CN109200989A - A kind of ferromagnetism hydroxyapatite heavy-metal adsorption material and preparation method thereof - Google Patents
A kind of ferromagnetism hydroxyapatite heavy-metal adsorption material and preparation method thereof Download PDFInfo
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- CN109200989A CN109200989A CN201811342934.8A CN201811342934A CN109200989A CN 109200989 A CN109200989 A CN 109200989A CN 201811342934 A CN201811342934 A CN 201811342934A CN 109200989 A CN109200989 A CN 109200989A
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- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
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Abstract
The invention belongs to field of environmental improvement, it is related to a kind of ferromagnetism hydroxyapatite heavy-metal adsorption material and preparation method thereof, this method uses " one kettle way, two stages " technique: the first stage passes through is added dropwise ferrous salt and the obtained Fe 3 O 4 magnetic material of alkali reaction simultaneously under aeration stirring；Magnetic hydroxylapatite is made by loading hydroxyapatite in Fe 3 O 4 magnetic material surface in second stage; preparation process is simple; it is easily controllable, organic solvent is not used, it is environmental-friendly; manufacturing cost is low; it is suitble to large-scale production and application, obtained magnetic hydroxylapatite has magnetic strong, is evenly coated and securely; the features such as good dispersion, can be used for the processing such as heavy metal polluted waste water, soil, solid waste.
Description
Technical field
The invention belongs to field of environmental improvement, it is related to a kind of ferromagnetism hydroxyapatite heavy-metal adsorption material and its preparation
Method can be used for the improvement of heavy metal-containing polluted water, soil and solid waste, realize Magneto separate and recycling.
Background technique
With the development of economy, industry is swift and violent increases, and environmental problem caused by water pollution caused by heavy metal is on the rise.
The source of heavy metal pollution of water environment mainly has the source of following three aspects: 1) industrial pollution, industrial wastewater such as textile waste are made
Paper waste water, smelting wastewater and light industry waste water etc. are unprocessed and are discharged into sewer, ditch, rivers,lakes and seas etc.；2) agricultural is dirty
Dye, the use and plant and animal residues decomposition of a large amount of chemical fertilizer, pesticide, veterinary drug in agricultural production process cause sternly water body
The pollution of weight；3) domestic pollution, many difficult natural degradation house refuses present in life, such as discarded metal, waste battery
Equally polluted caused by water body.These are as caused by mankind's activity.In addition, existing in nature a large amount of rich in a huge sum of money
The Minerals And Rocks of category, can react with substances long terms such as empty gas and water, carbon dioxide causes heavy metal solution to dissolve out from rock
Water body and soil are subsequently entered, this is also that heavy metal is enriched with one of reason in the natural environment.
When heavy metal ion pollutant dissolves in aquatic ecosystem, plant, fish, zoobenthos in water body etc. are taken the photograph
Entering these heavy metal elements may.Since heavy metal contaminants can not voluntarily degrade, it can be transmitted by Food chain and generate richness
Collection, although such as ferro element, copper, Zn-ef ficiency and chromium common metal element be human body and other animal and plant growths not
It can or lack, but when the concentration of these metallic elements is when too low or excessively high, corresponding shadow can be generated to the health of organism
It rings, harm also will be no less than nonessential metallic elements such as intake lead, mercury.
