CN108940194A - A kind of graphene oxide/modification clay multidimensional composite material and preparation method - Google Patents
A kind of graphene oxide/modification clay multidimensional composite material and preparation method Download PDFInfo
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- CN108940194A CN108940194A CN201810647873.XA CN201810647873A CN108940194A CN 108940194 A CN108940194 A CN 108940194A CN 201810647873 A CN201810647873 A CN 201810647873A CN 108940194 A CN108940194 A CN 108940194A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a kind of graphene oxide/modification clay multidimensional composite material and preparation method, preparation method is uniformly mixed comprising steps of firstly, modified slurry is added in graphene oxide suspension;Then obtained mixed liquor is subjected to ultrasonic disperse and/or microwave treatment, obtains brown mixed liquor;Further, it by gained brown mixed liquor stewing process, then filtered, wash precipitating, filter cake is freeze-dried, graphene oxide/modification clay composite material is made.Preparation method provided by the invention is simple to operation, low in cost, environmentally protective.Composite material is combined with close electrostatic force, the obvious accumulation weakened between concave convex rod, solve the problems, such as that graphene oxide is easy to reunite or it is evenly dispersed to be difficult to, it is good with absorption property, be easily isolated, the advantage that cyclic utilization rate is high, the efficient process to waste water can be realized by environmental protection, low consumption, quick mode.
Description
Technical field
The invention belongs to technical field of composite materials and technical field of waste water processing more particularly to a kind of multidimensional composite adsorptions
The preparation method and application of material.
Background technique
Clay is a kind of octahedra stratiform alumina magnesia silicate, have special intensity and structure, high specific surface area,
The features such as stronger absorption property, cheap rich reserves and advantage have in the treatment of waste water using clay as adsorbent
Wider application range and apparent cost advantage, gradually attracts wide attention.Meanwhile the surface-active of clay is higher, but
It is easy to happen aggregation.Therefore, surface is carried out to clay to be modified, improve its dispersibility in the base and the interface work with matrix
With, be realize its effective use critical problem.Graphene oxide is the two-dimension nano materials being made of single layer of carbon atom, tool
There is high-specific surface area, contains aromatic structure and a large amount of oxygen-containing group (hydroxyl, carboxyl, carbonyl etc.) on lamella.These oxygen-containing groups
Group makes it have good dispersibility and hydrophily, is conducive to be surface modified graphene oxide or carry out with other materials
It is compound, excellent absorption property is shown to organic matter, heavy metal, is very suitable to the processing of waste water.By graphene oxide with
Modified clay progress is compound, by the high-specific surface area, stronger absorption property and graphene oxide dispersibility of effective comprehensive clay
The advantages such as good, mechanical strength height are realized in the high mode of cheap, easy recycling, cyclic utilization rate to organic matter, the huge sum of money in waste water
Category is handled.
107159118 A of Chinese patent CN provides a kind of efficient uranium absorption agent of bentonite grafted graphene oxide
Preparation method, i.e., under NaOH effect, using epoxychloropropane as crosslinking agent, ammonium sulfate and sodium hydrogensulfite as initiator,
Bentonite and graphene oxide are subjected to Chemical assembly and prepare uranium absorption agent.107266951 A of Chinese patent CN discloses one kind
The preparation method and applications of silicate mineral reductive modification graphene oxide, take reduction coacervation, in graphene oxide point
Reducing agent and silicate mineral modifying agent are added in dispersion liquid, is used to prepare water-based anticorrosive paint.Chinese patent CN 105885092
A discloses the method for modifying of a kind of polymer graphene oxide-attapulgite clay compounded modifying agent and polymer, by KH-550
The attapulgite being modified is mixed with graphene oxide, and ultrasonic disperse is uniform, and graphene oxide-bumps are made after being centrifuged and drying
Stick soil composite modifier.106943997 A of Chinese patent CN provides a kind of preparation method of graphene oxide composite material,
Graphene oxide is mixed with through ferric trichloride modified kaolinite particle according to mass ratio for 1:200-500, freeze-dried rear shape
At micron-sized graphene oxide-modified kaolinite composite material, for removing underground water heavy metal.Chinese patent CN
106902759 A provide a kind of preparation method of graphene oxide-attapulgite modified composite adsorbing material of organic ammonium salt,
It is that suspension is respectively prepared as raw material using the modified attapulgite of graphite oxide and organic ammonium salt, after mixing under ultrasound condition
It is made after being persistently stirred to react 1-4h.Chinese patent CN105903438 A is by using stirring-stratification method, partially with six
Sodium phosphate is that dispersing agent prepares attapulgite suspension;It is anti-by hydro-thermal is carried out after attapulgite and graphene oxide respectively ultrasound
It answers, dries, be prepared for powdered attapulgite-graphene oxide compound adsorbent.
