CN104772113A - Graphene / montmorillonite nano composite material, and preparation method and application thereof - Google Patents
Graphene / montmorillonite nano composite material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN104772113A CN104772113A CN201510106039.6A CN201510106039A CN104772113A CN 104772113 A CN104772113 A CN 104772113A CN 201510106039 A CN201510106039 A CN 201510106039A CN 104772113 A CN104772113 A CN 104772113A
- Authority
- CN
- China
- Prior art keywords
- graphene
- montmorillonite
- composite material
- suspension
- preparation
- 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.)
- Granted
Links
Abstract
The invention discloses a graphene / montmorillonite nano composite material, and a preparation method and application thereof. The preparation method of the graphene / montmorillonite nano composite material is as below: uniformly mixing cetyl trimethyl ammonium bromide modified montmorillonite suspension and graphene oxide suspension subjected to ultrasonic treatment, fully stirring, adding a reducing agent for reduction, so as to obtain a black flocculent precipitate after the reaction, and conducting washing, suction filtration, drying, grinding and screening to obtain the graphene / montmorillonite nano composite material. The graphene / montmorillonite nano composite material prepared by the method can be used as an adsorbent in the field of water pollution control, especially adsorption and removal of the heavy metal pollutants in wastewater, and has the advantages of simple preparation method, high adsorption speed, easy regeneration, and reuse. The raw materials have wide sources, low cost and high actual application value.
Description
Technical field
The present invention relates to technical field of water pollution control, be specifically related to a kind of Graphene/montmorillonite nano-composite material and preparation method thereof and application.
Background technology
Along with the development of industrial economy, the increasing waste water containing heavy metal or organic pollution is discharged in natural water, and ecological environment and human health in serious harm.Water pollution problems is many countries, especially developing country in world wide, the main Environmental Problems faced.China has a large amount of manufacturing and processing enterprises, and Water Pollution Problem allows of no optimist naturally.Heavy metal contaminants in waste water has the large and easy feature such as accumulation in vivo of difficult degradation, toxicity, huge to the potential hazard of natural environment and the mankind, is therefore the focus of various countries researcher discussion to the removal of heavy metal pollution in wastewater thing always.Hexavalent chromium is a kind of heavy metal contaminants common in industrial wastewater, and it is widely used in the industries such as intermetallic composite coating, process hides, plating and pigment manufacture.Cr VI has carcinogenicity, is listed in one of priority pollutants.For the improvement of the hexavalent chromium in waste water, absorption method is low with expense in numerous method, be easy to the advantages such as operation, effective, recyclable heavy metal and adsorbent be renewable becomes conventional method.Up to the present, the various different sorbing material of the software engineering researchers invent of various countries removes the hexavalent chromium in waste water, although some sorbing materials show good adsorption effect, but these materials can recycling rate of waterused lower, this will certainly cause the wasting of resources, increase operating cost, and likely can bring secondary pollution.Graphene is a kind of two-dimension nano materials risen nearly ten years, and huge specific area becomes a kind of adsorbent of good performance.But in preparation process, graphene platelet can occur irreversible again stacking, makes it lose most specific area, thus limit Graphene as the application of adsorbent in water pollution control.
Summary of the invention
An object of the present invention be for the removal of Pollutants in Wastewater a kind of economy, environmental protection be provided, be easy to prepare, can the high Graphene/montmorillonite nano-composite material adsorbent of recycling rate of waterused.
Two of object of the present invention is a kind of preparation method providing above-mentioned Graphene/montmorillonite nano-composite material, and the method technique is simple, equipment requirement is low, be easy to large-scale production.
Three of object of the present invention is to provide above-mentioned Graphene/montmorillonite nano-composite material as adsorbent in the application of removing hexavalent chromium in heavy metal-containing waste water.
The technical solution used in the present invention is:
A kind of preparation method of Graphene/montmorillonite nano-composite material, step is: by the graphene oxide suspension Homogeneous phase mixing after montmorillonite suspension modified for softex kw and ultrasonic process, fully ultrasonic, stir after add reducing agent and reduce, obtain black flocculent deposit after having reacted, after washing, suction filtration, drying and grinding are sieved, obtain Graphene/montmorillonite nano-composite material.
Said method comprises the steps:
(1) oxidation graphite solid is added to the water, after ultrasonic process, obtains graphene oxide suspension;
(2) be dispersed in water modified montmorillonite used for softex kw, obtain organically modified montmorillonite clay suspension;
(3) graphene oxide suspension obtained in step (1) and step (2) and organically modified montmorillonite clay uniform suspension are mixed, under mechanical agitation and ultrasonication, obtain even, stable suspension;
(4) the suspension heating water bath to 70 DEG C will obtained in step (3), adds reducing agent under mechanical agitation, obtain black flocculent deposit after having reacted;
(5) the black flocculent deposit obtained in step (4) is washed, suction filtration, drying and grinding obtain Graphene/montmorillonite nano-composite material after sieving.
In said method, described in step (1), sonication treatment time is 90 ~ 150 min, and sonification power is 180 ~ 200 W; The concentration of described graphene oxide suspension is 0.2 ~ 0.3 g/L.
