CN105797682A - Functional magnetic carbon nanotube composite material, preparation method thereof and application of functional magnetic carbon nanotube composite material to water treatment - Google Patents
Functional magnetic carbon nanotube composite material, preparation method thereof and application of functional magnetic carbon nanotube composite material to water treatment Download PDFInfo
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Abstract
The invention provides functional magnetic carbon nanotube composite material, a preparation method thereof and application of the functional magnetic carbon nanotube composite material to water treatment. The composite material comprises a carbon nanotube modified by magnetic iron oxide and polyaluminum chloride composited to the carbon nanotube. The functional magnetic carbon nanotube composite material has the advantages that the composite material integrates the good coagulation performance of the polyaluminum chloride and the unique nano effect of the carbon nanotube, and the humic acid and turbidity in water can be synchronously efficiently removed; meanwhile, under the effect of an external magnetic field, the functional magnetic carbon nanotube can be fast separated from the liquid medium and is recyclable and low in cost; experiment results show that when the composite material is used to treat the water, the removing rate of the humic acid can reach 99%, the removing rate of the turbidity can reach 94%, a remarkable removing effect is achieved, and the composite material is safe, economical and environmentally friendly; the magnetic separation process creates conditions for subsequent recycling, low cost is achieved, sludge amount after treatment is not increased, and the composite material is promising in application prospect in the field of treatment of slightly-polluted water sources.
Description
Technical field
The present invention relates to functional nanomaterials technical field, particularly relate to the magnetic carbon-nano tube composite material of a kind of functionalization, its preparation method and the application in water processes thereof.
Background technology
Humic acid (or humic acids) is that a class is widely present in nature, as soil, river, lake natural polymer Organic substance, the basic structure of its macromole is aromatic ring and alicyclic ring, and ring is connected with the functional groups such as carboxyl, hydroxyl, carbonyl, quinonyl, methoxyl group.Humic acid can produce unpleasant color and abnormal smells from the patient in water body, and particularly in chlorination process, itself and chlorine react generation disinfection byproduct (DBP), have carcinogenic or mutagenic action, and health produces harm greatly.But the conventional treatment of drinking water is very difficult to remove humic acids, therefore its removal is always up emphasis and the difficult point that drink water purifying processes.
At present, the method removing humic acid in drink water purifying mainly includes strengthening conventional treatment process, Biological Pretreatment, membrane technology, high-level oxidation technology and absorption method etc..Wherein, conventional coagulation technology only has 20～30% for organic clearance, and due to the existence of dissolved organic matter, is unfavorable for destroying the stability of colloid and making conventional water treatment process that the removal effect of raw water turbidity to be declined, and clearance is only 50～60%.Organic removal effect is increased by enhanced coagulation technique, but there are some problems, as increased the dosage of coagulant, makes the sludge quantity that water treatment system produces increase；The removal ability of dissolved organic matter is improved limited etc..
And absorption method is a kind of efficient, easy, energy-conservation water technology, adsorbable species range is very wide, and on water processes, adaptability is big, so it is conventional method.In absorption method water technology, conventional adsorbent is activated carbon, but it is not ideal to the removal effect of humic acid.CNT is novel adsorbent, has huge specific surface area, high adsorption capacity.But, the price of CNT is generally higher, and nano material is separated from water difficulty, it is impossible to recycling, these all limit CNT widely using in water treatment field.
Summary of the invention
In view of this, the application provides the magnetic carbon-nano tube composite material of a kind of functionalization, its preparation method and the application in water processes thereof, the magnetic carbon nano-tube material of functionalization provided by the invention can realize the synchronous high-efficiency of humic acid and turbidity in water and remove, and be easy to recycle, save cost.
The present invention provides the magnetic carbon-nano tube composite material of a kind of functionalization, including:
The CNT that magnetic iron oxide is modified；
With the aluminium polychlorid being compound on described CNT.
Preferably, in the magnetic carbon-nano tube composite material of described functionalization, C element content is 50～70wt%, Al constituent content be 2～5wt%, Fe constituent content is 5～20wt%.
Preferably, described magnetic iron oxide includes Fe3O4With γ-Fe2O3。
Preferably, there is meso-hole structure in the magnetic carbon-nano tube composite material of described functionalization.
The preparation method that the present invention provides the magnetic carbon-nano tube composite material of a kind of functionalization, comprises the following steps:
A) carbon nano-tube material that magnetic iron oxide is modified is provided；
B) utilize carbon nano-tube material and aluminium polychlorid compound that described magnetic iron oxide modified by microwave, obtain the magnetic carbon-nano tube composite material of functionalization.
Preferably, described step A) particularly as follows:
In the basic conditions, by CNT, divalent iron salt and trivalent iron salt hybrid reaction in water, aged, obtain the carbon nano-tube material that magnetic iron oxide is modified.
