CN105056891A - Graphene modified biochar composite as well as preparation method and application thereof - Google Patents
Graphene modified biochar composite as well as preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims abstract description 15
- 244000082946 Tarchonanthus camphoratus Species 0.000 claims abstract description 15
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 abstract 3
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- ZRGONDPMOQPTPL-UHFFFAOYSA-N 1-[2-(2-hydroxyethylsulfanyl)ethyl]-2-methyl-5-phenylpyrrole-3-carboxylic acid Chemical compound OCCSCCN1C(C)=C(C(O)=O)C=C1C1=CC=CC=C1 ZRGONDPMOQPTPL-UHFFFAOYSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
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- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides graphene modified biochar composite as well as a preparation method and an application thereof. The graphene modified biochar composite comprises graphene, sodium dodecyl benzene sulfonate and biochar, wherein graphene is supported on the biochar through sodium dodecyl benzene sulfonate to form a net-like support structure. The preparation method comprises steps as follows: graphene is added to a sodium dodecyl benzene sulfonate solution and subjected to ultrasonic dissolution, so that graphene is finally peeled off to form graphene slice layers, and a graphene suspension liquid is obtained; camphorwood saw dust is added to the graphene suspension liquid, stirred and dried, and a mixture is obtained; the mixture is subjected to pyrolysis, and the graphene modified biochar composite is obtained. The graphene modified biochar composite has the characteristics of high adsorption capacity, high adsorption efficiency and the like and can be applied to removal of Pb<2+> in water on a large scale.
Description
Technical field
The present invention relates to a kind of material and environmental area, charcoal composite being specifically related to a kind of graphene modified and preparation method thereof, also relate to Pb in the charcoal composite process water body of graphene modified
2+application.
Background technology
In recent years, along with rapid development of economy, a large amount of uses of industrial or agricultural field chemical reagent, make China's major part surface water and groundwater receive pollution in various degree, its pollutant comprises heavy metal and organic matter etc.If contaminated water body does not add process or deals with improperly, serious harm will be caused to publilc health and ecological environment.Such as: heavy metal Pb
2+, can not only to be extensively present in soil and surface water water body in, can also circulate in underground water.Kidney can be caused, nervous centralis, reproductive system, the grievous injury of liver and reproductive system.
The method of current process polluted-water mainly contains filtration, biological adsorption, chemical precipitation method, electro-deposition, membranous system, ion-exchange etc.Compared with additive method, absorption method because it is easy to operate, the wide variety of adsorbent, operating cost are low, efficiency is high, flexible design, regenerating easily, process waste water be suitable for the advantages such as recycling and become one and be widely used and processing method efficiently.At present, energy Adsorption of Heavy Metals and organic composite have caused and have studied interest widely.In recent years, comprising with the pollutant in charcoal and charcoal composite water body by technology of rising new in absorption method Environment control field.At this, charcoal be a kind of can the engineering carbon of extensive use, it can by various biological material in the absence of oxygen pyrolysis obtain.As active carbon, charcoal can be widely used in the process of waste water mainly because it has larger specific area and the aperture structure more stable than comparatively dense.With existing charcoal technology and emerging biology, nanometer technology combines to create environmentally friendly, and the advanced composite material (ACM) of economic and practical type, receives much concern in recent years.Anaerobic grain sludge is had, nano zero valence iron, magnetic oxide, CNT, AlOOH, clay, magnesium, bitter earth nano sheet, MnO in research in the past
xwith the compound of charcoal, these composites all have good physical property, and efficiently can remove various pollutant in water body.
Physicalchemical structure and the fullerene of Graphene are closely similar, but Graphene has the feature of the low and general applicability of price, and can carry out synthesizing new hybrid nano composite material as " coating agent and packaging agent ", the composite of its synthesis can efficiently remove organic or inorganic pollutant.Therefore, Graphene can be widely used in environmental improvement.Successful synthesizing graphite alkene parcel titanium dioxide in research in the past, graphene modified carbon nano tube compound material, magnetic graphene composite etc. are for the removal of aromatic compound and heavy metal.Zhang is by 1,3,6,8-pyrene tetrasulfonic acid tetrasodium salt has synthesized Graphene-charcoal composite, and methylene blue can be removed efficiently from waste water, but the size of the composite of its synthesis is larger, can not form nano level synthetic material, there is no the impact that systematic research is removed methylene blue simultaneously, particularly do not study the process removing heavy metal in polluted-water with this composite.
