CN112023889A - Method for microwave-assisted in-situ one-step modification of activated carbon by oleic acid - Google Patents
Method for microwave-assisted in-situ one-step modification of activated carbon by oleic acid Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 title claims abstract description 48
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000005642 Oleic acid Substances 0.000 title claims abstract description 48
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 title claims abstract description 48
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 43
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- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003830 anthracite Substances 0.000 claims description 3
- 238000004134 energy conservation Methods 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 42
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- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 9
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
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- 206010028813 Nausea Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 amine modified activated carbon Chemical class 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
The invention discloses a microwave-assisted method for in-situ one-step modification of activated carbon by oleic acid, which is implemented according to the following steps: step 1, pretreating a coal sample; step 2, mixing the pretreated coal sample obtained in the step 1 with a modifier in a mixed solution of absolute ethyl alcohol and deionized water, stirring for 4 hours at 65 ℃, placing the mixture in a vacuum drying oven, drying for 12 hours at 65 ℃ to obtain a dried sample, uniformly mixing the dried sample with an activator, placing the mixture in a quartz tube, installing the quartz tube on a microwave reactor, and adding N2Carrying out microwave radiation under protection, and taking out after the reaction is finished and cooling to obtain an oleic acid in-situ modified microwave-assisted preparation sample; step 3, carrying out acid treatment on the oleic acid in-situ modified microwave-assisted prepared sample obtained in the step 2Alkali treatment, washing with distilled water until the filtrate is neutral, and drying in a 110 ℃ oven for 4h to obtain the modified coal-based activated carbon, which has the characteristics of short modification time and energy conservation.
Description
Technical Field
The invention belongs to the technical field of active carbon modification, and relates to a method for modifying active carbon by oleic acid in situ in one step under the assistance of microwaves.
Background
Polycyclic aromatic hydrocarbons are compounds with benzene ring structures and belong to persistent organic pollutants. Can exist in air and water for a long time and is difficult to biodegrade. They can interact with DNA, promoting mutagenesis or carcinogenesis. Naphthalene, as a typical polycyclic aromatic hydrocarbon, is widely used in actual production and life, and the main source of the naphthalene is coal tar produced in the petroleum refining process. Prolonged contact with it can lead to symptoms such as hemolytic anemia, jaundice, lethargy, headache, confusion, nausea, vomiting, cataract and respiratory toxicity. They are difficult to remove effectively by conventional physicochemical methods such as coagulation, flocculation, sedimentation, filtration, ozonation, and the like. Adsorption treatment is currently a simple and effective method for removing organic contaminants from solutions. The activated carbon is a common porous material with a high specific surface area, and is widely applied to the fields of gas-phase and liquid-phase separation/purification, toxic substance removal, groundwater remediation, fuel storage, catalyst carriers and the like. The removal of polycyclic aromatic hydrocarbons by activated carbon adsorption has been reported.
Along with the development of industrial production in recent years, coal-based activated carbon with unique pore structure and excellent adsorption performance, which is processed by taking coal as a raw material, plays an increasingly important role in the field of environmental protection, has an increasing demand at home and abroad, and becomes an indispensable adsorption material for improving the living environment of human beings. However, the conventional activated carbon has a limited effect of removing high-concentration polycyclic aromatic hydrocarbons, and the technical problem which needs to be solved at present is how to improve the hydrophobic groups on the surface of the activated carbon and realize the rapid and efficient adsorption and removal of the polycyclic aromatic hydrocarbons mainly because the polycyclic aromatic hydrocarbons have strong hydrophobicity.
