CN103055806A - Carbon-coated attapulgite clay composite material and its preparation method - Google Patents
Carbon-coated attapulgite clay composite material and its preparation method Download PDFInfo
- Publication number
- CN103055806A CN103055806A CN2011103167915A CN201110316791A CN103055806A CN 103055806 A CN103055806 A CN 103055806A CN 2011103167915 A CN2011103167915 A CN 2011103167915A CN 201110316791 A CN201110316791 A CN 201110316791A CN 103055806 A CN103055806 A CN 103055806A
- Authority
- CN
- China
- Prior art keywords
- attapulgite clay
- carbon
- clay composite
- coated
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention provides a carbon-coated attapulgite clay composite material, which consists of: attapulgite clay and carbon nano-particles coated on the surface of the attapulgite clay. The invention also provides a preparation method of the carbon-coated attapulgite clay composite material. The method comprises the steps of: mixing attapulgite clay with glucose in water, and leaving them to undergo a carbonization reaction so as to obtain the carbon-coated attapulgite clay composite material. The carbon-coated attapulgite clay composite material provided in the invention has a strong adsorption capacity, can achieve a significant effect in adsorption removal of heavy metals from water, and has a good adsorption removal capacity on both bivalent lead ions and hexavalent chromium ions in water. Experimental results show that, when used for removal of heavy metal ions in water, the carbon-coated attapulgite clay composite material provided in the invention has an adsorption capacity higher than that of attapulgite clay, activated carbon, oxidative activated carbon, carbon aerogels, carbon nanotubes, chitosan polymer and other adsorbents.
Description
Technical field
The invention belongs to technical field of nano material, relate in particular to a kind of carbon and coat attapulgite clay composite and preparation method thereof.
Background technology
Heavy metal pollution refers to the environmental pollution that caused by heavy metal or its compound, such as lead, chromium, cadmium, mercury, arsenic etc., mainly thought due to the factor by mining, toxic emission, sewage irrigation and use heavy metal goods etc., during major part showed that water pollutes, small part showed in atmosphere pollution and the solid waste pollution.Heavy metal not only can not be biodegradable, and has bioaccumulation, can cause serious harm to environmental and human health impacts.As, when containing a large amount of hexavalent chromium in the drinking water, can increase the risk of diseases such as suffering from diarrhoea, carcinoma of urinary bladder, liver cancer, kidney, cutaneum carcinoma; Lead（II） ion can affect human intelligence, red blood cell and nervous system etc.; Mercury ion directly sinks to liver, and is very big to the destructiveness of brain, nerve, eyesight; Chromium can cause the symptoms such as abdominal discomfort, diarrhoea, allergic dermatitis, eczema, pharyngitis, bronchitis.
Prior art discloses the method for heavy metal ion in the multiple removal water, such as the precipitation method, ion-exchange, hyperfiltration, membrane separation process, electrochemical method etc., but these methods all exist cost higher, be applied to the shortcomings such as feasibility in the industry is relatively poor.And absorption method refers to utilize the method for porous solid-phase material adsorbing separation water pollutant, and it has low, the simple operation and other advantages of cost, is one of study hotspot of removing at present heavy metal ion in the water.Remove in the process of heavy metal ion in the water in the employing absorption method, porous solid-phase material, be that adsorbent is key factor that determine to remove efficient, adsorbent commonly used comprises the aeroge, CNT, chitosan complexes, activated coal, coke, cinder, resin, wood chip of activated carbon, oxidation activity carbon, carbon etc. at present.But these adsorbents all have the shortcomings such as adsorption capacity is little, absorption is incomplete.
Attapulgite clay is a kind of silicate clay mineral that contain Shuifu County's magnalium, has a layer chain structure, and its desirable chemical molecular formula is Mg
5Si
8O
20(OH)
2(OH
2)
44H
2O.Attapulgite clay has unique structure, and its crystal is needle-like, fibrous agrregate, and the diameter of single fiber crystalline substance is about 20nm, and length can reach 4 μ m, can be used as the presoma of nano material.Attapulgite clay has cation exchange property, larger specific area, preferably suspension and salt tolerance, thereby has preferably colloidal suspension buoyancy and absorption property.The inventor considers, after attapulgite clay is carried out surface treatment and increases the absorption property of attapulgite clay, can be used for removing the heavy metal ion in the sewage.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of carbon to coat attapulgite clay composite and preparation method thereof, and preparation method's technique provided by the invention is simple, and it is larger that the carbon that obtains coats attapulgite clay composite adsorption capacity.
The invention provides a kind of carbon and coat the attapulgite clay composite, comprising: attapulgite clay and the carbon nano-particle that is coated on described attapulgite clay surface.
Preferably, the mass ratio of described attapulgite clay and described carbon nano-particle is 1: (0.5～3.5).
Preferably, the diameter of described carbon nano-particle is 0.5nm～20nm.
