CN108031440A - A kind of composite material and its preparation and absorption, remove water body in chromium application - Google Patents
A kind of composite material and its preparation and absorption, remove water body in chromium application Download PDFInfo
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- CN108031440A CN108031440A CN201711349500.6A CN201711349500A CN108031440A CN 108031440 A CN108031440 A CN 108031440A CN 201711349500 A CN201711349500 A CN 201711349500A CN 108031440 A CN108031440 A CN 108031440A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention belongs to Materials Science and Engineering and environmental science, specifically a kind of preparation of magnetic multi-wall carbon nano-tube composite material and its in absorption, remove the application of chromium in water body.Using a step solvent-thermal method, amino functional is carried out to magnetic ferroferric oxide nano-particles through 1,6 hexamethylene diamine, functionalized multi-wall carbonnanotubes surface is then incorporated in by amino.The present invention prepares magnetic multi-wall carbon nano-tube composite material for one pot using a step solvent-thermal method, building-up process is simple, of low cost, pattern uniformly, it is magnetic it is good, when being adsorbed for Cr VI, absorption method and Magneto separate process are easy to operate, can effectively avoid secondary pollution problem, and the repeat performance of composite material is good, reuse 5 times, 80% or so is still maintained to the removal efficiency of Cr VI.
Description
Technical field
The invention belongs to Materials Science and Engineering and environmental science, a kind of specifically magnetic multi-walled carbon nanotube
Composite material preparation and its absorption, remove water body in chromium application.
Background technology
Cr VI toxicity is stronger, has the function that carcinogenic and modificator gene is mutated, can pass through alimentary canal, respiratory tract, skin
Enter with mucous membrane in human body, be accumulated in liver, kidney and incretory.Cr VI is mainly derived from plating, weaving, process hides, dyestuff
In the various industrial process such as processing, papermaking and chrome ore exploitation.Supervirulent Cr VI is once entered in environment water, it will with
The form of the stronger oxo-anions of dissolubility exists, and will eventually be entered by bioconcentration into the human body, serious shadow
Ring human health.In order to reduce risk of the mankind in strong toxicity chromium environment, before the discharge of various industrial wastewater containing chromiums, need
By water treatment procedure and by chromium content control within the limits prescribed.Environmental Protection Agency 1991 to drinking water in total chromium
Content provides, maximum acceptable concentration is limited to 0.1mg/L levels.Therefore, it is a series of efficient, quick, high there is an urgent need for developing
The technology of selectivity is used for the removal of chromium in water body.
In terms of the removal of Cr VI, electrochemical deposition, ion exchange, biological treatment, photocatalysis, film point have developed
The methods of from, solvent extraction and absorption and technology.Wherein, absorption method is with cost is low, easy to operate, toxic by-products are few and go
It is the most commonly used application strategy currently used for hexavalent chromium removal except advantages such as efficiency height.In absorption method, the choosing of adsorbent
It is the most important factor for determining adsorption effect to select.In numerous adsorbents, carbon nanotubes is as a kind of new carbon nanometer
Material, has excellent physicochemical properties, such as big specific surface area, unique space structure and higher stability, wide
The general removal for heavy metal and organic pollution, but there is the problem of water-soluble bad and separation is difficult.Magnetic Nano material,
Especially ferriferrous oxide nanometer material, has stronger superparamagnetism, by applying external magnetic field, in the short period of time
It can be separated from aqueous solution, reduce extra centrifugation, filtration step, save the time, can effectively solve to adsorb
The problem of material separation is difficult, while it also avoid secondary pollution problem caused by remaining adsorbent in the solution.However, by
Contain substantial amounts of hydroxyl in ferroso-ferric oxide surface, be oxidized easily in acid condition, cause the reduction of adsorption efficiency.At present
Common solution method is modified in ferroso-ferric oxide surface modification functional group or parcel shell structure, makes its property more steady
Determine, be not easy to be aoxidized.Such as, Burks etc. modifies ferroso-ferric oxide surface and is used it for water-soluble using 3- mercaptopropionic acids
The removal of Cr VI in liquid.Luo etc. is used in water sample in surface of graphene oxide modified magnetic cyclodextrin-Chitosan Composites
The absorption of Cr VI.Although existing various types of adsorbents are used for the removal of Cr VI in water sample, certain change is still suffered from
Into space, such as simplify the synthesis step of adsorbent, the selectivity, water solubility and the absorption that reduce material manufacturing cost, improve material
Capacity etc..
