CN109731542A - A kind of hydroxyapatite and the preparation method and application thereof with absorption heavy metal lead ion - Google Patents
A kind of hydroxyapatite and the preparation method and application thereof with absorption heavy metal lead ion Download PDFInfo
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Abstract
The invention discloses a kind of hydroxyapatite and preparation method thereof with absorption heavy metal lead ion, it is by Peel of Navel Orange, conch meal is broken, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate and propionamide are made.The present invention is made up of the optimum feed stock that a large number of experiments filters out hydroxyapatite, it is creative using Peel of Navel Orange as biological template, with conch meal etc. for Material synthesis, experiment shows have the function of adsorbing the lead ion in high-concentration waste water well, has good governance role to pollution of waterhead.The present invention filters out optimal synthesis technologic parameter by a large number of experiments, and the hydroxyapatite adsorbent with fine adsorpting lead ion performance can efficiently be prepared.Experiment shows to heavy metal lead ion remaval rate up to 92% or more, and it can desorb and regenerate, can be widely applied to the adsorption treatment of lead ion in high-concentration waste water, can overcome at high cost in the prior art, many deficiencies such as Adsorption low efficiency have important social effect and economic benefit.
Description
Technical field
The present invention relates to a kind of heavy metal treatment agents, and in particular to a kind of hydroxy-apatite with absorption heavy metal lead ion
Stone and the preparation method and application thereof belongs to environmental friendly material field.
Background technique
Heavy metal can enter people by food chain because of its physics toxic, high bio-toxicity, difficult to degrade and persistence
Body simultaneously causes to seriously affect by accumulating amplification to human body and animals and plants.For example lead ion is exceeded will invade human body hematopoiesis
System, nerve fiber and kidney, so as to cause neurasthenia, globular anemia and hypochrosis, even
Brain and kidney portion lesion can be caused.In addition to this, lead has centainly the nervous system of human body, digestive system and cardiovascular system
Damage.Copper ion will lead to cutaneous necrosis, hemoglobin denaturation etc., to influence to be metabolized, cause the disease of cardiovascular one kind.
There is a large amount of research in terms of handling commercial metal waste water at present, main processing technique has followingization
Learn the precipitation method, ion-exchange, biological restoration, absorption method etc..
Hydroxyapatite (HAP) is as a kind of novel environmental functional mineral material, because it is with biggish specific surface
Long-pending, special cavernous structure and good ion exchange and absorption property become the important suction for administering heavy metal wastewater thereby
Enclosure material.
Summary of the invention
Goal of the invention: it is renewable the purpose of the invention is to provide a kind of raw material to be easy to get, it is at low cost, easily promote and apply,
Efficiently, the high-efficiency adsorbent of economic, environmental protection heavy metal lead ion, another object of the present invention are to provide the suction of heavy metal lead ion
Attached dose of preparation method and applications.
Technical solution: in order to achieve the object of the present invention, the technical solution adopted by the present invention are as follows:
A kind of hydroxyapatite with absorption heavy metal lead ion, it includes that the raw materials of following parts by weight is made:
Peel of Navel Orange, conch meal be broken, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and propionamide.
Preferably, the above-described hydroxyapatite with absorption heavy metal lead ion, it includes following heavy
The raw material of amount number is made:
20~40 parts of Peel of Navel Orange, 5~10 parts of conch meal, 1.5~3 parts of ammonium dihydrogen phosphate, 1.9~3.8 parts of diammonium hydrogen phosphate
With 0.5~1 part of propionamide.
Preferably, the above-described hydroxyapatite with absorption heavy metal lead ion, it is by following weight
The raw material of number is made:
20 parts of Peel of Navel Orange, 5 parts of conch meal, 7.72 parts of ammonium dihydrogen phosphate, 1.98 parts and 0.5 part of propionamide of diammonium hydrogen phosphate.