In said method, described in step (2), the preparation method of organically modified montmorillonite clay suspension is as follows:
Montmorillonite powder is joined in softex kw solution, by after mechanic whirl-nett reaction 100 ~ 150 min under the water bath condition of 50 ~ 70 DEG C, by deionized water, filtering and washing is carried out to product, until not bromine ion-containing in product, then product is scattered in water again, obtain organically modified montmorillonite clay suspension, wherein the consumption of softex kw is the montmorillonite cation exchange capacity of 1.0 ~ 1.5 times.
In said method, described in step (3), the concrete steps of mechanical agitation and ultrasonication are: the acting in conjunction times of mechanical agitation and ultrasonic two kinds of effects are 60 min, mechanical agitation 120 min more subsequently; Addition between graphene oxide suspension and organically modified montmorillonite clay suspension meets: the mass ratio of graphene oxide and montmorillonite is (1 ~ 3): 10.
In said method, described in step (4), reducing agent is ascorbic acid, and its consumption is 8 ~ 12 times of graphene oxide quality.
A kind of Graphene/montmorillonite nano-composite material, described Graphene/montmorillonite nano-composite material comprises Graphene, softex kw and montmorillonite.
Preferably, described softex kw inserts between montmorillonite layer by ion exchange; Described Graphene is combined by electrostatic attraction or hydroxyl effect and montmorillonite.
A kind of Graphene/montmorillonite nano-composite material is applied to the process of heavy metal-containing waste water as adsorbent.
In above-mentioned application, the hexavalent chromium in described removal heavy metal-containing waste water, concrete steps are as follows:
The dosage of Graphene/montmorillonite nano-composite material is 3 ~ 6 g/L, and controlling wastewater temperature is 20 ~ 30 DEG C, fully shakes, and is separated by adsorbent, completes the Adsorption to hexavalent chromium in waste water after reaching set treatment effect with waste water; Carry out desorption with the sodium hydroxide solution of 0.1 mol/L ~ 1 mol/L to the saturated adsorbent of absorption, controlling wastewater temperature is 25 ~ 35 DEG C, fully shakes, and is recycled by adsorbent after desorption is complete.
Compared with prior art, the invention has the beneficial effects as follows:
(1) material preparation process of the present invention is simple, equipment requirement is low, is easy to realize large-scale mass production;
(2) raw material rich reserves required for the present invention, cheap, and in use to environment, can not can obtain larger economic benefit with lower input;
(3) in the present invention the combination of montmorillonite and Graphene to successfully avoid graphene platelet again stacking in reduction process;
(4) Graphene/montmorillonite nano-composite material of preparing of the present invention can hexavalent chromium fast and efficiently in Adsorption waste water as adsorbent, can with simple method desorption and regeneration after this adsorbent is saturated, realize the dual recycling of adsorbent and adsorbate, not only can not bring secondary pollution, and greatly reduce the processing cost of waste water.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of Graphene/montmorillonite nano-composite material prepared by embodiments of the invention 1.
Fig. 2 be embodiments of the invention 1,2 and 3 prepare Graphene/montmorillonite nano-composite material and organically modified montmorillonite clay, montmorillonite Fourier transform infrared spectroscopy contrast schematic diagram.
Fig. 3 be embodiments of the invention 1,2 and 3 prepare Graphene/montmorillonite nano-composite material and organically modified montmorillonite clay, montmorillonite X-ray diffraction contrast schematic diagram.
Fig. 4 be embodiments of the invention 1,2 and 3 prepare Graphene/montmorillonite nano-composite material and montmorillonite under different solutions pH value condition, schematic diagram is contrasted to the adsorbance of hexavalent chromium.
Fig. 5 is that Graphene/montmorillonite nano-composite material prepared by embodiments of the invention 3 contrasts schematic diagram to the adsorbance of hexavalent chromium from montmorillonite under different adsorption time condition.
Fig. 6 is that Graphene/montmorillonite nano-composite material prepared by embodiments of the invention 3 contrasts schematic diagram to the adsorbance of hexavalent chromium from montmorillonite under the condition of different dosage.
Fig. 7 is that Graphene/montmorillonite nano-composite material prepared by embodiments of the invention 3 is taken turns in adsorption-desorption experiment the adsorbance of hexavalent chromium and desorption degree schematic diagram 6.
Detailed description of the invention
Do specifically to describe in detail further to the present invention below in conjunction with specific embodiment, but embodiments of the present invention are not limited thereto, for the technological parameter do not indicated especially, can refer to routine techniques and carry out.