Hydroxyapatite molecular formula is Ca10(PO4)6(OH)2, there is special crystal structure, be human body and animal skeleton
Chief component.It is a kind of adsorbent being made of inorganic matter, absorption property and biocompatibility with higher, to gold
Belonging to ion and dyestuff has absorption fixed function, can be used for handling the metal ion in waste water.Hydroxyapatite is changed
Into, so that it has been had magnetism, it can be convenient for the separation and recycling of adsorbent.It generallys use at present and first prepares magnetic material and hydroxyl phosphorus
Lime stone, then using physical mechanical mixing by the way of be made magnetic hydroxylapatite, it is microcosmic on see the active force between two kinds of materials
Difference is unevenly distributed, thus specific surface area reduces, and reduces to the adsorption capacity of heavy metal, and preparation process is complicated, energy consumption
Height limits its industrialization and application.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of ferromagnetism hydroxyapatite heavy-metal adsorption material and its preparation side
Method rapidly and efficiently prepares the strong magnetic core of ferroso-ferric oxide by aerating oxidation using the preparation process of " one kettle way, two stages ", then
Hydroxyapatite is loaded while synthesizing on magnetic core surface, hydroxyapatite is achieved and is uniformly firmly dispersed in magnetic core table
Face, to prepare magnetic strong, the magnetic hydroxylapatite of strong adsorption.Its preparation process includes the following steps:
(1) it prepares ferroso-ferric oxide: being packed into water in beaker, aeration stirring is heated to 40-80 DEG C, drips simultaneously into beaker
Add lye and ferrous salt solution, maintain pH9-11, be added dropwise, constant temperature aeration reaction, ferroso-ferric oxide emulsion is made；
(2) it prepares magnetic hydroxylapatite: calcium salt is added into the ferroso-ferric oxide emulsion under step (1) constant temperature
Solution, phosphate solution, and pH9-11 is maintained with lye, addition finishes, continues to stir, isothermal reaction, natural after fully reacting
It is cooled to room temperature, is aged, Magneto separate is washed to neutrality, dries stand-by.
Preferably, alkali described in step (1) and (2) is one or both of sodium hydroxide, potassium hydroxide mixture, dense
Degree is 0.1-5M, preferably 0.5-4M, more preferably 1-2M.
Preferably, step (1) and (2) described pH are 10-11.
Preferably, ferrous salt described in step (1) is in ferrous sulfate, frerrous chloride, ferrous nitrate, ferrous sulfate amine
One or more, concentration 0.1-5M, preferably 0.5-4M, more preferably 1-2M.
Preferably, aeration quantity described in step (1) is 0.1-10L/min, preferably 0.5-5L/min.
Preferably, step (1) constant temperature aeration reaction time is 1-6 hours, preferably 1-3 hours.
Preferably, step (2) described calcium salt is one or both of calcium chloride, calcium nitrate, concentration 0.1-5M, preferably
For 0.5-4M, more preferably 1-2M.
Preferably, step (2) described phosphate is tertiary sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, tripotassium phosphate, phosphorus
One of sour hydrogen dipotassium, potassium dihydrogen phosphate, phosphoric acid triamine, diammonium hydrogen phosphate and phosphoric acid dihydro amine are a variety of, concentration 0.1-
5M, preferably 0.5-4M, more preferably 1-2M.
More specifically, the adding manner of calcium salt soln and phosphate solution described in step (2), which can be, is first added calcium salt
Solution adds phosphate solution, is also possible to that phosphate solution is first added, adds calcium salt soln, it is molten to be also possible to calcium salt
Both liquid and phosphate solution are alternately added, and can also be while calcium salt soln and phosphate solution is added dropwise.
Still more preferably, calcium ion and phosphate anion molar ratio in step (2) raw material are as follows: 4:3-2:1, more preferably
For 5:3.
Preferably, step (2) the isothermal reaction time is 2-8 hours, preferably 2-6 hours, 2-4 hours more preferable.
Preferably, rapid (2) digestion time is 6-72 hours, 12-48 hours more preferable, 18-24 hours more preferable.
The invention further relates to the ferromagnetism hydroxyapatite materials of method described in any of the above embodiments preparation in an absorption huge sum of money
Application in category.
It is furthermore preferred that the adsorbable processing water of ferromagnetism hydroxyapatite material of method described in any of the above embodiments preparation or
Chromium, cadmium, lead, arsenic, nickel, copper, zinc, copper heavy metal in soil.
The present invention prepares ferromagnetism hydroxyapatite using the technique of " one kettle way, two stages ", and the first stage is to pass through exposure
Ferrous salt is added dropwise under gas agitating simultaneously and alkali reacts and Fe 3 O 4 magnetic material is made；Second stage is by aoxidizing three four
Magnetic hydroxylapatite is made in ferrimagnet area load hydroxyapatite.Obtained magnetic hydroxylapatite has magnetism
By force, it is evenly coated and securely, the features such as good dispersion.Magnetic hydroxylapatite has stronger adsorption capacity to heavy metal ion,
Magneto separate recycling, recycles, and can be used for the processing such as heavy metal polluted waste water, soil, solid waste.Preparation process of the present invention is simple, easily
Control, low energy consumption, is suitble to large-scale production.
