CN110038514A - A kind of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent and the preparation method and application thereof - Google Patents
A kind of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent and the preparation method and application thereof Download PDFInfo
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- CN110038514A CN110038514A CN201910310349.8A CN201910310349A CN110038514A CN 110038514 A CN110038514 A CN 110038514A CN 201910310349 A CN201910310349 A CN 201910310349A CN 110038514 A CN110038514 A CN 110038514A
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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
- B01J20/04—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
- 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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- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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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
- B01J20/28—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
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to solid-phase grinding dry method modification technical fields, it is related to a kind of preparation and application of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent, this method are as follows: nanometer hydroxyapatite and nano black carbon are mixed in a certain proportion, obtain the black carbon of modified Nano by solid-phase sequencing after mixing；The mass ratio of HAP and MBC is 3:4-1:1；Nanometer hydroxyapatite dry method modification nano black carbon Cu in absorption waste water as adsorbent2+、Cd2+Application, obtain nanometer hydroxyapatite dry method modification nano black carbon to Cu2+Saturated extent of adsorption be 478.89mmol/kg；To Cd2+Saturated extent of adsorption be 423.49mmol/kg.
Description
Technical field
The disclosure belongs to solid-phase grinding dry method modification technical field, and in particular to a kind of nanometer hydroxyapatite dry method modification
Nano black carbon prepares heavy metal absorbent and its preparation and application.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Heavy metal has very strong toxicity, and the pollutant containing heavy metal is largely discharged into environment, can heavy metal be existed
It is constantly accumulated in environment, therefore heavy metal pollution problem is urgently to be resolved.Processing containing heavy metal containing sewage at present mostly uses absorption heavy
Shallow lake method.Research and development are economical, heavy metal absorbent efficiently, safe is the key that improve heavy metal-containing wastewater treatment effect.Nanometer material
Material is especially modified by surface because of its huge specific surface, high chemical activity and strong absorption property, greatly improves
To the absorption property of heavy metal, become the hot spot of current heavy metal high-efficiency adsorbent research.Inventors have found that every kind of absorption
Agent all has certain limitation: first is that, modified adsorbent multipair Pb, Cu, Zn, Ni have stronger adsorptivity, to Cd
Absorption property it is poor；Second is that modified adsorbent Selective long-range DEPT, tends not to be applied to various heavy while locate
Reason.When for wastewater treatment containing various heavy, replacement adsorbent increases processing cost and time；Third is that Pb, Cu,
Height of the discharge standard of Zn, Ni more than the Cd being more toxic asks higher to Cd processing in wastewater treatment containing various heavy,
That is require modified adsorbent higher to the absorption property of Cd.
Especially when adsorbent, which is applied to heavy-metal contaminated soil passivation, to be repaired, when soil is by the compound dirt of several heavy metal species
It is worse to the absorption passivation effect of Cd when dye.Even if soil is not polluted by heavy metal Pb, Cu, Zn etc., Cd pollution is only received,
The content of Pb, Cu, Zn in the soil is also much higher than Cd.Such as, national " soil environment quality-farming land soil pollution risk management and control
Standard (tentative) " soil risk screening value in (CB15618-2018), when soil pH >=7.5, the risk screening of Pb, Cu, Zn
Value (other) is respectively 170mg/kg, 100mg/kg and 300mg/kg, and the limit value of Cd is then 0.6mg/kg.That is, Cd
Pollution is more than that 160~500 times of limitation is just suitable with the uncontaminated content of Pb, Cu, Zn.
Summary of the invention
For above-mentioned problems of the prior art, a purpose of the disclosure is to provide a kind of nanometer hydroxyapatite
The method of the black carbon heavy metal absorbent of solid-phase grinding modified Nano.Nanometer hydroxyapatite to Cd have high chemical activity and
Strong adsorption capacity, the black carbon of modified Nano have stronger adsorption capacity to Cu.Nitric acid-height can be allowed by solid-phase sequencing
The black carbon of potassium manganate modified Nano is mixed well with nanometer hydroxyapatite, is combined, and increases the adsorption capacity to Cu and Cd.