Modification of activated carbon can be achieved essentially by three methods: grafting, physical impregnation and dual functionalization. In the specific implementation process of modification, the conventional modification method and the in-situ modification method can be divided according to the addition of the modifier in different stages in the preparation process of the activated carbon. The in-situ modification method is a novel method for modifying the activated carbon, which has the advantages of low cost, high efficiency, low energy consumption and simple and convenient operation. Compared with the traditional modification method in which finished activated carbon is used as a modification object, the in-situ modification method has the advantages that the raw material is used as the modification object, and is mixed with the modifier and the activating agent to prepare the high-efficiency modified activated carbon through one-step carbonization, activation and modification. The in-situ modification method reported at present is mostly used for biomass materials and agricultural wastes, for example, the modified activated carbon prepared by the in-situ modification method from cane shoots [ Enhancement of Cr (VI) removal modified activated carbon with tarctic acid reducing phosphoric acid activation ] and the like used as raw materials in Liu Hai and the like of China is used for adsorbing and removing ions in water. Various organic substances such as tartaric acid, humic acid and ethylenediaminetetraacetic acid are selected as modifiers. Due to the strong operability and the simplified preparation process, the method is considered to have wide application prospect and even can be used for large-scale production in factories.
Oleic acid is a common fatty acid, whose molecule consists of a long hydroxyl group head and a hydrophobic hydrocarbyl chain tail, and is useful as a hydrophobic modifier. Wherein, the hydroxyl group at the head can be grafted to the surface of the activated carbon through esterification reaction. Meanwhile, the long hydrocarbyl chain tail can provide a large amount of active adsorption sites for pollutants in water, and is beneficial to removing the pollutants. The existing reports prove that the method can improve the adsorption removal capacity of the activated carbon on organic matters in water. The common method for modifying the adsorbent by using oleic acid is generally a traditional modification method, namely modified activated carbon is prepared by modifying a finished product of activated carbon or biomass raw material by using a modifier. However, the development of the method for modifying the coal-based activated carbon in situ by using the oleic acid has the advantages of simple process, rapidness and energy conservation, has practical application value and has important application prospect.
As a new heating technology, the microwave technology can greatly improve the chemical reaction rate, reduce the reaction time and simplify the post-treatment procedure. At present, the traditional heating method commonly used for preparing the activated carbon, for example, Chinese patent (application No. 201210246423.2) adopts Chinese chestnut shells as raw materials and zinc chloride as an activating agent to obtain the Chinese chestnut shell activated carbon with higher adsorption performance, and the reaction needs to be carried out at the temperature of 300-550 ℃ for 60-90 minutes. Likewise, the manner of heating can also affect the modification process and further affect the properties of the modified activated carbon. Therefore, microwave heating as a novel heating technology is applied to the field of activated carbon preparation and modification, and the carbon material is prepared and modified more efficiently. At present, most reports of microwave modified activated carbon take the activated carbon as a base for modification. Such as Liu Xiao Yang et al [ Microwave-assisted ammonium modification of activated carbon for effective removal of phenol from water: DFT and experimental study ] amine modified activated carbon was prepared using Microwave assistance for the removal of phenols from water. However, the research on the removal of polycyclic aromatic hydrocarbon naphthalene by the modified coal-based active carbon prepared by the oleic acid in-situ modification microwave-assisted method is not reported.
Disclosure of Invention
The invention aims to provide a method for modifying activated carbon by oleic acid in situ in one step with the assistance of microwaves, which has the characteristics of short modification time and energy conservation.
The technical scheme adopted by the invention is that a microwave-assisted method for modifying activated carbon by oleic acid in situ in one step is implemented according to the following steps:
step 1, pretreating a coal sample;
step 2, mixing the pretreated coal sample obtained in the step 1 with a modifier in a mixed solution of absolute ethyl alcohol and deionized water, stirring for 4 hours at 65 ℃, placing the mixture in a vacuum drying oven, drying for 12 hours at 65 ℃ to obtain a dried sample, uniformly mixing the dried sample with an activator, placing the mixture in a quartz tube, installing the quartz tube on a microwave reactor, and adding N2Carrying out microwave radiation under protection, and taking out after the reaction is finished and cooling to obtain an oleic acid in-situ modified microwave-assisted preparation sample;
and 3, carrying out acid-base treatment on the oleic acid in-situ modified microwave-assisted preparation sample obtained in the step 2, washing the sample with distilled water until the filtrate is neutral, and drying the filtrate in a drying oven at 110 ℃ for 4 hours to obtain the modified coal-based activated carbon.
The invention is also characterized in that:
step 1 is specifically carried out as follows: crushing and grinding the coal sample, and screening the coal sample by a 100-mesh screen to prepare anthracite powder; cleaning with distilled water to remove impurities such as coal tar; and then, drying the sample in a drying oven at 110 ℃ for 4h to obtain the coal sample pretreated coal sample.