Preferably, described step B) in utilize microwave compound particularly as follows:
Carbon nano-tube material that described magnetic iron oxide modifies and the mixed liquor of aluminium polychlorid will be included when power is 600W, microwave 2～10min, obtain the magnetic carbon-nano tube composite material of functionalization.
The present invention provides a kind of method removing humic acid and turbidity from water, comprises the following steps:
Pending water conservancy chemical reagent is carried out coagulation, the water outlet after being processed；
Described chemical reagent is the magnetic carbon-nano tube composite material of function described above.
Preferably, in described pending water, humic acid concentration is 10～30mg/L, and turbidity is 40～80NTU.
Preferably, described coagulation carries out when room temperature and pH value are 4～7.5.
Preferably, the process of described coagulation divides three phases: the mixing speed of first stage is 200～300r/min, and the time is 10～20s；The mixing speed of second stage is 120～200r/min, and the time is 4～10min；The mixing speed of phase III is 40～60r/min, and the time is 15～20min.
Preferably, described chemical reagent adds at twice when coagulation: first time toss area is before first stage stirring starts, and second time toss area is in the last 30s of second stage stirring；
The single dosage of described chemical reagent and the ratio of pending water are (0.2～0.6) g:1000mL.
Compared with prior art, composite provided by the invention utilizes CNT for support skeleton, it is modified with magnetic iron oxide, then is compound on the magnetic carbon nano-tube formed by aluminium polychlorid.Products obtained therefrom of the present invention combines the good coagulation performance of aluminium polychlorid and the nano effect of CNT uniqueness, can synchronize, efficiently remove humic acid and turbidity in water.Further, under the effect of externally-applied magnetic field, can making functional magnetic CNT of the present invention and liquid media sharp separation recyclable regeneration, cost is low, thus solving the problem that nano material reclaims difficulty.Test result indicate that, adopting composite provided by the invention to process water, humic acid clearance is up to 99%, and turbidity removal rate is up to 94%, and removal effect is considerable, has the feature of safety, economy, environmental protection；Magneto separate process is that subsequent recovery regeneration creates condition simultaneously, saves cost, does not increase the sludge quantity after process, have wide practical use in Micro-polluted Water field.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified；
Fig. 2 is the EDS figure of the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified；
Fig. 3 is the SEM figure of the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified；
Fig. 4 is the adsorption-desorption curve chart of the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified；
Fig. 5 is the graph of pore diameter distribution of the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
The invention provides the magnetic carbon-nano tube composite material of a kind of functionalization, including:
The CNT that magnetic iron oxide is modified；
With the aluminium polychlorid being compound on described CNT.
The magnetic carbon-nano tube composite material of functionalization provided by the invention can realize synchronous high-efficiency and remove the purpose of humic acid and turbidity in water, moreover it is possible to solves the problem that nano material reclaims difficulty, cost is high, has wide practical use in Micro-polluted Water field.
Composite provided by the invention includes magnetic carbon nano-tube, its CNT modified for magnetic iron oxide.The embodiment of the present invention utilizes CNT (CNTs) this porous media material to be support skeleton, modifies with magnetic iron oxide.Wherein, the embodiment of the present invention can adopt multi-walled carbon nano-tubes (MWCNTs)；Described magnetic iron oxide preferably includes Fe3O4With γ-Fe2O3.In embodiments of the present invention, in the magnetic carbon-nano tube composite material of described functionalization, C element content is preferably 50～70wt%, more preferably 55～65wt%；Fe constituent content is preferably 5～20wt%, more preferably 8～15wt%.
The source of the CNT that described magnetic iron oxide is modified is not particularly limited by the present invention, preferably prepare in accordance with the following methods: CNT with containing iron salt in the way of chemical coprecipitation, at carbon nano tube surface coated magnetic iron oxides, obtain magnetic carbon nano-tube.Concrete, the embodiment of the present invention can in the basic conditions, by CNT, divalent iron salt and trivalent iron salt hybrid reaction in water, aged, obtain the CNT that magnetic iron oxide is modified.
In an embodiment of the present invention, carbon nano tube suspension is provided respectively, includes divalent iron salt and the mixed liquor of trivalent iron salt, alkali liquor, then hybrid reaction.Concrete, the embodiment of the present invention weighs carbon nano-tube material, is suspended in water, and ultrasonic disperse obtains carbon nano tube suspension.Wherein, described carbon nano-tube material adopts commercially available prod.As preferably, the external diameter < 8nm of described carbon nano-tube material, length is 10～30 μm；Purity > 95%.Present invention preferably employs distilled water；The ratio of carbon nano-tube material and water can be (0.2～0.5) g:(70～175) mL, it is preferred to (0.2～0.5) g:(70～125) mL.In some embodiments of the invention, the supersonic frequency of described ultrasonic disperse can be 45KHz, and power can be 0.4W/cm2.The present invention preferably under the ultrasound condition that temperature is 10～50 DEG C, more preferably 20～40 DEG C, ultrasonic disperse 15min, obtain carbon nano tube suspension.Before hybrid reaction, when the embodiment of the present invention is preferably by magnetic agitation that described carbon nano tube suspension low whipping speed is 400～500r/min, heating in water bath is to 60 DEG C.