Compared with prior art, carbon provided by the invention coats the carbon nano-particle that the attapulgite clay composite comprises attapulgite clay and is coated on described attapulgite clay surface.Carbon provided by the invention coats the attapulgite clay composite and has stronger adsorption capacity, has remarkable result when being used for the heavy metal of Adsorption sewage, and the lead（II） ion in the water and hexavalent chromium are all had good Adsorption ability.Experimental result shows, when carbon coating attapulgite clay composite provided by the invention is used for removing the heavy metal ion of water, its adsorption capacity is higher than the multiple adsorbents such as aeroge, CNT and chitosan polymer of attapulgite clay, active carbon, oxidisability active carbon, carbon, its the pH value be 6.0 o'clock to water in the high adsorption capacity of lead（II） ion be 263.83mg/g, be 4930 times of attapulgite clay adsorbance; Its pH value be 2.0 o'clock to water in the high adsorption capacity of hexavalent chromium be 177.74mg/g, be 2.5 times of attapulgite clay adsorbance.
The present invention also provides a kind of carbon to coat attapulgite clay composite manufacture method, may further comprise the steps:
Attapulgite clay is mixed in water with glucose, occur to obtain carbon coating attapulgite clay composite after the carburizing reagent.
Preferably, the mass ratio of described attapulgite clay and described glucose is 1: (3～8).
Preferably, the mass ratio of described glucose and described water is (3～8): 76.
Preferably, the time of described carburizing reagent is 24h～48h.
Preferably, the temperature of described carburizing reagent is 160 ℃～180 ℃.
Preferably, also comprise:
Described carbon is coated the attapulgite clay composite to be washed.
Preferably, described washing specifically comprises:
Adopt water that described carbon is coated the attapulgite clay composite and carry out the washing first time;
Adopt ethanol that described carbon is coated the attapulgite clay composite and carry out the washing second time.
The present invention is take attapulgite clay as template, obtain carbon after take glucose as raw material generation carburizing reagent and coat the attapulgite clay composite, cheap, the wide material sources of cost of material, the preparation method is simple, environmentally safe, the carbon that obtains coats in the attapulgite clay composite and contains the functional groups such as carbonyl, carboxyl, can with water in the effects such as heavy metal ion generation ion exchange, redox reaction, have remarkable result when being used for absorption except the heavy metal ion of anhydrating.
Description of drawings
The carbon that Fig. 1 provides for the embodiment of the invention 1 coats the low power stereoscan photograph of attapulgite clay composite;
The carbon that Fig. 2 provides for the embodiment of the invention 1 coats the high power stereoscan photograph of attapulgite clay composite;
The carbon that Fig. 3 provides for the embodiment of the invention 1 coat the attapulgite clay composite in times stereoscan photograph;
The carbon that Fig. 4 provides for the embodiment of the invention 1 coats the transmission electron microscope photo of attapulgite clay composite;
The carbon that Fig. 5 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of lead（II） ion;
The carbon that Fig. 6 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of hexavalent chromium;
The carbon that Fig. 7 provides for the embodiment of the invention 2 coats the low power stereoscan photograph of attapulgite clay composite;
The carbon that Fig. 8 provides for the embodiment of the invention 2 coats the high power stereoscan photograph of attapulgite clay composite;
The carbon that Fig. 9 provides for the embodiment of the invention 3 coats the low power stereoscan photograph of attapulgite clay composite;
The carbon that Figure 10 provides for the embodiment of the invention 3 coats the high power stereoscan photograph of attapulgite clay composite;
The carbon that Figure 11 provides for the embodiment of the invention 3 coats the attapulgite clay composite to the isothermal adsorption curve of lead（II） ion;
The carbon that Figure 12 provides for the embodiment of the invention 3 coats the attapulgite clay composite to the isothermal adsorption curve of hexavalent chromium;
The stereoscan photograph of the attapulgite clay that Figure 13 provides for comparative example 1 of the present invention;
The transmission electron microscope photo of the attapulgite clay that Figure 14 provides for comparative example 1 of the present invention;
The attapulgite clay that Figure 15 provides for comparative example 1 of the present invention is to the isothermal adsorption curve of lead（II） ion;
The attapulgite clay that Figure 16 provides for comparative example 1 of the present invention is to the isothermal adsorption curve of hexavalent chromium.
The specific embodiment
The invention provides a kind of carbon and coat the attapulgite clay composite, comprising: attapulgite clay and the carbon nano-particle that is coated on described attapulgite clay surface.
Coat in the attapulgite clay composite at described carbon, described attapulgite clay is template, makes carbon nano-particle be coated on described attapulgite clay surface, avoids forming the carbon ball.Described attapulgite clay is a kind of silicate clay mineral that contain Shuifu County's magnalium, has cation exchange property, larger specific area, preferably suspension and salt tolerance, can be used as adsorbent.The present invention does not have particular restriction to described attapulgite clay, purchases available attapulgite clay on the market and gets final product.
Coat the attapulgite clay surface at described carbon and be coated with carbon nano-particle, described carbon nano-particle has larger specific area, have good adsorption capacity so that described carbon coats the attapulgite clay composite, have remarkable result when being used for the metal ion of Adsorption water.In the present invention, the diameter of described carbon nano-particle is preferably 0.5nm～20nm, and more preferably 1nm～15nm most preferably is 5nm～10nm.The mass ratio of described attapulgite clay and described carbon nano-particle is preferably 1: (0.5～3.5), more preferably 1: (0.8～3) most preferably is 1: (1.2～2.8).
In the present invention, described carbon coats the attapulgite clay composite and is preferably club shaped structure, and its diameter is preferably 20nm～100nm, and more preferably 30nm～80nm most preferably is 40nm～60nm; Its length is micron order, is preferably 1 μ m～10 μ m, and more preferably 1.5 μ m～8 μ m most preferably are 2 μ m～7 μ m.