Although charcoal composite has achieved certain achievement in research in environmental area application, but be also in the starting stage compared with the application in the environment of systematic research charcoal composite, the particularly Synthesis and applications of engineering compound bio charcoal, does not almost also obtain due extensive research.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, there is provided a kind of adsorption capacity large, adsorption efficiency is high, have the charcoal composite of the graphene modified that engineer applied is worth, additionally provide a kind of simple preparation method of charcoal composite of graphene modified, Pb in water body removed by the charcoal composite simultaneously providing graphene modified
2+investigation and application.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
A charcoal composite for graphene modified, the charcoal composite of described graphene modified comprises Graphene, neopelex and charcoal, and described Graphene forms network structure by neopelex load on charcoal.
As a total technical conceive, present invention also offers a kind of preparation method of charcoal composite of above-mentioned graphene modified, comprise the following steps:
(1) added by Graphene in neopelex solution, ultrasonic dissolution, makes Graphene finally peel off into graphene sheet layer, obtains graphene suspension;
(2) camphorwood sawdust is joined in the Graphene aaerosol solution that described step (1) prepares, stir, drying obtains mixture;
(3) mixture of preparation in described step (2) is carried out the charcoal composite that pyrolysis obtains graphene modified.
Above-mentioned preparation method, preferably, in neopelex solution described in described step (1), the concentration of neopelex is 0.1 ~ 0.8g/L.Preferred further, in neopelex solution, the concentration of neopelex is 0.4g/L.
Above-mentioned preparation method, preferably, in graphene suspension described in described step (1), the concentration of Graphene is 0.01g/100mL ~ 0.08g/100mL.Preferred further, in described graphene suspension, the concentration of Graphene is 0.02g/100mL.
Above-mentioned preparation method, preferably, in described step (2), the mass ratio of described camphorwood sawdust and Graphene is 2.0: 0.01 ~ 0.08.Further preferred, the mass ratio of described camphorwood sawdust and Graphene is 2.0: 0.02.
Above-mentioned preparation method, preferably, camphorwood sawdust adopts through 80 DEG C of dried camphorwood sawdust, and the particle diameter of camphorwood sawdust is 0.15mm ~ 0.25mm.
Above-mentioned preparation method, preferably, the time of described stirring is 0.5 ~ 1h.Preferred further, the time of stirring is 1h.
Above-mentioned preparation method, preferably, the temperature of described drying is 70 ~ 90 DEG C.Preferred further, dry temperature is 80 DEG C.
Above-mentioned preparation method, preferably, in described step (3), described pyrolysis is specially: under nitrogen atmosphere, with 600 ~ 650 DEG C of pyrolysis 1h.
Above-mentioned preparation method, preferably, in pyrolytic process, heating rate is 5 ~ 8 DEG C/min.
As a total technical conceive, present invention also offers charcoal composite Pb in process water body of the graphene modified that a kind of charcoal composite of above-mentioned graphene modified or above-mentioned preparation method prepare
2+application, its application process is: add in water body by the charcoal composite of graphene modified, stir, with membrane filtration, complete Pb in water body
2+process.
Above-mentioned application, preferably, the consumption of the charcoal composite of described graphene modified is Pb in water body
2+25 ~ 30 times of content.
Above-mentioned application, preferably, described mixing time is 2h ~ 8h.Preferred further, mixing time is 5h.
Above-mentioned application, preferably, Pb in described water body
2+concentration be 1 ~ 60mg/L.Further preferred, Pb
2+concentration be 1 ~ 20mg/L.
Above-mentioned application, preferably, the pH of water body is 2 ~ 8.