In an embodiment of the present invention, ferrous iron and ferric mol ratio can be 1:1.75.Described divalent iron salt is preferably Ferrous ammonium sulfate；Described trivalent iron salt is preferably ammonium ferric sulfate.In a preferred embodiment of the invention, by CNT and the theoretical Fe generated3O4Mass ratio be 5:2；Weigh divalent iron salt and trivalent iron salt respectively.The trivalent iron salt weighing gained is first dissolved in a certain amount of water by the embodiment of the present invention, and heats；Then the divalent iron salt weighing gained is dissolved in wherein, obtains including the mixed liquor of divalent iron salt and trivalent iron salt.In the process, it is preferred to use distilled water dissolves；The consumption of water can be 30～75mL.Described heating adopts water bath with thermostatic control to carry out；Temperature is generally 55～65 DEG C, it is preferred to 60 DEG C.
The embodiment of the present invention can adopt natrium carbonicum calcinatum and sodium hydroxide, it is provided that alkali condition.In some embodiments of the invention, anhydrous Na2CO3Can be 5:3 with the mol ratio of NaOH；The embodiment of the present invention can prepare the solution of above-mentioned mixed base by a certain percentage.The mixed liquor of above-mentioned iron salt is preferably first added in carbon nano tube suspension by the embodiment of the present invention, then is added wherein by the solution of mixed base, hybrid reaction, aged, obtains magnetized CNT.Wherein, the temperature of described hybrid reaction is preferably 55～65 DEG C, more preferably 60 DEG C；The pH value of described hybrid reaction is preferably 11～12.
In some embodiments of the invention, keeping under 60 DEG C of constant temperature stirring conditions, by the slow titration carbon nano-tube solution system of mixed ammonium/alkali solutions of heating, controlling titration end-point solution ph is 11～12, and titration is isothermal reaction at such a temperature after completing.Carry out when described hybrid reaction is preferably in stirring, can constant temperature stirring reaction 30～60min.After stopping stirring, the embodiment of the present invention preferably constant temperature ageing 30～60min again.After ageing terminates, embodiment of the present invention washing reaction product to neutral, can at 80 DEG C vacuum drying 16～24h, grind, obtain magnetic carbon nano-tube, the CNT that namely magnetic iron oxide is modified.
On the CNT that described magnetic iron oxide is modified, composite provided by the invention includes being compound in aluminium polychlorid thereon.In embodiments of the present invention, except being loaded with magnetic iron oxide on CNT, also it is loaded with aluminium polychlorid particulate matter in its surface, is surface-functionalized magnetic carbon nano-tube.In the magnetic carbon-nano tube composite material of described functionalization, Al constituent content is preferably 2～5wt%, more preferably 3～4.5%.The composite contained substance that the embodiment of the present invention provides has multi-walled carbon nano-tubes, Fe3O4、γ-Fe2O3And aluminium polychlorid；C element content is 50～70wt%, Al constituent content be 2～5wt%, Fe constituent content is 5～20wt%.Concrete, C, Al, Cl, Fe, O constituent content can be 62.18%, 4.12%, 1.18%, 8.35%, 24.17% respectively.
In an embodiment of the present invention, the magnetic carbon-nano tube composite material of described functionalization includes meso-hole structure.In general, mesoporous pore size is 2～50nm, and macropore diameter is more than 50nm, and micropore size is less than 2nm.In some embodiments of the invention, the most probable pore size of described composite is 23.77.Described composite is mesoporous with macropore and the porous material deposited, and occupies the majority with mesoporous.
Correspondingly, the preparation method that present invention also offers the magnetic carbon-nano tube composite material of a kind of functionalization, comprise the following steps:
A) carbon nano-tube material that magnetic iron oxide is modified is provided；
B) utilize carbon nano-tube material and aluminium polychlorid compound that described magnetic iron oxide modified by microwave, obtain the magnetic carbon-nano tube composite material of functionalization.
The embodiment of the present invention utilizes aluminium polychlorid that magnetic carbon nano-tube is carried out finishing, obtain aluminium polychlorid and modify the carbon nano tube compound material of carried magnetic iron oxides, it can remove humic acid and turbidity in micro-polluted source water by synchronous high-efficiency, also can separate with liquid under additional the action of a magnetic field, and recovery and reusing and recycling, there is the feature of safety, economy, environmental protection.
First the embodiment of the present invention provides the carbon nano-tube material that magnetic iron oxide is modified, it is preferable that method as described above prepares, and does not repeat them here.