Embodiment 1
(1) 0.25g oxidation graphite solid is added to the water, after ultrasonic process 2 h, obtains the graphene oxide suspension that concentration is 0.25 g/L;
Graphite oxide in the present embodiment adopts the Hummers legal system of improvement standby, concrete steps are: the 120 ml concentrated sulfuric acids are added 1 L beaker and is placed in ice-water bath, with electric mixer, it is slowly stirred, when its temperature is down to about 4 DEG C, add 5 g graphite and 2.5 g sodium nitrate, slowly add 15 g potassium permanganate after continuing stirring 30 min, keep the temperature of reaction system not higher than 20 DEG C in process, sustained response 90 min; Beaker is moved in the thermostat water bath of 35 DEG C, when system temperature rises to 35 DEG C, continue stirring reaction 30 min; 230 ml deionized waters continued to add in beaker lentamente, hierarchy of control temperature is below 98 DEG C, and heating water bath keeps system temperature at about 90 DEG C, adds the hydrogen peroxide of 30 ml 30 ﹪ after continuing reaction 30 min in beaker.Continue to stir until no longer include bubble generation in system.Products therefrom is carried out vacuum filtration, and with the washing of the hydrochloric acid solution of 5 ﹪ until no longer sulphate-containing ion in filtrate, then by appropriate deionized water, centrifuge washing is carried out to its pH in neutral to product, after the vacuum drying chamber finally product being placed in 60 DEG C is dried to constant weight, obtain the oxidation graphite solid of brown.
(2) be dispersed in water by organically modified montmorillonite clay, its consumption meets: the mass ratio of graphene oxide and montmorillonite is 1:10;
In the present embodiment, the preparation method of organically modified montmorillonite clay is: take be equivalent to montmorillonite cation exchange capacity (CEC) 1.25 times softex kw in 100 ml beakers, adding deionized water 62.5 ml makes it dissolve, 2.5 g montmorillonites are added again in solution, beaker is placed in thermostat water bath, keep temperature to be 60 DEG C, electric stirring reacts 2 h.Products therefrom is spent deionized water, until not bromine ion-containing in product.
(3) graphene oxide suspension obtained in step (1) is placed in ultrasonic cleaning machine, ultrasonic and slowly add the organically modified montmorillonite clay suspension obtained in step (2) while (350 rpm) being stirred to it with electric mixer, fully stir and make both mix; Continual ultrasonic stops ultrasonic after stirring 1 h, then stir (300 rpm) and allow system react 2 h, finally obtain uniform and stable brown suspension; This suspension being spent deionized water is dispersed in 1 L deionized water for several times;
(4) the brown suspension obtained in step (3) is placed in the thermostat water bath of 70 DEG C, and in suspension, add ascorbic acid (graphene oxide and ascorbic acid mass ratio are 1:10), electric stirring (200 rpm) reacts 90 min, finally obtains black product;
(5) the product deionized water filtering and washing several will obtained in step (4), gained filter cake is placed in air dry oven and is dried to constant weight in 50 DEG C, grind, cross 200 mesh sieves, obtain Graphene/montmorillonite nano-composite material powder (GCM10).
Embodiment 2
(1) 0.5g oxidation graphite solid is added to the water, after ultrasonic process 2h, obtains the graphene oxide suspension that concentration is 0.25 g/L;
(2) be dispersed in water by organically modified montmorillonite clay, addition meets: the mass ratio of graphene oxide and montmorillonite is 2:10;
(3) graphene oxide suspension obtained in step (1) is placed in ultrasonic cleaning machine, ultrasonic and slowly add the organically modified montmorillonite clay suspension obtained in step (2) while (350 rpm) being stirred to it with electric mixer, fully stir and make both mix; Continual ultrasonic stops ultrasonic after stirring 1 h, then stir (300 rpm) and allow system react 2 h, finally obtain uniform and stable brown suspension; This suspension being spent deionized water is dispersed in 1 L deionized water for several times;
(4) the brown suspension obtained in step (3) is placed in the thermostat water bath of 70 DEG C, and in suspension, add appropriate ascorbic acid (graphene oxide and ascorbic acid mass ratio are 1:10), electric stirring (200 rpm) reacts 90 min, finally obtains black product;
(5) the product deionized water filtering and washing several will obtained in step (4), gained filter cake is placed in air dry oven and is dried to constant weight in 50 DEG C, grind, cross 200 mesh sieves, obtain Graphene/montmorillonite nano-composite material powder (GCM20).
The preparation method of the graphene oxide in the present embodiment is identical with embodiment 1.
The preparation method of the organically modified montmorillonite clay in the present embodiment is identical with embodiment 1.
Embodiment 3
(1) 0.75g oxidation graphite solid is added to the water, after ultrasonic process 2h, obtains the graphene oxide suspension that concentration is 0.25 g/L;
(2) be dispersed in water by appropriate organically modified montmorillonite clay, the consumption of organically modified montmorillonite clay meets: the mass ratio of graphene oxide and montmorillonite is 3:10;
(3) graphene oxide suspension obtained in step (1) is placed in ultrasonic cleaning machine, ultrasonic and slowly add the organically modified montmorillonite clay suspension obtained in step (2) while (350 rpm) being stirred to it with electric mixer, fully stir and make both mix; Continual ultrasonic stops ultrasonic after stirring 1 h, then stir (300 rpm) and allow system react 2 h, finally obtain uniform and stable brown suspension; This suspension being spent deionized water is dispersed in 1 L deionized water for several times;
(4) the brown suspension obtained in step (3) is placed in the thermostat water bath of 70 DEG C, and in suspension, add appropriate ascorbic acid (graphene oxide and ascorbic acid mass ratio are 1:10), electric stirring (200 rpm) reacts 90 min, finally obtains black product;
(5) the product deionized water filtering and washing several will obtained in step (4), gained filter cake is placed in air dry oven and is dried to constant weight in 50 DEG C, grind, cross 200 mesh sieves, obtain Graphene/montmorillonite nano-composite material powder (GCM30).