As a total technical conceive, present invention also offers charcoal composite Pb in process water body of the graphene modified that a kind of charcoal composite of above-mentioned graphene modified or above-mentioned preparation method prepare
2+application, its application process is: the charcoal composite of graphene modified is put into column and fixes adsorption system, water body flows through fixing adsorption system, completes Pb in water body
2+process.
Above-mentioned application, preferably, Pb in described water body
2+concentration be 1 ~ 20mg/L.
Above-mentioned application, preferably, the thickness that described column fixes adsorption layer in adsorption system is 2mm ~ 4mm.Preferred adsorbent layer thickness is 4mm.
Above-mentioned application, preferably, the flow rate of water body is 1mL/min ~ 5mL/min.Preferred flow rate is 3mL/min.
Above-mentioned application, preferably, the essential structure that column fixes adsorption system is the glass column of 20cm × 2cm.
Compared with prior art, the invention has the advantages that:
(1) the invention provides a kind of charcoal composite of graphene modified, by graphene-supported on charcoal (sheet interlayer spacing of Graphene is 0.378nm), add the specific area of material, add the gluing effect of neopelex, Graphene is made to be weldingly fixed on charcoal on the surface, the Size Distribution of composite, at 200 ~ 2000nm, forms a supporting structure, not easily reunites.In the charcoal composite of graphene modified, the effect of Graphene is mainly the surface of load at charcoal, modified biological charcoal, Van der Waals force between minimizing charcoal and the effect between pi-pi bond, a kind of network structure of common formation, makes charcoal not easily reunite, and improves charcoal to Pb
2+adsorption capacity, simultaneously Graphene self also has absorption Pb
2+effect, there is the advantages such as adsorption capacity is large, adsorption efficiency is high.
(2) the invention provides a kind of preparation method of charcoal composite of graphene modified, preparation process is simple, synthetic method is simple, and material is easy to get, can large-scale production and application.
(3) the present invention adopts Pb in the charcoal composite process water body of graphene modified
2+, have processing method simple, the advantages such as cost is low, and material is easy to get, and adsorption capacity is large, efficiently can remove the Pb in polluted-water
2+, reduce it to toxicity biological in environment, can be used as the contaminated water body of engineering material with carbon element process.
Accompanying drawing explanation
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is the SEM figure of the not processed charcoal in comparative example 1 of the present invention.
Fig. 2 is the SEM figure of the charcoal composite of graphene modified in the embodiment of the present invention 1.
Fig. 3 is the TGA figure of charcoal composite (b) of the not processed charcoal (a) in comparative example 1 of the present invention and the graphene modified in embodiment 1.
Fig. 4 is the XRD figure of the charcoal composite of graphene modified in the embodiment of the present invention 1.
Fig. 5 is that in embodiment 2, Pb in water body removed by the charcoal composite of pH to not processed charcoal and graphene modified
2+impact.
Fig. 6 is that in embodiment 3, Pb in water body removed by the charcoal composite of adsorption time to not processed charcoal and graphene modified
2+impact.
Fig. 7 is Pb in embodiment 4
2+pb in water body removed by the charcoal composite of concentration to not processed charcoal and graphene modified
2+impact.
Fig. 8 is that in embodiment 5, Pb in water body removed by the charcoal composite of adsorbent layer thickness to not processed charcoal and graphene modified
2+impact.
Fig. 9 is that in embodiment 6, Pb in water body removed by the charcoal composite of flow rate to not processed charcoal and graphene modified
2+impact.
Figure 10 is Pb in enforcement 7
2+to the breakthrough curve of the charcoal composite of not processed charcoal and graphene modified.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Embodiment
The material adopted in following examples and instrument are commercially available.
Embodiment 1:
A charcoal composite for graphene modified of the present invention, comprises Graphene, neopelex and charcoal.Neopelex plays connection function, makes graphene-supported on charcoal, and the Size Distribution of its composite, at 200 ~ 2000nm, forms network structure jointly.