After obtaining magnetic carbon nano-tube material, the embodiment of the present invention makes aluminium polychlorid be deposited on this carbon nano-tube material surface by microwave method again, obtains aluminium polychlorid modified magnetic carbon nano tube compound material.Concrete, the present invention preferably will include the mixed liquor of described carbon nano-tube material and aluminium polychlorid when power is 600W, and microwave 2～10min obtains the magnetic carbon-nano tube composite material of functionalization.
The embodiment of the present invention weighs a certain amount of magnetic carbon nano-tube material and aluminium polychlorid respectively, can be suspended in polyaluminium aluminum water solution by magnetic carbon nano-tube, be made into mixed liquor.Wherein, described magnetic carbon nano-tube material is preferably (0.1～0.2) with the mass ratio of aluminium polychlorid: 0.2.In described mixed liquor, the concentration of aluminium polychlorid can be 8g/L.
Before microwave, described mixed liquor is preferably carried out ultrasonic disperse by the present invention.In some embodiments of the invention, the supersonic frequency of described ultrasonic disperse can be 45KHz, and power can be 0.4W/cm2.Described ultrasonic disperse carries out when being 10～50 DEG C, more preferably 20～40 DEG C preferably in temperature；The time of described ultrasonic disperse is preferably 12～20min, more preferably 15～18min.
Mixed liquor after ultrasonic can be put in microwave oven by the embodiment of the present invention, the microwave when power is 600W.The time of described microwave is preferably 2～10min, more preferably 4～7min.Mixture after microwave is cooled to room temperature by the embodiment of the present invention, is washed with distilled water to supernatant clarification, vacuum drying, finally grinds, obtain aluminium polychlorid modified magnetic carbon nano tube compound material.Wherein, described vacuum drying temperature is preferably 70～85 DEG C；The described vacuum drying time is preferably 8～16 hours, more preferably 10～14 hours.Described it is ground to technological means well known to those skilled in the art；Then cross 200 mesh sieves, obtain composite.
After obtaining composite, it is carried out physical and chemical performance detection by the present invention.This material is carried out X-ray diffraction analysis (XRD), X-ray energy spectrum analysis (EDS), scanning electron microscope analysis (SEM) by the present invention respectively, it is shown that magnetic iron oxide and aluminium polychlorid are carried on CNT；Prepare the aluminium polychlorid modified magnetic carbon nanotube dust of gained in tubular construction, its surface is loaded with above-mentioned particulate matter.This material is carried out absorption property test and pore analysis by the present invention, it is shown that described composite comprises mesoporous, its isothermal line belongs to the IV type adsorption isotherm in IUPAC classification.
It follows that the embodiment of the present invention utilizes CNT for support skeleton, it is modified with magnetic iron oxide, then aluminium polychlorid is deposited on the magnetic carbon nano-tube surface formed, prepare composite.Products obtained therefrom of the present invention combines the good coagulation performance of aluminium polychlorid and the nano effect of CNT uniqueness, can synchronize, efficiently remove humic acid and turbidity in water.Further, functional magnetic CNT of the present invention with liquid media sharp separation, can be beneficial to recovery and reusing and recycling under the effect of externally-applied magnetic field, and cost is low, thus solving the problem that nano material reclaims difficulty.
Present invention also offers a kind of method removing humic acid and turbidity from water, comprise the following steps:
Pending water conservancy chemical reagent is carried out coagulation, the water outlet after being processed；
Described chemical reagent is the magnetic carbon-nano tube composite material of function described above.
The present invention utilizes surface-functionalized magnetic carbon nano-tube to synchronize to remove humic acid and turbidity in water, and removal effect is better, also will not increase the sludge quantity after process, have wide practical use in Micro-polluted Water field.
In the present invention, described pending water is containing finite concentration humic acid and turbidity.Wherein, owing to water containing the microgranule of suspension and colloidal state so that originally water white water produces turbid phenomenon, and the degree of its muddiness is called turbidity, is called for short turbidity.Turbidity unit is the kaolin suspended substance of JTU, 1JTU=1mg/L；The turbidity that modern instrument shows is nephelometric turbidity unit NTU, also referred to as TU.In some embodiments of the invention, in described pending water, humic acid concentration is preferably 10～30mg/L, more preferably 15～25mg/L；Turbidity is preferably 40～80NTU, more preferably 50～70NTU.The embodiment of the present invention carries out coagulation Beaker Test, and the volume of pending water can be 50mL.
The present invention utilizes the magnetic carbon-nano tube composite material of function described above, and pending water is carried out coagulating treatment, the water outlet after being processed.In a preferred embodiment of the invention, being added in pending water at twice by above-mentioned modified carbon nano-tube material, a point three phases is stirred coagulation, to synchronize to remove humic acid and turbidity in water.