It is compound for handling waste water in the prior art about graphene oxide and other adsorbent materials, exist and repeats benefit
With rate is lower, preparation method pollution is larger, more complex problem is operated, for the above-mentioned problems in the prior art, this hair
It is bright to provide a kind of preparation method of graphene oxide/modification clay multidimensional composite material.
Summary of the invention
The object of the present invention is to provide a kind of graphene oxide/modification clay multidimensional composite material preparation methods.This hair
The preparation method of bright offer is simple to operation, low in cost, environmentally protective.Composite material is combined with close electrostatic force, hence it is evident that
Weaken the accumulation between concave convex rod, solve the problems, such as that graphene oxide is easy to reunite or it is evenly dispersed to be difficult to, there is absorption property
Well, it is easily isolated, the advantage that cyclic utilization rate is high, the efficient place to waste water can be realized by environmental protection, low consumption, quick mode
Reason.
A kind of graphene oxide provided by the invention/modification clay multidimensional composite material preparation method, including walk as follows
It is rapid:
(1), modified slurry is added in graphene oxide suspension, is uniformly mixed;
(2), the mixed liquor of step (1) is subjected to ultrasonic disperse and/or microwave treatment 1-3h, obtains brown mixed liquor;
(3), the brown mixed liquor of step (2) is stood into 6-24h, is then filtered, washs precipitating, filter cake is chilled
It is dry, graphene oxide/modification clay composite material is made.
Wherein, the preparation process of the modified clay are as follows:
(11), after clay original soil being activated 2h at 300-400 DEG C, modifying agent is added, and stir 90- at 30-80 DEG C
150min;
(12), step (11) treated mixture is subjected to ultrasonic disperse and/or microwave treatment 5-60min, successively passed through
Cross separation, deionized water is washed to the washing of neutral and saturated sodium chloride solution, dried at 40-70 DEG C;
(13), by the drying object of step (12) at 90-150 DEG C high-temperature activation 10-60min, crushed, be modified
Clay.
Further, the clay is at least one of attapulgite, kaolin, montmorillonite, bentonite and galapectite.
Preferably, the modifying agent is at least one of KH-560, KH-570, hydrochloric acid and humic acid.Specifically, described
The additional amount of hydrochloric acid is 1-4 times of clay quality, and the additional amount of the humic acid is the 5-20% of clay quality;The KH-560
Additional amount with KH-570 is the 3-10% of clay quality.
Preferably, in the step (1), the mass ratio of graphene oxide and modified clay is (0.1-0.9): 1, the filter
The temperature of cake freeze-drying is -30 to -80 DEG C.
The present invention also provides a kind of graphene oxide/modification clay multidimensional composite materials, are by system described above
Obtained by Preparation Method.
Compared with prior art, the present invention has the advantage that
(1) preparation process of the present invention uses ultrasonic disperse and/or microwave handling method, and composite material is made to have very strong suction
Attached ability and the cracking rate of adsorption can effectively remove amine organic matter and heavy metal ion in waste water.In addition the side of preparation
Method is simple, mild condition, time-consuming short, is suitble to industrial production.
(2) composite material prepared by the present invention is environmentally protective, not will cause secondary pollution, meets environmentally friendly product
It is required that;Simultaneously because clay rich reserves, low in cost, the cost of wastewater treatment, utility value with higher are reduced.
(3) composite material high recycling rate prepared by the present invention, greatly reduces the use cost of adsorbent, is suitble to work
Industryization is promoted.
Detailed description of the invention
Fig. 1 is that the KH-560 of the embodiment of the present invention attapulgite modified, graphene oxide and graphene oxide/modification are concave-convex
The infrared spectrogram of stick soil (graphene oxide is 0.1:0.9 with attapulgite modified mass ratio).
Fig. 2 is the scanning electron microscope (SEM) photograph of the graphene oxide of the embodiment of the present invention.
Fig. 3 is graphene oxide/attapulgite modified (graphene oxide and attapulgite modified of the embodiment of the present invention
Mass ratio is 0.4:1) scanning electron microscope (SEM) photograph of composite material.
