CN113750967A - Preparation method and application of graphene oxide modified activated carbon - Google Patents

Preparation method and application of graphene oxide modified activated carbon Download PDF

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Publication number
CN113750967A
CN113750967A CN202111195614.6A CN202111195614A CN113750967A CN 113750967 A CN113750967 A CN 113750967A CN 202111195614 A CN202111195614 A CN 202111195614A CN 113750967 A CN113750967 A CN 113750967A
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Prior art keywords
graphene oxide
activated carbon
modified activated
oxide modified
adsorption
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方小琴
乔宇
张水水
孙树青
金鑫
张利名
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Inner Mongolia Jingtai Environmental Science And Technology Co ltd
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Inner Mongolia Jingtai Environmental Science And Technology Co ltd
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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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a preparation method of graphene oxide modified activated carbon, which comprises the following steps: soaking activated carbon in a graphene oxide aqueous solution, adsorbing graphene oxide in the solution by utilizing the adsorption effect of the activated carbon, then separating solid activated carbon from liquid graphene oxide solution, and drying in a constant temperature environment to obtain the graphene oxide improved activated carbon material. The invention discloses application of the graphene oxide modified activated carbon, and the activated carbon modified by the graphene oxide modified activated carbon has the advantages that the adsorption speed of common heavy metal ions such as copper, chromium and cadmium in a solution is obviously increased, and the adsorption quantity is increased. The technology has the advantages of low preparation cost, easily obtained raw materials, simple operation, high efficiency and stable operation effect, and has wide application prospect in the aspect of removing heavy metal ions in water.

Description

Preparation method and application of graphene oxide modified activated carbon
The technical field is as follows:
the invention relates to a preparation method and application of graphene oxide modified activated carbon, and belongs to the field of application of graphene carbon-based materials.
Background art:
with the growth of mankind and the rapid development of agriculture and industry, many countries are facing the problems of water resource shortage and poor water quality. Among them, heavy metals in industrial production and mining industries are released into water without being properly treated, resulting in deterioration of water quality, and water resources which are originally very short are polluted, which has become one of global concerns. More seriously, if the water rich in heavy metal ions is not treated in time, the water can cause serious pollution to the surrounding environment, and the heavy metal ions exist in the environment stably, cannot be biodegraded, tend to be bio-enriched, easily pass through a food chain and seriously harm the health of human beings. Therefore, how to effectively remove heavy metal ions in water has become an urgent problem to be solved.
At present, for removing heavy metal ions in water, common treatment methods are as follows: ion exchange, chemical precipitation, reverse osmosis, electrochemical, membrane separation, adsorption, and the like. The adsorption method is the most common method for treating heavy metal pollution in water at present due to the simple method, strong universality and low operation cost, and has higher application value. Carbon-based materials such as activated carbon and biochar are often used as adsorbents to adsorb pollutants in water. However, with the advent of new materials, such as graphene oxide, carbon nanotubes, metal organic framework materials, and the like, the application of traditional adsorbents such as activated carbon in the field of removal of heavy metal ions in water is limited due to their relatively small adsorption capacity and low pollutant removal efficiency. Therefore, it is important to improve the adsorption capacity of the conventional activated carbon material by using the novel nano material.
The invention content is as follows:
the first purpose of the invention is to provide a preparation method of graphene oxide modified activated carbon;
the second purpose of the invention is to provide the application of the graphene oxide modified activated carbon.
