CN113797895A - Activated carbon/graphene composite material and preparation method and application thereof - Google Patents
Activated carbon/graphene composite material and preparation method and application thereof Download PDFInfo
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- CN113797895A CN113797895A CN202111223120.4A CN202111223120A CN113797895A CN 113797895 A CN113797895 A CN 113797895A CN 202111223120 A CN202111223120 A CN 202111223120A CN 113797895 A CN113797895 A CN 113797895A
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- 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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- 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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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
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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
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Abstract
The invention provides an activated carbon/graphene composite material and a preparation method and application thereof, wherein a biomass carbonized material and graphene oxide are linked together by virtue of the linking effect of a fermentation type biomass linking agent, key components of the fermentation type biomass linking agent are easy to release and have a strong linking effect, and then the activated carbon/graphene composite material is synthesized by a one-step method, so that the activation of the biomass carbonized material can be realized, the in-situ reduction of the graphene oxide can be realized at the same time, the secondary processing of commercial activated carbon is not needed, and the energy consumption cost is reduced; the graphene oxide has stronger heat conduction capability, and the graphene formed in the temperature rising process can accelerate the diffusion rate of water vapor or carbon dioxide on the surface of the carbonized material in the activation reaction process, so that the rapid activation and pore-forming are realized.
Description
Technical Field
The invention belongs to the technical field of preparation of environment-friendly materials, and particularly relates to an activated carbon/graphene composite material as well as a preparation method and application thereof.
Background
The characteristics of emerging organic pollutants in water such as low concentration, difficult degradation, easy enrichment, biological toxicity and the like are one of the problems to be solved urgently at present. The activated carbon has the advantages of large specific surface area, developed pores, adjustable and controllable surface composition, low price, wide application range and the like, and is widely applied to the field of environmental remediation. The adsorption capacity, adsorption efficiency and adsorption selectivity are important indexes for evaluating the performance of the activated carbon, and the indexes are important subjects in the field of current adsorption research and key links for the innovation and breakthrough of practical application technology. The adsorption performance of activated carbon is largely determined by its physical pore structure and surface chemistry. Therefore, how to improve the adsorption performance of activated carbon by properly adjusting the structure and surface chemical properties is an important research direction.
The surface loading of the nano material on the activated carbon is one of effective ways for improving the adsorption performance. The nanometer material has multiplied surface atom number due to nanometer size effect, thereby increasing the active sites on the surface and improving the reaction efficiency. At present, most of modification modes aiming at the activated carbon are used for obtaining the activated carbon composite material by loading the activated carbon in situ through liquid phase reduction or carbon thermal reduction. The idea makes the active carbon repeatedly processed, which significantly increases the preparation cost. Graphene is a carbon element generating SP2The hybridized two-dimensional material has huge specific surface area and adsorption property. In recent years, graphene has been loaded on biochar or living organismsThe carbon can improve the conductivity or the specific surface area, and the performance of the biological carbon or the activated carbon is obviously improved.
CN104587956B discloses a preparation method of coated nano zero-valent iron using multilayer activated carbon coated graphene oxide composite powder as a carrier, which comprises the following steps: firstly, preparing the coated nano zero-valent iron: then preparing multilayer activated carbon-coated graphene oxide composite powder; and adding the obtained multilayer activated carbon coated graphene oxide composite powder into water, performing ultrasonic dispersion for 1-3 hours to obtain a graphene oxide suspension, adding the prepared coated nano zero-valent iron, fully stirring, performing suction filtration, washing and drying to obtain the coated nano zero-valent iron adsorbent taking the multilayer activated carbon coated graphene oxide composite powder as a carrier. The invention uses cheap and harmless flavonol, polymeric ferric sulfate and polyacrylamide as surface modifiers to prepare the coated nano zero-valent iron, thereby improving the removal rate of heavy metals in water.