The preparation method of the graphene oxide in the present embodiment is identical with embodiment 1.
The preparation method of the organically modified montmorillonite clay in the present embodiment is identical with embodiment 1.
The effect of embodiment 1-3 products obtained therefrom is shown in that Fig. 1-3, Fig. 1 is the transmission electron microscope picture of Graphene/montmorillonite nano-composite material, and as can be seen from the figure, montmorillonite particle and graphene platelet successfully combine.In figure, comparatively dark, the sharp outline of color is montmorillonite particle; And material is transparent and what have pleated structure is graphene platelet.Fig. 2 is the Fourier transform infrared spectroscopy figure of Graphene/montmorillonite nano-composite material, and as seen from Figure 2, montmorillonite, after organically-modified, belongs to symmetry (2850 cm that softex kw fat connects c h bond
1) and antisymmetry (2919 cm
1) stretching vibration peak appears in the diffraction pattern of organically modified montmorillonite clay, illustrate that softex kw is successfully inserted in Montmorillonite Crystal lamella and form organically modified montmorillonite clay with it; And in the infrared spectrogram of embodiment 1-3 gained sample, 1725,1572 and 1417 cm
1the diffraction maximum at place corresponds respectively to the flexural vibrations of O-H key on carboxyl that the characteristic diffraction peak of phenyl ring in C=O key stretching vibration on carboxyl or epoxy functionality that Graphene does not reduce completely, graphene-structured and Graphene do not reduce completely, and these results prove that Graphene and organically modified montmorillonite clay coexist in this nano composite material.Fig. 3 is the X-ray diffractogram of embodiment 1-3 gained sample and raw material thereof, can find from figure, montmorillonite its interlamellar spacing after organically-modified expands 2.2902 nm to by 1.514 nm, again proves that softex kw successfully enters into Montmorillonite Crystal interlayer; And along with the increase of Graphene, both montmorillonites mass ratio in Graphene/montmorillonite nano-composite material, the interlamellar spacing of montmorillonite reduces gradually, illustrate that the introducing of Graphene makes a part of softex kw discharge between montmorillonite layer, as the connection bridge of montmorillonite and Graphene, both are made to combine.
Embodiment 4
Test 1
Contrast the adsorbance of hexavalent chromium in solution Graphene/montmorillonite nano-composite material under different solutions initial pH value condition, concrete steps are:
(1) hexavalent chromium solution drawing the different pH value of 25 ml adds the tool plug conical flask of 50 ml respectively, then 0.15 g Graphene/montmorillonite nano-composite material is added conical flask and jam-pack glass stopper, then conical flask is placed in constant-temperature table;
(2) solution ph in above-mentioned conical flask is respectively 2,4,6,8,10,12, and constant-temperature table temperature is set as 25 DEG C, speed setting is 180 rpm, and adsorption time is 2h;
(3) above-mentioned adsorption process terminates rear adsorbent in each conical flask to be separated from solution, completes the Adsorption of hexavalent chromium in the aqueous solution, measure remain hexavalent chromium in solution concentration, calculate adsorbance.
(4) test result as shown in Figure 4, and along with the reduction of solution ph, Graphene/montmorillonite nano-composite material increases gradually to the adsorbance of hexavalent chromium in solution, shows that acid condition is conducive to the carrying out adsorbed; Graphene/montmorillonite nano-composite material to the adsorbance of hexavalent chromium much larger than montmorillonite original soil (Mt).
Test 2
Contrast the adsorbance of hexavalent chromium in solution Graphene/montmorillonite nano-composite material under different adsorption time condition, concrete steps are:
(1) the tool plug conical flask that 25 ml hexavalent chromium solution add 50 ml is respectively drawn, again 0.15 g Graphene/montmorillonite nano-composite material (embodiment 3 products obtained therefrom) is added conical flask and jam-pack glass stopper, then conical flask is placed in constant-temperature table;
(2) solution ph in above-mentioned conical flask is 2, and constant-temperature table temperature is set as 25 DEG C, speed setting is 180 rpm, and adsorption time is respectively 1,3,5,10,20,30,40,60,120,240 min;
(3) above-mentioned adsorption process terminates rear adsorbent in each conical flask to be separated from solution, completes the Adsorption of hexavalent chromium in the aqueous solution, measure remain hexavalent chromium in solution concentration, calculate adsorbance.
(4) test result as shown in Figure 5, along with the increase of adsorption time, Graphene/montmorillonite nano-composite material increases gradually to the adsorbance of hexavalent chromium in solution, close to adsorption equilibrium when adsorption time is 2 h, the adsorption effect of Graphene/montmorillonite nano-composite material to hexavalent chromium is far superior to montmorillonite original soil.