The preparation method of the charcoal composite of the graphene modified of the present embodiment, specifically comprises the following steps:
(1) Graphene of 0.02g being joined 100mL concentration is that in the neopelex solution of 0.4g/L, (neopelex solution ultra-pure water is prepared, prepare rear stirring 1 hour), ultrasonic dissolution 1 hour, make Graphene finally peel off into graphene sheet layer, obtain graphene suspension.
In above-mentioned step (1), in neopelex solution, the concentration of neopelex is that 0.1 ~ 0.8g/L all can implement.The addition of Graphene is that 0.01 ~ 0.08g/100mL all can implement.
(2) the camphorwood sawdust of 2.0g, (camphorwood sawdust adopts through 80 DEG C of dried camphorwood sawdust, the particle diameter of camphorwood sawdust is 0.15mm ~ 0.25mm) join in Graphene aaerosol solution, after stirring 1h, at 80 DEG C, drying obtains solid-state mixture.
In above-mentioned step (2), mixing time is 0.5h ~ 1h, and dry temperature is 70 ~ 90 DEG C and all can implements.
(3) mixture that step (2) prepares is put in quartz ampoule, then quartz ampoule is put into tube furnace, under nitrogen atmosphere, be warming up to 600 DEG C with the speed of 5 DEG C/min (heating rate is that 5 ~ 8 DEG C/min all can implement), and slow pyrolysis obtains the charcoal composite of graphene modified for 1 hour at 600 DEG C.Cleaned by the charcoal composite ultra-pure water of graphene modified, to remove the impurity formed in pyrolytic process, then freeze drying 24 hours at-70 ~-55 DEG C, is stored in container.
Be 600 ~ 650 DEG C in the temperature of the middle pyrolysis of above-mentioned steps (3) all can implement.
Comparative example 1
A kind of preparation method of charcoal:
2.0g is dry at 80 DEG C through the camphorwood sawdust (particle diameter of camphorwood sawdust is 0.1 ~ 0.25mm) of screening, be put in quartz ampoule, then quartz ampoule is put into tube furnace, under nitrogen atmosphere, be warming up to 600 DEG C with the speed of 5 DEG C/min, at 600 DEG C, slow pyrolysis obtains charcoal in 1 hour.Clean charcoal with ultra-pure water, to remove the impurity formed in pyrolytic process, at-70 ~-55 DEG C, freeze drying 12 hours, is stored in container.
Respectively scanning electron microscope analysis is carried out to the charcoal composite of the graphene modified in the charcoal in comparative example 1 and embodiment 1, electron-microscope scanning result as depicted in figs. 1 and 2: the charcoal composite of charcoal and graphene modified all has more aperture structure.In the charcoal composite of graphene modified, unanimously and be fixed on the surface of charcoal stably, and charcoal still remains initial structural form to graphene sheet layer.This illustrates that neopelex can make Graphene successfully be pasted onto the surface of charcoal, is a kind of heat processed adhesive preferably.
Simultaneously due to the process of neopelex, the adsorption efficiency of the charcoal of graphene modified is improved, illustrate that promotion that neopelex can be positive is to Pb
2+absorption.
Respectively thermogravimetric analyzer is placed in the charcoal composite of the not processed charcoal in comparative example 1 and the graphene modified in embodiment 1 and carries out thermogravimetric analysis, as shown in Figure 3: the not processed charcoal in the charcoal composite of the graphene modified in the embodiment of the present invention 1 and comparative example 1 is in temperature progressively elevation process, and weight change is very little.Wherein the change of the not processed charcoal of comparative example 1 before 405 DEG C is very little, and start violent minimizing after 405 DEG C, until 540 DEG C of quality no longer change, its Mass lost is close to 89%; And adopting the charcoal composite of the graphene modified obtained by the present invention in 270 ~ 390 DEG C of change procedures, mass change is very little, and this illustrates neopelex almost approach exhaustion in pyrolytic process.Meanwhile, the charcoal composite of graphene modified is more stable than not processed charcoal.