CN107055532B discloses a method for loading graphene on activated carbon, the preparation process of the material is as follows: crushing the activated carbon powder to 1000 meshes, carrying out acidification treatment on the activated carbon powder, washing and drying: carrying out ultrasonic treatment on the graphene oxide solution to form a uniform solution: then immersing the acidified active carbon into the solution, fully stirring, adding an ethylenediamine solution, reacting in a water bath at the temperature of 80 ℃, and after the reaction is finished, carrying out dialysis treatment on the graphene-loaded active carbon: and finally, washing, filtering and drying in vacuum to obtain the material. The method provided by the invention has the advantages of simple process and simplicity and convenience in operation, and the graphene-loaded activated carbon composite material with higher conductivity and lower cost is prepared by utilizing the excellent conductivity of the graphene, so that the agglomeration phenomenon of the graphene due to the surface electrostatic action is overcome, the conductivity of the activated carbon is improved, and the conductivity of the composite material is increased by nearly 100 times.
However, the above inventions all have the problems of using a large amount of reducing agent in the secondary processing of activated carbon and the reduction of graphene oxide, which further causes the problems of higher process energy consumption and cost increase, thereby limiting the practical applicability of the composite material.
Therefore, a new process needs to be developed to load graphene oxide on activated carbon, so that synchronous reduction of graphene oxide can be realized, steps can be simplified, and secondary processing is avoided.
Disclosure of Invention
The invention aims to provide an active carbon/graphene composite material and a preparation method and application thereof, wherein a biomass carbonization material and graphene oxide are linked together by virtue of the linking effect of a fermentation type biomass linking agent, key components of the fermentation type biomass linking agent are easy to release and have a strong linking effect, and then the active carbon/graphene composite material is synthesized by a one-step method, so that the activation of the biomass carbonization material can be realized, the in-situ reduction of the graphene oxide can be realized simultaneously, secondary processing is not needed to be carried out on commercial active carbon, and the energy consumption cost is reduced; the graphene oxide has stronger heat conduction capability, and the graphene formed in the temperature rising process can accelerate the diffusion rate of water vapor or carbon dioxide on the surface of the carbonized material in the activation reaction process, so that the rapid activation and pore-forming are realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the present invention is to provide a preparation method of an activated carbon/graphene composite material, wherein the preparation method comprises the following steps:
(1) mixing a biomass carbonized material, graphene oxide and a first solvent, adding a fermentation type biomass linking agent for reaction, and carrying out solid-liquid separation to obtain the biomass carbonized material/graphene oxide;
(2) and (2) carrying out an activation reaction on the biomass carbonized material/graphene oxide obtained in the step (1) to obtain the activated carbon/graphene composite material.
According to the preparation method disclosed by the invention, the biomass carbonized material and the graphene oxide are used as raw materials, and the active carbon/graphene composite material is synthesized by a one-step method by virtue of the linking effect of the fermented biomass linking agent, so that the high-efficiency compounding of the active carbon and the graphene is realized.
The biomass carbonization material used in the invention is obtained by carbonizing a biomass raw material at 450-460 ℃ for 3-6 h.
As a preferable technical scheme of the invention, the fermentation type biomass linking agent in the step (1) is obtained by sequentially performing fermentation treatment and first drying on the biomass linking agent.
Preferably, the biomass linking agent comprises any one of, or a combination of at least two of, sorghum flour, tapioca flour, wheat hulls, corn flour, or potato flour, typical but non-limiting examples of which include a combination of tapioca flour and wheat hulls, sorghum flour and tapioca flour, a combination of sorghum flour and wheat hulls, a combination of wheat hulls and corn flour, a combination of wheat hulls and potato flour, or a combination of tapioca flour and potato flour.
Preferably, a second solvent is added during the fermentation process.
Preferably, the mass ratio of the second solvent to the biomass linking agent is 1 (2.0-3.5), and may be, for example, 1:2.0, 1:2,1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.0, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, etc., but is not limited to the recited values, and other non-recited values within the above numerical range are equally applicable.
Preferably, the second solvent comprises deionized water.
Preferably, the size of the biomass linking agent is 100-300 meshes, and may be, for example, 100 meshes, 120 meshes, 140 meshes, 160 meshes, 180 meshes, 200 meshes, 220 meshes, 240 meshes, 260 meshes, 280 meshes, 300 meshes, etc., but is not limited to the enumerated values, and other unrecited values within the above numerical range are also applicable.
Preferably, the fermentation temperature is 25-40 deg.C, such as 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C, 30 deg.C, 31 deg.C, 32 deg.C, 33 deg.C, 34 deg.C, 35 deg.C, 36 deg.C, 37 deg.C, 38 deg.C, 39 deg.C, 40 deg.C, etc., but is not limited to the recited values, and other values not recited in the above range of values are also applicable.