Beneficial effects of the present invention:
1, the ferromagnetism hydroxyapatite of the method for the present invention preparation is prepared using the technique of " one kettle way, two stages ", in magnetic
Core surface synthesizes and is uniformly distributed hydroxyapatite, forms the integral structure of hydroxyapatite package magnetic core；
2, the ferromagnetism hydroxy-apatite heavy metal adsorption of the method for the present invention preparation is strong, in adsorbable processing water or soil
Chromium, cadmium, lead, arsenic, nickel, copper, zinc, copper heavy metal；
3, the ferromagnetism hydroxyapatite of the method for the present invention preparation is magnetic strong, magnetic lasting, sharp again conducive to the recycling of material
With；
4, " one kettle way, two stages " preparation process of inventive method is simple, easily controllable, and organic solvent, environment is not used
Close friend, manufacturing cost is low, is suitble to large-scale production and application.
Detailed description of the invention
The following further describes the present invention with reference to the drawings
Fig. 1 is the structural schematic diagram of ferromagnetism hydroxyapatite
1 is magnetic core；2 be hydroxyapatite
Fig. 2 is the magnetic demonstration graph of 1 ferromagnetism hydroxyapatite of embodiment
Fig. 3 is the XRD diagram of 1 ferromagnetism hydroxyapatite of embodiment
Specific embodiment
The present invention will be further described with reference to the examples below, and described embodiment and its result are only used for this hair
It is bright, without the present invention described in claims should will not be limited.
Comparative example 1
Hydroxyapatite preparation
Step 1: the calcium chloride solution 50ml and concentration that compound concentration is 1.67M are 1M disodium phosphate soln 50ml；
Step 2: it is packed into water 200ml in 500ml beaker, under stirring, is heated to 60 DEG C；
Step 3: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 4: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 2 hours；
Step 5: natural cooling room temperature is aged 24 hours；
Step 6: Magneto separate is washed to neutrality, and contrast material 1 is made in naturally dry.
Comparative example 2
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 100ml that compound concentration is 2M sodium hydroxide 100ml and concentration is 1M；
Step 2: water 200ml, room temperature aeration quantity 1L/min aeration stirring are packed into 500ml beaker；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH10；
Step 4: ferrous sulfate solution is added dropwise, and room temperature aeration reaction 4 hours, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 1.67M are 1M disodium phosphate soln 50ml；
Step 6: above-mentioned ferroso-ferric oxide emulsion is stirred at room temperature；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and reaction 4 is stirred at room temperature
Hour；
Step 9: ageing 24 hours；
Step 10: Magneto separate is washed to neutrality, and contrast material 2 is made in naturally dry.
Comparative example 3
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 100ml that compound concentration is 2M sodium hydroxide 100ml and mass concentration is 0.01M；
Step 2: being packed into water 200ml in 500ml beaker, aeration quantity 1L/min aeration stirring is heated to 80 DEG C；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH10；
Step 4: ferrous sulfate solution is added dropwise, and constant temperature aeration reaction 1 hour, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 1.67M are 1M disodium phosphate soln 50ml；
Step 6: by above-mentioned ferroso-ferric oxide emulsion, under stirring, 80 DEG C are heated to；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 2 hours；
Step 9: natural cooling room temperature is aged 24 hours；
Step 10: Magneto separate is washed to neutrality, and contrast material 3 is made in naturally dry.
Comparative example 4
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 100ml that compound concentration is 2M sodium hydroxide 100ml and mass concentration is 1M；
Step 2: being packed into water 200ml in 500ml beaker, aeration quantity 1L/min aeration stirring is heated to 80 DEG C；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH10；
Step 4: ferrous sulfate solution is added dropwise, and constant temperature aeration reaction 1 hour, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 0.0167M are 0.01M disodium phosphate soln
50ml；
Step 6: by above-mentioned ferroso-ferric oxide emulsion, under stirring, 80 DEG C are heated to；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 2 hours；
Step 9: natural cooling room temperature is aged 24 hours；
Step 10: Magneto separate is washed to neutrality, and contrast material 4 is made in naturally dry.
