CN109621913A - A kind of biology shell load hydroxyapatite composite material and its preparation method and application - Google Patents
A kind of biology shell load hydroxyapatite composite material and its preparation method and application Download PDFInfo
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- CN109621913A CN109621913A CN201811607886.0A CN201811607886A CN109621913A CN 109621913 A CN109621913 A CN 109621913A CN 201811607886 A CN201811607886 A CN 201811607886A CN 109621913 A CN109621913 A CN 109621913A
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- composite material
- shell
- hydroxyapatite composite
- hydroxyapatite
- biological
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of biological shell load hydroxyapatite composite materials and its preparation method and application, belong to water process adsorbent material field.Shell material is immersed in phosphatic aqueous solution by the present invention, is reacted under room temperature to boiling conditions, and the biological shell nanometer material of load hydroxyapatite ordered nano array is obtained.It uses biological shell prepared by the present invention to load nano hydroxyapatite composite material and has the advantages that the hydroxyapatite of (1) biological shell surface growth mainly as the ordered nano stick array on vertical biological shell surface, adsorption activity is strong；(2) the biological shell that hydroxyapatite depends on is grade massive material, is not easily runed off, easy to use；(3) natural material, green non-pollution are used.Biology shell load nano hydroxyapatite composite material disclosed by the invention can be used as the pollutants such as fluorine ion, heavy metal ion in efficient water-purifying material removal drinking-water.
Description
Technical field
The invention belongs to water process field of nanometer material technology, and in particular to it is a kind of biology shell load hydroxyapatite composite material and
Preparation method and application.
Background technique
Hydroxyapatite is a kind of environmentally friendly material.A large number of studies show that nanometer hydroxyapatite can be as one kind
Efficient adsorbent.For example, being capable of the pollutants such as fluorine ion, heavy metal in Adsorption water body.Patent (CN1544318A)
Disclose it is a kind of using calcium nitrate, ammonium dihydrogen phosphate be raw material, using urea as precipitating reagent, utilize evening chemical precipitating principle preparation
The method of nanometer hydroxyapatite.Patent (CN101734635A) disclose it is a kind of using polyethylene glycol be pattern regulator prepare
The method of nanometer hydroxyapatite.Patent (CN101428779A) discloses a kind of synthesis of hollow structure nanometer hydroxyapatite
Method.Patent (CN103420364A), which discloses, a kind of utilizes hydro-thermal reaction synthesizing graphite alkene/nanometer hydroxyapatite method.
Although can obtain in these processes, partial size is small, and the high nanometer hydroxyapatite of activity, obtained material is unordered receives
Rice flour body, there are cost of material height in application process, the separation of product difficulty, the shortcomings that easily blocking, material are easy to run off.By nano-hydroxy
The carrier surface that apatite is supported on bulky grain can solve these that nanometer hydroxyapatite faces during purification of water quality
Problem.Patent (CN101891175A) reports the nano-hydroxy that oriented growth is prepared using double base polyelectrolyte as template direction agent
The synthetic method of apatite.It using hydrophobicity organic acid and alcohol is prepared by template that patent (CN103803489B), which discloses a kind of,
The preparation method of large scale hydroxyapatite micrometre tube oldered array.Although these methods can obtain the orderly of hydroxyapatite
Nanostructure, but need using organic formwork agent, higher cost.Patent (CN103241719B) describes one kind in inertia base
The method of bottom surface oriented growth nanometer hydroxyapatite oldered array.But although this method is not needed using template, but need
Successively substrate to be impregnated in calcium solution and grow hydroxyapatite in phosphate solution, operating procedure is cumbersome, unfavorable
In large-scale production.