Concrete, the process of described coagulation is preferably divided into three phases, is namely followed successively by first stage, second stage and phase III.Wherein, the mixing speed of first stage is preferably 200～300r/min；Time is preferably 10～20s.The mixing speed of second stage is preferably 120～200r/min, more preferably 150～180r/min；Time is preferably 4～10min, more preferably 5～8min.The mixing speed of phase III is preferably 40～60r/min；Time is preferably 15～20min.
When coagulation, described this chemical reagent of modified magnetic CNT is preferably divided into twice and adds.The single dosage of described chemical reagent is preferably (0.2～0.6) g:1000mL with the ratio of pending water, more preferably (0.3～0.5) g:1000mL.In a preferred embodiment of the invention, the first time toss area of described chemical reagent is before first stage stirring starts；Second time toss area is in the last 30s of second stage stirring.
In the present invention, when described aluminium polychlorid modified magnetic carbon nano tube compound material is 4～7.5 preferably in pH value, synchronize to remove humic acid and turbidity in water by coagulating treatment.It is to say, described coagulation carries out when being 4～7.5, more preferably 6～7.3 preferably in pH value.In some embodiments of the invention, the hydrochloric acid solution of 0.1mol/L and the sodium hydroxide solution of 0.1mol/L can be adopted to regulate pH value.Described coagulation generally at room temperature carries out, if temperature is at 20～30 DEG C.
In a preferred embodiment of the invention, pending water, when room temperature and pH value are 4～7.5, is carried out coagulating treatment, the water outlet after being processed by described aluminium polychlorid modified magnetic carbon nano tube compound material.Test result indicate that, adopting composite provided by the invention to process water, humic acid clearance is up to 99%, and turbidity removal rate is up to 94%, and removal effect is considerable, has the feature of safety, economy, environmental protection；Magneto separate process is that subsequent recovery regeneration creates condition simultaneously, saves cost, does not increase the sludge quantity after process, have wide practical use in Micro-polluted Water field.
In order to be further appreciated by the application, below in conjunction with embodiment, the magnetic carbon-nano tube composite material of the functionalization that the application provides, its preparation method and the application in water processes thereof are specifically described.
In following example, carbon nano-tube material used is provided by Chengdu Organic Chemistry Inst., Chinese Academy of Sciences, its external diameter < 8nm, long 10～30 μm, purity > 95%；Aluminium polychlorid (analytical pure) is purchased from the prosperous prosperous Chemical Co., Ltd. in Tianjin.
Embodiment 1
(1) magnetic iron oxide is modified
1. weigh carbon nano-tube material 0.2000g, be suspended in 70mL distilled water, and be 45KHz, power by this suspension in supersonic frequency be 0.4W/cm2, temperature is under the ultrasound condition of 20 DEG C, ultrasonic disperse 15min；By CNT and the theoretical Fe generated3O4Mass ratio is 5:2, ferrous iron and ferric iron mol ratio (M2+/M3+) for 1:1.75, weigh Ferrous ammonium sulfate and ammonium ferric sulfate respectively.Weighing gained ammonium ferric sulfate is dissolved in 30mL distilled water, and this solution is placed in 60 DEG C of water bath with thermostatic control heating；
2. by anhydrous Na2CO3It is 5:3 with NaOH mol ratio, prepares mixed ammonium/alkali solutions, be placed in 60 DEG C of water bath with thermostatic control heating；
3., when by the magnetic agitation that carbon nano tube suspension low whipping speed is 400r/min after ultrasonic, heating in water bath is to 60 DEG C；
4. weighing gained Ferrous ammonium sulfate is dissolved in heating to the ammonium ferric sulfate solution of 60 DEG C, and the mixed liquor of this iron salt is joined in the carbon nano tube suspension after heating in 3.；
5. keeping under 60 DEG C of constant temperature stirring conditions, 4. include the carbon nano-tube solution of iron salt with the slow titration of mixed ammonium/alkali solutions of 2. middle heating to 60 DEG C, controlling titration end-point solution ph is 11～12.The complete stirring reaction 30min of constant temperature at such a temperature of titration, constant temperature ageing 30min after stopping stirring, washing, to neutrality, vacuum drying 24h at 80 DEG C, grinding, obtains magnetic carbon nano-tube material, standby.
(2) aluminium polychlorid load
1. adopting gained magnetic carbon nano-tube material in (1) of 0.15g, be suspended in the polymeric aluminum chlorides solution that 25mL concentration is 8g/L, being subsequently placed in supersonic frequency be 45KHz, power is 0.4W/cm2, temperature is under the ultrasound condition of 20 DEG C, ultrasonic disperse 15min；
2. the mixed liquor after ultrasonic in 1. is put in microwave oven, the microwave 6min when power is 600W；
3. the mixture after microwave in 2. is taken out, is cooled to room temperature, be washed with distilled water to supernatant clarification, 70 DEG C of vacuum dryings 8 hours, grind, cross 200 mesh sieves, obtain aluminium polychlorid carried magnetic carbon nano tube compound material.