Carbon provided by the invention coats the attapulgite clay composite and has larger specific area, stronger adsorption capacity, can be used as the adsorbent of removing heavy metal in the water.Experiment shows, carbon provided by the invention coats the attapulgite clay composite and has preferably absorption property, adsorption capacity is better than the multiple adsorbents such as aeroge, CNT and chitosan polymer of attapulgite clay, active carbon, oxidisability active carbon, carbon, its the pH value be 6.0 o'clock to water in the high adsorption capacity of lead（II） ion be 263.83mg/g, be 4930 times of attapulgite clay adsorbance; Its pH value be 2.0 o'clock to water in the high adsorption capacity of hexavalent chromium be 177.74mg/g, be 2.5 times of attapulgite clay adsorbance.
The present invention also provides a kind of carbon to coat attapulgite clay composite manufacture method, may further comprise the steps:
Attapulgite clay is mixed in water with glucose, occur to obtain carbon coating attapulgite clay composite after the carburizing reagent.
The present invention is take attapulgite clay as template, obtain carbon after take glucose as raw material generation carburizing reagent and coat the attapulgite clay composite, cheap, the wide material sources of cost of material, the preparation method is simple, environmentally safe, the carbon that obtains coats the attapulgite clay composite and has good adsorption capacity, is used for having remarkable result when absorption removes the heavy metal ion of anhydrating.
The present invention at first mixes with glucose attapulgite clay in water, after stirring, glucose forms carbon nano-particle take attapulgite clay as template generation carburizing reagent on the attapulgite clay surface, obtains carbon and coats the attapulgite clay composite.Compare with the polysaccharide such as starch, maltose and sucrose and fructose, carry out the formation that carburizing reagent can be avoided the carbon ball take glucose as raw material, it is comparatively even to make the carbon that obtains coat attapulgite clay composite size.
In the present invention, the mass ratio of described attapulgite clay and described glucose is preferably 1: (3～8), and more preferably 1: (4～6) most preferably are 1: (4.5～5.5); The mass ratio of described glucose and described water is preferably (3～8): 76, more preferably (4～6): 76, most preferably be (4.5～5.5): 76.That is to say that in the present invention, the mass concentration of described attapulgite clay is preferably 13.16g/L, the mass concentration of described glucose is preferably 39.47g/L～105.26g/L.In the present invention, the mass ratio of described glucose and water has larger impact to the dimensional homogeneity that carbon coats the attapulgite clay composite, and those skilled in the art can obtain by the mass ratio of adjusting glucose and water preferably carbon coating of dimensional homogeneity attapulgite clay composite.
In the present invention, the temperature of described glucose generation carburizing reagent is preferably 160 ℃～180 ℃, more preferably 165 ℃～175 ℃; The time of described glucose generation carburizing reagent is preferably 24h～48h, and more preferably 30h～45h most preferably is 35h～40h.In the present invention, the temperature and time of described carburizing reagent is to affect the key factor that carbon coats attapulgite clay composite diameter and carbon nano-particle diameter, and those skilled in the art can need obtain the carbon of diameter to coat the concave convex rod composite by time and the temperature of adjusting carburizing reagent.
The present invention at first mixes attapulgite clay and glucose in water after, preferably in hydrothermal reaction kettle, carry out carburizing reagent, after carburizing reagent is complete, described hydrothermal reaction kettle is cooled to room temperature, the product that obtains is filtered, and preferably adopting the aperture is the membrane filtration of 220nm, and the product that will obtain after preferably will filtering washs, more preferably at first adopt water that the product that obtains is carried out the washing first time, adopt again ethanol that the product that obtains is carried out the washing second time.Wash complete after, the product that obtains heated 24h in 60 ℃ of baking ovens after, obtain carbon and coat the attapulgite clay composite.
The present invention carries out carburizing reagent and obtains carbon coating attapulgite clay composite take glucose as raw material, it contains more carbonyl, carboxyl isoreactivity group, can with water in heavy metal ion generation ion exchange, redox reaction etc., thereby be conducive to Adsorption to the heavy metal ion in the water.In addition, the present invention can also coat the attapulgite clay composite to described carbon carry out modification, improves its adsorption capacity and to the Selective adsorption of special metal ion.
After obtaining carbon coating attapulgite clay composite, it is carried out heavy metal ion adsorbed performance test, the result shows, its adsorption capacity is better than the multiple adsorbents such as aeroge, CNT and chitosan polymer of attapulgite clay, active carbon, oxidisability active carbon, carbon, its the pH value be 6.0 o'clock to water in the high adsorption capacity of lead（II） ion be 263.83mg/g, be 4930 times of attapulgite clay adsorbance; Its pH value be 2.0 o'clock to water in the high adsorption capacity of hexavalent chromium be 177.74mg/g, be 2.5 times of attapulgite clay adsorbance.
In order to further specify the present invention, below in conjunction with embodiment carbon provided by the invention is coated attapulgite clay composite and preparation method thereof and be described in detail.
Below among each embodiment, it is the adsorbent attapulgite clay of L60 that attapulgite clay is available from the bright U.S. mineral chemical industry in Anhui Co., Ltd, specification.