The temperature of the fermentation treatment in the invention is 25-40 ℃, if the temperature is higher than 40 ℃, the microorganisms on the surface of the biomass linking agent die, and the fermented biomass linking agent cannot be obtained; if the temperature is lower than 25 ℃, incomplete fermentation is caused, and the linking effect is further influenced.
The biomass linking agent disclosed by the invention is firstly subjected to biological fermentation, so that protein molecules are mutually interwoven to form a net structure, key components of the linking agent are easier to release, and a stronger linking effect is generated.
Preferably, the fermentation time is 1-2h, such as 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, etc., but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the temperature of the first drying is 100-110 ℃, and may be, for example, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃ and the like, but is not limited to the recited values, and other values not recited in the above-mentioned value range are also applicable.
Preferably, the first drying time is 12-24h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, etc., but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
In a preferred embodiment of the present invention, the mass ratio of the biomass charring material to the graphene oxide in the step (1) is (100-.
Preferably, the mass ratio of the graphene oxide to the fermentative biomass linking agent in step (1) is 1 (20-40), and may be, for example, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:40, etc., but is not limited to the enumerated values, and other non-enumerated values within the above numerical range are also applicable.
The mass ratio of the graphene oxide to the fermentation type biomass linking agent is 1 (20-40), if the mass ratio is higher than 1:20, namely the fermentation type biomass linking agent is too little and the graphene oxide is too much, the effective recombination rate of the graphene oxide and the biomass carbonization material is reduced, so that the loss of the graphene oxide is possibly caused, and the graphene oxide and the biomass carbonization material are not fully compounded due to insufficient linking components released from the fermentation type biomass linking agent; if the ratio is less than 1:40, that is, if the amount of the fermentation type biomass linking agent is too large and the amount of the graphene oxide is too small, the active carbon pore channels are blocked by the linking agent molecules.
Preferably, the biomass carbonized material in the step (1) has a size of 80-200 meshes, such as 80 meshes, 100 meshes, 110 meshes, 120 meshes, 130 meshes, 140 meshes, 150 meshes, 160 meshes, 170 meshes, 180 meshes, 190 meshes, 200 meshes, but not limited to the enumerated values, and other unrecited values in the above numerical range are also applicable.
In a preferred embodiment of the present invention, the mass ratio of the graphene oxide to the first solvent in step (1) is 1 (2000) -3000, and examples thereof include 1:2000, 1:2100, 1:2200, 1:2300, 1:2400, 1:2500, 1:2600, 1:2700, 1:2800, 1:2900, and 1:3000, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned numerical range are also applicable.
Preferably, the first solvent of step (1) comprises deionized water.
Preferably, the mixing manner in the step (1) is stirring.
Preferably, the temperature of the mixing in step (1) is 50-70 deg.C, such as 50 deg.C, 52 deg.C, 54 deg.C, 56 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 64 deg.C, 66 deg.C, 68 deg.C, 70 deg.C, etc., but it is not limited to the values listed, and other values not listed in the above range are also applicable.
Preferably, the mixing time in step (1) is 5-10min, such as 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min, 10min, etc., but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
As a preferred embodiment of the present invention, the temperature of the reaction in the step (1) is 80 to 100 ℃ and may be, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃ or the like, but it is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the reaction time in step (1) is 5-15min, such as 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, etc., but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the solid-liquid separation method in the step (1) is suction filtration.
Preferably, the biomass carbonization material/graphene oxide obtained in the step (1) is subjected to secondary drying.
Preferably, the temperature of the second drying is 100-110 ℃, and may be, for example, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃ and the like, but is not limited to the recited values, and other values not recited in the above-mentioned value range are also applicable.
Preferably, the second drying time is 12-24h, such as 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, etc., but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
As a preferable technical scheme of the present invention, before the activation reaction in step (2), the temperature of the biomass carbonization material/graphene oxide is raised.
Preferably, the rate of temperature rise is 6-8 ℃/min, and can be, for example, 6 ℃/min, 6.2 ℃/min, 6.4 ℃/min, 6.5 ℃/min, 6.6 ℃/min, 6.8 ℃/min, 7 ℃/min, 7.2 ℃/min, 7.4 ℃/min, 7.5 ℃/min, 7.6 ℃/min, 7.8 ℃/min, 8 ℃/min, and the like, but is not limited to the recited values, and other values not recited within the above range of values are equally applicable.