The mass ratio of the pretreated coal sample obtained in the step 1 in the step 2 to the modifier is 1: 0.2-1.
The volume ratio of the absolute ethyl alcohol to the deionized water in the step 2 is 1: 1.
The mass ratio of the dried sample to the activating agent in the step 2 is 1: 1-2.
The modifier in the step 2 is oleic acid.
The activating agent in step 2 is KOH.
The microwave time in step 2 is 8-20min, and the microwave power is 300-.
The invention has the beneficial effects that: the invention aims to provide a microwave-assisted oleic acid in-situ one-step modified activated carbon method which has the characteristics of short modification time and energy conservation. The prepared modified coal-based activated carbon has the advantages of large adsorption capacity, high adsorption rate, obvious treatment effect and the like on naphthalene, has good economic and environmental benefits, realizes synchronous processes of carbonization, activation and modification, shortens the modification time, saves energy, reduces the cost of the modified activated carbon, improves the surface hydrophobicity, better adsorbs nonpolar polycyclic aromatic hydrocarbon pollutants, is favorable for improving the aperture, the pore volume and the specific surface area of the activated carbon, has the advantages of strong adsorption capacity, high adsorption rate, obvious treatment effect and the like for removing the naphthalene, and is an economic and efficient preparation method.
Drawings
FIG. 1 is a scanning electron microscope image of activated carbon and oleic acid in-situ modified activated carbon in the microwave-assisted method for oleic acid in-situ one-step modification of activated carbon.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a method for microwave-assisted in-situ one-step modification of activated carbon by oleic acid, which is implemented according to the following steps:
step 1, pretreating a coal sample;
step 1 is specifically carried out as follows: crushing and grinding the coal sample, and screening the coal sample by a 100-mesh screen to prepare anthracite powder; cleaning with distilled water to remove impurities such as coal tar; and then, drying the sample in a drying oven at 110 ℃ for 4h to obtain the coal sample pretreated coal sample.
Step 2, mixing the pretreated coal sample obtained in the step 1 with a modifier in a mixed solution of absolute ethyl alcohol and deionized water, stirring for 4 hours at 65 ℃, placing the mixture in a vacuum drying oven, drying for 12 hours at 65 ℃ to obtain a dried sample, uniformly mixing the dried sample with an activator, placing the mixture in a quartz tube, installing the quartz tube on a microwave reactor, and adding N2Carrying out microwave radiation under protection, and taking out after the reaction is finished and cooling to obtain an oleic acid in-situ modified microwave-assisted preparation sample;
the mass ratio of the pretreated coal sample obtained in the step 1 in the step 2 to the modifier is 1: 0.2-1.
The volume ratio of the absolute ethyl alcohol to the deionized water in the step 2 is 1: 1.
The mass ratio of the dried sample to the activating agent in the step 2 is 1: 1-2.
The modifier in the step 2 is oleic acid.
The activating agent in step 2 is KOH.
The microwave time in step 2 is 8-20min, and the microwave power is 300-.
And 3, carrying out acid-base treatment on the oleic acid in-situ modified microwave-assisted preparation sample obtained in the step 2, washing the sample with distilled water until the filtrate is neutral, and drying the filtrate in a drying oven at 110 ℃ for 4 hours to obtain the modified coal-based activated carbon.
The method for removing naphthalene by using the modified coal-based activated carbon prepared by the microwave-assisted method for in-situ one-step modification of the activated carbon by oleic acid comprises the following steps: accurately measuring 100mL of simulated wastewater containing 30mg/L of naphthalene with initial concentration, placing the simulated wastewater in a 250mL conical flask with a plug, placing the conical flask in a water bath constant-temperature oscillator with the temperature of 30 ℃ and the rotating speed of 140rpm for preheating for 5min, then adding 0.015g of the modified coal-based activated carbon prepared in the step 1, adsorbing for 40min, quickly taking out and carrying out suction filtration, and detecting the residual concentration.