Embodiment 1
Under the room temperature condition, 0.5g attapulgite clay and 1.5g glucose are dissolved in the 38mL water, after stirring the mixed solution that obtains are transferred in the polytetrafluoroethylene (PTFE) reactor; Reactor is warming up to 160 ℃, isothermal reaction 48h; Then reactor being cooled to room temperature, is the membrane filtration of 220nm with the product that obtains with the aperture, again with filtration product respectively water and ethanol clean, in 60 ℃ of baking ovens, dry 24h, obtain carbon and coat the attapulgite clay composite.
Described carbon is coated the attapulgite clay composite carry out the field emission scanning electron microscope observation, the result is referring to Fig. 1, Fig. 2 and Fig. 3, the carbon that Fig. 1 provides for the embodiment of the invention 1 coats the low power stereoscan photograph of attapulgite clay composite, the carbon that Fig. 2 provides for the embodiment of the invention 1 coats the high power stereoscan photograph of attapulgite clay composite, the carbon that Fig. 3 provides for the embodiment of the invention 1 coat the attapulgite clay composite in times stereoscan photograph; Described carbon is coated the attapulgite clay composite carry out a transmission electron microscope observation, the result is referring to Fig. 4, and the carbon that Fig. 4 provides for the embodiment of the invention 1 coats the transmission electron microscope photo of attapulgite clay composite.By Fig. 1, Fig. 2, Fig. 3 and Fig. 4 as can be known, the present invention obtains carbon and coats the carbon nano-particle that the attapulgite clay composite comprises attapulgite clay and is coated on described attapulgite clay surface, the diameter of described carbon nano-particle is about 1nm～5nm, the diameter of described composite is about 30nm～60nm, and its length can reach several microns.
NaOH solution with 0.1mol/L is adjusted to 6.0 with the pH value that 50.0mL contains the solution of Pb (II), and the carbon coating attapulgite clay composite vigorous stirring that 10.0mg embodiment 1 is prepared is scattered in the described aqueous solution; At room temperature, detect the concentration of adsorbing lead（II） ion in the rear solution with inductively coupled plasma (ICP) after stirring 30h, the result is referring to Fig. 5, the carbon that Fig. 5 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of lead（II） ion, as shown in Figure 5, the carbon coating attapulgite clay composite of embodiment 1 preparation is 114.16mg/g to the maximal absorptive capacity of Pb (II).
Hydrochloric acid solution with 0.1mol/L is adjusted to 2.0 with the pH value that 15.0mL contains the solution of Cr (VI), and the carbon coating attapulgite clay composite vigorous stirring that 10.0mg embodiment 1 is prepared is scattered in the described aqueous solution; At room temperature, after stirring 30h, aqueous solution color is shoaled by orange-yellow, detect the concentration of hexavalent chromium in the rear solution of absorption with inductively coupled plasma (ICP), the result is referring to Fig. 6, the carbon that Fig. 6 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of hexavalent chromium, and as shown in Figure 6, the carbon coating attapulgite clay composite of embodiment 1 preparation is 77.51mg/g to the maximal absorptive capacity of Cr (VI).
Under the room temperature condition, 0.5g attapulgite clay and 4.0g glucose are dissolved in the 38mL water, after stirring the mixed solution that obtains are transferred in the polytetrafluoroethylene (PTFE) reactor; Reactor is warming up to 160 ℃, isothermal reaction 48h; Then reactor being cooled to room temperature, is the membrane filtration of 220nm with the product that obtains with the aperture, again with filtration product respectively water and ethanol clean, in 60 ℃ of baking ovens, dry 24h, obtain carbon and coat the attapulgite clay composite.
Described carbon is coated the attapulgite clay composite carry out the field emission scanning electron microscope observation, the result is referring to Fig. 7 and Fig. 8, the carbon that Fig. 7 provides for the embodiment of the invention 2 coats the low power stereoscan photograph of attapulgite clay composite, and the carbon that Fig. 8 provides for the embodiment of the invention 2 coats the high power stereoscan photograph of attapulgite clay composite.By Fig. 7 and Fig. 8 as can be known, the present invention obtains carbon and coats the attapulgite clay composite except comprising attapulgite clay and being coated on the carbon nano-particle on described attapulgite clay surface, and also comprise a large amount of carbon balls, the diameter of described carbon ball is about 800nm.
NaOH solution with 0.1mol/L is adjusted to 6.0 with the pH value that 50.0mL contains the solution of Pb (II), and the carbon coating attapulgite clay composite vigorous stirring that 10.0mg embodiment 2 is prepared is scattered in the described aqueous solution; At room temperature, detect the concentration of adsorbing lead（II） ion in the rear solution with inductively coupled plasma (ICP) after stirring 30h, the result is referring to Fig. 5, the carbon that Fig. 5 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of lead（II） ion, as shown in Figure 5, the carbon coating attapulgite clay composite of embodiment 2 preparations is 125.18mg/g to the maximal absorptive capacity of Pb (II).
Hydrochloric acid solution with 0.1mol/L is adjusted to 2.0 with the pH value that 15.0mL contains the solution of Cr (VI), and the carbon coating attapulgite clay composite vigorous stirring that 10.0mg embodiment 2 is prepared is scattered in the described aqueous solution; At room temperature, after stirring 30h, aqueous solution color is shoaled by orange-yellow, detect the concentration of hexavalent chromium in the rear solution of absorption with inductively coupled plasma (ICP), the result is referring to Fig. 6, the carbon that Fig. 6 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of hexavalent chromium, and as shown in Figure 6, the carbon coating attapulgite clay composite of embodiment 2 preparations is 222.04mg/g to the maximal absorptive capacity of Cr (VI).