Preferably, the temperature of the end point of the temperature rise is 850-.
Preferably, the temperature rise is N2The reaction is carried out under an atmosphere.
Preferably, said N is2The flow rate of (A) is 0.3 to 0.5L/min, and may be, for example, 0.30L/min, 0.32L/min, 0.34L/min, 0.35L/min, 0.36L/min, 0.38L/min, 0.40L/min, 0.42L/min, 0.44L/min, 0.45L/min, 0.46L/min, 0.48L/min, 0.50L/min, etc., but is not limited to the enumerated values, and other non-enumerated values within the above-mentioned numerical range are also applicable.
As a preferred embodiment of the present invention, the temperature of the activation reaction in step (2) is 850-950 ℃, and may be, for example, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃ or the like, but is not limited to the values listed, and other values not listed in the above range of values are also applicable.
The temperature of the activation reaction is 850-950 ℃, and if the temperature exceeds 950 ℃, the loss on ignition of the carbon is too large, the yield is low, and the energy is consumed, because the reaction of the activation reaction gas and the biomass carbonized material is more violent at the temperature; if the temperature is lower than 850 ℃, the activation reaction is not complete, the proportion of micropores is low, and the use performance is reduced. This is because the reaction of carbon atoms with water vapor is incomplete and the degree of activation reaction is insufficient at an excessively low activation reaction temperature.
Preferably, the activation reaction time in step (2) is 30-80min, such as 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, etc., but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the activation reaction of step (2) is performed in an activation reaction gas atmosphere.
Preferably, the activated reactant gas comprises water vapor and/or carbon dioxide.
Preferably, the flow rate of the activating reaction gas is 0.2-0.4mL/min, and may be, for example, 0.2L/min, 0.23L/min, 0.25L/min, 0.27L/min, 0.3L/min, 0.33L/min, 0.35L/min, 0.38L/min, 0.4L/min, etc., but is not limited to the values listed, and other values not listed in the above numerical range are equally applicable.
Preferably, the temperature rise and the activation reaction in the step (3) are both carried out in an activation reaction furnace.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing 80-200 meshes of biomass carbonized material and graphene oxide with a first solvent according to the mass ratio of (100-;
wherein the mass ratio of the graphene oxide to the fermentation type biomass linking agent is 1 (20-40); the fermentation type biomass linking agent is obtained by sequentially fermenting 100-300 mesh biomass linking agents at 25-40 ℃ for 1-2h and then drying the biomass linking agents at 100-110 ℃ for 12-24 h; the biomass linking agent comprises any one or a combination of at least two of sorghum flour, cassava flour, wheat hulls, corn flour and potato flour; the mass ratio of the second solvent to the biomass linking agent is 1 (2.0-3.5) during fermentation treatment;
(2) putting the biomass carbonized material/graphene oxide into an activation reaction furnace, and adding N2Under the atmosphere, keeping N2The flow rate is 0.3-0.5L/min, the temperature is raised to 850 ℃ and 950 ℃ at the speed of 6-8 ℃/min, and the N is stopped to be introduced after the temperature rise is finished2Then carrying out activation reaction at 850-950 ℃ for 30-80min to obtain the activated carbon/graphene composite material; wherein the activation reaction is controlled to be carried out in the atmosphere of water vapor and/or carbon dioxide of 0.2-0.4 mL/min.
The second purpose of the present invention is to provide an activated carbon/graphene composite material, which is obtained by the preparation method according to the first purpose.
