM of the adsorbent of the preparation method and applications of the recyclable adsorbent of magnetic of the present invention shines
Piece；
Fig. 2 is a kind of XRD spectrum of the adsorbent of the preparation method and applications of the recyclable adsorbent of magnetic of the present invention；
Fig. 3 is a kind of FT-IR collection of illustrative plates of the adsorbent of the preparation method and applications of the recyclable adsorbent of magnetic of the present invention；
【Embodiment】
A kind of embodiment of the preparation method and applications of the recyclable adsorbent of magnetic of the present invention presented below.
Embodiment 1
A kind of recyclable adsorbent of magnetic, specific saturation magnetization are 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 specific preparation process are：
(a) preparation of hydroxyl ferrum collosol
The aqueous solution of iron chloride and frerrous chloride is added in ethylenediamine solution, the pH by ethylenediamine control system is
8.5~9.0,45~60min is then reacted in 60~80 DEG C, hydroxyl ferrum collosol is prepared；
Described iron chloride and the molar ratio of frerrous chloride are 2: 1；
Described ferric chloride in aqueous solution molar concentration is 0.1mol/L；
(b) preparation of the Coated With Hydroxyapatite iron carbonyl of high doped carbonate
After the cleaning three times of discarded eggshell, it is put into mass fraction and sloughs egg to be heated to 40~60 DEG C in 5% formic acid solution
Inner membrance in shell, then cleaned with distilled water, dry, crushed into powder is carried out using three-roll grinder, controls the average grain of powder
Footpath is 20~50 μm and pretreatment eggshell powder is prepared；Then it is by pretreated eggshell powder, input mass fraction again
In 10% plant acid solution, 30~45min of stirring reaction, then insert again in supersonic reaction device, controlling reaction temperature 30
~45 DEG C, 0.5~2h is reacted, after the dissolving of eggshell powder, the hydroxyl ferrum collosol of above-mentioned steps (a) preparation is added, adds simultaneously
Enter ethylenediamine as pH adjusting agent, the pH of control system is 9.8~10.2, after system pH is stable, then is transferred to water-bath synthesis
Reacted in reactor, reaction temperature is 150~180 DEG C, and the reaction time is 4~6h, then adds citric acid solution, regulation system
PH be after solution after 6.5~6.9 and then water-bath transfers under normal temperature condition 2~3h of ultrasound curing, to carry out normal temperature
Concentration of reaction solution, making system, it is 75% to control concentration fluid solid content, and high doped carbonate is prepared into viscous liquid
Coated With Hydroxyapatite iron carbonyl；
Phytic acid has excellent phosphor-containing structure, and required phosphorus element-containing can be not only provided in preparation process, is planted simultaneously
Acid has organic matter carbon, oxide structure, by absorption chelation of the phosphate group in phytic acid to calcium ion in preparation process, makes
Calcium ion is enriched in the surface of phytic acid, while organic matter carbon, oxide structure form carbonate in calcination process in phytic acid, beneficial to hydroxyl
The chanza of base apatite, especially in high-temperature burning process, carbon, oxide structure in phytic acid are decomposed to form gaseous dioxy
Change carbon, can not only improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide of generation exists
Contacted on molecular structure with hydroxyapatite, therefore the activation energy needed for during doping is lower, while gaseous carbon dioxide sheet
As high activity can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore for prepared doping
Hydroxyapatite specific surface area is bigger, and 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, while in ethylenediamine after firing
Phase decomposes, and produces ammonia or nitrogen, improves the specific surface area of adsorbent, beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, duck's egg, goose egg.Residue composition is single after eggshell calcining
For calcium carbonate, and eggshell wide material sources, it is domestic refuse, the raw material production cost to turn waste into wealth is low.
Described pretreatment eggshell powder and Ca/P in phytic acid molar ratio are 1.27: 1；
(c) preparation of the recyclable adsorbent of magnetic
The Coated With Hydroxyapatite iron carbonyl for the high doped carbonate that above-mentioned steps (b) are prepared, with 5~10
DEG C/min programming rate under, be warming up under 300~350 DEG C of aerobic conditions and pre-oxidized by normal temperature, then with 20~30
DEG C/min programming rates under, be warming up under the conditions of 450~600 DEG C and calcined by Pre oxidation, then after natural cooling, is prepared into
To the recyclable adsorbent of magnetic.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15~20min, institute
During the calcining of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate for the high doped carbonate stated
Between be 75~90min.