The report that hydroxyapatite is prepared using egg shell as raw material is referred in the document of part.For example, paper (eggshell calcining
The preparation and characterization of synthesizing hydroxylapatite, environmental project journal, 2011,5 (9): 2156-2160) with 900 DEG C of calcination processings
Eggshell and calcium phosphate are raw material, using high-temperature calcination (1100 DEG C) synthesizing hydroxylapatite powder；Paper (close by eggshell hydro-thermal method
At hydroxyapatite, Hebei Normal University Journal, 2013,37 (1): 60-64.) with the eggshell and phosphoric acid hydrogen of 900 DEG C of calcination processings
Diammonium is raw material, using hydrothermal Synthesis of Hydroxy Apatite powder.Although the method mentioned in these papers is with cheap egg
Shell is raw material, but requires egg shell being sintered into calcium oxide at 900 DEG C in technical solution, not only increase high-temperature process at
This, and the original structure of egg shell is destroyed, obtained product is unordered hydroxy apatite powder.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the invention discloses a kind of biological shells to load hydroxyl phosphorus
Biological shell composite nano materials of lime stone ordered nano array and preparation method thereof, this method is with hydroxyapatite nano stick in life
It is main technology characteristics that the oriented growth in situ on object shell surface, which becomes ordered nano array,.Comprehensively utilize nanometer hydroxyapatite
It the advantages of high activity and the large scale of biological shell material, good biocompatibility, is provided for purifying of drinking water and has excellent performance composite Nano
Adsorbent.
Primary and foremost purpose of the present invention is to provide a kind of biological shell load hydroxyapatite composite material.
Another object of the present invention is to provide the preparation method of above-mentioned biological shell load hydroxyapatite composite material.
Another object of the present invention is to provide the application of above-mentioned biological shell load hydroxyapatite composite material.
The invention is realized by the following technical scheme:
A kind of preparation method of biology shell load hydroxyapatite composite material, comprising the following steps:
(1) phosphoric acid and/or phosphate are configured to aqueous solution, obtain phosphoric acid growth-promoting media；
(2) biological shell material is first eluted with water, is then impregnated with aqueous slkali or acid solution, is most washed afterwards, removed
Surface impurity obtains pretreated biological shell material；
(3) it will be immersed in phosphoric acid growth-promoting media made from step (1) in step (2) by pretreated biological shell material,
It impregnates and can be prepared by the biological shell load hydroxyapatite composite material after completion of the reaction.
Preferably, step (1) phosphate is sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and phosphoric acid hydrogen two
At least one of potassium.
Preferably, step (1) the phosphate growth liquid concentration is calculated as 0.01~2mol/L with phosphorus.
Preferably, pH>11 of step (2) described aqueous slkali, pH<3 of the acid solution.
Preferably, biology shell material described in step (2) is shell, eggshell and its crushing and processing product.
Preferably, the temperature of step (3) described immersion is 0~100 DEG C, and the time of immersion is greater than 1min.Temperature will affect
Reaction rate, temperature is higher, and reaction rate is faster.Even if being reacted at 0 DEG C, as long as the reaction time is greater than 2 days, can also successfully make
Standby biology shell loads hydroxyapatite composite material.At 100 DEG C, reaction rate is greatly speeded up, even if only 1 minute, it can also
Success prepares biological shell and loads hydroxyapatite composite material.Reaction temperature is higher, and the time is longer, hydroxyl in obtained composite material
The content of base apatite is higher.
The biological shell load hydroxyl that a kind of preparation method of above-mentioned biological shell load hydroxyapatite composite material is prepared
Base apatite composite material.
Fluorine ion and heavy metal pollution of the above-mentioned biology shell load hydroxyapatite composite material in Adsorption water body
Application in object.
The biology shell material such as present invention application egg shell, shell serves not only as the calcium source of hydroxyapatite, and as new
The carrier of raw hydroxyapatite ordered nano-structure.In addition, the present invention does not need high-temperature calcination technique, it is more energy saving.Finally, this
It invents obtained product and loads hydroxyapatite composite material for biological shell, be different from hydroxyl involved in existing literature, patent
The unordered powder body material of apatite.
Compared with prior art, the invention has the following advantages and beneficial effects:
(1) the invention discloses biological shells to load hydroxyapatite composite material, nanometer character is ordered into, on microcosmic
It can use the high adsorption activity of nanometer hydroxyapatite, meanwhile, macroscopically, which is grade material, Yi Chen
It forms sediment, easily filters, it is easy to use.