The third purpose of the invention is to provide an application of the activated carbon/graphene composite material for the second purpose, wherein the application comprises the application of the activated carbon/graphene composite material for treating anionic pollutant wastewater and/or organic matter wastewater.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between any of the above-recited numerical ranges not otherwise recited, and for the sake of brevity and clarity, the present disclosure is not intended to be exhaustive of the specific numerical values encompassed within the range.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fermented biomass linking agent is obtained by fermenting the biomass linking agent in a short time, can realize the enhancement of the linking function, has stronger linking effect compared with the unfermented biomass linking agent with the same dosage, and provides a new idea for the effective use of the linking agent;
(2) according to the preparation method of the activated carbon/graphene composite material, under the action of the fermentation type biomass linking agent with the strengthened linking function, graphene oxide is loaded on the surface of the biomass carbonized material, and meanwhile, the in-situ reduction of the graphene oxide is realized, secondary processing is not needed to be carried out on commercial activated carbon, so that the energy consumption cost is reduced;
(3) in the preparation process of the activated carbon/graphene composite material, the graphene oxide has stronger heat conduction capability, and the graphene formed in the heating process can accelerate the diffusion rate of water vapor or carbon dioxide on the surface of a carbonized material in the activation reaction process, so that the activation reaction pore-forming is realized more quickly.
Drawings
Fig. 1 is an SEM image of the activated carbon/graphene composite material described in example 1;
FIG. 2 is an SEM image of the activated carbon of comparative example 3;
fig. 3 is a graph showing a sedimentation comparison of example 1, comparative example 1 and comparative example 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an activated carbon/graphene composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing 150-mesh biomass carbonized material, graphene oxide and deionized water according to the mass ratio of 200:1:3000, stirring for 8min at 60 ℃, heating to 90 ℃, adding fermented potato powder for reacting for 10min, performing solid-liquid separation, and drying for 20h at 105 ℃ to obtain biomass carbonized material/graphene oxide;
wherein the mass ratio of the graphene oxide to the fermented potato powder is 1: 30; mixing deionized water and potato powder of 200 meshes according to the mass ratio of 1:2.8, fermenting at 40 ℃ for 1h, and drying at 105 ℃ for 20h to obtain fermented potato powder;
(2) putting the biomass carbonized material/graphene oxide into an activation reaction furnace, and adding N2Under the atmosphere, keeping N2The flow rate of the nitrogen-containing gas is 0.4L/min, the temperature is increased to 900 ℃ at the speed of 8 ℃/min, and the N introduction is stopped after the temperature is increased2Then carrying out activation reaction at 900 ℃ for 60min to obtain an activated carbon/graphene composite material; wherein the activation reaction is controlled to be carried out in a water vapor atmosphere of 0.4 mL/min.
The SEM image of the activated carbon/graphene composite material obtained in this example is shown in fig. 1.
Example 2
The embodiment provides an activated carbon/graphene composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing 80-mesh biomass carbonized material, graphene oxide and deionized water according to the mass ratio of 150:1:2500, stirring for 10min at 50 ℃, heating to 80 ℃, adding fermented cassava powder for reacting for 15min, performing solid-liquid separation, and drying for 24h at 100 ℃ to obtain biomass carbonized material/graphene oxide;
wherein the mass ratio of the graphene oxide to the fermented cassava flour is 1: 40; mixing deionized water and cassava powder of 100 meshes according to the mass ratio of 1:3.5, fermenting at 25 ℃ for 2h, and drying at 100 ℃ for 24h to obtain fermented cassava powder;
(2) putting the biomass carbonized material/graphene oxide into an activation reaction furnace, and adding N2Under the atmosphere, keeping N2The flow rate of the nitrogen-containing gas is 0.3L/min, the temperature is increased to 850 ℃ at the speed of 6 ℃/min, and the N introduction is stopped after the temperature increase is finished2Then carrying out activation reaction for 80min at 850 ℃ to obtain an activated carbon/graphene composite material; wherein the activation reaction is controlled to be carried out in a carbon dioxide atmosphere of 0.5 mL/min.
Example 3
The embodiment provides an activated carbon/graphene composite material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing 200-mesh biomass carbonized material, graphene oxide and deionized water according to the mass ratio of 100:1:2000, stirring for 5min at 70 ℃, heating to 100 ℃, adding fermented potato powder for reacting for 5min, performing solid-liquid separation, and drying for 12h at 110 ℃ to obtain biomass carbonized material/graphene oxide;
wherein the mass ratio of the graphene oxide to the fermented potato powder is 1: 30; mixing deionized water and 300-mesh potato powder according to the mass ratio of 1:2.0, fermenting at 30 ℃ for 1.5h, and drying at 110 ℃ for 12h to obtain fermented potato powder;
(2) putting the biomass carbonized material/graphene oxide into an activation reaction furnace, and adding N2Under the atmosphere, keeping N2The flow rate of the nitrogen-containing gas is 0.5L/min, the temperature is increased to 950 ℃ at the speed of 7 ℃/min, and the N introduction is stopped after the temperature increase is finished2Then carrying out activation reaction for 30min at 950 ℃ to obtain an activated carbon/graphene composite material; wherein the activation reaction is controlled to be carried out in a water vapor atmosphere of 0.3 mL/min.