The content of the invention
It is an object of the invention to provide a kind of preparation of magnetic multi-wall carbon nano-tube composite material and its in absorption, removal
The application of chromium in water body.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of magnetism multi-wall carbon nano-tube composite material, using a step solvent-thermal method, through 1,6- hexamethylene diamines to magnetic four oxygen
Change three Fe nanometer particles and carry out amino functional, functionalized multi-wall carbonnanotubes surface is then incorporated in by amino.
Further, using a step solvent-thermal method, by 1,6- hexamethylene diamines to magnetic ferroferric oxide nano-particles table
Face carries out amination modification, and amidized magnetic ferroferric oxide nano-particles can be with multi-walled carbon nanotube passing through of surface carboxyl groups
Bond is learned to close, meanwhile, 1,6- hexamethylene diamine also can be combined directly with multi-walled carbon nanotube, pass through the hydrogen bond action between amino and water
Power increases the water solubility of material.
The functionalized multi-wall carbonnanotubes are used for the preparation of magnetic carbon-nano tube composite material, carboxylated multi-wall carbon nano-tube
The external diametrical extent of pipe is between 10~50nm, and length range is between 0.5~30 μm；Specially 3 kinds, be respectively that 1# carboxylated is more
Wall carbon nano-tube pipe outside diameter is 10~20nm, and length is 10~30 μm；2# functionalized multi-wall carbonnanotubes outside diameter is 20~30nm, long
Spend for 0.5~2 μm；3# functionalized multi-wall carbonnanotubes outside diameter is 30~50nm, and length is 10~20 μm.
A kind of preparation of magnetism multi-wall carbon nano-tube composite material, using a step solvent-thermal method, through 1,6- hexamethylene diamines to magnetic
Property ferriferrous oxide nano-particle carry out amino functional, functionalized multi-wall carbonnanotubes surface is then incorporated in by amino；
Wherein, the dosage of the magnetic ferroferric oxide nano-particles of amino functional and functionalized multi-wall carbonnanotubes for 100~
600mg：50~100mg.
Further：
1) iron chloride is dissolved in ethylene glycol, adds after anhydrous sodium acetate fully mixes, add 1,6- hexamethylene diamines, stirring
To whole dissolvings；Wherein the quality volume (g/ml) of iron chloride, anhydrous sodium acetate, 1,6- hexamethylene diamines, ethylene glycol is than being 1~2:
1.5~2:6~10:20~40；
2) functionalized multi-wall carbonnanotubes are added in above-mentioned solution, ultrasonic disperse, obtains homogeneous solution；Overall solution volume
Amount ratio with carbon nanotubes is 1:1.9~4；
3) solution is transferred in reaction kettle, reaction is heated at 198~200 DEG C by one pot of preparation method of solvent-thermal method
8~12h, obtains magnetic carbon-nano tube composite material.
Iron chloride is dissolved in ethylene glycol by the step 1), is added after anhydrous sodium acetate fully mixes, add 1,6- oneself
Diamines, stirring extremely dissolving, obtains uniform yellow solution at 50~60 DEG C, stand-by.
The step 2) is under the stirring condition of 150-250rpm by step 1) resulting solution and carboxylated multi-wall carbon nano-tube
Pipe mixes, and then the ultrasonic disperse under 40KHz frequencies, obtains uniform dark solution.
Solution is placed in polytetrafluoroethylene (PTFE) as being reacted in the stainless steel cauldron of liner by the step 3), and question response kettle is cold
But to after room temperature, liner is taken out, upper solution is discarded, obtains black magnetic carbon nano tube compound material.