Fig. 4 is that graphene oxide/attapulgite modified adsorption dynamics adsorption kinetics to aniline prepared by the embodiment of the present invention 1 is bent
Line.
Specific embodiment
1-4 and specific implementation case with reference to the accompanying drawing, to graphene oxide of the invention/clay composite adsorbing material
Preparation is explained in detail.Following embodiment is served only for that invention is further explained, should not be understood as to the present invention
The limitation of protection scope, the person skilled in the art in the field can make some nonessential change to the present invention according to above content
Into and adjustment.
Embodiment 1
A kind of preparation method of graphene oxide/modification clay multidimensional composite material, includes the following steps:
(1) 0.1g graphene oxide powder is dispersed in 50mL deionized water, obtains graphene oxide suspension;It takes
0.9g KH-560 modified attapulgite is scattered in 180mL deionized water, obtains attapulgite modified suspension;It will be described
Attapulgite modified suspension is added in graphene oxide suspension, is mixed evenly;
(2) the resulting mixed liquor of step (1) is subjected to ultrasonic disperse and handles 3h, obtain the mixed liquor of brown;
(3) after the mixed liquor of brown obtained by step (2) being stood 6h, successively filtered, washing precipitating, by filter cake-
It is freeze-dried at 30 DEG C and graphene oxide/modified attapulgite soil composite material is made.
Wherein, described attapulgite modified to be prepared by following steps:
The attapulgite powder of 150mL ethyl alcohol (80%) and 3g after 300 DEG C of high-temperature activations is added in three-necked flask, then
0.09g KH-560 is added and stirs 150min at 30 DEG C, then microwave treatment 60min, uses second alcohol and water respectively after the reaction was completed
Washed product repeatedly, 40 DEG C of low temperature dryings finally obtain modified attapulgite in 150 DEG C of activation 10min.
The graphene oxide as made from above-mentioned preparation method/modified attapulgite soil composite material, after tested, the composite material
Absorption to aniline: when at 25 DEG C, pH=6, adsorption rate reaches 90%, and adsorption-desorption cycle reuses number up to 8
It is secondary, and adsorbance will not be remarkably decreased.
Embodiment 2
A kind of preparation method of graphene oxide/modification clay multidimensional composite material, includes the following steps:
(1) 0.3g graphene oxide powder is dispersed in 50mL deionized water, obtains graphene oxide suspension, simultaneously
The montmorillonite for taking 0.7g humic acid modified is scattered in 180mL deionized water, modified montmorillonite used suspension is obtained, by the modification
Montmorillonite suspension is added in graphene oxide suspension, is mixed evenly;
(2) the resulting mixed liquor of step (1) is subjected to ultrasonic disperse and handles 3h, obtain the mixed liquor of brown;
(3) mixed liquor of brown obtained by step (2) is stood into 12h, successively by filtering, washing precipitating, by filter cake -50
Graphene oxide/modified Montmorillonite Composites are made after being freeze-dried at DEG C.
Wherein, described modified montmorillonite used to be prepared by following steps:
It weighs the dry montmorillonite of 5g to be put into beaker, water 20mL (as long as suspension can be formed) is added to obtain montmorillonite
Suspension, it is spare;Separately 0.25g humic acid is dissolved in 500mL deionized water;It is filtered after humic acid is completely dissolved,
Filtrate is added in above-mentioned montmorillonite suspension, adjusting solution ph to 2-5, and at 80 DEG C, is thoroughly mixed
120min, then carries out microwave treatment 5min, and ageing for 24 hours, it is modified montmorillonite used to obtain humic acid.It further, will be obtained
Humic acid is modified montmorillonite used after 70 DEG C of low temperature dryings, 90 DEG C of activation 60min, storage.
Graphene oxide/modified Montmorillonite Composites as made from above-mentioned preparation method, after tested, the composite material pair
Cr3+ absorption: in 25 DEG C, pH=2, adsorption rate is up to 99%.
Embodiment 3
A kind of preparation method of graphene oxide/modification clay multidimensional composite material, includes the following steps:
(1) 0.5g graphene oxide powder is dispersed in 50mL deionized water, obtains graphene oxide suspension, simultaneously
It takes the kaolin of 0.5g hydrochloric Acid Modification to be scattered in 180mL deionized water and obtains modified kaolin suspension, it will be described modified high
Ridge soil suspension is added in graphene oxide suspension, is mixed evenly;
(2) the resulting mixed liquor of step (1) is subjected to microwave treatment 1h, obtains the mixed liquor of brown;
(3) mixed liquor of step (2) resulting brown is stood into 12h, successively by filtering, washing precipitating, by filter cake-
Graphene oxide/modified kaolin composite material is made after being freeze-dried at 80 DEG C.