Example 4
This example provides an activated carbon/graphene composite material and a method for preparing the same, except that the temperature of the fermentation treatment in step (1) is changed from 40 ℃ to 50 ℃, and the conditions are exactly the same as those in example 1.
Example 5
This example provides an activated carbon/graphene composite material and a method for preparing the same, except that the temperature of the fermentation treatment in step (1) is changed from 40 ℃ to 18 ℃, and the conditions are the same as those in example 1.
Comparative example 1
The present comparative example provides an activated carbon/graphene composite material and a method for preparing the same, which are described with reference to example 1, except that: the preparation method comprises the following steps of:
(1) mixing 150-mesh biomass carbonized material, graphene oxide and deionized water according to the mass ratio of 200:1:3000, stirring for 8min at 60 ℃, heating to 90 ℃, adding potato powder for reacting for 10min, performing solid-liquid separation, and drying for 20h at 105 ℃ to obtain biomass carbonized material/graphene oxide;
wherein the mass ratio of the graphene oxide to the potato powder is 1: 30;
(2) putting the biomass carbonized material/graphene oxide into an activation reaction furnace, and adding N2Under the atmosphere, keeping N2The flow rate of the nitrogen-containing gas is 0.4L/min, the temperature is increased to 900 ℃ at the speed of 8 ℃/min, and the N introduction is stopped after the temperature is increased2Then carrying out activation reaction at 900 ℃ for 60min to obtain an activated carbon/graphene composite material; wherein the activation reaction is controlled to be carried out in a water vapor atmosphere of 0.4 mL/min.
Comparative example 2
The comparative example provides an activated carbon/graphene composite material and a preparation method thereof, except that the quality of the fermented potato powder and the like in the step (1) is replaced by ethylenediamine, and other conditions are completely the same as those in the example 1.
Comparative example 3
The present comparative example provides an activated carbon and a method for preparing the same, the method comprising the steps of:
(1) carbonizing a biomass raw material at 450 ℃ for 6 hours to obtain a biomass carbonized material;
(2) putting biomass carbonized material into an activation reaction furnaceIn N at2Under the atmosphere, keeping N2The flow rate of the nitrogen-containing gas is 0.4L/min, the temperature is increased to 900 ℃ at the speed of 8 ℃/min, and the N introduction is stopped after the temperature is increased2Then carrying out activation reaction for 60min at 900 ℃ to obtain activated carbon; wherein the activation reaction is controlled to be carried out in a water vapor atmosphere of 0.4 mL/min.
The SEM image of the activity of this comparative example is shown in FIG. 2.
First, the surface morphology of the activated carbon/graphene composite material described in example 1 and the surface morphology of the activated carbon described in comparative example 3 are observed by SEM, fig. 1 is an SEM image of the activated carbon/graphene composite material obtained in example 1, fig. 2 is an SEM image of the activated carbon obtained in comparative example 3, and comparing fig. 1 with fig. 2, it can be seen that: the surface of the activated carbon/graphene composite material in fig. 1 is pleated, and the pleated material is graphene, while the surface of the activated carbon in fig. 2 is smooth, so that it can be proved that the graphene loading can be realized by using the fermented potato powder as the linking agent in example 1.
(II) in order to verify the difference of the linking effect of different linking agents, selecting the embodiment 1, the comparative example 1 and the comparative example 2 for comparison, wherein the specific method comprises the following steps:
mixing a biomass carbonization material, graphene oxide and deionized water, adding a linking agent for reaction to obtain a biomass carbonization material/graphene oxide turbid liquid, standing the biomass carbonization material/graphene oxide turbid liquid for 2 hours, and observing the settlement condition of the turbid liquid.
Because the weight of the graphene oxide is light, the graphene oxide usually floats on deionized water, the settlement condition of a biomass carbonization material/graphene oxide turbid liquid which is not subjected to solid-liquid separation after the reaction is finished is observed, if the linking effect is good, the lighter graphene oxide is mostly loaded on the biomass carbonization material and then settles, and the upper layer is clear liquid.