The magnetic carbon-nano tube composite material cleans and removes solvent and unreacted 1,6- repeatedly through water and absolute ethyl alcohol
Hexamethylene diamine, 10~12h is dried in vacuo at 40~50 DEG C, obtains magnetic multi-wall carbon nano-tube composite material.
A kind of application of magnetism multi-wall carbon nano-tube composite material, the magnetism multi-wall carbon nano-tube composite material is to sample
In product Cr VI absorption, remove in application.
Advantage for present invention：
The present invention is separated for carbon nano-tube material difficulty from solution, magnetic ferroferric oxide nano-particles are easily aoxidized,
The problems such as composite material preparation process is complicated, magnetic multi-wall carbon nano-tube composite material is prepared for one pot using a step solvent-thermal method,
The absorption of the Cr VI larger for aqueous solution Poisoning, remove.
The addition of 1,6- hexamethylene diamines in building-up process of the present invention, on the one hand can be to magnetic ferroferric oxide nano-particles surface
Carry out amination modified, improve the oxidation resistance of material；The amino on one side magnetic ferroferric oxide surface can pass through chemistry
Key is incorporated in functionalized multi-wall carbonnanotubes surface, multi-walled carbon nanotube is had magnetic behavior；Another aspect 1,6- hexamethylene diamines
In amino also can be directly with multi-wall carbon nano-tube pipe surface carboxyl combined, pass through the Hyarogen-bonding between amino and water, increase
Add the water solubility of material.And three kinds of different multi-walled carbon nanotubes carry out processing three kinds of different magnetism of acquisition to diameter, length
A kind of composite material, there is provided synthetic method of universality.
The magnetic multi-wall carbon nano-tube composite material building-up process that the present invention prepares gained is simple, of low cost, and performance
Stablize, easily regeneration, it is reusable, and reuse 5 times after, 80% still can reach to the removal efficiency of Cr VI.To molten
The magnetic behavior of material is taken full advantage of in liquid in the absorption of Cr VI, it is not necessary to the operation such as centrifuge, filter, can be used magnet will
Material is separated from solution, is avoided as incomplete recycling secondary pollution problem caused by solution of adsorbent.Meanwhile
Absorption of the material to Cr VI also shows of a relatively high adsorption capacity and selectivity, is the removal of Cr VI in actual water body
Provide a kind of sorbing material with potential using value.
Brief description of the drawings
Fig. 1 is the preparation process schematic diagram of magnetic multi-wall carbon nano-tube composite material provided in an embodiment of the present invention.
Fig. 2 is the scanning electron microscope and transmission electricity of three kinds provided in an embodiment of the present invention magnetic multi-wall carbon nano-tube composite materials
Mirror figure.a,b:1# magnetism multi-wall carbon nano-tube composite materials；c,d:2# magnetism multi-wall carbon nano-tube composite materials；e,f:3# is magnetic
Multi-wall carbon nano-tube composite material.
Fig. 3 is used for Cr VI in aqueous solution to be provided in an embodiment of the present invention using magnetic multi-wall carbon nano-tube composite material
Absorption and the flow chart of Magneto separate
Fig. 4 is used for Cr VI in aqueous solution for 2# magnetism multi-wall carbon nano-tube composite material provided in an embodiment of the present invention and inhales
When attached, A. pH value of solution；B. adsorbent amount；C. temperature；D. influence of the adsorption time to removal efficiency.
Fig. 5 is right in the presence of other ions for three kinds provided in an embodiment of the present invention magnetic multi-wall carbon nano-tube composite materials
The block diagram that the removal efficiency of Cr VI influences.A.1# magnetic multi-wall carbon nano-tube composite material；B.2# magnetic multi-wall carbon nano-tube
Pipe composite material；C.3# magnetic multi-wall carbon nano-tube composite material.