In order to solve the above technical problems, the technical solution of the disclosure are as follows:
A kind of preparation method of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent, detailed process
Are as follows: nanometer hydroxyapatite (HAP) is mixed in a certain proportion with nano black carbon (MBC), passes through solid-phase sequencing after mixing
Obtain nanometer hydroxyapatite dry method modification nano black carbon；
The nano black carbon is first with nitric acid and the modified nano black carbon of potassium permanganate.
Every kind of adsorbent is different the adsorption capacity of different heavy metals, nano black carbon itself to the adsorption capacity of Cd compared with
Weak, stronger to the adsorption capacity of Cu, HAP is to Cd's and Cu's all has preferable adsorption capacity, so nano black carbon and HAP
The few problem of Cd adsorbance can all occur during being used alone during absorption, HAP due to containing Ca ion,
There is specific adsorption to Cd.Nano black carbon and HAP are nano-substances, and the specific surface of nano-substance is larger, interfacial energy
It is larger higher, all there is stronger adsorption capacity each other, be adhered to one another during grinding.By milling time and
Two kinds of adsorbent proportions, can have preferable adsorption effect to Cu and Cd.Inventors discovered through research that in HAP and nanometer
Black carbon can enable the Cd adsorption site of HAP by the limitation of grinding ratio and milling time during solid-phase grinding
Preferably it is exposed, while the combination of HAP and nano black carbon does not cover in the adsorption site of Cd.
In some embodiments, nanometer hydroxyapatite (HAP) mass fraction >=97%, partial size < 100nm.
In some embodiments, partial size≤100nm of nano black carbon.
In some embodiments, the mass ratio of HAP and MBC is 3:4~1:1.In some embodiments, HAP and MBC
Mass ratio is 3:4.
In some embodiments, the temperature of grinding is 20-30 DEG C；In some embodiments, grinding temperature is 25 DEG C.
In some embodiments, milling time 10-20min；In some embodiments, milling time 15min.
Above-mentioned preparation method obtains a kind of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent.
Above-mentioned nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent Cu in absorption waste water2+、Cd2+'s
Using.
Nano black carbon is 16.45mg/g to the saturated extent of adsorption of Cu；The modified black carbon of HAP is to the saturated extent of adsorption of Cu
30.43mg/g.Nano black carbon is 5.75mg/g to the saturated extent of adsorption of Cd；Saturated extent of adsorption of the modified black carbon of HAP to Cd
For 47.60mg/g.
A kind of hydroxyapatite dry method modification nano black carbon heavy metal absorbent Cu in absorption waste water2+、Cd2+Method,
Specific steps are as follows: Xiang Hanyou Cu, Cd waste water in be added hydroxyapatite dry method modification nano black carbon, oscillation, centrifugation or it is quiet
Only to remove Cu, Cd ion in waste water.
In some embodiments, dosage of the nano black carbon heavy metal absorbent of hydroxyapatite dry method modification in waste water
For 4-6g/L.
In some embodiments, adsorption temp is 23-27 DEG C；The balanced oscillations time is 1.5-2.5h；Centrifugal rotational speed is
3800-4200r/min；Centrifugation time is 8-12min.
In some embodiments, the heavy metal ions in wastewater is one or both of Cu and Cd ion.
In some embodiments, (mol/L) in the waste water containing Cu:Cd is 0:1-1:0, Cu the and Cd ion of processing is dense
Degree≤260mg/L.
In some embodiments, the pH of the waste water is 5.5-8.0.
Grinding makes mineral lattice structure, crystal form etc. change, and can increase in system, and grinding temperature increases, and promotes particle
Dissolution, generates free radical or ion at thermal decomposition, enhances mineral surface active, and mineral and other substances is promoted to react or phase
Mutually attachment reaches the modified purpose in surface.