As can be seen from fig. 3, since the unfermented potato powder is used as the linking agent in comparative example 1, and the non-biomass ethylenediamine is used as the linking agent in comparative example 2, the biomass carbonized material/graphene oxide suspension described in comparative examples 1 and 2 has no obvious layering after standing, and the fermented potato powder is used as the linking agent in example 1, the obtained biomass carbonized material/graphene oxide suspension has obvious layering, and the supernatant liquid is clear, so that the linking effect of the fermented biomass linking agent is obviously better than that of the unfermented biomass linking agent and the non-biomass linking agent.
And (III) carrying out adsorption performance test on the activated carbon/graphene composite materials obtained in the above examples 1-5 and comparative examples 1 and 2 and the activated carbon obtained in the comparative example 3, wherein the test method comprises the following steps:
placing an adsorbent with mass M into a volume V and an initial concentration C0The ibuprofen solution of (1) was sampled at 72h to test the concentration of ibuprofen remaining in the solution and noted CiThe adsorption quantity of ibuprofen, namely (C) can be obtained by calculation0-Ci) X V/M, wherein C050mg/L, 0.05L V and 0.02g M.
The adsorption amounts of ibuprofen to the materials obtained in the above examples and comparative examples are shown in table 1.
TABLE 1
The following points can be derived from table 1:
(1) comparing example 1 with examples 4 and 5, it can be seen that the temperature of the fermentation treatment in step (1) of example 4 is 50 ℃, which exceeds 25-40 ℃ preferred in the present invention, and thus the microorganisms on the surface of the biomass linking agent die, and the fermented biomass linking agent cannot be obtained, which results in the poor linking effect of the linking agent, and further results in the decrease of the adsorption amount of ibuprofen to 99.7mg g of the activated carbon/graphene composite material obtained in example 4-1(ii) a Since the temperature of the fermentation treatment in step (1) of example 5 is 18 ℃ or lower than the preferred temperature of 25-40 ℃ in the present invention, incomplete fermentation is caused, which affects the linking effect, and finally, the temperature of the fermentation treatment in example 5 is 18 ℃ or lowerThe adsorption quantity of the activated carbon/graphene composite material to ibuprofen is reduced to 102.8mg g-1；
(2) Comparing example 1 with comparative example 1, it can be seen that the adsorption amount of ibuprofen on the activated carbon/graphene composite material obtained by using the fermented potato powder as the linking agent in example 1 is 126.7mg g-1In comparative example 1, unfermented potato powder is used as a linking agent, and the adsorption capacity of the obtained activated carbon/graphene composite material to ibuprofen is reduced to 98.4mg g-1(ii) a Therefore, the fermented biological linking agent has a stronger linking effect, the effective loading rate of graphene in the activated carbon/graphene is further improved through the fermented linking agent, the specific surface area is increased, and the acting force between the activated carbon/graphene and ibuprofen molecules is also increased;
(3) comparing example 1 with comparative example 2, it can be seen that, when fermented potato powder is used as a linking agent in example 1 and non-biomass ethylenediamine is used as a linking agent in comparative example 2, the adsorption amount of ibuprofen on the activated carbon/graphene composite material obtained in comparative example 2 is reduced to 77.2mg g-1(ii) a Therefore, the non-biomass linking agent has poor linking effect, and is inferior to the biomass linking agent and the fermented biomass linking agent;
(4) comparing example 1 with comparative example 3, it can be seen that the activated carbon obtained in comparative example 3 has no graphene loaded thereon, and the adsorption effect is the worst, only 75.4mg g-1。
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the activated carbon/graphene composite material is characterized by comprising the following steps:
(1) mixing a biomass carbonization material, graphene oxide and a first solvent, adding a fermentation type biomass linking agent for reaction, and performing solid-liquid separation to obtain the biomass carbonization material/graphene oxide;
(2) and (2) carrying out an activation reaction on the biomass carbonized material/graphene oxide obtained in the step (1) to obtain the activated carbon/graphene composite material.