Embodiment 3
Under the room temperature condition, 0.5g attapulgite clay and 2.5g glucose are dissolved in the 38mL water, after stirring the mixed solution that obtains are transferred in the polytetrafluoroethylene (PTFE) reactor; Reactor is warming up to 160 ℃, isothermal reaction 48h; Then reactor being cooled to room temperature, is the membrane filtration of 220nm with the product that obtains with the aperture, again with filtration product respectively water and ethanol clean, in 60 ℃ of baking ovens, dry 24h, obtain carbon and coat the attapulgite clay composite.
Described carbon is coated the attapulgite clay composite carry out the field emission scanning electron microscope observation, the result is referring to Fig. 9 and Figure 10, the carbon that Fig. 9 provides for the embodiment of the invention 3 coats the low power stereoscan photograph of attapulgite clay composite, and the carbon that Figure 10 provides for the embodiment of the invention 3 coats the high power stereoscan photograph of attapulgite clay composite.By Fig. 9 and Figure 10 as can be known, the present invention obtains carbon and coats the carbon nano-particle that the attapulgite clay composite comprises attapulgite clay and is coated on described attapulgite clay surface, the diameter of described carbon nano-particle is about 1nm～10nm, the diameter of described composite is about 40nm～80nm, and its length can reach several microns.
NaOH solution with 0.1mol/L is adjusted to 6.0 with the pH value that 50.0mL contains the solution of Pb (II), and the carbon coating attapulgite clay composite vigorous stirring that 10.0mg embodiment 3 is prepared is scattered in the described aqueous solution; At room temperature, detect the concentration of adsorbing lead（II） ion in the rear solution with inductively coupled plasma (ICP) after stirring 30h, the result is referring to Fig. 5 and Figure 11, the carbon that Fig. 5 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of lead（II） ion, the carbon that Figure 11 provides for the embodiment of the invention 3 coats the attapulgite clay composite to the isothermal adsorption curve of lead（II） ion, by Fig. 5 and Figure 11 as can be known, to coat the attapulgite clay composite be 263.83mg/g to the maximal absorptive capacity of Pb (II) to the carbon of embodiment 3 preparations.
Hydrochloric acid solution with 0.1mol/L is adjusted to 2.0 with the pH value that 15.0mL contains the solution of Cr (VI), and the carbon coating attapulgite clay composite vigorous stirring that 10.0mg embodiment 3 is prepared is scattered in the described aqueous solution; At room temperature, after stirring 30h, aqueous solution color is shoaled by orange-yellow, detect the concentration of hexavalent chromium in the rear solution of absorption with inductively coupled plasma (ICP), the result is referring to Fig. 6 and Figure 12, the carbon that Fig. 6 provides for the embodiment of the invention coats the attapulgite clay composite to the isothermal adsorption curve of hexavalent chromium, the carbon that Figure 12 provides for the embodiment of the invention 3 coats the attapulgite clay composite to the isothermal adsorption curve of hexavalent chromium, by Fig. 6 and Figure 12 as can be known, to coat the attapulgite clay composite be 177.74mg/g to the maximal absorptive capacity of Cr (VI) to the carbon of embodiment 3 preparations.
Comparative example 1
Attapulgite clay is carried out field emission scanning electron microscope observe, the result is referring to Figure 13, the stereoscan photograph of the attapulgite clay that Figure 13 provides for comparative example 1 of the present invention; Described attapulgite clay is carried out a transmission electron microscope observation, and the result is referring to Figure 14, the transmission electron microscope photo of the attapulgite clay that Figure 14 provides for comparative example 1 of the present invention.
NaOH solution with 0.1mol/L is adjusted to 6.0 with the pH value that 50.0mL contains the solution of Pb (II), and the attapulgite clay vigorous stirring that 10.0mg comparative example 1 is provided is scattered in the described aqueous solution; At room temperature, detect the concentration of adsorbing lead（II） ion in the rear solution with inductively coupled plasma (ICP) after stirring 30h, the result is referring to Figure 15, the attapulgite clay that Figure 15 provides for comparative example 1 of the present invention is to the isothermal adsorption curve of lead（II） ion, as shown in Figure 15, the attapulgite clay that provides of comparative example 1 is 0.05mg/g to the maximal absorptive capacity of Pb (II).
Hydrochloric acid solution with 0.1mol/L is adjusted to 2.0 with the pH value that 15.0mL contains the solution of Cr (VI), and the attapulgite clay vigorous stirring that 10.0mg comparative example 1 is provided is scattered in the described aqueous solution; At room temperature, after stirring 30h, aqueous solution color is shoaled by orange-yellow, detect the concentration of hexavalent chromium in the rear solution of absorption with inductively coupled plasma (ICP), the result is referring to Figure 16, the attapulgite clay that Figure 16 provides for comparative example 1 of the present invention is to the isothermal adsorption curve of hexavalent chromium, and as shown in Figure 16, the attapulgite clay that comparative example 1 provides is 71.1mg/g to the maximal absorptive capacity of Cr (VI).