The solubility very little of nano black carbon and nanometer hydroxyapatite in the solution is modified in the liquid phase and is unfavorable for instead
The progress answered, two kinds of material proportions differ greatly in addition, are not easy sufficiently to combine in solution phase.In the application nano black carbon and
Nanometer hydroxyapatite can make nanometer hydroxyapatite and nano black carbon surface introduce functional group's hair by the effect of grinding
Raw reaction, is attached to each other, and improves nano black carbon to the adsorption capacity of heavy metal, therefore the disclosure uses solid-phase sequencing.
The disclosure the utility model has the advantages that
1) solid phase method does not need that solvent, reaction speed be fast, mild condition, easy to operate, highly selective, high yield, low energy
Consumption, environmental-friendly, common practicability, and can adverse effect of the elimination solvent to functional complexes, avoid liquid phase method there is
For water as solvent, the reaction time is long, low yield, the deficiency that waste liquid need to be handled；
2) mass ratio of nanometer hydroxyapatite and nano black carbon is 3:4-1:1, within this range, HAP and nano black
The combination of carbon is added to more oxygen-containing functional groups in nano black carbon surface and black carbon increases the absorption property of heavy metal.
3) nano black carbon is 16.45mg/g to the saturated extent of adsorption of Cu before nanometer hydroxyapatite dry method modification；Nanometer hydroxyl
Black carbon after base apatite dry method modification is 30.43mg/g to the saturated extent of adsorption of Cu.Before nanometer hydroxyapatite dry method modification
Nano black carbon is 5.75mg/g to the saturated extent of adsorption of Cd；Modified black carbon is to Cd before nanometer hydroxyapatite dry method modification
Saturated extent of adsorption be 47.60mg/g.The modified adsorption capacity to Cu and Cd balances, more conducively to the absorption of Cd.
4) nano black carbon is light granules, is difficult to remove from waste water by free settling when handling heavy metal-containing waste water
It goes, centrifugal rotational speed reaches 10000r/min or more, and centrifugation time reaches 20min or more, could preferably be separated by solid-liquid separation.Through nanometer hydroxyl
Base apatite is modified, and the revolving speed of centrifuge separation is 3800-4200r/min；Centrifugation time is 8-12min, can preferably be consolidated
Liquid separation.It is modified to reduce processing cost, save the processing time.Nano black carbon is light granules, is applied to heavy metal-polluted
When contaminating soil remediation, it is not easy to contaminated soil mixing, is had after pouring water in upper soll layer clustering phenomena, greatly reduces reparation effect
Rate.
5) the nano black carbon of hydroxyapatite modified is to be modified in advance with nitric acid-potassium permanganate, in acid condition surely
It is fixed.Nanometer hydroxyapatite is unstable in pH < 5.5, there is surface dissolution phenomena, when hydroxyapatite through dry grinding with change
Property nano black carbon combine, stability greatly enhances in acid condition.Therefore the present invention could in pH value of solution < 5.5,
There is higher adsorbance.Simultaneously heavy metal-containing waste water be often acid waste water, obtain in acid condition higher adsorbance and
More stable adsorbent material is particularly significant.
Detailed description of the invention
The Figure of description for constituting a part of this disclosure is used to provide further understanding of the disclosure, and the disclosure is shown
Meaning property embodiment and its explanation do not constitute the improper restriction to the disclosure for explaining the application.
Fig. 1 be 1 nano black carbon HAP of embodiment before modified after SEM and TEM characterization, A-1 nano black carbon SEM table before modified
Sign, the modified SEM characterization of B-1 nano black carbon, the TEM characterization of A-2 nano black carbon before modified, B-2 nano black carbon are modified
TEM characterization；
Fig. 2 is embodiment 1-7 difference HAP, MBC with comparison Cu2+、Cd2+The influence of removal rate；
Fig. 3 is adsorption isotherm of the modified MBC of HAP to Cu and Cd.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the disclosure.Unless another
It indicates, all technical and scientific terms used herein has logical with disclosure person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular shape
Formula be also intended to include plural form, additionally, it should be understood that, when in the present specification use term "comprising" and/or
When " comprising ", existing characteristics, step, operation, device, component and/or their combination are indicated.