Fig. 6 is used for Cr VI in aqueous solution for three kinds provided in an embodiment of the present invention magnetic multi-wall carbon nano-tube composite materials
The block diagram of the reuse number of removal.A.1# magnetic multi-wall carbon nano-tube composite material；B.2# magnetic multi-walled carbon nanotube
Composite material；C.3# magnetic multi-wall carbon nano-tube composite material.
Embodiment
Explanation that the present invention will be further explained with reference to the accompanying drawings and examples.
Embodiment 1
A. 2g iron chloride 40mL ethylene glycol is added in beaker to dissolve, and adds 2g anhydrous sodium acetates, 10g is added after dissolving
1,6- hexamethylene diamine, stirring extremely dissolving, obtains uniform yellow solution at 50 DEG C.Again by 100mg 1# carboxylated multi-wall carbon nano-tubes
(outside diameter is 30~50nm, and length is for pipe (outside diameter is 10~20nm, and length is 10~30 μm) or 3# functionalized multi-wall carbonnanotubes
10~20 μm) it is separately added into above-mentioned solution, the ultrasonic disperse under 40KHZ frequencies, obtains uniform dark solution.Solution is turned
100mL polytetrafluoroethylene (PTFE) is moved to as in the stainless steel cauldron of liner, 200 DEG C are reacted 12h.Reaction terminates, and question response kettle is cold
But to after room temperature, liner is taken out, upper solution is discarded, obtains black material, transfer them in beaker.The water of 50mL is used respectively
Respectively cleaned 3 times with the absolute ethyl alcohol of 50mL, Magneto separate carried out by external magnet, remove solvent and unreacted 1,6- oneself two
Amine, is dried in vacuo 12h at 50 DEG C by the magnetic multi-wall carbon nano-tube composite material cleaned up, respectively obtains 1# magnetism multi walls
Carbon nano tube compound material；3# magnetism multi-wall carbon nano-tube composite materials.
B. 1.5g iron chloride 30mL ethylene glycol is added in beaker to dissolve, and is added 2g anhydrous sodium acetates, is added after dissolving
8g 1,6- hexamethylene diamine, stirring extremely dissolving, obtains uniform yellow solution at 50 DEG C.Again by 100mg 2# carboxylated multi wall carbon
Nanotube (outside diameter is 20~30nm, and length is 0.5~2 μm) is added in above-mentioned solution, and the ultrasonic disperse under 40KHZ frequencies, obtains
To uniform dark solution.Solution is transferred to 100mL polytetrafluoroethylene (PTFE) as in the stainless steel cauldron of liner, 200 DEG C anti-
Answer 10h.Reaction terminates, and after question response kettle is cooled to room temperature, takes out liner, discards upper solution, obtain black material, by its turn
Move in beaker.Respectively cleaned 3 times with the water of 50mL and the absolute ethyl alcohol of 50mL respectively, Magneto separate is carried out by external magnet, is gone
Except solvent and unreacted 1,6- hexamethylene diamines, by the 2# magnetism multi-wall carbon nano-tube composite material cleaned up at 50 DEG C vacuum
Dry 12h, synthetic schemes are as shown in Figure 1.
Embodiment 2
Three kinds of magnetic multi-wall carbon nano-tube composite material powder for taking above-described embodiment to obtain respectively are sticked to conducting resinl respectively
On, to increase the electric conductivity of material, after carrying out metal spraying processing to material, with scanning electron microscope to the pattern of composite material into
Row characterization (referring to Fig. 2 a, c, shown in e), it is seen that the magnetic Fe of spherical morphology3O4Uniform particle is attached to carbon nano tube surface.
Three kinds of magnetic multi-wall carbon nano-tube composite material powder for taking above-described embodiment to obtain respectively are dissolved in ultra-pure water respectively
In, after ultrasonic disperse 15min, take the solution of 5~15 μ L to drip on copper mesh, transmission electron microscope test (ginseng is carried out after drying
Fig. 2 b, d are seen, shown in f), it can be seen from the figure that the dispersiveness of three kinds of composite materials is preferably, the spherical shape that particle diameter is about 50nm
The magnetic ferroferric oxide of looks is uniformly attached to carbon nano tube surface.