Embodiment 1
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 100ml that compound concentration is 2M sodium hydroxide 100ml and concentration is 1M；
Step 2: being packed into water 200ml in 500ml beaker, aeration quantity 1L/min aeration stirring is heated to 60 DEG C；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH10；
Step 4: ferrous sulfate solution is added dropwise, and constant temperature aeration reaction 2 hours, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 1.67M are 1M disodium phosphate soln 50ml；
Step 6: by above-mentioned ferroso-ferric oxide emulsion, under stirring, 60 DEG C are heated to；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 4 hours；
Step 9: natural cooling room temperature is aged 24 hours；
Step 10: Magneto separate is washed to neutrality, and material 1 is made, for use in naturally dry.
Embodiment 2
The same method of embodiment 1, step 1 replace the sulfuric acid that concentration is 1M sub- with concentration by the solution of ferrous chloride of 1M
Material 2 is made with embodiment 1 in ferrous solution, remaining method.
Embodiment 3
The same method of embodiment 1, it is 1.67M calcium chloride that step 7, which replaces concentration by 1.67M calcium nitrate solution with concentration,
Material 3 is made with embodiment 1 in solution, remaining method.
Embodiment 4
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 100ml that compound concentration is 2M sodium hydroxide 100ml and concentration is 1M；
Step 2: being packed into water 200ml in 500ml beaker, aeration quantity 0.5L/min aeration stirring is heated to 80 DEG C；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH10；
Step 4: ferrous sulfate solution is added dropwise, and constant temperature aeration reaction 1 hour, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 1.67M are 1M disodium phosphate soln 50ml；
Step 6: by above-mentioned ferroso-ferric oxide emulsion, under stirring, 80 DEG C are heated to；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 2 hours；
Step 9: natural cooling room temperature is aged 24 hours；
Step 10: Magneto separate is washed to neutrality, and material 4 is made in naturally dry.
Embodiment 5
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 200ml that compound concentration is 2M sodium hydroxide 100ml and concentration is 1M；
Step 2: being packed into water 200ml in 500ml beaker, aeration quantity 5L/min aeration stirring is heated to 80 DEG C；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH10；
Step 4: ferrous sulfate solution is added dropwise, and constant temperature aeration reaction 1 hour, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 1.67M are 1M disodium phosphate soln 50ml；
Step 6: by above-mentioned ferroso-ferric oxide emulsion, under stirring, 80 DEG C are heated to；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 2 hours；
Step 9: natural cooling room temperature is aged 24 hours；
Step 10: Magneto separate is washed to neutrality, and material 5 is made in naturally dry.
Magnetism of material intensity evaluation
It weighs 10 grams of materials and is packed into hermetic bag, the intensity of each material is tested with magnetite, magnetic intensity the results are shown in Table 1
1 magnetic intensity result of table
| Material number | Magnetic intensity |
| Contrast material 1 | X |
| Contrast material 2 | О |
| Contrast material 3 | О |
| Contrast material 4 | ◎ |
| Material 1 | ◎ |
| Material 2 | ◎ |
| Material 3 | ◎ |
| Material 4 | ◎ |
| Material 5 | ◎ |
Remarks: ◎ --- it is magnetic strong；О --- it is magnetic weak；X --- without magnetism.
As the result is shown: the magnetic hydroxylapatite material of 1-5 of embodiment of the present invention preparation is magnetic strong, and with preparation temperature
80 DEG C are increased to from 60 DEG C, magnetic enhancement, hydroxyapatite prepared by comparative example 1 does not have magnetic core, and without magnetism, comparative example 2 exists
The magnetic hydroxylapatite prepared under room temperature, it is magnetic weak；Magnetic hydroxylapatite magnetic core ratio prepared by comparative example 3 is smaller, magnetic
Property is weak；Magnetic hydroxylapatite magnetic core ratio prepared by comparative example 4 is big, magnetic strong.
Material heavy metal adsorption performance evaluation
Cu is prepared with copper sulphate2+Concentration is the simulated wastewater of 1000mg/L, is separately added into 1 gram of contrast material 1-4, material 1-
5, it is stirred to react 1 hour, then Magneto separate, with Cu in ICP test liquid2+Concentration the results are shown in Table 2.