(2) biological shell load hydroxyapatite composite material prepared by the present invention is grown in biological shell material surface in situ
It obtains, so, hydroxyapatite nanoparticle is fixed by biological shell material, is easily isolated, and is not easily runed off and is generated nanometer pollution
Object.The hydroxyapatite of synthesis is rodlike ordered nano array, and absorption property is excellent.
Detailed description of the invention
Fig. 1 is that egg shell made from embodiment 1 loads scanning of the hydroxyapatite composite material under different amplification
Electron micrograph.
Fig. 2 is the Ca/P Elemental redistribution energy spectrum diagram that egg shell made from embodiment 1 loads hydroxyapatite composite material.
Fig. 3 is that egg shell made from embodiment 1 loads hydroxyapatite composite material and its X-ray of egg husk as raw material is spread out
Penetrate map and corresponding standard card diffracting spectrum, wherein a is the diffracting spectrum and CaCO of egg husk as raw material3Standard is spread out
Card figure is penetrated, b is the diffracting spectrum and hydroxyapatite standard diffraction card figure that egg shell loads hydroxyapatite composite material.
Fig. 4 is that the load hydroxyapatite composite material of egg shell made from commercially available nanometer hydroxyapatite and embodiment 1 exists
Photo figure after ten minutes is settled in water, wherein a corresponds to commercially available nanometer hydroxyapatite, and b corresponds to egg shell load hydroxy-apatite
Stone composite material.
Fig. 5 is that shell made from embodiment 2 loads scanning electricity of the hydroxyapatite composite material under different amplification
Sub- microscope photo.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of egg shell load hydroxyapatite composite material, comprising the following steps:
(1) by egg shell material fragmentation, washing removes impurity；
(2) egg shell material is impregnated 2 minutes with 5wt% acetum (pH=2.6 of acetum), is washed, removed
Surface impurity obtains pretreated egg shell material；
(3) sodium dihydrogen phosphate is configured to the aqueous solution that phosphorus concentration is 0.1mol/L and obtains phosphoric acid growth-promoting media；
(4) the pretreated egg shell material of step (2) is immersed in phosphoric acid growth-promoting media described in step (3), 80 DEG C of items
It is reacted 60 minutes under part, the egg shell load hydroxyapatite composite material can be obtained.
Fig. 1 is that egg shell made from embodiment 1 loads scanning of the hydroxyapatite composite material under different enlargement ratios
Electron microscope picture, as can be seen from the figure hydroxyapatite is nano bar-shape, and hydroxyapatite nano stick is perpendicular to eggshell
Surface growth, forms orderly nanometer stick array structure.This is that the present invention is different from the most important of other hydroxyapatite materials
Place.A large amount of hydroxyapatite patent and paper can only obtain unordered nano-powder at present, although absorption property is excellent,
But nano-powder is difficult sedimentation separation or is separated by filtration, and hydroxyapatite nano-powder itself, which is possible to be lost, generates nanometer dirt
Object is contaminated, it is extremely inconvenient to use.And the egg shell of the method for the present invention production is applied to load hydroxyapatite composite material, hydroxyl
Apatite nanorod growth forms orderly nano-array on the surface of egg shell.
Fig. 2 is a kind of Ca/P Elemental redistribution power spectrum of egg shell load hydroxyapatite composite material made from embodiment 1
Figure.It can be seen from the figure that there are a large amount of Ca and P element, Ca/P ratios on egg shell load hydroxyapatite composite material surface
It is 1.688, substantially close to hydroxyapatite (Ca5(PO4)3OH theoretical Ca/P ratio (1.667)).