Wherein, the hydrochloric Acid Modification kaolin is prepared by following steps:
After kaolin original soil is activated 2h at 400 DEG C, it is added 180mL hydrochloric acid (1mol/L), and constant temperature stirs at 80 DEG C
Mix 90min;Ultrasonic treatment 30min is then carried out, is separated by filtration to obtain filter cake, filter cake, which is first washed with deionized to solution, is
Property, then after being washed with saturated sodium chloride solution, the low temperature drying at 50 DEG C activates 30min at 110 DEG C, crushes, obtains modified viscous
Soil.
The graphene oxide as made from above-mentioned preparation method/modified kaolin composite material, after tested, the composite material pair
The absorption of ortho-aminotoluene: in 25 DEG C, pH=6, adsorption rate reaches 90% or so.
Embodiment 4
A kind of preparation method of graphene oxide/modification clay multidimensional composite material, includes the following steps:
(1) 0.1g graphene oxide powder is dispersed in 50mL deionized water, obtains graphene oxide suspension, simultaneously
The galapectite for taking 0.9g KH-560 modified is scattered in 180mL deionized water, is obtained modified galapectite suspension, is changed described
Property galapectite suspension is added in graphene oxide suspension, is mixed evenly;
(2) mixed liquor obtained by step (1) is subjected to ultrasonic treatment 3h, obtains the mixed liquor of brown;
(3) mixed liquor of step (2) resulting brown is stood into 6h, successively by filtering, washing precipitating, by filter cake-
It is freeze-dried at 30 DEG C and graphene oxide/modification halloysite composite material is made.
Wherein, the modified galapectite is prepared by following steps:
The galapectite powder of addition 150mL ethyl alcohol (80%) and 3g after 300 DEG C of high-temperature activations in three-necked flask, then plus
Enter 0.3g KH-560 and stir 150min at 30 DEG C, then carries out microwave treatment 60min, use ethyl alcohol respectively after the reaction was completed
Washed product, 40 DEG C of low temperature dryings finally obtain modified galapectite in 150 DEG C of activation 10min repeatedly with water.
The graphene oxide as made from above-mentioned preparation method/modification halloysite composite material, after tested, the composite material pair
The absorption of U (VI): when at 25 DEG C, pH=6, adsorption rate reaches 90%, and adsorption-desorption cycle reuses number up to 8 times,
And adsorbance will not be remarkably decreased.
Embodiment 5
A kind of preparation method of graphene oxide/modification clay multidimensional composite material, includes the following steps:
(1) 0.3g graphene oxide powder is dispersed in 50mL deionized water, obtains graphene oxide suspension, simultaneously
The bentonite for taking 0.7g humic acid modified is scattered in 180mL deionized water, modified alta-mud suspension is obtained, by the modification
Bentonite suspension is added in graphene oxide suspension, is mixed evenly;
(2) step (1) resulting mixed liquor is subjected to ultrasonic treatment 3h, obtains the mixed liquor of brown;
(3) mixed liquor of step (2) resulting brown is stood into 12h, successively by filtering, washing precipitating, by filter cake-
Graphene oxide/bentone soil composite material is made after being freeze-dried at 50 DEG C.
Wherein, the modified alta-mud is prepared by following steps:
It weighs the dry bentonite of 5g to be put into beaker, water 20mL (as long as suspension can be formed) is added to obtain bentonite
Suspension, it is spare.Separately 1g humic acid is dissolved in 500mL deionized water, is filtered after humic acid is completely dissolved, by filtrate plus
Enter into above-mentioned bentonite suspension, adjusting solution ph to 2-5, and carries out being thoroughly mixed 120min at 80 DEG C, and
Microwave treatment 5min is carried out afterwards, and ageing for 24 hours, obtains humic acid modified alta-mud.Further, humic acid bentone will be obtained
Soil is after 70 DEG C of low temperature dryings, 90 DEG C of activation 60min, storage.
The graphene oxide as made from above-mentioned preparation method/bentone soil composite material, after tested, the composite material pair
Cu3+ absorption: in 25 DEG C, pH=2, adsorption rate is up to 99%.