The preparation method of the hydroxyapatite with absorption heavy metal lead ion of the present invention, comprising the following steps:
Step (1): weighing Peel of Navel Orange in parts by weight and mix with distilled water, boil, and filtering obtains Peel of Navel Orange extracting solution；
Step (2): conch meal is crushed, and is crossed 150 the polished standard screens and is sufficiently dried, takes the shellfish dried in parts by weight
Distilled water is added and Peel of Navel Orange extracting solution that step (1) is prepared as in beaker in shell powder, is placed on magnetic stirrer and stirs
It mixes；Ammonium dihydrogen phosphate, diammonium hydrogen phosphate and propionamide are added in parts by weight, after mixing evenly, are transferred quickly to reaction kettle
Middle reaction obtains；
Step (3): then reaction kettle cooled to room temperature cleans up to it solution in reaction kettle with centrifuge
PH and distilled water close to (pH6.5), until thermostatic drying chamber it is dry to get.
Preferably, the preparation method of the above-described hydroxyapatite with absorption heavy metal lead ion, packet
Include following steps:
Step (1): weighing Peel of Navel Orange in parts by weight and mix with distilled water, boil 10~20min, and filtering obtains Peel of Navel Orange
Extracting solution；
Step (2): weighing shell in parts by weight, is crushed, and crosses 150 the polished standard screens and sufficiently dries；5g is taken to dry
Conch meal as in beaker, and the Peel of Navel Orange extracting solution that the step of distilled water and 10mL of 200mL is added (1) is prepared,
It is placed in 30~60min of stirring on magnetic stirrer；Ammonium dihydrogen phosphate, diammonium hydrogen phosphate and propionamide is added in parts by weight again,
It is transferred quickly in reaction kettle after mixing evenly, sealing is reacted 24 hours as at a temperature of 180 DEG C；
Step (3): then reaction kettle cooled to room temperature cleans up to it solution in reaction kettle with centrifuge
PH and distilled water close to (pH6.5), until 80 DEG C of thermostatic drying chambers it is dry to get.
Preferably, the preparation method of the above-described hydroxyapatite with absorption heavy metal lead ion, step
Suddenly (2).
It is a kind of to have at the hydroxylapatite adsorptions for adsorbing heavy metal lead ion with claims 1 to 3 is described in any item
Manage metallic lead ion method, the condition of processing are as follows: HAP injected volume be 0.1~0.2g (concentration after conversion is 0.002~
0.004g/mL), pH is 4~5, and the reaction time is 60~120min, and reaction temperature is 25~35 DEG C.
It is a kind of to have at the hydroxylapatite adsorptions for adsorbing heavy metal lead ion with claims 1 to 3 is described in any item
Manage metallic lead ion method, the condition of processing are as follows: HAP injected volume is 0.2g (concentration after conversion is 0.004g/mL), pH 5,
Reaction time is 120min, and reaction temperature is 35 DEG C.
A kind of method that desorption and regeneration has the hydroxyapatite of absorption heavy metal lead ion, which is characterized in that 45~
At 60 DEG C, the Ca (NO for being 3mol/L with concentration3)2Impregnate hydroxyapatite., it is 3mol/L with concentration particularly preferably at 60 DEG C
Ca (NO3)2Impregnate hydroxyapatite.
The hydroxyapatite with absorption heavy metal lead ion of the present invention is in processing ion waste water containing heavy metal lead
In application.