High-temperature calcination technique then is being carried out using the aerobic pre-oxidation of low temperature is first carried out, due to the six-membered ring structure in phytic acid
Decomposed between 300-350 DEG C, and active carbon dioxide gas is produced under aerobic conditions, it is therefore desirable to which carrying out low temperature has
Oxygen pre-oxidizes, and decomposes six-membered ring structure of the absorption in phytate molecule structure, improves carbonate doping activity, while decompose production
Raw steam is beneficial to react with hydroxyapatite at high temperature, hydroxyl activity in hydroxyapatite molecule is improved, beneficial to further
Carbonate adulterates process, in high-temperature burning process, the hydroxyapatite of doping carbonate is further changed completely, is formed steady
Fixed high fluffy high-carbon acid group doped hydroxyapatite structure, improves the absorption property of adsorbent, is prepared with magnetic junction
Structure and high fluffy sorbent material；
It is the electromicroscopic photograph of the recyclable adsorbent of magnetic prepared in embodiment 1 corresponding to Fig. 1, the scanning of adsorbent is electric
Mirror photo illustrates that adsorbent has relatively good gap structure, and particle aggregation, and surface has excellent microcellular structure；
The XRD spectrum of the recyclable adsorbent of magnetic corresponding to Fig. 2 prepared by embodiment 1；Detected respectively in collection of illustrative plates
Carbonate hydroxyapatite (CHAP) and ferroso-ferric oxide (Fe3O4) characteristic absorption peak, therefore explanation synthesize successfully carbonate hydroxyapatite
And ferroso-ferric oxide；Fig. 3 is the FT-IR collection of illustrative plates of the adsorbent prepared corresponding to embodiment 1；Sample characteristic absworption peak base in collection of illustrative plates
Originally CHAP and Fe-HAP infrared signature collection of illustrative plates is met.In Fig. 3 it can be seen that in 3572.32cm-1、3420.90cm-1With
1634.74cm-1There is OH-Stretching vibration peak, 1459.21cm-1And 1414.85cm-1For CO in crystal structure3 2-Two division
Peak, 1037.75cm-1、961.55cm-1And 605.67cm-1、567.09cm-1Respectively PO4 3-V1、v2And v3、v4Absorption of vibrations
Peak, 572.12cm-1For Fe3O4Fe-O flexible HAP and CHAP characteristic peak position, therefore the carbon in prepared material
Hydroxyapatite is successfully prepared.CO simultaneously3 2-Characteristic absorption peak 1459.21cm-1And 1414.85cm-1Area S1 and PO4 3-It is special
Levy absworption peak 1037.75cm-1Area S2 ratios be 1: 4.96, hence it is demonstrated that carbonate doping enters in sample, and CO3 -2
It is 1: 4.15 in hydroxyapatite doping, CO in sample3 -2With PO4 3-Ratio be 1: 4.96, while Fe3O4Also it is wrapped in
In sample.
Embodiment 2
A kind of recyclable adsorbent of magnetic, specific saturation magnetization are 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 specific preparation process are：
(a) preparation of hydroxyl ferrum collosol
The aqueous solution of iron chloride and frerrous chloride is added in ethylenediamine solution, the pH by ethylenediamine control system is
8.5~9.0,45~60min is then reacted in 60~80 DEG C, hydroxyl ferrum collosol is prepared；
Described iron chloride and the molar ratio of frerrous chloride are 2: 1；
Described ferric chloride in aqueous solution molar concentration is 0.3mol/L；
(b) preparation of the Coated With Hydroxyapatite iron carbonyl of high doped carbonate
After the cleaning three times of discarded eggshell, it is put into mass fraction and sloughs egg to be heated to 40~60 DEG C in 8% formic acid solution
Inner membrance in shell, then cleaned with distilled water, dry, crushed into powder is carried out using three-roll grinder, controls the average grain of powder
Footpath is 20~50 μm and pretreatment eggshell powder is prepared；Then it is by pretreated eggshell powder, input mass fraction again
In 20% plant acid solution, 30~45min of stirring reaction, then insert again in supersonic reaction device, controlling reaction temperature 30
~45 DEG C, 0.5~2h is reacted, after the dissolving of eggshell powder, the hydroxyl ferrum collosol of above-mentioned steps (a) preparation is added, adds simultaneously
Enter ethylenediamine as pH adjusting agent, the pH of control system is 9.8~10.2, after system pH is stable, then is transferred to water-bath synthesis