Embodiment 3
Weigh respectively the above-mentioned acquisition different models of 5mg magnetic multi-wall carbon nano-tube composite material (be respectively 1# or 2# or
3#) it is placed in 10mL round bottom centrifuge tubes, the hexavalent chromium solution of addition 5mL various concentrations, after ultrasonic disperse, is placed on constant temperature gas bath
On oscillator, 25 DEG C, 6h is vibrated under the conditions of 150rpm.After adsorption reaction, apply external magnetic field using magnet, by composite wood
Material separates (referring to Fig. 3) with solution, takes the content of Cr VI in solution measure solution after separating.As seen from Figure 3 in external magnetic field
Under effect, composite material can be kept completely separate with solution, avoid the material secondary pollution caused by environment of residual in the solution
Problem.
Embodiment 4
A. influence of the pH value of solution to removal efficiency.The above-mentioned acquisition 2# magnetism multi-wall carbon nano-tube composite materials of 5mg are weighed to put
In 10mL round bottom centrifuge tubes, 5mL 5mg/L hexavalent chromium solutions are added, the pH of solution is passed through into 1mol/L HCl or 1mol/L
NaOH is adjusted to pH as 1.0~9.0.Under 40KHZ frequencies after ultrasonic disperse, it is placed on constant temperature gas bath oscillator, 25 DEG C,
Vibration absorption 6h under the conditions of 150rpm (referring to shown in Fig. 4 A).As seen from the figure when pH is 2.0, removal efficiency highest.
B. influence of the adsorbent amount to removal efficiency.Weigh the 2# magnetism multi-wall carbon nano-tube composite materials of different quality
It is respectively placed in 10mL round bottom centrifuge tubes, the 5mg/L hexavalent chromium solutions that 5mL pH are 2 is added in each centrifuge tube, in 40KHZ frequency
Under rate after ultrasonic disperse, it is placed on constant temperature gas bath oscillator, 25 DEG C, vibration absorption 6h is (referring to Fig. 4 B institutes under the conditions of 150rpm
Show).When adsorbent amount is 1.0g/L as seen from the figure, removal efficiency highest.
C. influence of the temperature to adsorbance.Weigh 5mg 2# magnetism multi-wall carbon nano-tube composite materials be placed in 10mL round bottoms from
In heart pipe, the solution that pH that 5mL hexavalent chromium solution concentration is 5~50mg/L is 2.0 is separately added into, then ultrasonic disperse respectively
Afterwards, the material containing different hexavalent chromium concentrations is placed on constant temperature gas bath oscillator, then respectively at 25 DEG C, 35 DEG C and 45 DEG C
Under, 150rpm vibration absorption 24h (referring to shown in Fig. 4 C).As seen from the figure at different temperatures, adsorbance is with hexavalent chromium concentration
Increase and increase, and under same concentration, adsorbance is raised and increased with temperature.
D. influence of the time to adsorbance.Weigh 5mg 2# magnetism multi-wall carbon nano-tube composite materials be placed in 10mL round bottoms from
In heart pipe, the solution that pH that 5mL hexavalent chromium solution concentration is 5mg/L, 10mg/L and 15mg/L is 2.0 is separately added into, is then divided
After other ultrasonic disperse, the material containing different hexavalent chromium concentrations is placed on constant temperature gas bath oscillator, 25 DEG C, 150rpm vibrations
Adsorb 5~360min (referring to shown in Fig. 4 D).Three concentration show similar adsorption tendency as seen from the figure, when absorption starts,
Adsorbance increases rapidly with time lengthening, and adsorption equilibrium state is basically reached in 90min, and the numerical value of adsorbance is steady afterwards
It is fixed, and content of 6-valence Cr ions is more up to longer to the time needed for adsorption equilibrium in solution.