One, craft screening is tested:
1, experimental material and scheme
1.1 experimental material
1.1.1 laboratory apparatus such as the following table 1:
Required instrument in the experiment of table 1
1.1.2 experimental raw and reagent
(1) experimental raw and reagent needed for are shown in Table 2
Required raw material and reagent in the experiment of table 2
| Reagent (raw material) title | Purity | Manufacturer |
| Peel of Navel Orange | - | - |
| Conch meal | - | - |
| Diammonium hydrogen phosphate | AR | Xilong Chemical Co., Ltd |
| Ammonium dihydrogen phosphate | AR | Sinopharm Chemical Reagent Co., Ltd. |
| Propionamide | AR | Shanghai fuzz Chemical Co., Ltd. |
| Plumbi nitras | AR | Tianjin good fortune morning chemical reagent factory |
| Calcium nitrate | AR | Shanghai fuzz Chemical Co., Ltd. |
| Nitric acid | AR | Nanjing chemical reagent limited liability company |
| Sodium hydroxide | AR | Tianjin good fortune morning chemical reagent factory |
(2) preparation of lead standard solution
Weigh 1.5999g Pb (NO3)2Solid is added 200mL deionized water and 10mL concentrated nitric acid (inhibits Pb in beaker2 +Hydrolysis) dissolved solid, be transferred to constant volume in the volumetric flask of 1000mL and shake up, be concentration be 1000mg/L Pb2+Standard solution.
(3)Ca(NO3)2The preparation of standard solution
Weigh 708.45g Ca (NO3)2Solid is placed in a beaker, and appropriate amount of deionized water is added and makes it completely dissolved, then turns
It moves to constant volume in the volumetric flask of 1000mL to shake up, is the Ca (NO of 1000mol/L3)2Standard solution.
The preparation of 2.2 hydroxyapatites (HAP) of the invention
The main component of fragrant citrus pericarp is: aurantiamarin, limonene, carrotene, essential oil, pectin.
With conch meal, (NH4)2HPO4、NH4H2PO4It is raw material with propionamide, the reaction equation of synthesizing hydroxylapatite is as follows:
10CaCO3+3(NH4)H2PO4+3(NH4)2HPO4→Ca10(PO4)6(OH)2+8H2O+10CO2+9NH3
10CaCO3+(NH4)H2PO4→Ca10(PO4)6(OH)2+8H2O+10CO2+6NH3
The synthetic method of hydroxyapatite is as follows:
Step (1): the Peel of Navel Orange for weighing 20g is mixed with the distilled water of 200mL, boils 10min, filtering.
Step (2): conch meal is crushed, and is crossed 150 the polished standard screens and is sufficiently dried.The conch meal for taking 5g to dry as
In beaker, and the distilled water of 200mL and the said extracted liquid of 10mL is added, is placed on magnetic stirrer and stirs 30min；It adds
1.72g ammonium dihydrogen phosphate, 1.98g diammonium hydrogen phosphate, 0.5g propionamide are transferred quickly in reaction kettle after mixing evenly, sealing
It is reacted 24 hours as at a temperature of 180 DEG C.
Step (3): then reaction kettle cooled to room temperature cleans up to it solution in reaction kettle with centrifuge
PH and distilled water are close to (pH6.5), until 80 DEG C of thermostatic drying chambers are dry, pack is hydroxyapatite HAP (following screening experiment
It is all made of the hydroxyapatite).
2.3 adsorption experiment schemes
(1) stability experiment of HAP
The distilled water for accurately moving into 50mL into 7 250mL conical flasks respectively, pH is adjusted to 4 respectively, 5,5.5,6,7,
7.5, distilled water (blank).0.1000g hydroxyapatite HAP is successively added, 120rpm reacts in constant temperature oscillation case at 25 DEG C
It is filtered after 1h, surveys Ca content (atomic absorption spectrophotometer) in its filtrate.
(2) screening of HAP dosage
The lead standard solution for accurately moving into 50mL 200mg/L into 6 250mL conical flasks respectively, pH is adjusted to
5.000 ± 0.005, do not add the hydroxyl of 0.0500g, 0.1000g, 0.2000g, 0.3000g, 0.4000g, 0.5000g successively
Apatite powder, 120rpm is filtered after reacting 2h in constant temperature oscillation case at 25 DEG C, surveys (the Atomic absorption point of Pb content in its filtrate
Light photometer).