Fig. 3 penetrates for the X that a kind of egg shell loads hydroxyapatite composite material and its egg husk as raw material made from embodiment 1
Ray diffraction diagram spectrum and corresponding standard card diffracting spectrum, wherein a is the diffracting spectrum and CaCO of egg husk as raw material3Mark
Quasi- diffraction card figure, b are the diffracting spectrum and hydroxyapatite standard diffraction card that egg shell loads hydroxyapatite composite material
Piece figure.The characteristic diffraction peak that can be clearly seen that hydroxyapatite shown in arrow from the b in Fig. 3, by with hydroxy-apatite
Stone standard diffraction card (09-0432) comparison, it can be verified that egg shell Surface Creation hydroxyapatite crystal phase.From Fig. 3
A can be seen that the diffraction maximum of egg shell and the CaCO of calcite crystal phase3Standard diffraction card figure it is consistent, illustrate egg shell
Main component is CaCO3。
Fig. 4 is that the load hydroxyapatite composite material of egg shell made from commercially available nanometer hydroxyapatite and embodiment 1 exists
Photo figure after ten minutes is settled in water, wherein a corresponds to commercially available nanometer hydroxyapatite, and b corresponds to egg shell load hydroxy-apatite
Stone composite material.From the figure, it can be seen that commercially available nanometer hydroxyapatite is difficult to settle in water, settle after ten minutes, water body
Still muddy, and egg shell load hydroxyapatite composite material is being macroscopically grade granular materials, sedimentation is rapid, water body
Clarification.
Embodiment 2
The preparation method of shell load hydroxyapatite composite material, comprising the following steps:
(1) shellfish material is crushed, is washed, remove impurity；
(2) shellfish material is impregnated 30 points with 1wt% sodium hydrate aqueous solution (pH=13.2 of sodium hydrate aqueous solution)
Clock, washing remove surface impurity, obtain pretreated shellfish material；
(3) sodium dihydrogen phosphate is configured to the aqueous solution that phosphorus concentration is 0.1mol/L and obtains phosphoric acid growth-promoting media；
(4) step (2) pretreated shellfish material is immersed in phosphoric acid growth-promoting media described in step (3), 40 DEG C of conditions
The shell load hydroxyapatite composite material can be obtained in lower reaction 7 days.
Scanning under a kind of different amplification of the load hydroxyapatite composite material of shell made from Fig. 5 embodiment 2
Electron micrograph figure, shell surface grown the nanometer hydroxyapatite of sheet as we can see from the figure.
Embodiment 3
The fluorine removal application of egg shell load hydroxyapatite composite material, comprising the following steps:
(1) the load hydroxyapatite composite material of egg shell obtained by 1g embodiment 1 is added to (fluorine in 1L fluorinated water
Content, 10mg/L), it boils 10 minutes.
(2) 1 minute is stood, egg shell load hydroxyapatite composite material is settled down to the bottom.
(3) supernatant is poured out, realize egg shell load hydroxyapatite composite material and handles the separation of water.
Content of fluoride ion can be reduced to 0.2mg/L in processing water, meet national drinking water standard (< 1.0mg/L).
Embodiment 4
Shell loads the application of hydroxyapatite composite material removal cadmium in drinking water, comprising the following steps:
(1) the load hydroxyapatite composite material of shell obtained by 1g embodiment 2 is added to the water of 1L 25ppm containing cadmium
In body.
(2) 2h is stirred at 20 °C.
(3) 1 minute is stood, shell load hydroxyapatite composite material is settled down to the bottom.
(4) supernatant is poured out, realize shell load hydroxyapatite composite material and handles the separation of water.
Cadmium content is reduced to 1.4ppm in processing water, meets national drinking water standard (cadmium < 5ppm).
Embodiment 5
Shell loads the application of lead in hydroxyapatite composite material removal drinking-water, comprising the following steps:
(1) shell will be obtained obtained by 1g embodiment 2 load the water that hydroxyapatite composite material is added to the leaded 50ppm of 1L
In body.
(2) 10min is stirred under the conditions of 80 DEG C.
(3) 1 minute is stood, shell load hydroxyapatite composite material is settled down to the bottom.
(4) supernatant is poured out, realize shell load hydroxyapatite composite material and handles the separation of water.