Comparative example 2～5
Lead（II） ion and hexavalent chromium in respectively take aeroge, CNT and the chitosan complexes of active carbon, oxidisability active carbon, carbon as the adsorbent adsorbed water, the result is referring to table 1, the adsorption capacity of the adsorbent that table 1 provides for the embodiment of the invention and comparative example.
The adsorption capacity of the adsorbent that table 1 embodiment of the invention and comparative example provide
In the table 1, comparative example 2 data from Babu, B.V.; Gupta, S.Adsorption 2008,14, and 85～92 and Goel, J.; Kadirvelu, K.; Rajagopal, C.; Garg, V.K.J.Hazard.Mater.2005,125,211～220; Comparative example 3 data from Zhao, N.Q.; Wei, N.; Li, J.J.; Qiao, Z.J.; Cui, J.; He, F.Chem.Eng.J.2005,115,133～138; Comparative example 4 data from Demir-Cakan, R.; Baccile, N.; Antonietti, M.; Titirici, M.M.Chem.Mater.2009,21,484～490; Comparative example 5 data from Liang, H.W.; Cao, X.; Zhang, W.J.; Lin, H.T.; Zhou, F.; Chen, L.F.; Yu, S.H.Submitted for publication; Comparative example 6 data from Boddu, V.M.; Abburi, K.; Talbott, J.L.; Smith, E.D.Environ.Sci.Technol.2003,37,4449～4456.
As shown in Table 1, compare with the adsorbents such as aeroge, CNT and chitosan complexes of the attapulgite clay that does not coat, active carbon, oxidisability active carbon, carbon, when carbon provided by the invention coats the attapulgite clay composite as adsorbent, lead（II） ion and hexavalent chromium are all had stronger adsorption capacity, be respectively 4930 times and 2.5 times of attapulgite clay such as the ability of its absorption Pb (II) and Cr (VI).
The above only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a carbon coats the attapulgite clay composite, comprising: attapulgite clay and the carbon nano-particle that is coated on described attapulgite clay surface.
2. carbon according to claim 1 coats the attapulgite clay composite, it is characterized in that the mass ratio of described attapulgite clay and described carbon nano-particle is 1: (0.5～3.5).
3. carbon according to claim 2 coats the attapulgite clay composite, it is characterized in that the diameter of described carbon nano-particle is 0.5nm～20nm.
4. a carbon coats attapulgite clay composite manufacture method, may further comprise the steps:
Attapulgite clay is mixed in water with glucose, occur to obtain carbon coating attapulgite clay composite after the carburizing reagent.
5. preparation method according to claim 4 is characterized in that, the mass ratio of described attapulgite clay and described glucose is 1: (3～8).
6. preparation method according to claim 4 is characterized in that, the mass ratio of described glucose and described water is (3～8): 76.
7. preparation method according to claim 4 is characterized in that, the time of described carburizing reagent is 24h～48h.
8. preparation method according to claim 4 is characterized in that, the temperature of described carburizing reagent is 160 ℃～180 ℃.
9. preparation method according to claim 4 is characterized in that, also comprises:
Described carbon is coated the attapulgite clay composite to be washed.
10. preparation method according to claim 9 is characterized in that, described washing specifically comprises:
Adopt water that described carbon is coated the attapulgite clay composite and carry out the washing first time;
Adopt ethanol that described carbon is coated the attapulgite clay composite and carry out the washing second time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103167915A CN103055806A (en) | 2011-10-18 | 2011-10-18 | Carbon-coated attapulgite clay composite material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103167915A CN103055806A (en) | 2011-10-18 | 2011-10-18 | Carbon-coated attapulgite clay composite material and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103055806A true CN103055806A (en) | 2013-04-24 |
Family
ID=48098874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103167915A Pending CN103055806A (en) | 2011-10-18 | 2011-10-18 | Carbon-coated attapulgite clay composite material and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103055806A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126757A (en) * | 2015-09-10 | 2015-12-09 | 中国矿业大学(北京) | Preparation method for diatomaceous earth-supported nanometer carbon composite adsorption material |
| CN105289495A (en) * | 2015-11-19 | 2016-02-03 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing multifunctional composite material by in situ reaction of waste clay mineral adsorbing dye |
| CN105461974A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Modified attapulgite for rubber reinforcing, and preparation method thereof |
| CN105461975A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Natural rubber/attapulgite nanometer composite material preparation method |
| JP2016113324A (en) * | 2014-12-16 | 2016-06-23 | 日立化成株式会社 | Aluminum silicate composite |
| EP3009399A4 (en) * | 2013-06-12 | 2016-12-14 | Hitachi Chemical Co Ltd | Aluminum silicate complex, conductive material, conductive material for lithium ion secondary cell, composition for forming lithium ion secondary cell negative electrode, composition for forming lithium ion secondary cell positive electrode, negative electrode for lithium ion secondary cell, positive electrode for lithium ion secondary cell, and lithium ion secondary cell |