After obtaining composite, this material is carried out X-ray diffraction analysis (XRD) by the present invention, and result is referring to the XRD figure that Fig. 1, Fig. 1 are the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified.It can be seen from figure 1 that except the characteristic diffraction peak of CNT, also have Fe3O4、γ-Fe2O3Diffraction maximum with aluminium polychlorid, it was shown that magnetic iron oxide and aluminium polychlorid are successfully carried on CNT.This material is carried out X-ray energy spectrum analysis (EDS) by the present invention, and result is referring to the EDS figure that Fig. 2, Fig. 2 are the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified.As it is clear from fig. 2 that this material is except CNT contains C element, also have Fe, Al, Cl, O element, further demonstrate that on CNT magnetic iron oxide and aluminium polychlorid in success load.
This material is scanned electronic microscope photos (SEM) by the present invention, and result is referring to the SEM figure that Fig. 3, Fig. 3 are the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified.It can be seen from figure 3 that prepare the aluminium polychlorid modified magnetic carbon nanotube dust of gained still in tubular construction, and its surface is loaded with particulate matter；Scheme it can be seen that carbon nano tube surface load is magnetic iron oxide and polyaluminium alumina particles in conjunction with XRD figure and EDS.
Utilizing specific surface area/pore-size distribution and pore analysis instrument, this material is carried out absorption property test by the present invention, and result is referring to the adsorption-desorption curve chart that Fig. 4, Fig. 4 are the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified.As seen from Figure 4, there is less hysteresis loop in this adsorption-desorption curve, this causes due to mesoporous middle generation capillary condensation effect, illustrates that this material comprises mesoporous.This isothermal line belongs to the IV type adsorption isotherm in IUPAC classification, and adsorption curve is almost parallel with desorption curve and in crescent, for H4 hysteresis loop.
Utilizing specific surface area/pore-size distribution and pore analysis instrument, this material is carried out pore analysis by the present invention, and result is referring to the graph of pore diameter distribution that Fig. 5, Fig. 5 are the magnetic carbon nano-tube that embodiment 1 gained aluminium polychlorid is modified.The pore-size distribution situation of this material as can be seen from Figure 5, most probable pore size is 23.77, it was shown that this material is mesoporous with macropore and the porous material deposited, and occupies the majority with mesoporous.
Embodiment 2
(1) magnetic iron oxide is modified
1. weigh carbon nano-tube material 0.5000g, be suspended in 175mL distilled water, and be 45KHz, power by this suspension in supersonic frequency be 0.4W/cm2, temperature is under the ultrasound condition of 30 DEG C, ultrasonic disperse 15min；By CNT and the theoretical Fe generated3O4Mass ratio is 5:2, ferrous iron and ferric iron mol ratio (M2+/M3+) for 1:1.75, weigh Ferrous ammonium sulfate and ammonium ferric sulfate respectively.Weighing gained ammonium ferric sulfate is dissolved in 75mL distilled water, and this solution is placed in 60 DEG C of water bath with thermostatic control heating；
2. by anhydrous Na2CO3It is 5:3 with NaOH mol ratio, prepares mixed ammonium/alkali solutions, be placed in 60 DEG C of water bath with thermostatic control heating；
3., when by the magnetic agitation that carbon nano tube suspension low whipping speed is 500r/min after ultrasonic, heating in water bath is to 60 DEG C；
4. weighing gained Ferrous ammonium sulfate is dissolved in heating to the ammonium ferric sulfate solution of 60 DEG C, and the mixed liquor of this iron salt is joined in the carbon nano tube suspension after heating in 3.；
5. keeping under 60 DEG C of constant temperature stirring conditions, 4. include the carbon nano-tube solution of iron salt with the slow titration of mixed ammonium/alkali solutions of 2. middle heating to 60 DEG C, controlling titration end-point solution ph is 11～12.The complete stirring reaction 30min of constant temperature at such a temperature of titration, constant temperature ageing 30min after stopping stirring, washing, to neutrality, vacuum drying 24h at 80 DEG C, grinding, obtains magnetic carbon nano-tube material, standby.
(2) aluminium polychlorid load
1. adopting gained magnetic carbon nano-tube material in (1) of 0.15g, be suspended in the polymeric aluminum chlorides solution that 25mL concentration is 8g/L, being subsequently placed in supersonic frequency be 45KHz, power is 0.4W/cm2, temperature is under the ultrasound condition of 25 DEG C, carries out ultrasonic disperse 15min；
2. the mixed liquor after ultrasonic in 1. is put in microwave oven, the microwave 4min when power is 600W；
3. the mixture after microwave in 2. is taken out, be cooled to room temperature, be washed with distilled water to supernatant clarification, 80 DEG C of vacuum dryings 10 hours, grind, cross 200 mesh sieves, obtain aluminium polychlorid carried magnetic carbon nano tube compound material.