Carry out X-ray diffraction analysis to the charcoal composite of graphene modified, analysis result as shown in Figure 4.As can be known from Fig. 4: adopt the peak value of the charcoal composite of the graphene modified synthesized by the present invention to appear at 2 θ=23.5 °, can calculate thus and be spaced apart 0.378nm between graphene sheet layer, and theoretical interlamellar spacing (0.34nm) between Graphene closely.This further illustrates charcoal surface and is covered by graphene sheet layer.Meanwhile, between Graphene, the increase of interlamellar spacing may be because there are some oxygenated functional groups in synthetic material, under the effect of functional group, interlamellar spacing is increased.
Embodiment 2
Pb in water body removed by the charcoal composite of the graphene modified in a kind of embodiments of the invention 1
2+application, with the removal Pb of the not processed charcoal in comparative example 1
2+effect compare, investigate pH on the impact of removal efficiency.Concrete application process is:
Experimental group: 4 0.5m are set respectively
3treatment pond, by Pb
2+concentration is that the aqueous solution of 20.012mg/L enters in aforementioned processing pond.Add in 4 treatment ponds wherein and be equivalent to Pb
2+the charcoal composite of the graphene modified in the embodiment 1 that gross mass is 26 times, the pH controlling the aqueous solution is respectively 2,4,6,8.After stirring 4h, be the membrane filtration treated water solution of 0.22 micron with aperture, detect Pb in filtrate
2+concentration.
Control group: add in other 4 treatment ponds and be equivalent to Pb
2+not processed charcoal in the comparative example 1 that gross mass is 26 times, the pH controlling the aqueous solution is respectively 2,4,6,8.After stirring 4h, be the membrane filtration treated water solution of 0.22 micron with aperture, detect Pb in filtrate
2+concentration.
Result is as shown in Figure 5: when pH≤6.0, the charcoal composite absorption Pb of the graphene modified in the embodiment of the present invention 1
2+efficiency apparently higher than not processed charcoal.But when when pH>6.0, both adsorption efficiencies are more or less the same.But the charcoal of adsorption efficiency still than not processed is high in neutral conditions for the charcoal composite of the graphene modified synthesized by the present invention.Can draw thus, the charcoal composite of the graphene modified synthesized by the present invention is to Pb
2+be absorbed with stronger pH adaptability, be specially adapted to the process of acidic industrial effluent.
Embodiment 3:
Pb in water body removed by the charcoal composite of the graphene modified in a kind of embodiments of the invention 1
2+application, with the removal Pb of the charcoal in comparative example 1
2+effect compare, investigate adsorption time on the impact of removal efficiency.Concrete application process is:
2 2m are set
3treatment pond, by Pb
2+concentration is that the aqueous solution of 20.028mg/L enters in aforementioned processing pond.Pb is incorporated in respectively in 2 treatment ponds
2+not processed charcoal in the charcoal composite of the graphene modified in the embodiment 1 that gross mass is 26 times and comparative example 1, keeps pH=7.0, respectively 5,10,15,30,60,120,180,240,360,480min samples, and is the aqueous solution of the membrane filtration sampling of 0.22 micron, detects Pb in filtrate with aperture
2+concentration.Testing result as shown in Figure 6.
Can draw from accompanying drawing 6, before 2h, the adsorption capacity of the charcoal composite of not processed charcoal and graphene modified significantly increases, and after 2h, adsorption rate starts to reduce, and reaches substantially saturated during 5h.This is because in the firm incipient stage, the adsorption site on the charcoal composite material surface of not processed charcoal and graphene modified is also very sufficient, soon by Pb
2+seize, after the adsorption site afterwards on surface is preempted, Pb
2+the aperture, inside entering the charcoal composite of not processed charcoal and graphene modified is adsorbed, so adsorption rate slows down until saturated.Meanwhile, the charcoal composite of graphene modified that accompanying drawing 6 also shows synthesized by the present invention significantly improves than the adsorption capacity of not processed charcoal.