Embodiment 6
A kind of preparation method of graphene oxide/modification clay multidimensional composite material, includes the following steps:
(1) 0.1g graphene oxide powder is dispersed in 50mL deionized water, obtains graphene oxide suspension, simultaneously
It takes 0.9g humic acid and the combined modified mixed clay of hydrochloric acid and is scattered in 180mL deionized water, obtain modified mixed clay
The modified mixed clay suspension is added in graphene oxide suspension, is mixed evenly by suspension;
(2) the resulting mixed liquor of step (1) is subjected to microwave and ultrasonic disperse handles 3h, obtain the mixed liquor of brown;
(3) after the mixed liquor of step (2) resulting brown being stood for 24 hours, successively by filtering, washing precipitating, by filter cake
Graphene oxide/modification mixed clay composite material is made after being freeze-dried at -80 DEG C.
Wherein, the modified mixed clay is prepared by following steps:
Mixed clay (mixing of bentonite and attapulgite) 5g after weighing 400 DEG C of high-temperature activations is simultaneously put into beaker,
20mL water is added to obtain mixed clay suspension (additional amount of water is not limited to 20mL, as long as suspension can be formed), it is standby
With.Separately 0.5g humic acid is dissolved in 500mL deionized water, is filtered after humic acid is completely dissolved, and filtrate is added
State in mixed clay suspension, at the same in mixed clay suspension be added 20mL hydrochloric acid (10.0mol/L), and at 80 DEG C into
Row is thoroughly mixed 150min, then carries out microwave combination and is ultrasonically treated 30min, ageing for 24 hours, obtains the modified mixing of humic acid
Clay.Further, the modified mixed clay of humic acid will be obtained after 60 DEG C of low temperature dryings, 90 DEG C of activation 60min, storage.
The graphene oxide as made from above-mentioned preparation method/modification mixed clay composite material, after tested, the composite material
To Cd2+ absorption: in 25 DEG C, pH=2, adsorption rate is up to 99% or more.
It is tested point below for graphene oxide of the invention/modification clay multidimensional composite material absorption property
Analysis.
Temperature is listed in table 1 to graphene oxide/attapulgite modified (as obtained by the method for above-described embodiment 1)
The influence relationship of adsorption effect, table 2 compare the influence relationship of adsorption effect for graphene oxide/attapulgite modified matching.
Table 1
Table 2
From the infrared spectrogram of Fig. 1 it is found that attapulgite is modified successfully (newly-increased 2976cm- through KH5601, 2926cm-1),
Characteristic peak (the 1660cm- that graphene oxide/modified attapulgite soil composite material occurs1,2358cm-1) show compound success.By
Fig. 2 and Fig. 3 comparison shows attapulgite modified to be successfully carried on surface of graphene oxide and interlayer.
Adsorption parameters:
Fig. 4 is graphene oxide/attapulgite modified absorption power to aniline prepared by the method for the embodiment of the present invention 1
Learn curve.As can be seen from Figure 4, usually in 120min, the adsorbance of aniline reaches balance.With the progress of absorption, reaction rate
It gradually decreases, the adsorbance of aniline does not have significant changes after 120min, and saturated extent of adsorption reaches 55.5mg/g.Using
Lagergren primary adsorption kinetic model and Lagergren secondary absorption kinetic model are fitted absorption parameter, tie
Fruit is shown in Table 3.As can be seen from Table 3, graphene oxide/modification clay meets second order dynamic model to the absorption of aniline, that is, inhales
Attached mainly to be controlled by rate process, graphene oxide/modification clay is 57.208mg/g to the Theoretical Equilibrium adsorbance of aniline, and
Experimental equilibrium adsorbance is close.
Table 3
In conclusion graphene oxide prepared by the present invention/modification clay multidimensional composite material rate of adsorption is fast and adsorbs
Capacity is big.
In the description of the embodiment of the present invention, it is to be understood that term " on ", "lower", "front", "rear", " left side ",
" right side ", " hard straight ", "horizontal", "center", "top", "bottom", " top ", " root ", "inner", "outside", " periphery ", " inboard ", " interior
The orientation or positional relationship of the instructions such as side ", " outside " is to be based on the orientation or positional relationship shown in the drawings, merely to making in retouching
It states the present invention and simplifies description, rather than the device or element of indication or suggestion meaning must have a particular orientation, with specific
Orientation construction and operation, therefore be not considered as limiting the invention.Wherein, the area that " inboard " refers to inside or fence up
Domain or space." periphery " refers to the region around certain particular elements or specific region.