(3) screening of pH factor
The lead standard solution for accurately moving into 50mL 200mg/L into 7 250mL conical flasks respectively, pH is adjusted to respectively
3,4,5,5.5,6,7,7.5.0.1000g hydroxyapatite powder is successively added, 120rpm is anti-in constant temperature oscillation case at 25 DEG C
It is filtered after answering 2h, surveys Pb content (atomic absorption spectrophotometer) in its filtrate.
(4) screening of dynamic experiment
The lead standard solution for accurately moving into 50mL 200mg/L into 7 250mL conical flasks respectively, pH is adjusted to
5.000 ± 0.005, and add 0.1000g hydroxyapatite powder.It is vibrated respectively under different temperatures (15 DEG C, 25 DEG C, 35 DEG C)
It is filtered after 10min, 30min, 60min, 90min, 120min, 150min, 180min, surveys Pb content (Atomic absorption in its filtrate
Spectrophotometer).
(5) adsorption isotherm experiment
It is accurate prepare initial concentration be 50mg/L, 100mg/L, 150mg/L, 200mg/L, 300mg/L, 40mg/L,
The lead standard solution of 600mg/L, takes 50mL in conical flask respectively, and pH is adjusted to 5.000 ± 0.005.Successively add
0.1000g hydroxyapatite simultaneously filters after vibrating 2h at 15 DEG C, 25 DEG C, 35 DEG C, and measuring content in its filtrate, (atom is inhaled
Receive spectrophotometer).
(6) desorption experiment
1. measuring the lead standard solution of the 600mg/L of 100mL respectively in 5 conical flasks, pH is adjusted to 5.000 ±
0.005.0.5000g hydroxyapatite powder is successively added, 120rpm is filtered after reacting 2h in constant temperature oscillation case at 25 DEG C, is surveyed
Pb content, leaves filter cake in its filtrate, as raw material for parsing.
2. taking concentration respectively is 0mol/L, 0.4mol/L, 0.8mol/L, 1.2mol/L, 1.5mol/L, 2mol/L, 3mol/
Ca (the NO of L3)2Standard solution 50mL successively adds the desorption raw material of 0.1g in 7 conical flasks, the constant temperature oscillation case at 25 DEG C
It is filtered after middle 120rpm reaction 2h, surveys Pb content (atomic absorption spectrophotometer) in its filtrate, obtain best Ca (NO3)2It is dense
Degree is in next step.
3. Ca (the NO of 3mol/L is added into 4 conical flasks respectively3)2Standard solution 50mL is in different temperatures (25 DEG C, 35
DEG C, 45 DEG C, 60 DEG C) under vibrate 2h respectively after filter, survey Pb content in its filtrate.
2.4 data processing
2.4.1 the calculating of adsorbance
The adsorbance of Staticadsorption experiment calculates as the following formula (1-1):
Removal rate calculates as the following formula (2-2):
Wherein: qeIt is unit mass HAP absorption Pb2+Amount, unit mg/g；
C0It is the Pb before adsorbing in solution2+Concentration, unit mg/L；
CeIt is the Pb after adsorbing in solution2+Equilibrium concentration, unit mg/L；
V is containing Pb2+The volume of solution, unit L；
M is the quality of HAP, unit g；
Y is Pb2+Removal rate.
3, results and discussion
The characterization of 3.1 materials
Fig. 1 is the XRD diagram of synthesized hydroxyapatite, it can be seen that the standard drawing of synthesized sample and HAP are basic
It coincide, the position of three characteristic peaks is at 32.0 °, 32.4 °, 33.3 °.Show that synthesis has obtained purer hydroxyapatite in experiment
Sample.