2 heavy metal adsorption performance of table
As the result is shown: the magnetic hydroxylapatite material of 1-5 of embodiment of the present invention preparation is to Cu2+Adsorption capacity it is strong, and
As preparation temperature is increased to 80 DEG C from 60 DEG C, adsorption capacity enhancing, although hydroxyapatite prepared by comparative example 1 is without magnetic
Property, but hydroxyapatite plays preferable Cu2+Adsorption capacity, the magnetic hydroxylapatite that comparative example 2 is prepared at normal temperature,
To Cu2+Adsorption capacity it is poor；Magnetic hydroxylapatite prepared by comparative example 3 is to Cu2+There is stronger adsorption capacity；Comparative example 4 is made
Hydroxyapatite ratio is smaller in standby magnetic hydroxylapatite, to Cu2+Adsorption capacity is poor.
In addition, ferromagnetism hydroxyapatite prepared by the present invention has structure shown in FIG. 1；1 ferromagnetism hydroxyl of embodiment
The magnetic demonstration graph of apatite is shown in Fig. 2；The XRD of 1 ferromagnetism hydroxyapatite of embodiment is shown in Fig. 3, the peak position of X-ray diffraction
It is corresponding with ferroso-ferric oxide, hydroxyapatite (HAP).
Embodiment 6
The same method of embodiment 4, it is 2M sodium hydroxide that step 1, which replaces concentration with 2M potassium hydroxide, remaining method is the same as real
Example 4 is applied, material 6 is made.
Embodiment 7
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 100ml that compound concentration is 1M sodium hydroxide 100ml and concentration is 0.5M；
Step 2: being packed into water 200ml in 500ml beaker, aeration quantity 0.5L/min aeration stirring is heated to 80 DEG C；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH10；
Step 4: ferrous sulfate solution is added dropwise, and constant temperature aeration reaction 2 hours, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 0.84M are 0.5M disodium phosphate soln 50ml；
Step 6: by above-mentioned ferroso-ferric oxide emulsion, under stirring, 80 DEG C are heated to；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH10 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 6 hours；
Step 9: natural cooling room temperature is aged 36 hours；
Step 10: Magneto separate is washed to neutrality, and material 7 is made in naturally dry.
Embodiment 8
(1) prepared by ferroso-ferric oxide
Step 1: the ferrous sulfate solution 100ml that compound concentration is 4M sodium hydroxide 100ml and concentration is 2M；
Step 2: being packed into water 200ml in 500ml beaker, aeration quantity 0.5L/min aeration stirring is heated to 80 DEG C；
Step 3: being added dropwise sodium hydroxide and ferrous sulfate solution simultaneously in step 2 beaker, maintains pH11；
Step 4: ferrous sulfate solution is added dropwise, and constant temperature aeration reaction 1 hour, ferroso-ferric oxide emulsion is made；
(2) prepared by magnetic hydroxylapatite
Step 5: the calcium chloride solution 50ml and concentration that compound concentration is 3.4M are 2M disodium phosphate soln 50ml；It can
With
Step 6: by above-mentioned ferroso-ferric oxide emulsion, under stirring, 80 DEG C are heated to；
Step 7: while calcium chloride solution and disodium phosphate soln is added dropwise, and maintain pH11 with lye；
Step 8: calcium chloride solution and disodium phosphate soln are added dropwise simultaneously, continue to stir, and isothermal reaction 2 hours；
Step 9: natural cooling room temperature is aged 18 hours；
Step 10: Magneto separate is washed to neutrality, and material 8 is made in naturally dry.
Embodiment 9
The same method of embodiment 4, it is 1M disodium hydrogen phosphate that step 5, which replaces concentration by 1M phosphoric acid triamine solution with concentration,
Material 9 is made with embodiment 4 in solution, remaining method.
Embodiment 10
The same method of embodiment 4, it is 1M phosphoric acid hydrogen two that step 5, which replaces concentration by 1M potassium dihydrogen phosphate with concentration,
Material 10 is made with embodiment 4 in sodium solution, remaining method.