Reacted in reactor, reaction temperature is 150~180 DEG C, and the reaction time is 4~6h, then adds citric acid solution, regulation system
PH be after solution after 6.5~6.9 and then water-bath transfers under normal temperature condition 2~3h of ultrasound curing, to carry out normal temperature
Concentration of reaction solution, making system, it is 75~90% to control concentration fluid solid content, and high doped carbonic acid is prepared into viscous liquid
The Coated With Hydroxyapatite iron carbonyl of root；
Phytic acid has excellent phosphor-containing structure, and required phosphorus element-containing can be not only provided in preparation process, is planted simultaneously
Acid has organic matter carbon, oxide structure, by absorption chelation of the phosphate group in phytic acid to calcium ion in preparation process, makes
Calcium ion is enriched in the surface of phytic acid, while organic matter carbon, oxide structure form carbonate in calcination process in phytic acid, beneficial to hydroxyl
The chanza of base apatite, especially in high-temperature burning process, carbon, oxide structure in phytic acid are decomposed to form gaseous dioxy
Change carbon, can not only improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide of generation exists
Contacted on molecular structure with hydroxyapatite, therefore the activation energy needed for during doping is lower, while gaseous carbon dioxide sheet
As high activity can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore for prepared doping
Hydroxyapatite specific surface area is bigger, and 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, while in ethylenediamine after firing
Phase decomposes, and produces ammonia or nitrogen, improves the specific surface area of adsorbent, beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, duck's egg, goose egg.Residue composition is single after eggshell calcining
For calcium carbonate, and eggshell wide material sources, it is domestic refuse, the raw material production cost to turn waste into wealth is low.
Described pretreatment eggshell powder and Ca/P in phytic acid molar ratio are 1.47: 1；
(c) preparation of the recyclable adsorbent of magnetic
The Coated With Hydroxyapatite iron carbonyl for the high doped carbonate that above-mentioned steps (b) are prepared, with 5~10
DEG C/min programming rate under, be warming up under 300~350 DEG C of aerobic conditions and pre-oxidized by normal temperature, then with 20~30
DEG C/min programming rates under, be warming up under the conditions of 450~600 DEG C and calcined by Pre oxidation, then after natural cooling, is prepared into
To the recyclable adsorbent of magnetic.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15~20min, institute
During the calcining of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate for the high doped carbonate stated
Between be 75~90min.
High-temperature calcination technique then is being carried out using the aerobic pre-oxidation of low temperature is first carried out, due to the six-membered ring structure in phytic acid
Decomposed between 300-350 DEG C, and active carbon dioxide gas is produced under aerobic conditions, it is therefore desirable to which carrying out low temperature has
Oxygen pre-oxidizes, and decomposes six-membered ring structure of the absorption in phytate molecule structure, improves carbonate doping activity, while decompose production
Raw steam is beneficial to react with hydroxyapatite at high temperature, hydroxyl activity in hydroxyapatite molecule is improved, beneficial to further
Carbonate adulterates process, in high-temperature burning process, the hydroxyapatite of doping carbonate is further changed completely, is formed steady
Fixed high fluffy high-carbon acid group doped hydroxyapatite structure, improves the absorption property of adsorbent, is prepared with magnetic junction
Structure and high fluffy sorbent material；
Embodiment 3
A kind of recyclable adsorbent of magnetic, specific saturation magnetization are 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 specific preparation process are：
(a) preparation of hydroxyl ferrum collosol
The aqueous solution of iron chloride and frerrous chloride is added in ethylenediamine solution, the pH by ethylenediamine control system is