| CN108295813A (en) * | 2018-03-17 | 2018-07-20 | 宁夏大学 | Montmorillonite/carbon ball compound adsorbent and preparation method thereof and its application and detection device |
| CN109370186A (en) * | 2018-11-22 | 2019-02-22 | 安徽汇创新材料有限公司 | A kind of preparation method of the glass toughening manure pit of low temperature resistant environmental protection |
| CN109603757A (en) * | 2019-01-22 | 2019-04-12 | 中南大学 | Five fluorine magnaliums/porous carbon composite and the preparation method and application thereof |
| CN109603758A (en) * | 2019-01-22 | 2019-04-12 | 中南大学 | Five fluorine magnaliums/attapulgite/porous carbon composite and the preparation method and application thereof |
| CN109701490A (en) * | 2019-01-07 | 2019-05-03 | 中南大学 | Magnetic cobalt carbon attapulgite composite material and preparation method and application |
| CN110420618A (en) * | 2019-07-24 | 2019-11-08 | 生态环境部南京环境科学研究所 | A kind of preparation method of novel attapulgite soil and its method for handling heavy metal wastewater thereby |
| CN110898808A (en) * | 2019-12-20 | 2020-03-24 | 北京化工大学 | Mechanochemical preparation method of sulfur-rich alkyne carbon material and application of sulfur-rich alkyne carbon material in heavy metal ion adsorption in aqueous solution |
| CN112058223A (en) * | 2020-08-25 | 2020-12-11 | 深圳务本材料科技有限公司 | Carbon product nano spar |
| CN112574482A (en) * | 2020-12-10 | 2021-03-30 | 界首市鑫豪塑胶有限公司 | Method for preparing high-performance PVC/NBR decorative material by using nano powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011070208A1 (en) * | 2009-12-09 | 2011-06-16 | Consejo Superior De Investigaciones Cientificas (Csic) | Use of fibrous clays as coadjuvants to improve the dispersion and colloidal stability of filamentous carbon materials in hydrophilic media |
| CN102179182A (en) * | 2011-03-29 | 2011-09-14 | 中国科学技术大学 | Method for preparing carbon nanofiber membrane |
-
2011
- 2011-10-18 CN CN2011103167915A patent/CN103055806A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011070208A1 (en) * | 2009-12-09 | 2011-06-16 | Consejo Superior De Investigaciones Cientificas (Csic) | Use of fibrous clays as coadjuvants to improve the dispersion and colloidal stability of filamentous carbon materials in hydrophilic media |
| CN102179182A (en) * | 2011-03-29 | 2011-09-14 | 中国科学技术大学 | Method for preparing carbon nanofiber membrane |
Non-Patent Citations (3)
| Title |
|---|
| LI-FENG CHEN ET AL: ""Synthesis of an Attapulgite Clay@Carbon Nanocomposite Adsorbent by a Hydrothermal Carbonization Process and Their Application in the Removal of Toxic Metal Ions from Water"", 《LANGMUIR》, vol. 27, 14 June 2011 (2011-06-14) * |
| 吴雪平等: ""凹凸棒石/C复合材料的制备及其对苯酚的吸附性能研究"", 《化工新型材料》, vol. 36, no. 11, 30 November 2008 (2008-11-30) * |
| 庆承松等: ""凹凸棒石/γ-Fe2O3/碳纳米复合材料的制备及其对苯酚的吸附作用"", 《环境科学研究》, vol. 22, no. 3, 31 March 2009 (2009-03-31) * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3009399A4 (en) * | 2013-06-12 | 2016-12-14 | Hitachi Chemical Co Ltd | Aluminum silicate complex, conductive material, conductive material for lithium ion secondary cell, composition for forming lithium ion secondary cell negative electrode, composition for forming lithium ion secondary cell positive electrode, negative electrode for lithium ion secondary cell, positive electrode for lithium ion secondary cell, and lithium ion secondary cell |
| CN105461974A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Modified attapulgite for rubber reinforcing, and preparation method thereof |
| CN105461975A (en) * | 2014-08-08 | 2016-04-06 | 兰州大学 | Natural rubber/attapulgite nanometer composite material preparation method |
| CN105461974B (en) * | 2014-08-08 | 2019-01-18 | 兰州大学 | A kind of preparation method of modified attapulgite used for rubber reinforcement |
| CN105461975B (en) * | 2014-08-08 | 2019-01-18 | 兰州大学 | A kind of preparation method of natural rubber/palygorskite nano composite material |
| JP2016113324A (en) * | 2014-12-16 | 2016-06-23 | 日立化成株式会社 | Aluminum silicate composite |
| CN105126757A (en) * | 2015-09-10 | 2015-12-09 | 中国矿业大学(北京) | Preparation method for diatomaceous earth-supported nanometer carbon composite adsorption material |
| CN105289495A (en) * | 2015-11-19 | 2016-02-03 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing multifunctional composite material by in situ reaction of waste clay mineral adsorbing dye |
| CN105289495B (en) * | 2015-11-19 | 2017-07-28 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Using adsorbing the method that the useless clay mineral reaction in-situ after dyestuff prepares multifunctional composite |
| CN108295813A (en) * | 2018-03-17 | 2018-07-20 | 宁夏大学 | Montmorillonite/carbon ball compound adsorbent and preparation method thereof and its application and detection device |
| CN109370186A (en) * | 2018-11-22 | 2019-02-22 | 安徽汇创新材料有限公司 | A kind of preparation method of the glass toughening manure pit of low temperature resistant environmental protection |
| CN109701490A (en) * | 2019-01-07 | 2019-05-03 | 中南大学 | Magnetic cobalt carbon attapulgite composite material and preparation method and application |