Wet process nano hydroxyapatite is described in " research of the nanometer hydroxyapatite modification biological charcoal to the absorption property of copper "
Lime stone modified biomass charcoal, the maximal absorptive capacity to Cu are only 57.01mg/g.
" nanometer carbonate hydroxyapatite is to Cd2+Absorption " describe carbonate and replace the obtained nano-sized carbon in phosphoric acid location of root
Hydroxyapatite, the maximal absorptive capacity to Cu are 86.17mg/g.
Maximal absorptive capacity in above-mentioned two document is higher, the reason is that:
(1) above-mentioned two author does in adsorption isotherm experimentation, supporting electrolyte is not added, therefore send out than us
Bright material wants high to the maximal absorptive capacity of Cu and Cd.But in actual application, no matter being applied to wastewater treatment or answering
It is passivated and repairs for heavy metal-polluted soil, electrolyte ion concentration can all influence absorption of the material to heavy metal in solution.Therefore,
We have added 0.01mol/LNaNO3Supporting electrolyte.With the increase of the concentration of supporting electrolyte, suction of the material to heavy metal
Attached amount reduces.By NaNO in the experiment of Kookana3Ion concentration when increasing from 0.01mol/L to 1.5mol/L (pH 5), cadmium
Absorption then drop to 0.05mmol/kg from 0.1mmol/kg.
Describe the type of supporting electrolyte in " the adsorption-desorption progress of cadmium in soil " in detail, concentration inhales material
The influence of attached heavy metal.
(2) pH has a significant impact the adsorbance of heavy metal.Generally with the raising of pH, material is to metal cation adsorption
Amount increases.In view of the waste water containing heavy metal is mostly acid waste water, the maximal absorptive capacity that we provide is only when pH is 5.5
Maximal absorptive capacity, and " nanometer carbonate hydroxyapatite is to Cd2+Absorption " what is provided is the maximal absorptive capacity of pH=8.0.
(3) it is already indicated above in " research of the nanometer hydroxyapatite modification biological charcoal to the absorption property of copper " and works as pH=6.5-
When 8.5, Cu starts to generate hydroxide precipitating.The adjustable pH coagulant sedimentation in water process, and do not have to absorption method.
Analysis method:
The disclosure purchase the Hei Tan factory in Jinan using nano black carbon, specific nature is shown in Table 1.
The fundamental property of the black carbon of table 1.
Nano black carbon used in the disclosure is according to patent of invention (ZL201310018352.2) first with nitric acid-Gao Meng
The sour modified nano black carbon solid of potassium.
Specific method of modifying: (1) pre-oxidizing: weighing nano black carbon raw material (g), be placed in glass container, is added
3.17mol/LHNO3—0.1mol/LKMnO4(or 20%HNO3- 1.58%KMnO4) hybrid oxidant (mL), make mass body
Product ratio=1:10, is placed in ventilating kitchen, is stored at room temperature for 24 hours, the nano black carbon after being pre-oxidized；(2) it aoxidizes: will pre-oxidize
Nano black carbon is heated using thermostat water bath afterwards, and temperature control is at 90 ± 2 DEG C, oxidation reaction 3 hours, the nanometer after must aoxidizing
Black carbon；(3) it washs: by the nano black carbon after oxidation at 4000 revs/min, being centrifuged 15 minutes, outwell supernatant.Add steaming
Distilled water, control are 180 revs/min in revolving speed, reciprocating vibration 10 minutes, are centrifuged off supernatant.Distilled water is rejoined again,
Repeat to be centrifuged, until 5.5 > supernatant pH after centrifugation, the black carbon of modified Nano after must washing；(4) it dries: will
The black carbon of modified Nano after cleaning is placed on spare in drier in 105 DEG C of drying, obtains product.
Nanometer hydroxyapatite used in the disclosure is to be purchased from Shanghai Mike's woods biochemical technology Co., Ltd, quality point
Number >=97%, 502.31 (MW), < 100nm (BET).