8.5~9.0,45~60min is then reacted in 60~80 DEG C, hydroxyl ferrum collosol is prepared；
Described iron chloride and the molar ratio of frerrous chloride are 2: 1；
Described ferric chloride in aqueous solution molar concentration is 0.5mol/L；
(b) preparation of the Coated With Hydroxyapatite iron carbonyl of high doped carbonate
After the cleaning three times of discarded eggshell, it is de- to be heated to 40~60 DEG C in 5~10% formic acid solutions to be put into mass fraction
Inner membrance in shell breaking, then cleaned with distilled water, dry, crushed into powder is carried out using three-roll grinder, control the flat of powder
Equal particle diameter is 20~50 μm and pretreatment eggshell powder is prepared；Then again by pretreated eggshell powder, input quality point
Number is in 10~30% plant acid solution, 30~45min of stirring reaction, then inserts in supersonic reaction device again, control reaction
Temperature is 30~45 DEG C, reacts 0.5~2h, and after the dissolving of eggshell powder, the iron carbonyl for adding above-mentioned steps (a) preparation is molten
Glue, while ethylenediamine is added as pH adjusting agent, the pH of control system is 9.8~10.2, after system pH is stable, then is transferred to
To be reacted in water-bath synthesis reaction vessel, reaction temperature is 150~180 DEG C, and the reaction time is 4~6h, then adds citric acid solution,
The pH of regulation system is that the solution after 6.5~6.9 and then water-bath is transferred under normal temperature condition after 2~3h of ultrasound curing,
Normal temperature concentration of reaction solution is carried out, making system, it is 75~90% to control concentration fluid solid content, and height is prepared into viscous liquid
Adulterate the Coated With Hydroxyapatite iron carbonyl of carbonate；
Phytic acid has excellent phosphor-containing structure, and required phosphorus element-containing can be not only provided in preparation process, is planted simultaneously
Acid has organic matter carbon, oxide structure, by absorption chelation of the phosphate group in phytic acid to calcium ion in preparation process, makes
Calcium ion is enriched in the surface of phytic acid, while organic matter carbon, oxide structure form carbonate in calcination process in phytic acid, beneficial to hydroxyl
The chanza of base apatite, especially in high-temperature burning process, carbon, oxide structure in phytic acid are decomposed to form gaseous dioxy
Change carbon, can not only improve the bulkiness of hydroxyapatite, increasing specific surface area, simultaneously because the gaseous carbon dioxide of generation exists
Contacted on molecular structure with hydroxyapatite, therefore the activation energy needed for during doping is lower, while gaseous carbon dioxide sheet
As high activity can reaction molecular, it is more abundant with the doping reaction of hydroxyapatite, therefore for prepared doping
Hydroxyapatite specific surface area is bigger, and 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, while in ethylenediamine after firing
Phase decomposes, and produces ammonia or nitrogen, improves the specific surface area of adsorbent, beneficial to raising absorption property.
Described discarded eggshell is the birds eggshells such as egg, duck's egg, goose egg.Residue composition is single after eggshell calcining
For calcium carbonate, and eggshell wide material sources, it is domestic refuse, the raw material production cost to turn waste into wealth is low.
Described pretreatment eggshell powder and Ca/P in phytic acid molar ratio are 1.57: 1；
(c) preparation of the recyclable adsorbent of magnetic
The Coated With Hydroxyapatite iron carbonyl for the high doped carbonate that above-mentioned steps (b) are prepared, with 5~10
DEG C/min programming rate under, be warming up under 300~350 DEG C of aerobic conditions and pre-oxidized by normal temperature, then with 20~30
DEG C/min programming rates under, be warming up under the conditions of 450~600 DEG C and calcined by Pre oxidation, then after natural cooling, is prepared into
To the recyclable adsorbent of magnetic.
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl of described high doped carbonate is 15~20min, institute
During the calcining of the Coated With Hydroxyapatite iron carbonyl of the carbonate hydroxyapatite high doped carbonate for the high doped carbonate stated
Between be 75~90min.