In the description of the embodiment of the present invention, term " first ", " second ", " third ", " the 4th " are only used for description mesh
, it is not understood to indicate or imply relative importance or implicitly indicates the quantity of indicated technical characteristic.It limits as a result,
There are the feature of " first ", " second ", " third ", " the 4th " to can explicitly or implicitly include one or more spy surely
Sign.In the description of the present invention, unless otherwise indicated, the meaning of " plurality " is two or more.
In the description of the embodiment of the present invention, it should be noted that unless otherwise clearly defined and limited, term
" installation ", " connected ", " connection ", " assembling " shall be understood in a broad sense, for example, it may be being fixedly connected, be also possible to detachably connect
It connects, or is integrally connected;It can be directly connected, can also can be inside two elements indirectly connected through an intermediary
Connection.For the ordinary skill in the art, above-mentioned term in the present invention specific can be understood with concrete condition
Meaning.
In the description of the embodiment of the present invention, particular features, structures, materials, or characteristics can at any one or
It can be combined in any suitable manner in multiple embodiment or examples.
In the description of the embodiment of the present invention, it is to be understood that "-" and "~" indicated is that two values are same
Range, and the range includes endpoint.Such as: " A-B " indicates to be greater than or equal to A, and is less than or equal to the range of B." A~B "
It indicates to be greater than or equal to A, and is less than or equal to the range of B.
In the description of the embodiment of the present invention, the terms "and/or", only it is a kind of describe affiliated partner pass
Connection relationship indicates may exist three kinds of relationships, for example, A and/or B, can indicate: individualism A exists simultaneously A and B, individually
There are these three situations of B.In addition, character "/" herein, typicallys represent the relationship that forward-backward correlation object is a kind of "or".
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of graphene oxide/modification clay multidimensional composite material preparation method, which comprises the steps of:
(1), modified slurry is added in graphene oxide suspension, is uniformly mixed;
(2), the mixed liquor of step (1) is subjected to ultrasonic disperse and/or microwave treatment 1-3h, obtains brown mixed liquor;
(3), the brown mixed liquor of step (2) is stood into 6-24h, is then filtered, washs precipitating, filter cake is chilled dry
It is dry, graphene oxide/modification clay composite material is made.
2. graphene oxide as described in claim 1/modification clay multidimensional composite material preparation method, which is characterized in that institute
State the preparation process of modified clay are as follows:
(11), after clay original soil being activated 2h at 300-400 DEG C, modifying agent is added, and stir 90- at 30-80 DEG C
150min;
(12), step (11) treated mixture is subjected to ultrasonic disperse and/or microwave treatment 5-60min, successively through excessive
It washs from, deionized water to the washing of neutral and saturated sodium chloride solution, is dried at 40-70 DEG C;
(13), by the drying object of step (12) at 90-150 DEG C high-temperature activation 10-60min, crushed, obtained modified viscous
Soil.
3. graphene oxide as claimed in claim 2/modification clay multidimensional composite material preparation method, it is characterised in that: institute
Stating clay is at least one of attapulgite, kaolin, montmorillonite, bentonite and galapectite.
4. graphene oxide as claimed in claim 2/modification clay multidimensional composite material preparation method, it is characterised in that: institute
Stating modifying agent is at least one of KH-560, KH-570, hydrochloric acid and humic acid.
5. graphene oxide as claimed in claim 2/modification clay multidimensional composite material preparation method, it is characterised in that: institute
Stating modifying agent is the hydrochloric acid that concentration is 1-10mol/L, and additional amount is 1-4 times of clay quality.
6. graphene oxide as claimed in claim 2/modification clay multidimensional composite material preparation method, it is characterised in that: institute
Stating modifying agent is humic acid, and the additional amount of the humic acid is the 5-20% of clay quality.
7. graphene oxide as claimed in claim 2/modification clay multidimensional composite material preparation method, it is characterised in that: institute
Stating modifying agent is KH-560 or KH-570, and the additional amount of KH-560 is the 3-10% of clay quality;The additional amount of KH-570 is viscous
The 3-10% of soil property amount.
8. graphene oxide as described in claim 1/modification clay composite material preparation method, it is characterised in that: the step
Suddenly in (1), the mass ratio of graphene oxide and modified clay is (0.1-0.9): 1.
9. graphene oxide as described in claim 1/modification clay composite material preparation method, it is characterised in that: the filter
The temperature of cake freeze-drying is -30 DEG C to -80 DEG C.
10. a kind of graphene oxide/modification clay composite material, which is characterized in that be by any one of claim 1-9 institute
The preparation method stated is made.
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