Embodiment 4:
Pb in water body removed by the charcoal composite of the graphene modified in a kind of embodiments of the invention 1
2+application, with the removal Pb of the charcoal in comparative example 1
2+effect compare, investigate Pb
2+concentration is on the impact of removal efficiency.Concrete application process is:
Experimental group: 5 0.5m are set respectively
3treatment pond, after testing, Pb in the treatment pond aqueous solution
2+concentration is respectively 1.1012,9.9874,20.1235,40.125,60.451mg/L.Pb is incorporated in respectively in 5 treatment ponds
2+the charcoal composite of the graphene modified in the embodiment 1 that gross mass is 26 times, keeps pH=7.0, after stirring 4h, is the membrane filtration treated water solution of 0.22 micron with aperture, detects Pb in filtrate
2+concentration.
Control group: 5 0.5m are set respectively
3treatment pond, after testing, Pb in the treatment pond aqueous solution
2+concentration is respectively 1.1012,9.9874,20.1235,40.125,60.451mg/L.Pb is incorporated in respectively in 5 treatment ponds
2+not processed charcoal in the comparative example 1 that gross mass is 26 times, keeps pH=7.0, after stirring 4h, is the membrane filtration treated water solution of 0.22 micron with aperture, detects Pb in filtrate
2+concentration.
Investigate Pb in experimental group and control group
2+removal efficiency, result is as shown in Figure 7.Can draw, along with Pb from accompanying drawing 7
2+the increase of concentration, adsorption capacity, in continuous increase, increase speed afterwards in continuous reduction, and adsorption efficiency constantly reduces in whole process.This is because the quantity of adsorption site contained by adsorbent is certain, when there being too much Pb
2+when existing, the adsorption capacity of adsorbent reaches capacity, can not adsorption fouling thing again, and adsorption efficiency can slowly diminish.By Lagrangian model to adsorption isotherm matching, can show that the charcoal composite of graphene modified is to Pb
2+adsorption capacity be more than 2 times of not processed charcoal.Thus, can show that the charcoal composite of the graphene modified synthesized by the present invention has obvious advantage than not processed charcoal in adsorption capacity.
Embodiment 5:
Pb in water body removed by the charcoal composite of the graphene modified in a kind of embodiments of the invention 1
2+application, with the removal Pb of the not processed charcoal in comparative example 1
2+effect compare, investigate adsorbent layer thickness on the impact of removal efficiency.Concrete application process is:
The glass cylindrical arranging 2 20cm × 2cm respectively fixes adsorption system, and one of them adopts the charcoal composite of the graphene modified in embodiment 1, and another adopts the not processed charcoal in comparative example 1.Respectively by Pb
2+concentration be the water body of 20mg/L with the flowing velocity of 3mL/min for by two fixing adsorption systems, regulate adsorption layer layer thickness in fixing adsorption system to be respectively 0.5mm, 1mm, 2mm, 3mm, 4mm.Investigate adsorption layer layer thickness to the impact of adsorption efficiency, as shown in Figure 8: along with the increase of the charcoal composite material adsorbent layer thickness of two kinds of not processed charcoals and graphene modified, adsorption efficiency also increases thereupon.This is because along with the increase of thickness, add the specific area of adsorbent, thus add Pb
2+with the contact site of adsorbent, chien shih Pb when having sufficient
2+contact with the avtive spot of adsorbent.
Embodiment 6:
Pb in water body removed by the charcoal composite of the graphene modified in a kind of embodiments of the invention 1
2+application, with the removal Pb of the not processed charcoal in comparative example 1
2+effect compare, investigate flow rate on the impact of adsorption efficiency, concrete application process is:
The glass cylindrical arranging 2 20cm × 2cm respectively fixes adsorption system, and one of them adopts the charcoal composite of the graphene modified in embodiment 1, and another adopts the not processed charcoal in comparative example 1.Adsorption layer layer thickness is 4mm, by Pb
2+concentration be 20mg/L water body respectively with the flowing velocity of 1mL/min, 3mL/min, 5mL/min, 7mL/min, 9mL/min by two fixing adsorption systems.Investigate flowing velocity to the impact of adsorption efficiency, investigate result as shown in Figure 9:, along with the increase of flowing velocity, Pb
2+removal efficiency reduce, this is because along with the increase of flowing velocity, Pb
2+do not have time enough to contact with adsorbent, do not have time enough to make Pb yet
2+be diffused in the micropore of adsorbent.