High-temperature calcination technique then is being carried out using the aerobic pre-oxidation of low temperature is first carried out, due to the six-membered ring structure in phytic acid
Decomposed between 300-350 DEG C, and active carbon dioxide gas is produced under aerobic conditions, it is therefore desirable to which carrying out low temperature has
Oxygen pre-oxidizes, and decomposes six-membered ring structure of the absorption in phytate molecule structure, improves carbonate doping activity, while decompose production
Raw steam is beneficial to react with hydroxyapatite at high temperature, hydroxyl activity in hydroxyapatite molecule is improved, beneficial to further
Carbonate adulterates process, in high-temperature burning process, the hydroxyapatite of doping carbonate is further changed completely, is formed steady
Fixed high fluffy high-carbon acid group doped hydroxyapatite structure, improves the absorption property of adsorbent, is prepared with magnetic junction
Structure and high fluffy sorbent material；
Embodiment 4
The application of the recyclable adsorbent of described magnetic is mainly to be applied to the processing of heavy metal ion in water sample, described
Heavy metal ion is mainly Cr (VI), Cu (II), Pb (II) solution or the pedotheque of high content；
The processing of heavy metal ion in water sample of the recyclable adsorbent of described magnetic uses the method with Static Adsorption, place
During reason, the recyclable adsorbent of magnetic that mass fraction is 0.5~1% is added in the heavy metal ion water sample of high content,
Then the adsorption treatment time is 30~45min, and described adsorption treatment temperature is 15~45 DEG C, in described water sample heavy metal from
Sub- concentration is 0.5~500mg/L；
Embodiment 5
The application of the recyclable adsorbent of described magnetic is mainly to be applied to the Passivation Treatment of heavy metal in soil ion, institute
The heavy metal ion stated is mainly Cr (VI), Cu (II), Pb (II) solution or the pedotheque of high content；
The recyclable adsorbent of described magnetic is used in the Passivation Treatment of heavy metal in soil ion to spray the side of pulvis
Method, in processing procedure, the recyclable adsorbent of magnetic is dispersed in the aqueous solution that mass concentration is 5%, then carries out spraying operation,
And the sprinkling quality of the recyclable adsorbent of magnetic is 0.1~1g/kg in the heavy metal ion soil of high content, described sprinkling
Processing temperature is 15~45 DEG C, and described heavy metal in soil ion concentration is 0.5~500mg/kg.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make some improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (5)
1. a kind of preparation method of the recyclable adsorbent of magnetic, it is characterised in that its specific preparation process is：
（a）The preparation of hydroxyl ferrum collosol
The aqueous solution of iron chloride and frerrous chloride is added in ethylenediamine solution, the pH by ethylenediamine control system is 8.5
~9.0,45~60min is then reacted in 60~80 DEG C, hydroxyl ferrum collosol is prepared；
（b）The preparation of the Coated With Hydroxyapatite iron carbonyl precursor of high doped carbonate
After the cleaning three times of discarded eggshell, it is put into mass fraction and sloughs eggshell to be heated to 40~60 DEG C in 5~10% formic acid solutions
In inner membrance, then cleaned, dried with distilled water, crushed into powder is carried out using three-roll grinder, controls the average grain diameter of powder
Pretreatment eggshell powder is prepared for 20~50 μm；Then again by pretreated eggshell powder, input mass fraction is 10
In~30% plant acid solution, 30~45min of stirring reaction, then insert again in supersonic reaction device, controlling reaction temperature 30
~45 DEG C, 0.5~2h is reacted, after the dissolving of eggshell powder, adds above-mentioned steps（a）The hydroxyl ferrum collosol of preparation, add simultaneously
Enter ethylenediamine as pH adjusting agent, the pH of control system is 9.8~10.2, after system pH is stable, then is transferred to water-bath synthesis
Reacted in reactor, reaction temperature is 150~180 DEG C, and the reaction time is 4~6h, then adds citric acid solution, regulation system
PH be 6.5~6.9, after the solution after water-bath is then transferred under normal temperature condition into 2~3h of ultrasound curing, carry out normal
Warm concentration of reaction solution, making system, it is 75~90% to control concentration fluid solid content, and high doped carbon is prepared into viscous liquid
The Coated With Hydroxyapatite iron carbonyl precursor of acid group；
（c）The preparation of the recyclable adsorbent of magnetic
Above-mentioned steps（b）The Coated With Hydroxyapatite iron carbonyl precursor for the high doped carbonate being prepared, with 5~10
DEG C/min programming rate under, be warming up under 300~350 DEG C of aerobic conditions and pre-oxidized by normal temperature, then with 20~30
DEG C/min programming rates under, be warming up under the conditions of 450~600 DEG C and calcined by Pre oxidation, then after natural cooling, is prepared into
To the recyclable adsorbent of magnetic.
2. a kind of preparation method of the recyclable adsorbent of magnetic as claimed in claim 1, it is characterised in that in step（a）In,
Described iron chloride and the molar ratio of frerrous chloride are 2：1.
3. a kind of preparation method of the recyclable adsorbent of magnetic as claimed in claim 1, it is characterised in that in step（a）In,
Described ferric chloride in aqueous solution molar concentration is 0.1~0.5mol/L.
4. a kind of preparation method of the recyclable adsorbent of magnetic as claimed in claim 1, it is characterised in that in step（b）In,
Described pretreatment eggshell powder and Ca/P in phytic acid molar ratio are 1.27~1.57:1.
5. a kind of preparation method of the recyclable adsorbent of magnetic as claimed in claim 1, it is characterised in that in step（c）In,
The preoxidation time of the Coated With Hydroxyapatite iron carbonyl precursor of described high doped carbonate is 15~20min, and it is forged
The burning time is 75~90min.
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