The average pore diameter of the modified coal-based activated carbon prepared by the microwave-assisted method for in-situ one-step modification of the oleic acid is more than 2.67nm, the modified coal-based activated carbon is mainly mesoporous, and the specific surface area is 821.84-943.64m2(g) total pore volume of 0.31cm3More than one gram of naphthalene, and the adsorption quantity of the naphthalene is 187.76 mg/gram.
Example 1
Crushing and grinding the coal sample, and screening the coal sample by a 100-mesh screen to prepare powder; cleaning with distilled water to remove impurities such as coal tar; drying the sample in a drying oven at 110 ℃ for 4h to obtain a pretreated coal powder product; 5.00g of the coal sample pretreatment product was mixed with 2.00g of oleic acid in a mixture of absolute ethanol and deionized water (v/v ═ 50mL/50mL), stirred at 65 ℃ for 4 hours, and then dried in a vacuum oven at 65 ℃ for 12 hours. 1.00g of the resulting dried sample was mixed with 1.00g of KOH, placed in a quartz tube and set in a microwave reactor under N2Protecting, wherein the microwave time is 8min, performing microwave radiation under the microwave power of 700W, and taking out the modified sample after the reaction is finished and cooled. Washing the obtained sample with hydrochloric acid, washing with distilled water until the filtrate is neutral, and drying in a drying oven at 110 ℃ for 4h to obtain the oleic acid in-situ modified coal-based activated carbon; the average pore diameter of the obtained modified coal-based activated carbon is 2.85nm, and the specific surface area is 821.84m2(g) total pore volume of 0.31cm3/g。
Accurately measuring 100mL of simulated wastewater containing 100mg/L of naphthalene with initial concentration, placing the simulated wastewater in a 250mL conical flask with a plug, placing the conical flask in a water bath constant-temperature oscillator with the temperature of 30 ℃ and the rotating speed of 140rpm for preheating for 5min, then adding 0.015g of modified coal-based activated carbon, adsorbing for 40min, quickly taking out and carrying out suction filtration, and detecting the residual concentration. The adsorption amount of naphthalene by the obtained modified coal-based activated carbon was 155.43 mg/g.
As shown in fig. 1, a is a scanning electron microscope image of activated carbon, b is modified coal-based activated carbon prepared by the method for microwave-assisted oleic acid in-situ one-step modification of activated carbon, and the comparison shows that the microwave-assisted oleic acid in-situ modified activated carbon has better pore structure and morphology than unmodified activated carbon.
Example 2
Crushing a coal sample, grinding, and screening by a 100-mesh screen to prepare powder; cleaning with distilled water to remove impurities such as coal tar; drying the sample in a drying oven at 110 ℃ for 4h to obtain a pretreated coal powder product; 5.00g of the coal sample pretreatment product was mixed with 2.00g of oleic acid in a mixture of absolute ethanol and deionized water (v/v 50mL:50mL), stirred at 65 ℃ for 4 hours, and then dried in a vacuum oven at 65 ℃ for 12 hours. 1.00g of the resulting dried sample was mixed with 2.00g of KOH, placed in a quartz tube and set in a microwave reactor under N2Protecting, performing microwave radiation under the microwave power of 900W for 8min, and taking out the modified sample after the reaction is finished and cooled. Washing the obtained sample with hydrochloric acid, washing with distilled water until the filtrate is neutral, and drying in a drying oven at 110 ℃ for 4h to obtain the oleic acid in-situ modified coal-based activated carbon; the average pore diameter of the obtained modified coal-based activated carbon was 4.05nm, and the specific surface area was 877.89m2Per g, total pore volume of 0.39cm3/g。
Accurately measuring 100mL of simulated wastewater containing 100mg/L of naphthalene with initial concentration, placing the simulated wastewater in a 250mL conical flask with a plug, placing the conical flask in a water bath constant-temperature oscillator with the temperature of 30 ℃ and the rotating speed of 140rpm for preheating for 5min, then adding 0.015g of modified coal-based activated carbon, adsorbing for 40min, quickly taking out and carrying out suction filtration, and detecting the residual concentration. The adsorption amount of naphthalene by the obtained modified coal-based activated carbon was 157.62 mg/g.