The first purpose of the invention is implemented by the following technical scheme: a preparation method of graphene oxide modified activated carbon is characterized by comprising the following steps:
s1, raw material pretreatment: washing, drying and crushing the raw material active carbon, and sieving the raw material active carbon with a 60-mesh sieve to obtain active carbon powder with the granularity of less than 60 meshes;
s2, preparing graphene oxide:
firstly, graphite powder with the granularity of 60-200 meshes is put into concentrated H2SO4、K2S2O8、P2O5In solution, the solution is 2.5gK2S2O8、2.5g P2O5Dissolving in 12ml 98% sulfuric acid, and continuously stirring at 75-85 deg.C for 4-6 hr;
then diluting with deionized water, centrifuging, washing and drying to obtain pre-oxidized graphite; then in concentrated H2SO4And KMnO4Further oxidizing; the further oxidation mode is that pre-oxidized graphite is added into 120ml sulfuric acid and stirred for 2-3 hours at 35 ℃, then 15g potassium permanganate is added, and finally stirred for 4 hours at 20-30 ℃.
Then, dilute with deionized water, add 30% H2O2Obtaining a graphene oxide product;
then, carrying out centrifugal washing on the product by using HCl and deionized water in a volume ratio of 1:9-10 to remove impurity ions;
finally, carrying out centrifugal separation at a speed of 3000-;
s3, active carbon improvement:
s1, soaking activated carbon in raw material pretreatment in a graphene oxide aqueous solution with the concentration of 0.005-10mg/mL, adsorbing graphene oxide in the solution by utilizing the adsorption effect of the activated carbon, soaking for 0.2-2h, and carrying out solid-liquid separation; and then, quickly placing the activated carbon adsorbed with the graphene oxide into a constant-temperature environment of 30-70 ℃ for drying, thus preparing the graphene oxide modified activated carbon material.
Further, in the S2. graphene oxide preparation, the concentration of the graphene oxide solution is 3-5 mg/mL.
Further, in the S2. graphene oxide preparation, the oxidation degree of the graphene oxide solution is 30%.
Further, in the improvement of the S3. the activated carbon, the concentration of the graphene oxide aqueous solution is 5 mg/mL.
Further, in the step S3 of activated carbon improvement, the soaking time is 1 h.
Further, in the s3. improvement of the activated carbon, the temperature for drying the activated carbon adsorbed with the graphene oxide is 60 ℃.
The second purpose of the invention is implemented by the following technical scheme: the application of the graphene oxide modified activated carbon is applied to adsorption and removal of heavy metal ions in a water environment.
The invention has the advantages that:
the preparation method is simple and efficient, wide in raw materials, low in cost, simple to operate and easy to industrially produce, and based on cation-pi interaction between heavy metal cations and the pi conjugated structure of the graphene oxide aromatic ring, the preparation method is high in removal efficiency of heavy metal ions in water and large in adsorption capacity.
Description of the drawings:
in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1: the copper ion adsorption performance diagram of the graphene oxide modified activated carbon prepared in example 1.
FIG. 2: the performance diagram of adsorbing chromium ions of the graphene oxide modified activated carbon prepared in example 1.
FIG. 3: the performance diagram of adsorbing cadmium ions of the graphene oxide modified activated carbon prepared in example 1.
FIG. 4: the performance diagram of the graphene oxide modified activated carbon for repeatedly adsorbing copper ions in example 2.
FIG. 5: the performance diagram of the graphene oxide modified activated carbon for repeatedly adsorbing chromium ions in example 2.
FIG. 6: the performance diagram of the graphene oxide modified activated carbon for repeatedly adsorbing cadmium ions in example 2.
FIG. 7: multiple repeated experimental performance plots of copper ion adsorption by graphene oxide modified activated carbon in example 3.
FIG. 8: multiple repeated experimental performance graphs of the graphene oxide modified activated carbon in example 3 on chromium ion adsorption.
FIG. 9: a performance diagram of multiple repeated experiments on cadmium ion adsorption by graphene oxide modified activated carbon in example 3.
Fig. 10 is a schematic diagram of a preparation method of graphene oxide-modified activated carbon in example 1.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Washing, drying and crushing the raw material active carbon, and sieving the raw material active carbon with a 60-mesh sieve to obtain active carbon powder.