2. The preparation method according to claim 1, wherein the fermentation type biomass linking agent in the step (1) is obtained by sequentially performing fermentation treatment and first drying on the biomass linking agent;
preferably, the biomass linking agent comprises any one or a combination of at least two of sorghum flour, tapioca flour, wheat hulls, corn flour or potato flour;
preferably, a second solvent is added during the fermentation treatment;
preferably, the mass ratio of the second solvent to the biomass linking agent is 1 (2.0-3.5);
preferably, the second solvent comprises deionized water;
preferably, the size of the biomass linking agent is 100-300 meshes;
preferably, the temperature of the fermentation treatment is 25-40 ℃;
preferably, the fermentation treatment time is 1-2 h;
preferably, the temperature of the first drying is 100-110 ℃;
preferably, the first drying time is 12-24 h.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the biomass carbonization material to the graphene oxide in the step (1) is (100-;
preferably, the mass ratio of the graphene oxide to the fermentation type biomass linking agent in the step (1) is 1 (20-40);
preferably, the biomass carbonized material in the step (1) has the size of 80-200 meshes.
4. The preparation method according to any one of claims 1 to 3, wherein the mass ratio of the graphene oxide to the first solvent in step (1) is 1 (2000-3000);
preferably, the first solvent of step (1) comprises deionized water;
preferably, the mixing manner in the step (1) is stirring;
preferably, the temperature of the mixing in the step (1) is 50-70 ℃;
preferably, the mixing time of step (1) is 5-10 min.
5. The method according to any one of claims 1 to 4, wherein the temperature of the reaction in step (1) is 80 to 100 ℃;
preferably, the reaction time of the step (1) is 5-15 min;
preferably, the solid-liquid separation method in the step (1) is suction filtration;
preferably, performing second drying on the biomass carbonization material/graphene oxide obtained in the step (1);
preferably, the temperature of the second drying is 100-110 ℃;
preferably, the time of the second drying is 12-24 h.
6. The method according to any one of claims 1 to 5, wherein the biomass char/graphene oxide is subjected to a temperature increase before the activation reaction in step (2);
preferably, the rate of temperature rise is 6-8 ℃/min;
preferably, the terminal temperature of the temperature rise is 850-950 ℃;
preferably, the temperature rise is N2The reaction is carried out under the atmosphere;
preferably, said N is2The flow rate of (A) is 0.3-0.5L/min.
7. The method as claimed in any one of claims 1 to 6, wherein the temperature of the activation reaction in step (2) is 850 ℃ and 950 ℃;
preferably, the time of the activation reaction in the step (2) is 30-80 min;
preferably, the activation reaction of step (2) is carried out in an activation reaction gas atmosphere;
preferably, the activating reactive gas comprises water vapor and/or carbon dioxide;
preferably, the flow rate of the activation reaction gas is 0.2-0.4 mL/min;
preferably, the temperature rise and the activation reaction in the step (3) are both carried out in an activation reaction furnace.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) mixing 80-200 meshes of biomass carbonized material and graphene oxide with a first solvent according to the mass ratio of (100-;
wherein the mass ratio of the graphene oxide to the fermentation type biomass linking agent is 1 (20-40); the fermentation type biomass linking agent is obtained by sequentially fermenting 100-300 mesh biomass linking agents at 25-40 ℃ for 1-2h and then drying the biomass linking agents at 100-110 ℃ for 12-24 h; the biomass linking agent comprises any one or a combination of at least two of sorghum flour, tapioca flour, wheat hulls, corn flour or potato flour; the mass ratio of the second solvent to the biomass linking agent is 1 (2.0-3.5) during fermentation treatment;
(2) putting the biomass carbonized material/graphene oxide into an activation reaction furnace, and adding N2Under the atmosphere, keeping N2The flow rate is 0.3-0.5L/min, the temperature is raised to 850 ℃ and 950 ℃ at the speed of 6-8 ℃/min, and the N is stopped to be introduced after the temperature rise is finished2Then carrying out activation reaction at 850-950 ℃ for 30-80min to obtain the activated carbon/graphene composite material; wherein the activation reaction is controlled to be carried out in the atmosphere of water vapor and/or carbon dioxide of 0.2-0.4 mL/min.
9. An activated carbon/graphene composite material, which is obtained by the preparation method according to any one of claims 1 to 8.
10. Use of the activated carbon/graphene composite material according to claim 9, comprising treatment of anionic pollutant wastewater and/or organic wastewater.
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