Disclosure instrument are as follows: HY-4 adjusts the speed horizontal oscillator；MP200B electronic balance；800 type electric centrifuges；
WFX-IE2 atomic absorption spectrophotometer (AAS)；Multi function parameter analyzer.
The disclosure measures Cu using atomic absorption spectrophotometry (AAS)2+/Cd2+Concentration analyzes number using SPSS software
According to progress one-way analysis of variance, using Langmuir or Freundlich equation model parameter characterization adsorbent to Cu2+With
Cd2+Maximal absorptive capacity and absorption property.
The disclosure is further illustrated below with reference to embodiment
Embodiment 1
The preparation of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent
A certain amount of nano black carbon and HAP are weighed in proportion in mortar, are fully ground 15min.Pass through experiment of single factor
Optimal Parameters, the mass ratio that HAP:MBC is arranged is 1:10, and obtained product is to heavy metal Cu2+And Cd2+Adsorbance be
Standard judges best preparation parameter.15min is ground under room temperature after mixing, nanometer hydroxyapatite dry method is finally obtained and changes
Property before the black carbon adsorbent of modified Nano, nano black carbon be first with the modified nano black carbon solid of nitric acid potassium permanganate.
As shown in Figure 1, SEM is characterized A-1 nano black carbon HAP before modified, the modified SEM characterization of B-1 nano black carbon HAP,
The TEM characterization of A-2 nano black carbon HAP before modified, the modified TEM characterization of B-2 nano black carbon HAP.
Embodiment 2
The mass ratio of HAP and MBC is 1:5 unlike the first embodiment.
Embodiment 3
The mass ratio of HAP and MBC is 1:3 unlike the first embodiment.
Embodiment 4
The mass ratio of HAP and MBC is 1:2 unlike the first embodiment.
Embodiment 5
The mass ratio of HAP and MBC is 3:4 unlike the first embodiment.
Embodiment 6
The mass ratio of HAP and MBC is 2:3 unlike the first embodiment.
Embodiment 7
Nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent is to Cu2+And Cd2+Absorption.
Nanometer hydroxyapatite dry method modification nano black carbon 0.10g is weighed in 50ml centrifuge tube, concentration, which is added, is
The Cu of 0.5mmol/l2+And Cd2It is filtered after being centrifuged 10min under solution 20ml, 25 DEG C of constant temperature oscillations 2h, 4000r/min, atom is inhaled
Receive Cu in spectrophotometry measurement filtrate2+、Cd2+Concentration.
Embodiment 8
The Cu of 0.8mmol/l is added in first centrifuge tube as different from Example 72+And Cd2Solution 20ml, other condition phases
Together.
Embodiment 9
The Cu of 1.5mmol/l is added in first centrifuge tube as different from Example 72+And Cd2Solution 20ml, other condition phases
Together.
Embodiment 10
The Cu of 2mmol/l is added in first centrifuge tube as different from Example 72+And Cd2Solution 20ml, other condition phases
Together.
Embodiment 11
The Cu of 2.5mmol/l is added in first centrifuge tube as different from Example 72+And Cd2Solution 20ml, other condition phases
Together.
Embodiment 12
The Cu of 3mmol/l is added in first centrifuge tube as different from Example 72+And Cd2Solution 20ml, other condition phases
Together.
Embodiment 13
The Cu of 3.5mmol/l is added in first centrifuge tube as different from Example 72+And Cd2Solution 20ml, other condition phases
Together.
By the increase with HAP adding proportion available in Fig. 2, for containing 2.5mmol/LCu in solution2+、Cd2+
Removal rate significantly increase (p < 0.05), but after the proportion of nanometer hydroxyapatite and nano black carbon reaches 3:4, continue
Increase the adding proportion of HAP, removal rate is without significant changes (p > 0.05).Therefore, nanometer hydroxyapatite and nano black carbon
Optimum proportioning is 3:4.
The nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent of embodiment 7-13 is to Cu2+And Cd2+Absorption
Characteristic
0.10g adsorbent is weighed respectively in 50ml centrifuge tube, and being separately added into concentration is 0.5mmol/l, 0.8mmol/l, 1
Mmol/l, 1.5mmol/l, 2mmol/l, 2.5mmol/l, 3mmol/l, 3.5mmol/l, pH value are 5.5 to be with concentration
0.01mol/l NaNO3The Cu of solution allocation2+And Cd2Solution 20ml, 25 DEG C of constant temperature oscillation 2h.It is centrifuged under 4000r/min
It is filtered after 10min, copper concentration c (Cu in atomic absorption detecting filtrate2+) and cadmium concentration c (Cd2+).As a result as shown in Figure 3.Fig. 3
Middle Cu2+And Cd2+Adsorption curve and Langmuir and Freundlich curve coincide substantially.
Test example
HAP dry method modification nano black carbon heavy metal absorbent is to Cu2+And Cd2+Adsorption isotherm can preferably use
Langmuir equation and Freundlich equation model (table 2).Saturated extent of adsorption be respectively 478.89mmol/kg and
423.49mmol/kg.Freundlich equation you and parameter 1/n are respectively 0.18 and 0.05, respectively less than 1, show that HAP is modified
Nano black carbon is to Cu2+And Cd2+Be adsorbed as preferential absorption, and Cu is better than to the absorption property of Cd.
Table 2.HAP dry method modification nano black carbon heavy metal absorbent is to Cu adsorption isotherm fitting parameter
The modified nano black carbon heavy metal absorbent of different method of modifying is to Cu2+And Cd2+Adsorption capacity compare.
Adsorbent is tested by adsorption isotherm, more different with Langmuir equation and Freundlich equation model
Method of modifying is modified same nano black carbon, to Cu2+、Cd2+Maximal absorptive capacity and characterization of adsorption, as a result such as table 3
It is shown.
The 3. difference modified MBC of method of modifying of table is to Cu2+And Cd2+Maximal absorptive capacity
Nano black carbon is through KMnO4-HNO3Surface is modified to Cu2+Adsorbance is up to 674mmol/kg, but for Cd2+It inhales
Attached amount is less than 100mmol/kg, is there is Cu2+And Cd2+It coexists in system, to Cd2+Adsorbance it is smaller.Even if being only used for containing Cu
Wastewater treatment is difficult to be separated by solid-liquid separation also because it belongs to light granules, and difficult wide application.Hydroxyapatite (Ca10(PO4)6
(OH)2) containing a large amount of phosphate radical and hydroxyl, pH has special chemical composition and crystal structure between 7~8.5, right
30~86mg/g of maximal absorptive capacity of individual Cd, to 37~51mg/g of maximal absorptive capacity of individual Pb, Cu, Zn.Nanometer hydroxyl
Base apatite is better than other heavy metals to the absorption property of Cd, this is mainly due to the radius of Cd is similar to the radius of Ca, solution
In Cd substitution hydroxyapatite in Ca be a kind of spontaneous process.The hydroxyapatite of nanometer particle size has huge specific surface
With surface energy, micron order hydroxyapatite is much larger than to the adsorbance of heavy metal.
Therefore, one kind is researched and developed to be easy to be separated by solid-liquid separation, lower production costs, process safety avoid secondary pollution, to Cd and
It is very necessary that Cu, which has highly selective adsorbent,.
Comparative example 1
The preparation of the wet-process modified nano black carbon heavy metal absorbent of nanometer hydroxyapatite
The HAP of the 2g constant volume in 1000mL volumetric flask is weighed in proportion, is transferred in beaker, it is suspended that ultrasound obtains HAP
Liquid weighs 20gMBC and is put into HAP suspension, and beaker is put into baking oven drying after stirring, and nano black carbon is first with nitric acid height
The modified nano black carbon solid of potassium manganate.The wet-process modified nano black carbon of nanometer hydroxyapatite is obtained after drying.