Example 3
Crushing a coal sample, grinding, and screening by a 100-mesh screen to prepare powder; cleaning with distilled water to remove impurities such as coal tar; drying the sample in a drying oven at 110 ℃ for 4h to obtain a pretreated coal powder product; 5.00g of the coal sample pretreatment product was mixed with 1.50g of oleic acid in a mixture of absolute ethanol and deionized water (v/v 50mL:50mL), stirred at 65 ℃ for 4 hours, and then dried in a vacuum oven at 65 ℃ for 12 hours. 1.00g of the resulting dried sample was mixed with1.50g KOH were mixed well, placed in a quartz tube and set up in a microwave reactor under N2Protecting, performing microwave radiation for 15min under the microwave power of 900W, and taking out the modified sample after the reaction is finished and cooled. Washing the obtained sample with hydrochloric acid, washing with distilled water until the filtrate is neutral, and drying in an oven at 110 deg.C for 4h to obtain oleic acid in-situ modified coal-based activated carbon with average pore diameter of 2.78nm and specific surface area of 912.89m2Per g, total pore volume of 0.44cm3/g。
Accurately measuring 100mL of simulated wastewater containing 100mg/L of naphthalene with initial concentration, placing the simulated wastewater in a 250mL conical flask with a plug, placing the conical flask in a water bath constant-temperature oscillator with the temperature of 30 ℃ and the rotating speed of 140rpm for preheating for 5min, then adding 0.015g of modified coal-based activated carbon, adsorbing for 40min, quickly taking out and carrying out suction filtration, and detecting the residual concentration. The adsorption amount of naphthalene by the obtained modified coal-based activated carbon was 187.76 mg/g.
Example 4
Crushing a coal sample, grinding, and screening by a 100-mesh screen to prepare powder; cleaning with distilled water to remove impurities such as coal tar; drying the sample in a drying oven at 110 ℃ for 4h to obtain a pretreated coal powder product; 5.00g of the coal sample pretreatment product was mixed with 1.50g of oleic acid in a mixture of absolute ethanol and deionized water (v/v 50mL:50mL), stirred at 65 ℃ for 4 hours, and then dried in a vacuum oven at 65 ℃ for 12 hours. 1.00g of the resulting dried sample was mixed with 2.00g of KOH, placed in a quartz tube and set in a microwave reactor under N2Protecting, performing microwave radiation for 10min under the microwave power of 700W, and taking out the modified sample after the reaction is finished and cooled. Washing the obtained sample with hydrochloric acid, washing with distilled water until the filtrate is neutral, and drying in an oven at 110 deg.C for 4h to obtain oleic acid in-situ modified coal-based activated carbon with average pore diameter of 2.67nm and specific surface area of 883.64m2(g) total pore volume of 0.37cm3/g。
Accurately measuring 100mL of simulated wastewater containing 100mg/L of naphthalene with initial concentration, placing the simulated wastewater in a 250mL conical flask with a plug, placing the conical flask in a water bath constant-temperature oscillator with the temperature of 30 ℃ and the rotating speed of 140rpm for preheating for 5min, then adding 0.015g of modified coal-based activated carbon, adsorbing for 40min, quickly taking out and carrying out suction filtration, and detecting the residual concentration. The adsorption amount of naphthalene by the obtained modified coal-based activated carbon was 178.79 mg/g.
Example 5
Crushing a coal sample, grinding, and screening by a 100-mesh screen to prepare powder; cleaning with distilled water to remove impurities such as coal tar; drying the sample in a drying oven at 110 ℃ for 4h to obtain a pretreated coal powder product; 5.00g of the coal sample pretreatment product was mixed with 2.00g of oleic acid in a mixture of absolute ethanol and deionized water (v/v 50mL:50mL), stirred at 65 ℃ for 4 hours, and then dried in a vacuum oven at 65 ℃ for 12 hours. 1.00g of the resulting dried sample was mixed with 2.00g of KOH, placed in a quartz tube and set in a microwave reactor under N2Protecting, performing microwave radiation for 15min under the microwave power of 700W, and taking out the modified sample after the reaction is finished and cooled. Washing the obtained sample with hydrochloric acid, washing with distilled water until the filtrate is neutral, and drying in an oven at 110 deg.C for 4h to obtain oleic acid in-situ modified coal-based activated carbon with average pore diameter of 2.82nm and specific surface area of 943.64m2(g) total pore volume of 0.45cm3/g。
Accurately measuring 100mL of simulated wastewater containing 100mg/L of naphthalene with initial concentration, placing the simulated wastewater in a 250mL conical flask with a plug, placing the conical flask in a water bath constant-temperature oscillator with the temperature of 30 ℃ and the rotating speed of 140rpm for preheating for 5min, then adding 0.015g of modified coal-based activated carbon, adsorbing for 40min, quickly taking out and carrying out suction filtration, and detecting the residual concentration. The adsorption amount of naphthalene by the obtained modified coal-based activated carbon was 168.79 mg/g.