Test 3
Contrast the adsorbance of hexavalent chromium in solution Graphene/montmorillonite nano-composite material under different adsorbent dosage condition, concrete steps are:
(1) draw the hexavalent chromium solution that 25ml initial concentration is 50 ppm, initial pH value is 2 in batches to add in 50 ml tool plug conical flasks, drop into appropriate adsorbent (embodiment 3 products obtained therefrom) subsequently successively;
(2) above-mentioned adsorbent dosage is respectively 2,4,8,12,16 g/L and 20 g/L, by unified for all tool plug conical flasks constant-temperature table being placed in temperature 25 DEG C, rotating speed 180 rpm, takes out after shaking 2 h;
(3) above-mentioned adsorption process terminates rear adsorbent in each conical flask to be separated from solution, completes the Adsorption of hexavalent chromium in the aqueous solution, measure remain hexavalent chromium in solution concentration, calculate adsorbance.
(4) test result as shown in Figure 6, and along with the increase of adsorbent dosage, in solution, the clearance of hexavalent chromium also continues to increase, and when dosage is 8 g/L, clearance reaches more than 90%.
Test 4
Carry out desorption and regeneration to the saturated Graphene/montmorillonite nano-composite material of absorption, concrete steps are:
(1) in the conical flask that the saturated adsorbent of absorption is housed, add sodium hydroxide solution, be placed in constant-temperature table shake unified for all conical flasks after jam-pack bottle stopper;
(2) concentration of above-mentioned sodium hydroxide solution is respectively 0.1 mol/L, and constant-temperature table temperature is 30 DEG C, rotating speed is 180 rpm, and the concussion time is 1.5 h;
(3) above-mentioned desorption process terminates rear adsorbent in each conical flask to be separated from solution, measures the concentration of the hexavalent chromium eluted in solution, calculates desorption rate.
(4) test result as shown in Figure 7, through 6 take turns adsorption-desorption experiment after it still has good adsorption capacity to hexavalent chromium, adsorbance declines and is only 13%, illustrate that Graphene/montmorillonite nano-composite material has good regenerability, can be used as a kind of excellent adsorbent and be generalized in practical application.
The above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (10)
1. the preparation method of Graphene/montmorillonite nano-composite material, it is characterized in that: by the graphene oxide suspension Homogeneous phase mixing after montmorillonite suspension modified for softex kw and ultrasonic process, fully ultrasonic, stir after add reducing agent and reduce, obtain black flocculent deposit after having reacted, after washing, suction filtration, drying and grinding are sieved, obtain Graphene/montmorillonite nano-composite material.
2. the preparation method of Graphene/montmorillonite nano-composite material according to claim 1, is characterized in that comprising the steps:
(1) oxidation graphite solid is added to the water, after ultrasonic process, obtains graphene oxide suspension;
(2) be dispersed in water modified montmorillonite used for softex kw, obtain organically modified montmorillonite clay suspension;
(3) graphene oxide suspension obtained in step (1) and step (2) and organically modified montmorillonite clay uniform suspension are mixed, under mechanical agitation and ultrasonication, obtain even, stable suspension;
(4) the suspension heating water bath to 70 DEG C will obtained in step (3), adds reducing agent under mechanical agitation, obtain black flocculent deposit after having reacted;
(5) the black flocculent deposit obtained in step (4) is washed, suction filtration, drying and grinding obtain Graphene/montmorillonite nano-composite material after sieving.
3. the preparation method of Graphene/montmorillonite nano-composite material according to claim 2, is characterized in that: described in step (1), sonication treatment time is 90 ~ 150 min, and sonification power is 180 ~ 200 W; The concentration of described graphene oxide suspension is 0.2 ~ 0.3 g/L.
4. the preparation method of Graphene/montmorillonite nano-composite material according to claim 2, is characterized in that: described in step (2), the preparation method of organically modified montmorillonite clay suspension is as follows:
Montmorillonite powder is joined in softex kw solution, by after mechanic whirl-nett reaction 100 ~ 150 min under the water bath condition of 50 ~ 70 DEG C, by deionized water, filtering and washing is carried out to product, until not bromine ion-containing in product, then product is scattered in water again, obtain organically modified montmorillonite clay suspension, wherein the consumption of softex kw is the montmorillonite cation exchange capacity of 1.0 ~ 1.5 times.
5. the preparation method of Graphene/montmorillonite nano-composite material according to claim 2, it is characterized in that: described in step (3), the concrete steps of mechanical agitation and ultrasonication are: the acting in conjunction times of mechanical agitation and ultrasonic two kinds of effects are 60 min, mechanical agitation 120 min more subsequently; Addition between graphene oxide suspension and organically modified montmorillonite clay suspension meets: the mass ratio of graphene oxide and montmorillonite is (1 ~ 3): 10.
6. the preparation method of Graphene/montmorillonite nano-composite material according to claim 2, is characterized in that: described in step (4), reducing agent is ascorbic acid, and its consumption is 8 ~ 12 times of graphene oxide quality.
7. a kind of Graphene/montmorillonite nano-composite material of preparing of preparation method described in any one of claim 1 ~ 6, is characterized in that: described Graphene/montmorillonite nano-composite material comprises Graphene, softex kw and montmorillonite.
8. Graphene/montmorillonite nano-composite material according to claim 7, is characterized in that: described softex kw inserts between montmorillonite layer by ion exchange; Described Graphene is combined by electrostatic attraction or hydroxyl effect and montmorillonite.