After obtaining composite, it is carried out physical and chemical performance detection by the present invention.It is shown that magnetic iron oxide and aluminium polychlorid are carried on CNT；Prepare the aluminium polychlorid modified magnetic carbon nanotube dust of gained in tubular construction, its surface is loaded with above-mentioned particulate matter.Described composite comprises mesoporous, and its isothermal line belongs to the IV type adsorption isotherm in IUPAC classification.
Embodiment 3
Adopting the aluminium polychlorid carried magnetic carbon nano tube compound material of embodiment 1 preparation, coagulation synchronizes to remove humic acid and turbidity in water.In beaker experiments, the humic acid initial concentration of pending water is 20mg/L, and turbidity is 72.2NTU, and solution ph is 7.30, and the volume of pending water is 50mL.
Coagulation process: the first stage, mixing speed was 300r/min in order quickly to mix 10s；Second stage is for quickly to stir 5min, and mixing speed is 200r/min；Phase III is low rate mixing 20min, and mixing speed is 60r/min.Described aluminium polychlorid carried magnetic carbon nano tube compound material adds at twice, and single dosage is 0.0250g, and first time toss area is before first stage stirring starts, and second time toss area is the last 30s of second stage stirring.
With ultraviolet spectrophotometer measure under UV254 water sample process before and after humic acid absorbance, obtain the clearance of humic acid；Utilize transmissometer to measure water sample and process the turbidity of front and back, draw turbidity removal rate.Result shows, humic acid clearance is 96.50%, and turbidity removal rate is 97.17%.
Embodiment 4
With the condition in above-described embodiment 3, embodiment 2 gained aluminium polychlorid carried magnetic carbon nano tube compound material is adopted to carry out coagulating treatment.Result shows, humic acid clearance is 94.13%, and turbidity removal rate is 97.49%.
Embodiment 5
Adopting the aluminium polychlorid carried magnetic carbon nano tube compound material of embodiment 1 preparation, coagulation synchronizes to remove humic acid and turbidity in water.In beaker experiments, the humic acid initial concentration of pending water is 20mg/L, and turbidity is 44.5NTU.
Other conditions are with embodiment 3, and result shows, humic acid clearance is 99.04%, and turbidity removal rate is 94.10%.
Comparative example 3 is visible, and in water, the change of the content of humic acid and turbidity can affect both removal effects, and within the specific limits, the amount of humic acid is constant, and the treatment effect of low-cloudy water has decline relatively, and the clearance of haze reduction then humic acid can increase.
Embodiment 6
Adopting the aluminium polychlorid carried magnetic carbon nano tube compound material of embodiment 1 preparation, coagulation synchronizes to remove humic acid and turbidity in water.In beaker experiments, the humic acid initial concentration of pending water is 20mg/L, and turbidity is 44.5NTU, and solution ph is 7.30, and the volume of contaminant water is 50mL.
In coagulation process, first, phase III hydraulics with embodiment 3, second stage is for quickly to stir 5min, and mixing speed is 150r/min.Described aluminium polychlorid carried magnetic carbon nano tube compound material adds at twice, and single dosage is 0.0250g, and first time toss area is before starting the first stage, and second time toss area is the last 30s of second stage stirring.
Water outlet after processing is detected, and result shows, humic acid clearance is 98.94%, and turbidity removal rate is 89.14%.
Embodiment 7
Adopting the aluminium polychlorid carried magnetic carbon nano tube compound material of embodiment 1 preparation, coagulation synchronizes to remove humic acid and turbidity in water.In coagulation process, first, second stage hydraulics is with embodiment 3, and the phase III is low rate mixing 15min, and mixing speed is 60r/min.Described aluminium polychlorid carried magnetic carbon nano tube compound material adds at twice, and single dosage is 0.0250g, and first time toss area is before starting the first stage, and second time toss area is the last 30s of second stage stirring.
Other conditions are with embodiment 6, and result shows, humic acid clearance is 98.34%, and turbidity removal rate is 89.06%.
Embodiment 8
Adopting the aluminium polychlorid carried magnetic carbon nano tube compound material of embodiment 1 preparation, coagulation synchronizes to remove humic acid and turbidity in water.In coagulation process, first, second stage hydraulics is with embodiment 3, and the phase III is low rate mixing 20min, and mixing speed is 50r/min.Described aluminium polychlorid carried magnetic carbon nano tube compound material adds at twice, and single dosage is 0.0250g, and first time toss area is before starting the first stage, and second time toss area is the last 30s of second stage stirring.
Other conditions are with embodiment 6, and result shows, humic acid clearance is 98.54%, and turbidity removal rate is 89.76%.
Contrast above example is visible, and the change of coagulation condition can affect turbidity removal effect, and within the specific limits, the reduction of mixing speed and the minimizing of mixing time all can make turbidity removal rate reduce.