| CN109603757A (en) * | 2019-01-22 | 2019-04-12 | 中南大学 | Five fluorine magnaliums/porous carbon composite and the preparation method and application thereof |
| CN109603758A (en) * | 2019-01-22 | 2019-04-12 | 中南大学 | Five fluorine magnaliums/attapulgite/porous carbon composite and the preparation method and application thereof |
| CN109603758B (en) * | 2019-01-22 | 2020-04-21 | 中南大学 | Pentafluoro magnesium-aluminum/attapulgite/porous carbon composite material and preparation method and application thereof |
| CN109603757B (en) * | 2019-01-22 | 2020-04-21 | 中南大学 | Pentafluoro magnesium-aluminum/porous carbon composite material and preparation method and application thereof |
| CN110420618A (en) * | 2019-07-24 | 2019-11-08 | 生态环境部南京环境科学研究所 | A kind of preparation method of novel attapulgite soil and its method for handling heavy metal wastewater thereby |
| CN110898808A (en) * | 2019-12-20 | 2020-03-24 | 北京化工大学 | Mechanochemical preparation method of sulfur-rich alkyne carbon material and application of sulfur-rich alkyne carbon material in heavy metal ion adsorption in aqueous solution |
| CN112058223A (en) * | 2020-08-25 | 2020-12-11 | 深圳务本材料科技有限公司 | Carbon product nano spar |
| CN112574482A (en) * | 2020-12-10 | 2021-03-30 | 界首市鑫豪塑胶有限公司 | Method for preparing high-performance PVC/NBR decorative material by using nano powder |
| CN112574482B (en) * | 2020-12-10 | 2022-10-28 | 界首市聚屹包装材料有限公司 | Method for preparing high-performance PVC/NBR decorative material by using nano powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055806A (en) | Carbon-coated attapulgite clay composite material and its preparation method | |
| Kamaraj et al. | Facile development of sunlit ZnO nanoparticles-activated carbon hybrid from pernicious weed as an operative nano-adsorbent for removal of methylene blue and chromium from aqueous solution: extended application in tannery industrial wastewater | |
| Fouda-Mbanga et al. | Carbohydrate biopolymers, lignin based adsorbents for removal of heavy metals (Cd2+, Pb2+, Zn2+) from wastewater, regeneration and reuse for spent adsorbents including latent fingerprint detection: A review | |
| Yang et al. | Corn straw-derived biochar impregnated with α-FeOOH nanorods for highly effective copper removal | |
| Wang et al. | Amino-functionalized biomass-derived porous carbons with enhanced aqueous adsorption affinity and sensitivity of sulfonamide antibiotics | |
| Lou et al. | Enhanced removal of As (III)/(V) from water by simultaneously supported and stabilized Fe-Mn binary oxide nanohybrids | |
| Raval et al. | Adsorptive amputation of hazardous azo dye Congo red from wastewater: a critical review | |
| Syeda et al. | Biosorption of heavy metals from aqueous solution by various chemically modified agricultural wastes: a review | |
| Jorfi et al. | Sono-assisted adsorption of a textile dye on milk vetch-derived charcoal supported by silica nanopowder | |
| Pan et al. | Nanodiamonds anchored on porous ZnSnO3 cubes as an efficient composite photocatalyst with improved visible-light photocatalytic degradation of tetracycline | |
| Honarmand et al. | Green synthesis of SnO2-bentonite nanocomposites for the efficient photodegradation of methylene blue and eriochrome black-T | |
| Talukder et al. | Chitosan-functionalized sodium alginate-based electrospun nanofiber membrane for As (III) removal from aqueous solution | |
| Mallakpour et al. | Sawdust, a versatile, inexpensive, readily available bio-waste: From mother earth to valuable materials for sustainable remediation technologies | |
| Hua | Synthesis and characterization of bentonite based inorgano–organo-composites and their performances for removing arsenic from water | |
| Liu et al. | Adsorption of low concentrations of bromide ions from water by cellulose-based beads modified with TEMPO-mediated oxidation and Fe (III) complexation | |
| CN112791714B (en) | Magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, preparation method and application | |
| WO2016192311A1 (en) | Hollow iron-manganese composite material prepared by etching template process and application thereof | |
| Liu et al. | Intrinsic Peroxidase‐like Activity of Porous CuO Micro‐/nanostructures with Clean Surface | |
| Mahdavi et al. | Aminoguanidine modified magnetic graphene oxide as a robust nanoadsorbent for efficient removal and extraction of chlorpyrifos residue from water | |
| Rabeie et al. | Morphological diversity effect of graphene quantum dot/MIL88A (Fe) composites on dye and pharmaceuticals (tetracycline and doxycycline) removal | |
| Yosef et al. | High performance graphene-based PVF foam for lead removal from water | |
| CN110947371B (en) | Preparation method of modified cellulose-based phosphorus removal adsorbent | |
| Madhusha et al. | Synthesis and structural characterization of copper nanoparticles doped activated carbon derived from coconut coir for drinking water purification | |
| Liang et al. | New insights into co-adsorption of Cr6+ and chlortetracycline by a new fruit peel based biochar composite from water: Behavior and mechanism | |
| Chauhan et al. | Nanoadsorbents for wastewater remediation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130424 |