Embodiment 5
Three kinds of magnetic multi-wall carbon nano-tube composite materials for weighing the above-mentioned acquisitions of 5mg respectively are distributed to 5mL Cr VIs respectively
In the solution that the pH that concentration is 10mg/L is 2.0, and it is separately added into the Na that concentration is 100mg/L+、K+、Ca2+、Mg2+、Ni2+、Cu2 +、Co2+、Pb2+、Cr3+Solution, the CO that concentration is 50mg/L3 2-、PO4 3-、NO3 -、Cl-Solution, 25 DEG C, 150rpm vibration absorption 6h,
Investigate the influence (shown in Figure 5) of the cation and anion that are coexisted in solution to hexavalent chromium removal efficiency.As seen from the figure three
The magnetic multi-wall carbon nano-tube composite material composite material acquired results of kind are similar, the cation of the 10 times of concentration coexisted with Cr VI
Cr VI in solution is adsorbed substantially without influence with the anion of 5 times of concentration, illustrate magnetic multi-wall carbon nano-tube proposed by the present invention
Absorption of the pipe composite material to Cr VI in solution has certain selectivity, can to avoid the interference of other ions, be its
The application of hexavalent chromium removal provides possibility in complicated actual water body.
Embodiment 6
The magnetic multi-wall carbon nano-tube composite material of three kinds of the above-mentioned acquisitions of 0.05g is weighed respectively is dispersed in 50mL Cr VIs respectively
In the solution that the pH that concentration is 5mg/L is 2.0,25 DEG C, vibration absorption 6h under the conditions of 150rpm.After absorption, with magnet by material
Separated from solution, discard solution, and be cleaned by ultrasonic magnetic material with ultra-pure water, remove the remaining Cr VI of material surface.Again
The sodium hydroxide that 100mL concentration is 0.5mol/L is added, ultrasonic disperse, vibration 12h, will adsorb Cr VI on the composite
Desorption is got off.After Magneto separate, stripping workshop is discarded, it is neutral to be cleaned with ultra-pure water to pH, and material is placed in 50 DEG C of vacuum and is done
Dry 12h in dry case.Dried desorption and regeneration material is used to the hexavalent chromium solution that concentration is 5mg/L to adsorb, then is solved
Inhale experiment.Above-mentioned absorption-desorption process is repeated five times using same material and calculates each removal efficiency (referring to Fig. 6).By
It is equal to the removal efficiency of Cr VI after scheming visible three kinds magnetic 5 absorption-desorptions experiments of multi-wall carbon nano-tube composite materials progress
Maintain 80% or so, illustrate magnetic carbon-nano tube composite material shown in the absorption of Cr VI higher stability and
Preferable reusability.Illustrate that magnetic multi-wall carbon nano-tube composite material stability provided by the invention is high, renewable and inhale
Attached process is easy to operate, and the removal of Cr VI in actual water body can be used for as a kind of cost-effective adsorbent.
Claims (10)
- A kind of 1. composite material, it is characterised in that：Using a step solvent-thermal method, magnetic ferroferric oxide is received through 1,6- hexamethylene diamines Rice corpuscles carries out amino functional, is then incorporated in functionalized multi-wall carbonnanotubes surface by amino, obtains magnetic multi wall carbon and receive Mitron composite material.
- 2. the composite material as described in claim 1, it is characterised in that：Using a step solvent-thermal method, pass through 1,6- hexamethylene diamines pair Magnetic ferroferric oxide nano-particles surface carry out amination modification, amidized magnetic ferroferric oxide nano-particles can with it is more Wall carbon nano tube surface carboxyl groups by chemical bonds, meanwhile, 1,6- hexamethylene diamine also can be combined directly with multi-walled carbon nanotube, lead to Cross the water solubility of the Hyarogen-bonding increase material between amino and water.
- 3. the composite material as described in claim 1 or 2, it is characterised in that：The functionalized multi-wall carbonnanotubes are used for magnetism The preparation of carbon nano tube compound material, between 10~50nm, length range exists the external diametrical extent of functionalized multi-wall carbonnanotubes Between 0.5~30 μm.