Pass through the scanning electron microscope of hydroxyapatite sample.The result shows that sample microscopic appearance be it is cotton-shaped, flocculent structure is deposited
In the specific surface area for being conducive to improve hydroxyapatite, be conducive to the absorption of heavy metal ion.It is obtained according to N2 adsorption method
Sample specific surface area and pore volume are respectively 42.940m3/g、0.3593mL/g。
3.2 stability test
HAP stability experiment is research pH value to Ca in HAP2+The influence of meltage passes through Ca under condition of different pH2+'s
Meltage judges its stability.Its result is as shown in Figure 2: from figure 2 it can be seen that the Ca being dissolved out2+Concentration with
The raising of pH and reduce, be in alkalescent this is because the pH value of water solution of HAP is between 7-9, and hydroxyapatite is in alkaline item
Difficult dissolution easy in acid condition is dissolved under part, dissolves Ca out2+It is easy to be replaced by metal ion.
The determination of 3.3 adsorbent amounts
The concentration for launching residue Pb ion in filtrate under different HAP quality requirements is measured with laboratory apparatus, is further counted
Calculate adsorbance.As a result as shown in Figure 3:
From figure 3, it can be seen that opposite relationship is presented with HAP dosage in adsorbance, adsorbance is with adsorbent amount
Increase and reduces, when the dosage of HAP is in 0.05g to 0.1g, Pb2+Absorption is most fast, when HAP dosage is more than 0.1g, the rate of adsorption
It reduces.This increase for being primarily due to HAP dosage provides a large amount of adsorption site, but in absorption Pb2+Many absorption in the process
Site does not react in competitive Adsorption.
Fig. 3 also demonstrates removal rate and adsorbent amount is positively correlated, and removal rate is mentioned with the increase of adsorbent amount
Height, after HAP reaches 0.2g, removal rate is stable simultaneously to reach 99%, analysis the reason is that when the dosage of HAP is not up to 0.2g,
With the increase of dosage, the absorption point that HAP is provided is very abundant, so removal rate rises obviously.When HAP dosage reaches 0.2g,
Basically reach removal Pb2+Purpose, remaining Pb2+Concentration is too low to be contacted with adsorbent, continue growing adsorbent only
Can increase invalid adsorption site, its removal rate reaches 99% at this time.So in order to improve removal rate in experiment, adsorbent is used
Amount is unsuitable excessive.
The influence of 3.4 pH
If Fig. 4 is that different pH value adsorb Pb to HAP2+The research of influence: from fig. 4, it can be seen that when pH is in 3.0-4.0,
The rate of adsorption is maximum, and when pH value is higher than 4.0, adsorbance growth rate slows down and gradually tends to be saturated, and after pH is greater than 5.0, inhales
Downward trend is presented in attached amount.This illustrates all to be unfavorable for Pb when pH is lower and higher2+Absorption.Because HAP is sent out under strong acid condition
Raw dissolution, causes the reduction of adsorbance.Under conditions of neutral or alkalinity, due to part Pb2+It is heavy to generate hydroxide
It forms sediment, causes the reduction of adsorbance, therefore this experimental selection Optimal pH is 5.0.In addition, research shows that influence of the pH to absorption property
May be it is related to the current potential of adsorbent surface, with the raising of pH value, the negative electrical charge for being conducive to the surface HAP increases, to have
Conducive to the raising of adsorption capacity.
3.5 dynamics research
Under condition of different temperatures, HAP adsorbs Pb2+Absorption dynamic curve it is as shown in Figure 5: as seen from Figure 5, reaction is rigid
HAP is to Pb when beginning2+Adsorption rate quickly, adsorbance amplification is obvious, when duration of oscillation be 60min when, adsorption rate starts
Slow down, adsorbance also gradually tends towards stability, and HAP is to Pb after 120min2+Adsorbance variation it is no longer significant.And when with oscillation
Between increase, almost without occur solve suction phenomenon, illustrate Pb2+Strong chemical bond is formed with adsorption site, it is not easy to be occurred again
Desorption.In order to make absorption sufficiently achieve balance, duration of oscillation is tested later and is selected as 120min.From this figure it can be seen that phase
With in the time, its adsorbance is also increasing as the temperature rises, and increasing trend is presented in saturated extent of adsorption, illustrates to improve anti-
Temperature is answered to be conducive to improve HAP to Pb2+Adsorption efficiency.