Weighing 5g of activated carbon powder, soaking in 100mL of graphene oxide solution with the concentration of 5mg/mL and the oxidation degree of 30%, and adsorbing graphene oxide in the solution by utilizing the adsorption effect of activated carbon per se, wherein the soaking time is 1 hour. Then, solid activated carbon and liquid graphene oxide solution are separated by a separation means of filtration. And then, quickly placing the activated carbon adsorbed with the graphene oxide into a constant temperature environment of 60 ℃ for drying, thus obtaining the graphene oxide modified activated carbon material.
The adsorption performance of the graphene oxide-modified activated carbon material prepared in example 1 is detected by the following detection method:
in 3 samples of 50mg/L containing copper, chromium and cadmium ions, respectively, 1g of the graphene oxide-modified activated carbon material prepared in example 1 was put at 25 ℃ to perform adsorption experiments, and the adsorption results are shown in FIGS. 1 to 3.
As can be seen from FIG. 1, after 180min, the copper ion content in the water had decreased to 3.48mg/L, and the calculated final adsorption efficiency was 94.25%, and the adsorption amount was 47.125 mg/g.
As can be seen from FIG. 2, after 240min, the content of chromium ions in water had been reduced to 5.4mg/L, and the calculated final adsorption efficiency was 89.75%, and the adsorption amount was 44.875 mg/g.
As can be seen from FIG. 3, after 360min, the cadmium ion content in the water had been reduced to 8.53mg/L, and the calculated final adsorption efficiency was 85.52%, and the adsorption amount was 42.760 mg/g.
Example 2
In order to evaluate the stability and regenerability of the prepared graphene oxide-modified activated carbon, adsorption-desorption treatment was performed on the adsorbent. On the premise of ensuring high adsorption capacity, the stable renewable performance can effectively reduce the cost of adsorption treatment. The activated carbon having adsorbed copper ions in example 1 was washed with 0.1M hydrochloric acid at 60 ℃ for 1 hour, and then washed with hot water at 60 ℃ again to effect desorption. The washed activated carbon was dried and then subjected to the experiment of example 1, and the experimental results are shown in fig. 4 to 6.
As can be seen from FIG. 4, in a repeated experiment, the activated carbon has substantially completed adsorption in 240min, the copper ion content in water has been reduced to 3.5mg/L, and finally, 93.12% of adsorption efficiency and 46.560mg/g of adsorption amount can still be maintained on the copper ions.
As can be seen from FIG. 5, in a repeated experiment, the activated carbon has substantially completed adsorption within 360min, the content of chromium ions in water has been reduced to 6.4mg/L, and finally, the adsorption efficiency of 87.32% and the adsorption amount of 43.660mg/g for chromium ions can be still maintained.
As can be seen from FIG. 6, in a repeated experiment, the activated carbon has substantially completed the adsorption at 720min, the cadmium ion content in water has been reduced to 7.9mg/L, and finally, 84.56% of adsorption efficiency and 42.280mg/g of adsorption amount can still be maintained on the cadmium ions.
Example 3
An adsorption-desorption experiment of the adsorbent was performed on the basis of example 2 in the same manner as in example 1 to determine the reproducibility of the graphene oxide-modified activated carbon. The results are shown in 7-9.
As can be seen from fig. 7, the improved adsorbent still has excellent adsorption performance for copper ions after repeating for 5 times, and the adsorption rates for copper ions for 5 times are 94.5%, 94.2%, 94.1%, 93.9% and 94.0%, respectively.
As can be seen from fig. 8, the improved adsorbent still has excellent adsorption performance for chromium ions after repeating for 5 times, and the adsorption rates for chromium ions for 5 times are 89.8%, 89.7% and 89.1%, respectively.