- A kind of 4. preparation of the magnetic multi-wall carbon nano-tube composite material described in claim 1, it is characterised in that：It is molten using a step Magnetic ferroferric oxide nano-particles are carried out amino functional through 1,6- hexamethylene diamines, are then incorporated in by amino by the hot method of agent Functionalized multi-wall carbonnanotubes surface；Wherein, the magnetic ferroferric oxide nano-particles of amino functional and carboxylated multi wall carbon The dosage of nanotube is 100~600mg：50~100mg.
- 5. the preparation of the magnetic multi-wall carbon nano-tube composite material as described in claim 4, it is characterised in that：1) iron chloride is dissolved in ethylene glycol, adds after anhydrous sodium acetate fully mixes, add 1,6- hexamethylene diamines, stir to complete Dissolve in portion；Wherein iron chloride, anhydrous sodium acetate, 1,6- hexamethylene diamines, the mass volume ratio of ethylene glycol are 1~2:1.5~2:6~ 10:20~40；2) functionalized multi-wall carbonnanotubes are added in above-mentioned solution, ultrasonic disperse, obtains homogeneous solution；Overall solution volume and carbon The amount ratio of nanotube is 1:1.9~4；3) solution is transferred in reaction kettle, by one pot of preparation method of solvent-thermal method heated at 198~200 DEG C reaction 8~ 12h, obtains magnetic carbon-nano tube composite material.
- 6. the preparation of the magnetic multi-wall carbon nano-tube composite material as described in claim 5, it is characterised in that：The step 1) will Iron chloride is dissolved in ethylene glycol, is added after anhydrous sodium acetate fully mixes, is added 1,6- hexamethylene diamines, stirred at 50~60 DEG C To dissolving, uniform yellow solution is obtained, it is stand-by.
- 7. the preparation of the magnetic multi-wall carbon nano-tube composite material as described in claim 5, it is characterised in that：The step 2) exists Step 1) resulting solution is mixed with functionalized multi-wall carbonnanotubes under the stirring condition of 150-250rpm, then in 40KHz frequencies Ultrasonic disperse under rate, obtains uniform dark solution.
- 8. the preparation of the magnetic multi-wall carbon nano-tube composite material as described in claim 5, it is characterised in that：The step 3) will Solution is placed in polytetrafluoroethylene (PTFE) as being reacted in the stainless steel cauldron of liner, after question response kettle is cooled to room temperature, takes out liner, Upper solution is discarded, obtains black magnetic carbon nano tube compound material.
- 9. the preparation of the magnetic multi-wall carbon nano-tube composite material as described in claim 5 or 8, it is characterised in that：The magnetism Carbon nano tube compound material cleans and removes solvent and unreacted 1,6- hexamethylene diamines repeatedly through water and absolute ethyl alcohol, at 40~50 DEG C 10~12h is dried in vacuo, obtains magnetic multi-wall carbon nano-tube composite material.