The research of 3.6 isothermal adsorptions
Under different temperatures, with CeFor abscissa, qeMake isothermal adsorption relational graph, such as Fig. 6 for ordinate:
As Fig. 6 be at three temperature HAP to Pb2+Adsorption curve.The trend steeply risen is presented in initial stage curve, is
Because HAP is to Pb2+With very strong compatibility, with the increase of original metal ion concentration, curve ascendant trend is gradually slow.
Show in a certain concentration, improve concentration be conducive to adsorb, when concentration reaches it is a certain amount of when, absorption, which will be saturated, to be increased again
Add.Curve can also be seen that as the temperature rises adsorbance is also increasing, and illustrate that HAP can be improved to Pb in temperature2+Suction
Attached effect.
4, desorption experiment
So-called desorption exactly removes adsorbate from the micropore of adsorbent with some way, restores its absorption again
Ability, to achieve the purpose that recycling.In view of HAP recycle and the recycling of heavy metal, the present invention to absorption Pb2+
The regeneration of HAP afterwards is studied, using the Ca (NO of various concentration3)2Come as strippant to Pb2+It is desorbed.Experiment
As a result such as Fig. 7:
As seen from Figure 7, with Ca (NO3)2The raising of concentration, desorption efficiency also increase with it.As Ca (NO3)2Concentration is
When 3mol/L, desorption efficiency reaches maximum, can reach 40.67%.This is because with Ca in strippant2+The increase of concentration, with Pb2 +Competitive Adsorption leads to more Pb on the active site on the surface HAP2+It is desorbed out.So selecting this concentration C a (NO3)2Make
For stripping medium.
Based on above-mentioned strippant concentration, the present invention continues to have studied the desorption of the strippant under condition of different temperatures
Effect, such as Fig. 8: as seen from Figure 8, as the temperature rises, strippant is to Pb2+Desorption efficiency increase, when temperature reaches 60
DEG C when, desorption efficiency reaches 37.78%.Reason may be the raising with reaction temperature, to the Pb in solution2+Provide energy
It is set to get rid of the constraint of adsorbent；Raising simultaneously temperature can be improved Pb2+Diffusion rate, be conducive to Ca (NO3)2To Pb2+'s
Desorption.
The utility model has the advantages that the high-efficiency adsorbent of heavy metal lead ion provided by the invention compared to the prior art have it is following excellent
Point:
1, the present invention is made up of the optimum feed stock that a large number of experiments filters out hydroxyapatite, is biological mould with Peel of Navel Orange
Plate, using conch meal as raw material, experiment shows have the function of adsorbing the lead ion in high-concentration waste water well, to pollution of waterhead
With good governance role.
2, the synthesis technology of hydroxyapatite provided by the invention filters out optimal synthesis technology by a large number of experiments
The hydroxyapatite adsorbent with fine adsorpting lead ion performance can be efficiently prepared in parameter.
3, the present invention screens different pH value by many experiments, different temperatures, adsorption time, the conditions such as adsorbent reactivation,
The optimum condition of adsorpting lead ion is filtered out, verifying shows that the Optimal pH in HAP absorption Pb2+ experiment provided by the invention is 5,
Optimum reacting time is 120min, and best HAP injected volume is 0.1g.It is reachable to the removal rate of the lead ion in high-concentration waste water
85% or more, it can be widely applied to the processing of the industrial wastewater containing lead ion, at high cost in the prior art, Adsorption can be overcome
Low efficiency, adsorbent such as cannot regenerate at many deficiencies, have important social effect.
Detailed description of the invention
Fig. 1 is the XRD diagram of synthesizing hydroxylapatite.