As can be seen from fig. 9, the improved adsorbent still has excellent adsorption performance for cadmium ions after 5 times of repetition, and the adsorption rates for chromium ions of 5 times are 85.5%, 85.1%, 85.2%, 84.6% and 84.8%, respectively.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (6)

1. A preparation method of graphene oxide modified activated carbon is characterized by comprising the following steps:
s1, raw material pretreatment: washing, drying and crushing the raw material active carbon, and sieving the raw material active carbon with a 60-mesh sieve to obtain active carbon powder with the granularity of less than 60 meshes;
s2, preparing graphene oxide:
firstly, graphite powder with the granularity of 60-200 meshes is put into concentrated H2SO4、K2S2O8、P2O5In solution, the solution is 2.5gK2S2O8、2.5g P2O5Dissolved in 12ml of 98% of sulfuric acid, and continuously stirring for 4-6h at 75-85 ℃;
then diluting with deionized water, centrifuging, washing and drying to obtain pre-oxidized graphite; then in concentrated H2SO4And KMnO4Further oxidizing;
then, dilute with deionized water, add 30% H2O2Obtaining a graphene oxide product;
then, carrying out centrifugal washing on the product by using HCl and deionized water in a volume ratio of 1:9-10 to remove impurity ions;
finally, carrying out centrifugal separation at a speed of 3000-;
s3, active carbon improvement:
s1, soaking activated carbon in raw material pretreatment in a graphene oxide aqueous solution with the concentration of 0.005-10mg/mL, adsorbing graphene oxide in the solution by utilizing the adsorption effect of the activated carbon, soaking for 0.2-2h, and carrying out solid-liquid separation; and then, quickly placing the activated carbon adsorbed with the graphene oxide into a constant-temperature environment of 30-70 ℃ for drying, thus preparing the graphene oxide modified activated carbon material.
2. The method for preparing graphene oxide modified activated carbon according to claim 1, wherein in the S2. graphene oxide preparation, the degree of oxidation of the graphene oxide solution is 30%.
3. The method of claim 1, wherein in the S3. activated carbon modification, the concentration of the graphene oxide aqueous solution is 5 mg/mL.
4. The method of claim 1, wherein in the S3. activated carbon modification, the soaking time is 1 h.
5. The method for preparing graphene oxide modified activated carbon according to claim 1, wherein in the S3. activated carbon modification, the temperature for drying the activated carbon adsorbed with graphene oxide is 60 ℃.
6. The application of the graphene oxide modified activated carbon prepared by the preparation method of the graphene oxide modified activated carbon according to any one of claims 1 to 5, wherein the graphene oxide modified activated carbon is applied to adsorption and removal of heavy metal ions in a water environment.
CN202111195614.6A 2021-10-14 2021-10-14 Preparation method and application of graphene oxide modified activated carbon Pending CN113750967A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012580A (en) * 2018-07-18 2018-12-18 山东利特纳米技术有限公司 A kind of preparation method of the multi-layer porous material of graphene-active carbon
CN109351327A (en) * 2018-10-25 2019-02-19 南华大学 A kind of active carbon graphene composite material, preparation method and application
CN112138631A (en) * 2020-07-21 2020-12-29 中欣环保科技有限公司 Preparation method of graphene oxide/activated carbon composite material
CN113000023A (en) * 2021-03-04 2021-06-22 上海晶宇环境工程股份有限公司 Graphene oxide modified activated carbon, preparation method thereof and water treatment method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012580A (en) * 2018-07-18 2018-12-18 山东利特纳米技术有限公司 A kind of preparation method of the multi-layer porous material of graphene-active carbon
CN109351327A (en) * 2018-10-25 2019-02-19 南华大学 A kind of active carbon graphene composite material, preparation method and application
CN112138631A (en) * 2020-07-21 2020-12-29 中欣环保科技有限公司 Preparation method of graphene oxide/activated carbon composite material
CN113000023A (en) * 2021-03-04 2021-06-22 上海晶宇环境工程股份有限公司 Graphene oxide modified activated carbon, preparation method thereof and water treatment method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
邱军科;王朋;张迪;石林;张凰;: "三维石墨烯基多孔碳材料的制备及对污染物的吸附性能研究进展", 材料导报, no. 13 *

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