- A kind of 10. application of the magnetic multi-wall carbon nano-tube composite material described in claim 1, it is characterised in that：The magnetism The absorption of multi-wall carbon nano-tube composite material Cr VI in sample, remove in application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108607514A (en) * | 2018-05-22 | 2018-10-02 | 华东理工大学 | A kind of preparation method of aminated magnetic porous microspheres |
| CN109364895A (en) * | 2018-12-14 | 2019-02-22 | 山东省计量科学研究院 | A kind of preparation method of the compound oil removing material of carboxylated ferroso-ferric oxide-poly- amidine |
| CN111392844A (en) * | 2020-02-18 | 2020-07-10 | 山东大学 | Method and system for accelerating removal of Cr (VI) in water body by using zero-valent iron sulfide based on surface functional group regulation |
| CN114229913A (en) * | 2021-12-21 | 2022-03-25 | 华南理工大学 | Nano ferroferric oxide/aminated carbon nanotube composite material based on hydrogen bonding and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110104576A1 (en) * | 2009-10-29 | 2011-05-05 | Uchicago Argonne, Llc | Lithium-oxygen electrochemical cells and batteries |
| CN102391831A (en) * | 2011-12-07 | 2012-03-28 | 复旦大学 | Carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application |
| CN103007887A (en) * | 2013-01-08 | 2013-04-03 | 长沙矿冶研究院有限责任公司 | Carbon-nanotube-loaded multi-stage nanometer ferroferric oxide adsorbent and preparation method and application thereof |
| CN103041773A (en) * | 2012-12-04 | 2013-04-17 | 天津大学 | Magnetic carbon nanotube composite material and preparation method and application thereof |
| CN103213967A (en) * | 2013-04-19 | 2013-07-24 | 郑州大学 | Magnetic water-soluble carbon nano tube as well as preparation method and application thereof |
| US20140294715A1 (en) * | 2013-03-27 | 2014-10-02 | Aisin Seiki Kabushiki Kaisha | Method of manufacturing ferrous oxide nanoparticle, method of forming carbon nanotube, and ferrous oxide nanoparticle |
| CN106031862A (en) * | 2015-03-20 | 2016-10-19 | 北京大学 | Magnetic carbon nanotube composite material and preparation method and application thereof and method for removing pollutants in water |
-
2017
- 2017-12-15 CN CN201711349500.6A patent/CN108031440A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110104576A1 (en) * | 2009-10-29 | 2011-05-05 | Uchicago Argonne, Llc | Lithium-oxygen electrochemical cells and batteries |
| CN102391831A (en) * | 2011-12-07 | 2012-03-28 | 复旦大学 | Carbon nanotube composite material modified by magnetic nanoparticles, its preparation method and application |
| CN103041773A (en) * | 2012-12-04 | 2013-04-17 | 天津大学 | Magnetic carbon nanotube composite material and preparation method and application thereof |
| CN103007887A (en) * | 2013-01-08 | 2013-04-03 | 长沙矿冶研究院有限责任公司 | Carbon-nanotube-loaded multi-stage nanometer ferroferric oxide adsorbent and preparation method and application thereof |
| US20140294715A1 (en) * | 2013-03-27 | 2014-10-02 | Aisin Seiki Kabushiki Kaisha | Method of manufacturing ferrous oxide nanoparticle, method of forming carbon nanotube, and ferrous oxide nanoparticle |
| CN103213967A (en) * | 2013-04-19 | 2013-07-24 | 郑州大学 | Magnetic water-soluble carbon nano tube as well as preparation method and application thereof |
| CN106031862A (en) * | 2015-03-20 | 2016-10-19 | 北京大学 | Magnetic carbon nanotube composite material and preparation method and application thereof and method for removing pollutants in water |
Non-Patent Citations (1)
| Title |
|---|
| WENHUI LU等: ""One-pot synthesis of magnetic iron oxide nanoparticle-multiwalled carbon nanotube composites for enhanced removal of Cr(VI) from aqueous solution"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607514A (en) * | 2018-05-22 | 2018-10-02 | 华东理工大学 | A kind of preparation method of aminated magnetic porous microspheres |
| CN109364895A (en) * | 2018-12-14 | 2019-02-22 | 山东省计量科学研究院 | A kind of preparation method of the compound oil removing material of carboxylated ferroso-ferric oxide-poly- amidine |
| CN111392844A (en) * | 2020-02-18 | 2020-07-10 | 山东大学 | Method and system for accelerating removal of Cr (VI) in water body by using zero-valent iron sulfide based on surface functional group regulation |
| CN111392844B (en) * | 2020-02-18 | 2021-07-02 | 山东大学 | Method and system for accelerating removal of Cr (VI) in water body by using zero-valent iron sulfide based on surface functional group regulation |
| CN114229913A (en) * | 2021-12-21 | 2022-03-25 | 华南理工大学 | Nano ferroferric oxide/aminated carbon nanotube composite material based on hydrogen bonding and preparation method thereof |
| CN114229913B (en) * | 2021-12-21 | 2022-09-20 | 华南理工大学 | Nano ferroferric oxide/aminated carbon nanotube composite material based on hydrogen bonding and preparation method thereof |
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