Fig. 2 is the curve graph of the stability test of HAP.
Fig. 3 is curve graph of the HAP dosage to absorption Pb2+.
Fig. 4 is the curve graph that pH adsorbs that Pb2+ is influenced on HAP.
Fig. 5 is the curve graph for the influence for different temperatures and time Pb2+ being adsorbed to HAP.
Fig. 6 is that Ce-qe schemes under different temperatures.
Fig. 7 is the curve graph that strippant concentration influences the desorption of Pb2+.
Fig. 8 is the curve graph for the influence that different temperatures desorbs Pb2+ to Ca (NO3) 2.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
The modification of form falls within the application range as defined in the appended claims.
A kind of synthetic method of the hydroxyapatite of embodiment 1 comprising following steps:
Step (1): the Peel of Navel Orange for weighing 20g is mixed with the distilled water of 200mL, boils 10min, filtering.
Step (2): conch meal is crushed, and is crossed 150 the polished standard screens and is sufficiently dried.The conch meal for taking 5g to dry as
In beaker, and the distilled water of 200mL and the said extracted liquid of 10mL is added, is placed on magnetic stirrer and stirs 30min；It adds
1.72g ammonium dihydrogen phosphate, 1.98g diammonium hydrogen phosphate, 0.5g propionamide are transferred quickly in reaction kettle after mixing evenly, sealing
It is reacted 24 hours as at a temperature of 180 DEG C.
Step (3): then reaction kettle cooled to room temperature cleans up to it solution in reaction kettle with centrifuge
PH and distilled water are close to (pH6.5), until 80 DEG C of thermostatic drying chambers are dry, pack is hydroxyapatite HAP (following screening experiment
It is all made of the hydroxyapatite).
2 lead ion of embodiment adsorbs clearance test
2 parts of industrial wastewater of the 20L containing lead ion is taken, puts into the hydroxyapatite that the embodiment of the present invention 1 is prepared respectively
80g (is converted) by 0.004g/mL, and adjustment reaction temperature is 35 DEG C, and adjustment wastewater pH is 5, and the reaction time is 120 minutes, is calculated
The removal rate of Pb In Exhausted Water ion is respectively 93.7% and 93.5%, shows that the hydroxyapatite that the present invention is prepared has very
The effect of good Adsorption Pb In Exhausted Water ion.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of hydroxyapatite with absorption heavy metal lead ion, which is characterized in that it includes the original of following parts by weight
Material is made:
Peel of Navel Orange, conch meal be broken, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and propionamide.
2. the hydroxyapatite with absorption heavy metal lead ion according to claim 1, which is characterized in that under it includes
The raw material of column parts by weight is made:
20~40 parts of Peel of Navel Orange, 5~10 parts of conch meal, 1.5~3 parts of ammonium dihydrogen phosphate, 1.9~3.8 parts of diammonium hydrogen phosphate and third
0.5~1 part of amide.
3. the hydroxyapatite with absorption heavy metal lead ion according to claim 2, which is characterized in that it is by following
The raw material of parts by weight is made:
20 parts of Peel of Navel Orange, 5 parts of conch meal, 7.72 parts of ammonium dihydrogen phosphate, 1.98 parts of diammonium hydrogen phosphate and 0.5 part of propionamide.
4. the preparation method of the described in any item hydroxyapatites with absorption heavy metal lead ion of claims 1 to 3, special
Sign is, comprising the following steps:
Step (1): weighing Peel of Navel Orange in parts by weight and mix with distilled water, boil, and filtering obtains Peel of Navel Orange extracting solution；
Step (2): conch meal is crushed, and is crossed 150 the polished standard screens and is sufficiently dried, takes the conch meal dried in parts by weight
As in beaker, and distilled water is added and Peel of Navel Orange extracting solution that step (1) is prepared, is placed on magnetic stirrer and stirs；
Ammonium dihydrogen phosphate, diammonium hydrogen phosphate and propionamide are added in parts by weight, are transferred quickly in reaction kettle after mixing evenly anti-
It should obtain；
Step (3): by reaction kettle cooled to room temperature, then with centrifuge to the solution in reaction kettle clean until its pH and
Distilled water close to (6.5), until thermostatic drying chamber it is dry to get.