9. Graphene/montmorillonite nano-composite material according to claim 7 is applied to the process of heavy metal-containing waste water as adsorbent.
10. the application of Graphene/montmorillonite nano-composite material according to claim 9, is characterized in that: the hexavalent chromium in described removal heavy metal-containing waste water, and concrete steps are as follows:
The dosage of Graphene/montmorillonite nano-composite material is 3 ~ 6 g/L, and controlling wastewater temperature is 20 ~ 30 DEG C, fully shakes, and is separated by adsorbent, completes the Adsorption to hexavalent chromium in waste water after reaching set treatment effect with waste water; Carry out desorption with the sodium hydroxide solution of 0.1 mol/L ~ 1 mol/L to the saturated adsorbent of absorption, controlling wastewater temperature is 25 ~ 35 DEG C, fully shakes, and is recycled by adsorbent after desorption is complete.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510106039.6A CN104772113B (en) | 2015-03-11 | 2015-03-11 | A kind of graphene/montmorillonite nano-composite material and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510106039.6A CN104772113B (en) | 2015-03-11 | 2015-03-11 | A kind of graphene/montmorillonite nano-composite material and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104772113A true CN104772113A (en) | 2015-07-15 |
| CN104772113B CN104772113B (en) | 2017-12-01 |
Family
ID=53614063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510106039.6A Active CN104772113B (en) | 2015-03-11 | 2015-03-11 | A kind of graphene/montmorillonite nano-composite material and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104772113B (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293625A (en) * | 2015-11-14 | 2016-02-03 | 常州大学 | Removal method for endocrine disrupting chemicals in micropollution raw water |
| CN105344319A (en) * | 2015-11-05 | 2016-02-24 | 江苏大学 | Preparation method and application of graphene/attapulgite/titanium dioxide composite material |
| CN106076272A (en) * | 2016-06-24 | 2016-11-09 | 四川大学 | A kind of preparation method of adsorbent for heavy metal |
| CN107082416A (en) * | 2017-04-17 | 2017-08-22 | 中国科学院化学研究所 | A kind of method that graphene is prepared based on ozone oxidation |
| CN108311110A (en) * | 2018-03-14 | 2018-07-24 | 烟台金潮宇科蓄电池有限公司 | A kind of preparation method of the leaded wastewater efficient adsorbent containing acid |
| CN108311111A (en) * | 2018-03-14 | 2018-07-24 | 烟台金潮宇科蓄电池有限公司 | One kind is containing the leaded wastewater efficient adsorbent of acid |
| CN108358199A (en) * | 2018-05-09 | 2018-08-03 | 中国地质大学（武汉） | A kind of preparation method of montmorillonite/stannic oxide/graphene nano aeroge |
| CN108441225A (en) * | 2018-03-15 | 2018-08-24 | 东北大学 | A kind of reparation medicament and preparation method thereof for repairing mercury contaminated soil |
| CN108654559A (en) * | 2018-05-02 | 2018-10-16 | 朱红艳 | A kind of magnetic oxygenated graphene/montmorillonite adsorbent and preparation method thereof |
| CN109056104A (en) * | 2018-09-21 | 2018-12-21 | 佛山皖和新能源科技有限公司 | A kind of preparation method of conducting polypropylene fiber |
| CN109126689A (en) * | 2018-09-27 | 2019-01-04 | 广西科学院 | A kind of modified montmorillonite used preparation method and applications |
| CN109248658A (en) * | 2018-09-28 | 2019-01-22 | 芜湖市鹏磊新材料有限公司 | A kind of production method of the graphene organic modified bentonite particle handled for humic acid in water |
| CN109289544A (en) * | 2018-09-26 | 2019-02-01 | 同济大学 | A method of preparing two-dimentional montmorillonite/cellulose composite filtering film |
| CN109364975A (en) * | 2018-11-19 | 2019-02-22 | 华东交通大学 | A kind of graphene-supported MMT/N-S-TiO2The preparation method of photocatalyst agent |
| CN109502624A (en) * | 2018-12-12 | 2019-03-22 | 安徽华塑股份有限公司 | The method for preparing calcium chloride using by-product hydrochloric acid |
| CN109647345A (en) * | 2019-01-10 | 2019-04-19 | 江西理工大学 | It is a kind of remove xanthate organically modified montmorillonite clay adsorbent and its application |
| CN110152613A (en) * | 2018-04-16 | 2019-08-23 | 兰州理工大学 | A kind of aeroge adsorbent and preparation method thereof |
| CN110237826A (en) * | 2019-06-21 | 2019-09-17 | 郑州大学 | A kind of inorganic porous material and its preparation and application for removing removing heavy metals |
| CN112076727A (en) * | 2020-08-21 | 2020-12-15 | 温州大学 | Heavy metal pollution repairing agent and preparation method thereof |
| CN112156764A (en) * | 2020-09-15 | 2021-01-01 | 凯盛石墨碳材料有限公司 | Nano TiO (titanium dioxide)2Modified graphene oxide/organic bentonite composite material and preparation method thereof |
| CN112741221A (en) * | 2021-01-13 | 2021-05-04 | 霍敏凯 | Immunity-improving cat food and preparation method thereof |