Lead content is reduced to 2.4ppm in processing water, meets national drinking water standard (lead < 10ppm).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of biology shell load hydroxyapatite composite material, which comprises the following steps:
(1) phosphoric acid and/or phosphate are configured to aqueous solution, obtain phosphoric acid growth-promoting media；
(2) biological shell material is first eluted with water, is then impregnated with aqueous slkali or acid solution, is most washed afterwards, remove surface
Impurity obtains pretreated biological shell material；
(3) it will be immersed in phosphoric acid growth-promoting media made from step (1), impregnate by pretreated biological shell material in step (2)
It can be prepared by the biological shell load hydroxyapatite composite material after completion of the reaction.
2. a kind of preparation method of biological shell load hydroxyapatite composite material according to claim 1, which is characterized in that
Step (1) the phosphate growth liquid concentration is calculated as 0.01~2mol/L with phosphorus.
3. a kind of preparation method of biological shell load hydroxyapatite composite material according to claim 2, which is characterized in that
The temperature of step (3) described immersion is 0~100 DEG C, and the time of immersion is greater than 1min.
4. a kind of preparation method of biological shell load hydroxyapatite composite material according to claim 3, which is characterized in that
PH>11 of step (2) described aqueous slkali, pH<3 of the acid solution.
5. any one a kind of preparation method of biological shell load hydroxyapatite composite material according to claim 1~4,
It is characterized in that, step (1) phosphate is sodium dihydrogen phosphate, disodium hydrogen phosphate, in potassium dihydrogen phosphate and dipotassium hydrogen phosphate
It is at least one.
6. any one a kind of preparation method of biological shell load hydroxyapatite composite material according to claim 1~4,
It is characterized in that, biology shell material described in step (2) is shell, eggshell and its crushing and processing product.
7. a kind of any one of claim 1~6 preparation method of biological shell load hydroxyapatite composite material is prepared into
The biological shell load hydroxyapatite composite material arrived.
8. biology shell described in claim 7 loads fluorine ion and a huge sum of money of the hydroxyapatite composite material in Adsorption water body
Belong to the application in pollutant.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111085158A (en) * | 2019-12-23 | 2020-05-01 | 暨南大学 | Method for preparing defluorination water purifying agent by using eggshells and application thereof |
| CN112158820A (en) * | 2020-09-06 | 2021-01-01 | 桂林理工大学 | Preparation method and application of fluorapatite solid solution |
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|---|---|---|---|---|
| CN102380350A (en) * | 2011-10-24 | 2012-03-21 | 上海海洋大学 | Method for removing hydroxyapatite modified eggshell adsorbent material and recycling phosphate from wastewater |
| CN103991856A (en) * | 2014-06-13 | 2014-08-20 | 淮海工学院 | Preparation method of hydroxyapatite nanosheets |
-
2018
- 2018-12-27 CN CN201811607886.0A patent/CN109621913A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380350A (en) * | 2011-10-24 | 2012-03-21 | 上海海洋大学 | Method for removing hydroxyapatite modified eggshell adsorbent material and recycling phosphate from wastewater |
| CN103991856A (en) * | 2014-06-13 | 2014-08-20 | 淮海工学院 | Preparation method of hydroxyapatite nanosheets |
Non-Patent Citations (3)
| Title |
|---|
| AMRUTA SAMANT ET AL.,: "Kinetics and mechanistic interpretation of fluoride removal by nanocrystalline hydroxyapatite derived from Limacine artica shells", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
| YAN XIA ET AL.,: "Facile defluoridation of drinking water by forming shell@fluorapatite nanoarray during boiling egg shell", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111085158A (en) * | 2019-12-23 | 2020-05-01 | 暨南大学 | Method for preparing defluorination water purifying agent by using eggshells and application thereof |
| CN112158820A (en) * | 2020-09-06 | 2021-01-01 | 桂林理工大学 | Preparation method and application of fluorapatite solid solution |
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Application publication date: 20190416 |