The magnetic intensity for evaluating the magnetic hydroxylapatite material 6-10 of embodiment 6-10 preparation, is ◎；Use copper sulphate
Prepare Cu2+Concentration is the simulated wastewater of 1000mg/L, is separately added into 1 gram of material 6-10, is stirred to react 1 hour, then Magneto separate, is used
ICP tests Cu in liquid2+Concentration, respectively less than 1mg/L.
Claims (10)
1. a kind of one kettle way, the method that two stages prepare ferromagnetism hydroxyapatite heavy-metal adsorption material, which is characterized in that packet
Containing following steps:
(1) it prepares ferroso-ferric oxide: being packed into water in beaker, aeration stirring is heated to 40-80 DEG C, and alkali is added dropwise simultaneously into beaker
Liquid and ferrous salt solution maintain pH9-11, are added dropwise, constant temperature aeration reaction, and ferroso-ferric oxide emulsion is made；
(2) it prepares magnetic hydroxylapatite: it is molten that calcium salt being added into the ferroso-ferric oxide emulsion under step (1) constant temperature
Liquid, phosphate solution, and pH9-11 is maintained with lye, addition finishes, continues to stir, isothermal reaction, naturally cold after fully reacting
But it to room temperature, is aged, Magneto separate is washed to neutrality, dries stand-by.
2. the method according to claim 1, wherein alkali described in step (1) and (2) is sodium hydroxide, hydrogen-oxygen
Change one or both of potassium mixture, concentration 0.1-5M, preferably 0.5-4M, more preferably 1-2M.
3. the method according to claim 1, wherein ferrous salt described in step (1) is selected from ferrous sulfate, chlorination
One of ferrous iron, ferrous nitrate, ferrous sulfate amine are a variety of, concentration 0.1-5M, preferably 0.5-4M, more preferably 1-
2M。
4. the method according to claim 1, wherein aeration quantity described in step (1) be 0.1-10L/min, it is excellent
It is selected as 0.5-5L/min.
5. the method according to claim 1, wherein step (1) constant temperature aeration reaction time be 1-6 hours, it is excellent
It is selected as 1-3 hours.
6. the method according to claim 1, wherein step (2) described calcium salt is calcium chloride, one in calcium nitrate
Kind or two kinds, concentration 0.1-5M, preferably 0.5-4M, more preferably 1-2M.
7. the method according to claim 1, wherein step (2) described phosphate is tertiary sodium phosphate, phosphoric acid hydrogen two
Sodium, sodium dihydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, phosphoric acid triamine, diammonium hydrogen phosphate and phosphoric acid dihydro amine
One of or a variety of, concentration 0.1-5M, preferably 0.5-4M, more preferably 1-2M.
8. the method according to claim 1, wherein step (2) the isothermal reaction time be 2-8 hours, preferably 2-6
Hour, it is 2-4 hours more preferable.
9. the method according to claim 1, wherein step (2) digestion time be 6-72 hours, more preferable 12-
It is 48 hours, 18-24 hours more preferable.
10. a kind of if the ferromagnetism hydroxyapatite material of the described in any item method preparations of claim 1-9 is in an absorption huge sum of money
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| CN110526300A (en) * | 2019-06-28 | 2019-12-03 | 中冶华天工程技术有限公司 | The one heavy metal species processing preparation method of magnetic Nano Fe-S material |
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| CN114558132A (en) * | 2022-02-22 | 2022-05-31 | 浙江理工大学 | Hydroxyapatite-loaded ferroferric oxide nano material as well as preparation method and application thereof |
| CN114939395A (en) * | 2022-05-05 | 2022-08-26 | 湖南艾布鲁环保科技股份有限公司 | Non-point source pollution adsorbent and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110526300A (en) * | 2019-06-28 | 2019-12-03 | 中冶华天工程技术有限公司 | The one heavy metal species processing preparation method of magnetic Nano Fe-S material |
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| CN114939395A (en) * | 2022-05-05 | 2022-08-26 | 湖南艾布鲁环保科技股份有限公司 | Non-point source pollution adsorbent and preparation method and application thereof |
| CN114939395B (en) * | 2022-05-05 | 2023-10-13 | 湖南艾布鲁环保科技股份有限公司 | Non-point source pollution adsorbent and preparation method and application thereof |
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