Embodiment 7:
Pb in water body removed by the charcoal composite of the graphene modified in a kind of embodiments of the invention 1
2+application, with the removal Pb of the not processed charcoal in comparative example 1
2+effect compare, investigate the breakthrough curve of two kinds of sorbing materials, concrete application process is:
The glass cylindrical arranging 2 20cm × 2cm respectively fixes adsorption system, and one of them adopts the charcoal composite of the graphene modified in embodiment 1, and another adopts the not processed charcoal in comparative example 1.Adsorption layer layer thickness is 4mm, by Pb
2+concentration be 20mg/L water body respectively with the flowing velocity of 3mL/min by two fixing adsorption systems, start to detect Pb in fixed bed efflux at 10min
2+concentration, then detect once every 20min, calculate Pb in efflux
2+concentration and the ratio of initial concentration, draw breakthrough curve, investigate shown in result Figure 10: the time of break-through of the charcoal composite of not processed charcoal and graphene modified is respectively 100,250min.This shows in actual applications, and the charcoal composite of the graphene modified synthesized by the present invention more has practical application potentiality than not processed charcoal.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, when not departing from Spirit Essence of the present invention and technical scheme, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (10)
1. the charcoal composite of a graphene modified, it is characterized in that, the charcoal composite of described graphene modified comprises Graphene, neopelex and charcoal, and described Graphene forms network structure by neopelex load on charcoal.
2. a preparation method for the charcoal composite of graphene modified described in claim 1, is characterized in that, comprise the following steps:
(1) added by Graphene in neopelex solution, ultrasonic dissolution, makes Graphene finally peel off into graphene sheet layer, obtains graphene suspension;
(2) camphorwood sawdust is joined in the Graphene aaerosol solution that described step (1) prepares, stir, drying obtains mixture;
(3) mixture of preparation in described step (2) is carried out the charcoal composite that pyrolysis obtains graphene modified.
3. preparation method according to claim 2, is characterized in that, in neopelex solution described in described step (1), the concentration of neopelex is 0.1 ~ 0.8g/L; In described graphene suspension, the concentration of Graphene is 0.01g/100mL ~ 0.08g/100mL.
4. preparation method according to claim 2, is characterized in that, in described step (2), the mass ratio of described camphorwood sawdust and Graphene is 2.0: 0.01 ~ 0.08, and the time of described stirring is 0.5 ~ 1h; The temperature of described drying is 70 ~ 90 DEG C.
5. preparation method according to claim 2, is characterized in that, in described step (3), described pyrolytic process is specially: under nitrogen atmosphere, with 600 DEG C ~ 650 DEG C pyrolysis 1h.
6. Pb in the charcoal composite process water body of graphene modified for preparing of preparation method described in the charcoal composite of a graphene modified according to claim 1 or claim 2 to 5
2+application.
7. application according to claim 6, is characterized in that, described application process is: add in water body by the charcoal composite of graphene modified, stirs, with membrane filtration, completes Pb in water body
2+process.
8. application according to claim 7, is characterized in that, the consumption of the charcoal composite of described graphene modified is Pb in water body
2+25 ~ 30 times of content; Described mixing time is 2 ~ 8h; Pb in described water body
2+concentration be 1 ~ 60mg/L; Controlling water body pH in described processing procedure is 2 ~ 8.
9. application according to claim 6, is characterized in that, described application process is: the charcoal composite of graphene modified is put into column and fixes adsorption system, water body flows through fixing adsorption system, completes Pb in water body
2+process.
10. application according to claim 9, is characterized in that, Pb in described water body
2+concentration be 1 ~ 20mg/L; The thickness that described column fixes adsorption layer in adsorption system is 2mm ~ 4mm; The flow rate of water body is 1mL/min ~ 5mL/min.
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