| CN113634221A (en) * | 2021-08-25 | 2021-11-12 | 天津大学 | Anionic dye-oriented Al2O3Modified Fe3O4Preparation and application of nanoparticles |
| CN114306708A (en) * | 2021-12-28 | 2022-04-12 | 山东中大药业有限公司 | Adult diaper containing montmorillonite |
| CN115463094A (en) * | 2021-06-10 | 2022-12-13 | 北京微著新材科技有限公司 | Oral radiotherapy protective agent and preparation method and application thereof |
| CN116376167A (en) * | 2023-05-22 | 2023-07-04 | 上海廉藤实业有限公司 | Modified plastic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073009A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Anionic clay/graphene nanocomposite material and preparation method thereof |
| CN103143319A (en) * | 2013-03-01 | 2013-06-12 | 暨南大学 | Graphene/clay composite material, and preparation method and application thereof |
| CN103787322A (en) * | 2014-01-25 | 2014-05-14 | 华南理工大学 | Graphene-carrying phyllosilicate nano composite material and preparation method thereof |
-
2015
- 2015-03-11 CN CN201510106039.6A patent/CN104772113B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073009A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Anionic clay/graphene nanocomposite material and preparation method thereof |
| CN103143319A (en) * | 2013-03-01 | 2013-06-12 | 暨南大学 | Graphene/clay composite material, and preparation method and application thereof |
| CN103787322A (en) * | 2014-01-25 | 2014-05-14 | 华南理工大学 | Graphene-carrying phyllosilicate nano composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘鸥: ""改性蒙脱石吸附废水中重金属研究"", 《中国优秀硕士论文全文数据库 工程科技I辑》 * |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105344319A (en) * | 2015-11-05 | 2016-02-24 | 江苏大学 | Preparation method and application of graphene/attapulgite/titanium dioxide composite material |
| CN105344319B (en) * | 2015-11-05 | 2017-12-05 | 江苏大学 | The preparation method and applications of graphene/attapulgite/composite titania material |
| CN105293625B (en) * | 2015-11-14 | 2017-07-28 | 汪振朴 | The minimizing technology of incretion interferent in a kind of micro-polluted raw |
| CN105293625A (en) * | 2015-11-14 | 2016-02-03 | 常州大学 | Removal method for endocrine disrupting chemicals in micropollution raw water |
| CN106076272B (en) * | 2016-06-24 | 2018-08-14 | 四川大学 | A kind of preparation method of adsorbent for heavy metal |
| CN106076272A (en) * | 2016-06-24 | 2016-11-09 | 四川大学 | A kind of preparation method of adsorbent for heavy metal |
| CN107082416A (en) * | 2017-04-17 | 2017-08-22 | 中国科学院化学研究所 | A kind of method that graphene is prepared based on ozone oxidation |
| CN108311110A (en) * | 2018-03-14 | 2018-07-24 | 烟台金潮宇科蓄电池有限公司 | A kind of preparation method of the leaded wastewater efficient adsorbent containing acid |
| CN108311111A (en) * | 2018-03-14 | 2018-07-24 | 烟台金潮宇科蓄电池有限公司 | One kind is containing the leaded wastewater efficient adsorbent of acid |
| CN108441225A (en) * | 2018-03-15 | 2018-08-24 | 东北大学 | A kind of reparation medicament and preparation method thereof for repairing mercury contaminated soil |
| CN110152613A (en) * | 2018-04-16 | 2019-08-23 | 兰州理工大学 | A kind of aeroge adsorbent and preparation method thereof |
| CN108654559A (en) * | 2018-05-02 | 2018-10-16 | 朱红艳 | A kind of magnetic oxygenated graphene/montmorillonite adsorbent and preparation method thereof |
| CN108358199B (en) * | 2018-05-09 | 2020-01-17 | 中国地质大学（武汉） | Preparation method of montmorillonite/graphene oxide nano aerogel |
| CN108358199A (en) * | 2018-05-09 | 2018-08-03 | 中国地质大学（武汉） | A kind of preparation method of montmorillonite/stannic oxide/graphene nano aeroge |
| CN109056104A (en) * | 2018-09-21 | 2018-12-21 | 佛山皖和新能源科技有限公司 | A kind of preparation method of conducting polypropylene fiber |
| CN109289544A (en) * | 2018-09-26 | 2019-02-01 | 同济大学 | A method of preparing two-dimentional montmorillonite/cellulose composite filtering film |
| CN109289544B (en) * | 2018-09-26 | 2021-09-03 | 同济大学 | Method for preparing two-dimensional montmorillonite/cellulose composite filtering membrane |
| CN109126689A (en) * | 2018-09-27 | 2019-01-04 | 广西科学院 | A kind of modified montmorillonite used preparation method and applications |
| CN109126689B (en) * | 2018-09-27 | 2020-12-01 | 广西科学院 | Preparation method and application of modified montmorillonite |
| CN109248658A (en) * | 2018-09-28 | 2019-01-22 | 芜湖市鹏磊新材料有限公司 | A kind of production method of the graphene organic modified bentonite particle handled for humic acid in water |
| CN109364975A (en) * | 2018-11-19 | 2019-02-22 | 华东交通大学 | A kind of graphene-supported MMT/N-S-TiO2The preparation method of photocatalyst agent |
| CN109502624A (en) * | 2018-12-12 | 2019-03-22 | 安徽华塑股份有限公司 | The method for preparing calcium chloride using by-product hydrochloric acid |