The invention aims to provide a microwave-assisted oleic acid in-situ one-step modified activated carbon method which has the characteristics of short modification time and energy conservation. The prepared modified coal-based activated carbon has the advantages of large adsorption capacity, high adsorption rate, obvious treatment effect and the like on naphthalene, has good economic and environmental benefits, realizes synchronous processes of carbonization, activation and modification, shortens the modification time, saves energy, reduces the cost of the modified activated carbon, improves the surface hydrophobicity, better adsorbs nonpolar polycyclic aromatic hydrocarbon pollutants, is favorable for improving the aperture, the pore volume and the specific surface area of the activated carbon, has the advantages of strong adsorption capacity, high adsorption rate, obvious treatment effect and the like for removing the naphthalene, and is an economic and efficient preparation method.
Claims (8)
1. A microwave-assisted method for in-situ one-step modification of activated carbon by oleic acid is characterized by comprising the following steps:
step 1, pretreating a coal sample;
step 2, mixing the pretreated coal sample obtained in the step 1 with a modifier in a mixed solution of absolute ethyl alcohol and deionized water, stirring for 4 hours at 65 ℃, placing the mixture in a vacuum drying oven, drying for 12 hours at 65 ℃ to obtain a dried sample, uniformly mixing the dried sample with an activator, placing the mixture in a quartz tube, installing the quartz tube on a microwave reactor, and adding N2Carrying out microwave radiation under protection, and taking out after the reaction is finished and cooling to obtain an oleic acid in-situ modified microwave-assisted preparation sample;
and 3, carrying out acid-base treatment on the oleic acid in-situ modified microwave-assisted preparation sample obtained in the step 2, washing the sample with distilled water until the filtrate is neutral, and drying the filtrate in a drying oven at 110 ℃ for 4 hours to obtain the modified coal-based activated carbon.
2. The method for microwave-assisted in-situ one-step modification of activated carbon with oleic acid according to claim 1, wherein the step 1 is specifically carried out as follows: crushing and grinding the coal sample, and screening the coal sample by a 100-mesh screen to prepare anthracite powder; cleaning with distilled water to remove impurities such as coal tar; and then, drying the sample in a drying oven at 110 ℃ for 4h to obtain the coal sample pretreated coal sample.
3. The method for microwave-assisted in-situ one-step modification of activated carbon by oleic acid according to claim 2, wherein the mass ratio of the pretreated coal sample obtained in step 1 in step 2 to the modifier is 1: 0.2-1.
4. The method for microwave-assisted in-situ one-step modification of activated carbon by oleic acid according to claim 2, wherein the volume ratio of absolute ethanol to deionized water in step 2 is 1: 1.
5. The method for in-situ one-step modification of activated carbon by using microwave-assisted oleic acid as claimed in claim 2, wherein the mass ratio of the dried sample to the activating agent in the step 2 is 1: 1-2.
6. The method for in-situ one-step modification of activated carbon by using microwave-assisted oleic acid as claimed in claim 2, wherein the modifying agent in the step 2 is oleic acid.
7. The method for in-situ one-step modification of activated carbon by oleic acid with microwave assistance as claimed in claim 2, wherein the activating agent in the step 2 is KOH.
8. The method for modifying activated carbon by oleic acid in situ by one step through microwave assistance as claimed in claim 2, wherein the microwave time in step 2 is 8-20min, and the microwave power is 300-900W.
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