The wet-process modified nano black carbon of nanometer hydroxyapatite and nanometer hydroxyapatite 0.1g are weighed respectively and 50ml is centrifuged
Guan Zhong, addition concentration are 0~3.5mmol/L, and it with concentration is 0.01mol/l NaNO that pH value, which is 5.5,3The Cu of solution allocation2+
And Cd2It is filtered after being centrifuged 10min under solution 20ml, 25 DEG C of constant temperature oscillations 2h, 4000r/min, atomic absorption spectrophotometry is surveyed
Determine Cu in filtrate2+、Cd2+Concentration.It is as shown in table 4 to compare absorption result.
The wet-process modified nano black carbon of 4 HAP of table and independent HAP maximal absorptive capacity
| Cu2+Maximal absorptive capacity (mg/g) | Cd2+Maximal absorptive capacity (mg/g) | |
| The wet-process modified nano black carbon of HAP | 30.43 | 47.60 |
| Independent HAP | 29.36 | 44.13 |
By the wet-process modified nano black carbon of the available HAP of table 4 to the adsorbance of Cu and Cd all than HAP wet process stemness nanometer
The adsorbance of black carbon is low, illustrates that the dry method modification nano black carbon of the disclosure can make nano black carbon and HAP preferably cooperate performance
The effect of absorption, because not by the process of grinding during wet-process modified, HAP cannot be sudden and violent by whole adsorption sites
Expose, the part that HAP and nano black carbon phase mutually cover is higher, cannot play the effect of mutually coordinated balance, individual HAP
Since Cu and Cd are existed simultaneously, the site that a part absorption Cd is covered after Cu absorption will make the adsorbance of Cd will not be very high, this
The HAP wet process stemness nano black carbon of open preparation can remove Cu and Cd effective balance simultaneously, in soil pollution, water pollution
The content of middle Cd is lower, in the higher situation of the content of Cu, can preferably remove the lower heavy metal Cd of content.
The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field
For art personnel, the disclosure can have various modifications and variations.It is all the disclosure spirit and principle within, it is made any
Modification, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.
Claims (10)
1. a kind of preparation method of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent, it is characterised in that: tool
Body step are as follows:
Nanometer hydroxyapatite is mixed in a certain proportion with nano black carbon, obtains a nanometer hydroxyl by solid-phase sequencing after mixing
Base apatite dry method modification nano black carbon；The nano black carbon is first with nitric acid and the modified nano black carbon of potassium permanganate.
2. preparation method according to claim 1, it is characterised in that: the nanometer hydroxyapatite mass fraction >=
97%, partial size < 100nm；Partial size≤100nm of nano black carbon.
3. preparation method according to claim 1, it is characterised in that: the mass ratio of HAP and MBC is 3:4-1:1；It is preferred that
, the mass ratio of HAP and MBC are 3:4.
4. preparation method according to claim 3, it is characterised in that: the temperature of grinding is 20-30 DEG C；Preferably, it grinds
Temperature is 25 DEG C.
5. preparation method according to claim 1, it is characterised in that: milling time 10-20min；Preferably, when grinding
Between be 15min.
6. nanometer hydroxyapatite dry method modification nano black carbon weight is prepared in the described in any item preparation methods of claim 1-5
Metal absorbent.
7. nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent as claimed in claim 6 Cu in absorption waste water2 +、Cd2+Application.
8. a kind of hydroxyapatite dry method modification nano black carbon heavy metal absorbent Cu in absorption waste water2+、Cd2+Method,
Be characterized in that: specific steps are as follows: Xiang You Cu, Cd waste water in be added hydroxyapatite dry method modification nano black carbon, oscillation, from
The heart is static to remove Cu, Cd ion in waste water.
9. according to the method described in claim 8, it is characterized by: hydroxyapatite dry method modification nano black carbon is in waste water
Dosage is 4-6g/L.
10. according to the method described in claim 8, it is characterized by: adsorption temp is 23-27 DEG C；Duration of oscillation is 1.5-
2.5h；Centrifuge RPMs are 3800-4200r/min；Centrifugation time is 8-12min.
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Cited By (1)
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| CN113578264A (en) * | 2021-08-03 | 2021-11-02 | 长安大学 | Hydroxyapatite modified biochar and preparation method and application thereof |
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