Comparative example 1
Adopting the magnetic carbon nano-tube material of preparation in embodiment 1, coagulation synchronizes to remove humic acid and turbidity in water.In beaker experiments, the humic acid initial concentration of pending water is 20mg/L, and turbidity is 72.2NTU, and solution ph is 7.30, and the volume of pending water is 50mL.
Coagulation process: the first stage, mixing speed was 300r/min in order quickly to mix 10s；Second stage is for quickly to stir 5min, and mixing speed is 200r/min；Phase III is low rate mixing 20min, and mixing speed is 60r/min.Described magnetic carbon nano-tube material adds at twice, and single dosage is 0.0250g, and first time toss area is before first stage stirring starts, and second time toss area is the last 30s of second stage stirring.
Water outlet after processing is detected, and result shows, humic acid clearance is 45.16%, and turbidity removal rate is 53.25%.
Comparative example 2
Adopting aluminium polychlorid to carry out coagulation beaker experiments, wherein, the humic acid initial concentration of pending water is 20mg/L, and turbidity is 72.2NTU, and solution ph is 7.30, and the volume of pending water is 50mL.
Coagulation process: the first stage, mixing speed was 300r/min in order quickly to mix 10s；Second stage is for quickly to stir 5min, and mixing speed is 200r/min；Phase III is low rate mixing 20min, and mixing speed is 60r/min.Described aluminium polychlorid adds at twice, and single dosage is 0.0250g, and first time toss area is before first stage stirring starts, and second time toss area is the last 30s of second stage stirring.
Water outlet after processing is detected, and result shows, humic acid clearance is 11.75%, and turbidity removal rate is 97.50%.
As seen from the above embodiment, adopting composite provided by the invention to process water, humic acid clearance is up to 99%, and turbidity removal rate is up to 94%, and removal effect is considerable, has the feature of safety, economy, environmental protection.Meanwhile, can be that subsequent recovery regeneration creates conditions by Magneto separate process, save cost, do not increase the sludge quantity after process, be beneficial to the application in water processes especially Micro-polluted Water field.
The above is only the preferred embodiment of the present invention; it should be pointed out that, the professional and technical personnel for making the art, under the premise without departing from the technology of the present invention principle; it is that by the multiple amendment to these embodiments, and these amendments also should be regarded as the scope that the present invention should protect.
Claims (10)
1. the magnetic carbon-nano tube composite material of a functionalization, it is characterised in that including:
The CNT that magnetic iron oxide is modified；
With the aluminium polychlorid being compound on described CNT.
2. composite according to claim 1, it is characterised in that in the magnetic carbon-nano tube composite material of described functionalization, C element content is 50～70wt%, Al constituent content be 2～5wt%, Fe constituent content is 5～20wt%.
3. composite according to claim 1 and 2, it is characterised in that the magnetic carbon-nano tube composite material of described functionalization exists meso-hole structure.
4. a preparation method for the magnetic carbon-nano tube composite material of functionalization, comprises the following steps:
A) carbon nano-tube material that magnetic iron oxide is modified is provided；
B) utilize carbon nano-tube material and aluminium polychlorid compound that described magnetic iron oxide modified by microwave, obtain the magnetic carbon-nano tube composite material of functionalization.
5. preparation method according to claim 4, it is characterised in that described step B) in utilize microwave compound particularly as follows:
Carbon nano-tube material that described magnetic iron oxide modifies and the mixed liquor of aluminium polychlorid will be included when power is 600W, microwave 2～10min, obtain the magnetic carbon-nano tube composite material of functionalization.
6. the method removing humic acid and turbidity from water, comprises the following steps:
Pending water conservancy chemical reagent is carried out coagulation, the water outlet after being processed；
Described chemical reagent is the magnetic carbon-nano tube composite material of the functionalization that the preparation method described in the magnetic carbon-nano tube composite material of the functionalization described in any one of claims 1 to 3 or claim 4 or 5 prepares.
7. method according to claim 6, it is characterised in that in described pending water, humic acid concentration is 10～30mg/L, turbidity is 40～80NTU.
8. method according to claim 6, it is characterised in that described coagulation carries out when room temperature and pH value are 4～7.5.
9. the method according to any one of claim 6～8, it is characterised in that the process of described coagulation divides three phases: the mixing speed of first stage is 200～300r/min, the time is 10～20s；The mixing speed of second stage is 120～200r/min, and the time is 4～10min；The mixing speed of phase III is 40～60r/min, and the time is 15～20min.
10. method according to claim 9, it is characterised in that described chemical reagent adds at twice when coagulation: first time toss area is before first stage stirring starts, and second time toss area is in the last 30s of second stage stirring；
The single dosage of described chemical reagent and the ratio of pending water are (0.2～0.6) g:1000mL.
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