5. the preparation method of the hydroxyapatite with absorption heavy metal lead ion according to claim 4, feature exist
In, comprising the following steps:
Step (1): weighing Peel of Navel Orange in parts by weight and mix with distilled water, boil 10~20min, filtering, obtains Peel of Navel Orange extraction
Liquid；
Step (2): weighing shell in parts by weight, is crushed, and crosses 150 the polished standard screens and sufficiently dries；Take the shellfish that 5g has been dried
Shell powder is as in beaker, and the Peel of Navel Orange extracting solution that the step of distilled water and 10mL of 200mL is added (1) is prepared, and is placed in
30~60min is stirred on magnetic stirrer；Ammonium dihydrogen phosphate, diammonium hydrogen phosphate and propionamide, stirring is added in parts by weight again
It is transferred quickly in reaction kettle after uniformly, sealing is reacted 24 hours as at a temperature of 180 DEG C；
Step (3): by reaction kettle cooled to room temperature, then with centrifuge to the solution in reaction kettle clean until its pH and
Distilled water close to (6.5 or so), until 80 DEG C of thermostatic drying chambers it is dry to get.
6. a kind of handled with the described in any item hydroxylapatite adsorptions with absorption heavy metal lead ion of claims 1 to 3
Metallic lead ion method, which is characterized in that the condition of processing are as follows: HAP injected volume be 0.1~0.2g (concentration be 0.002g/mL~
0.004g/mL), pH is 4~5, and the reaction time is 60~120min, and reaction temperature is 25~35 DEG C.
7. a kind of handled with the described in any item hydroxylapatite adsorptions with absorption heavy metal lead ion of claims 1 to 3
Metallic lead ion method, which is characterized in that the condition of processing are as follows: HAP injected volume be 0.1~0.2g (concentration be 0.002g/mL~
0.004g/mL), 5 pH, reaction time 120min, reaction temperature are 35 DEG C.
8. a kind of method that desorption and regeneration has the hydroxyapatite of absorption heavy metal lead ion, which is characterized in that 45~60
At DEG C, the Ca (NO for being 3mol/L with concentration3)2Impregnate hydroxyapatite.
9. described in claim 11 to 3 described in any item hydroxyapatites with absorption heavy metal lead ion contain in processing
Application in heavy metal lead ion waste water.
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| CN201910191150.8A CN109731542A (en) | 2019-03-13 | 2019-03-13 | A kind of hydroxyapatite and the preparation method and application thereof with absorption heavy metal lead ion |
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| CN111135801A (en) * | 2020-01-19 | 2020-05-12 | 浙江大学 | Preparation method of hydroxyapatite flat plate wire composite material with heavy metal adsorption function |
| CN111495315A (en) * | 2020-04-23 | 2020-08-07 | 齐鲁工业大学 | Pb in water body2+Application and preparation method of adsorbing material |
| CN112427029A (en) * | 2020-11-20 | 2021-03-02 | 西安交通大学 | Desorption method based on calcined bone apatite after heavy metal ion adsorption |
| CN113332960A (en) * | 2021-03-23 | 2021-09-03 | 中南大学 | Supported apatite composite adsorption material and preparation method and application thereof |
| CN115591536A (en) * | 2022-09-15 | 2023-01-13 | 北京交通大学（Cn） | Application of shell powder as adsorbing material to adsorb heavy metal |
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| CN115591536A (en) * | 2022-09-15 | 2023-01-13 | 北京交通大学（Cn） | Application of shell powder as adsorbing material to adsorb heavy metal |
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