| CN109647345A (en) * | 2019-01-10 | 2019-04-19 | 江西理工大学 | It is a kind of remove xanthate organically modified montmorillonite clay adsorbent and its application |
| CN110237826A (en) * | 2019-06-21 | 2019-09-17 | 郑州大学 | A kind of inorganic porous material and its preparation and application for removing removing heavy metals |
| CN110237826B (en) * | 2019-06-21 | 2022-03-25 | 郑州大学 | Inorganic porous material for removing heavy metal and preparation and application thereof |
| CN112076727A (en) * | 2020-08-21 | 2020-12-15 | 温州大学 | Heavy metal pollution repairing agent and preparation method thereof |
| CN112156764A (en) * | 2020-09-15 | 2021-01-01 | 凯盛石墨碳材料有限公司 | Nano TiO (titanium dioxide)2Modified graphene oxide/organic bentonite composite material and preparation method thereof |
| CN112741221A (en) * | 2021-01-13 | 2021-05-04 | 霍敏凯 | Immunity-improving cat food and preparation method thereof |
| CN115463094A (en) * | 2021-06-10 | 2022-12-13 | 北京微著新材科技有限公司 | Oral radiotherapy protective agent and preparation method and application thereof |
| CN115463094B (en) * | 2021-06-10 | 2023-07-04 | 北京微著新材科技有限公司 | Oral radiotherapy protective agent and preparation method and application thereof |
| CN113634221A (en) * | 2021-08-25 | 2021-11-12 | 天津大学 | Anionic dye-oriented Al2O3Modified Fe3O4Preparation and application of nanoparticles |
| CN114306708A (en) * | 2021-12-28 | 2022-04-12 | 山东中大药业有限公司 | Adult diaper containing montmorillonite |
| CN116376167A (en) * | 2023-05-22 | 2023-07-04 | 上海廉藤实业有限公司 | Modified plastic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104772113B (en) | 2017-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104772113A (en) | Graphene / montmorillonite nano composite material, and preparation method and application thereof | |
| Huang et al. | Modified bentonite adsorption of organic pollutants of dye wastewater | |
| Shen et al. | Alginate modified graphitic carbon nitride composite hydrogels for efficient removal of Pb (II), Ni (II) and Cu (II) from water | |
| CN105498707A (en) | Preparation method and application of modified graphene oxide/chitosan composite material | |
| Ademiluyi et al. | Effect of chemical activation on the adsorption of heavy metals using activated carbons from waste materials | |
| CN104307491B (en) | A kind of modified graphene of efficient absorption methyl orange dye and preparation method thereof | |
| CN105457597B (en) | A kind of graphene/silicon dioxide/nano zero-valence iron composite material and preparation method and application | |
| CN104787831A (en) | Method for removing hexavalent chromium in wastewater through magnetic adsorbent compounded by chitosan and magnetic biological carbon | |
| CN110756166A (en) | Corncob-loaded magnesium-modified adsorption material and preparation method and application thereof | |
| Bayram et al. | BR13 dye removal using sodium dodecyl sulfate modified montmorillonite: Equilibrium, thermodynamic, kinetic and reusability studies | |
| CN104190385B (en) | Polypyrrole/Fe3o4/ graphene composite material and its preparation method and application | |
| CN101549873B (en) | Surface active agent modification zeolites, method of preparing thereof and usage | |
| CN111229157B (en) | Preparation method of inorganic polymer modified bentonite adsorption material | |
| Ren et al. | Comparison of Cd2+ adsorption onto amphoteric, amphoteric-cationic and amphoteric-anionic modified magnetic bentonites | |
| CN101913676B (en) | Method for removing phosphorus in water by utilizing ferric salt-modified eggshells | |
| Yang et al. | Facile preparation and adsorption performance of low-cost MOF@ cotton fibre composite for uranium removal | |
| CN107159172A (en) | The preparation method of zeolite denitrogenation dephosphorizing agent and zeolite denitrogenation dephosphorizing agent | |
| CN105478072A (en) | Method for preparing modified shell powder | |
| CN104001471B (en) | Preparation method of silicon dioxide immobilized hydroxyapatite material | |
| CN104437359A (en) | Preparation method and application of composite bentonite for wastewater treatment | |
| CN107519846A (en) | A kind of graphene/silicon dioxide Pt/Polypyrrole composite material and preparation method and application | |
| CN104069822A (en) | Microwave organic modified particle bentonite/attapulgite adsorbent and preparation method thereof | |
| CN105817196A (en) | High-aluminum fly ash heavy metal ion adsorbent and preparation method thereof | |
| CN104828916B (en) | A kind of chromate waste water inorganic agent and preparation method thereof | |
| Liu et al. | Enhancement adsorption of hexavalent chromium from aqueous solution on polypyrrole using ethylamine group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |