CN111498841B - Preparation method of expanded graphite and application of expanded graphite in aromatic compound adsorption - Google Patents
Preparation method of expanded graphite and application of expanded graphite in aromatic compound adsorption Download PDFInfo
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- CN111498841B CN111498841B CN202010339775.7A CN202010339775A CN111498841B CN 111498841 B CN111498841 B CN 111498841B CN 202010339775 A CN202010339775 A CN 202010339775A CN 111498841 B CN111498841 B CN 111498841B
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Abstract
The invention relates to a preparation method of expanded graphite and application thereof in aromatic compound adsorption, belonging to the field of adsorbents. Mixing one or more kinds of low boiling point alcohols with water, and adding natural crystalline flake graphite to obtain pre-intercalated graphite; adding weak or nonpolar low boiling point organic compound into the pre-intercalated graphite, mixing, and sealing and heating in a high-pressure kettle for intercalation; cooling to room temperature after intercalation, and performing microwave expansion. The expanded graphite prepared by the method does not use sulfuric acid, nitric acid, perchloric acid and other strong corrosive articles, and does not use potassium permanganate, potassium dichromate and other strong oxidants; low consumption and energy conservation; the FEG product has obvious advantages in adsorbing organic compounds, particularly aromatic compounds.
Description
Technical Field
The invention relates to a preparation method of expanded graphite and application thereof in aromatic compound adsorption, belonging to the field of adsorbents.
Background
Expanded Graphite (EG) is typically Expanded rapidly by pre-oxidation intercalation followed by high temperature or microwave treatment to obtain fluffy, large surface area, vermicular flexible Graphite material, which is prepared from natural flake Graphite obtained by purification from natural Graphite ore. In the traditional preparation method of the expanded graphite, a large amount of oxidizing strong acid such as concentrated sulfuric acid, concentrated nitric acid and concentrated perchloric acid, and high-concentration strong oxidizing agents such as potassium permanganate, potassium dichromate, hydrogen peroxide and the like are consumed, and sometimes, phosphoric acid is used for assisting; or direct electrochemical treatment in sulfuric acid solution to embed various intercalators into the graphite flake layers, thereby obtaining intercalated graphite or pre-oxidized graphite. These intercalation or pre-oxidation methods, in addition to consuming a large amount of strongly oxidizing, corrosive chemicals, resulting in the discharge of a large amount of waste acid and strong oxidizing agent, also have a great potential corrosivity to the production equipment, so that the cost of the production process remains high, and the production process also has a great risk. Although researchers spend great effort and time to improve the oxidation intercalation process, the defects of high consumption and high emission are not fundamentally improved.
Disclosure of Invention
Aiming at the problems existing in the preparation process of the expanded graphite at the present stage, the invention adopts environment-friendly raw materials such as sulfur-free and strong oxidant-free to prepare the expanded graphite (FEG, F-friendly) which has good adsorption effect on aromatic compounds, and simultaneously provides the preparation method of the expanded graphite.
A preparation method of expanded graphite comprises the following steps:
(1) mixing one or more kinds of low boiling point alcohols with water, adding natural crystalline flake graphite, uniformly mixing, and performing ultrasonic treatment for 30-90 minutes; then filtering and fully washing, drying, and cooling to room temperature in a dryer to obtain pre-intercalated graphite;
(2) adding weak or nonpolar low boiling point organic compound into the pre-intercalated graphite, mixing, and sealing and heating in a high-pressure kettle for intercalation;
(3) cooling to room temperature after intercalation, and performing microwave expansion.
Preferably, the alcohol in step (1) is methanol, ethanol or propanol.
The temperature of the autoclave heating intercalation in the step (2) is between the boiling point of the liquid intercalation agent and the critical temperature, the intercalation time is 0.5-2 h, the microwave power is within 1000 watts, and the microwave expansion time is not more than 5 min.
The low boiling point compound in the step (2) is one or more of benzene, toluene, xylene, n-hexane, cyclohexane, petroleum ether, ethyl acetate, dichloromethane, chloroform and carbon tetrachloride, and is a weak or non-polar compound.
The application of the expanded graphite prepared by the method in adsorbing aromatic compounds.
Drawings
FIG. 1 is a scanning electron microscope image of graphite as received SEG;
FIG. 2 is a scanning electron microscope photograph of the expanded graphite of example 1;
FIG. 3 is a scanning electron microscope photograph of the expanded graphite of example 2;
FIG. 4 is an x-ray diffraction pattern of graphite as received;
FIG. 5 is an x-ray diffraction pattern of the expanded graphite of example 1;
FIG. 6 is an x-ray diffraction pattern of the expanded graphite of example 2.
The invention has the advantages of
(1) Almost non-toxic: the method does not use sulfuric acid, nitric acid, perchloric acid and other strong corrosive articles, and does not use potassium permanganate, potassium dichromate and other strong oxidizing agents; (2) low consumption: the addition amount of the organic solvent or water is limited, and the organic solvent can be recovered, so the discharge is very low, and the discharged organic solvent is only the organic solvent, and the recovery is also convenient; (3) energy conservation: the graphite is only added above the boiling point and is kept at the constant temperature for a period of time during intercalation, the microwave power is lower, and the time during expansion is short, so the total power consumption is less; (4) the FEG product has obvious advantages in adsorbing organic compounds, particularly aromatic compounds.
Detailed Description
Example 1
A preparation method of expanded graphite comprises the following steps:
adding 5g of natural crystalline flake graphite (80 meshes, 99% of carbon content, Hongda graphite product Co., Ltd.) into 5 ml of methanol and 2 ml of water, uniformly mixing, performing 500-watt ultrasonic treatment for 30 minutes, directly performing suction filtration and washing for 5 times, drying at 105 ℃ for 1 hour, and cooling to below 50 ℃ to obtain pre-expanded graphite;
transferring the obtained pre-expanded graphite into a high-pressure kettle, adding 0.5 ml of benzene, sealing and intercalating in the high-pressure kettle at 120 ℃ for 90 minutes, and then cooling to room temperature;
opening the autoclave cover, transferring the intercalated graphite into 1000mL glass beakers for 5 times, and respectively expanding for 1 minute under 500 watts of microwave power to obtain the FEG of the invention;
the swelling ratio of the product measured by a measuring cylinder method is 76 times.
Example 2
A preparation method of expanded graphite comprises the following steps:
5g of natural crystalline flake graphite (80 meshes, 99% of carbon content, Hongda graphite product Co., Ltd. of south Villa of Qingdao), adding 4 ml of ethanol and 4 ml of water, uniformly mixing, directly performing suction filtration and washing for 5 times after ultrasonic treatment is performed for 40 minutes at 500 watts, drying for 1.5 hours at 105 ℃, and cooling to below 50 ℃ to obtain pre-expanded graphite;
transferring the pre-expanded graphite into a high-pressure kettle, adding 0.25 ml of petroleum ether and 0.25 ml of benzene, sealing and intercalating in the high-pressure kettle at 150 ℃ for 60 minutes, and then cooling to room temperature;
opening the autoclave cover, transferring the intercalated graphite into 1000mL glass beakers for 5 times, and respectively expanding for 40 seconds under 500 watts of microwave power to obtain the FEG of the invention;
the expansion ratio of the material is 101 times by measuring cylinder method.
Example 3
A preparation method of expanded graphite comprises the following steps:
adding 5g of natural crystalline flake graphite (80 meshes, 99% of carbon content, Hongda graphite product Co., Ltd.) into 4 ml of propanol and 4 ml of water, uniformly mixing, performing 500-watt ultrasonic treatment for 60 minutes, directly performing suction filtration and washing for 5 times, drying at 105 ℃ for 1.5 hours, and cooling to below 50 ℃ to obtain pre-expanded graphite;
transferring the pre-expanded graphite into a high-pressure kettle, adding 0.1 ml of petroleum ether, 0.2 ml of benzene and 0.2 ml of n-hexane, sealing and intercalating in the high-pressure kettle at 150 ℃ for 60 minutes, and then cooling to room temperature;
opening the autoclave cover, transferring the intercalated graphite into 1000mL glass beakers for 5 times, and respectively expanding for 40 seconds under 500 watts of microwave power to obtain the FEG of the invention;
the expansion ratio of the composite material measured by a measuring cylinder method is 108 times.
Example 4
A preparation method of expanded graphite comprises the following steps:
5g of natural crystalline flake graphite (80 meshes, 99% carbon content, Hongda graphite product Co., Ltd. of south villa of Qingdao), adding 2 ml of methanol, 2 ml of propanol and 4 ml of water, uniformly mixing, then directly performing suction filtration and washing for 5 times after 500 watts of ultrasound for 90 minutes, then drying for 1.5 hours at 105 ℃, and cooling to below 50 ℃ to obtain pre-expanded graphite;
transferring the pre-expanded graphite into a high-pressure kettle, adding 0.1 ml of petroleum ether, 0.2 ml of benzene and 0.2 ml of n-hexane, sealing and intercalating in the high-pressure kettle at 150 ℃ for 60 minutes, and then cooling to room temperature;
opening the autoclave cover, transferring the intercalated graphite into 1000mL glass beakers for 5 times, and respectively expanding for 40 seconds under 500 watts of microwave power to obtain the FEG of the invention;
the expansion ratio of the material is 110 times by measuring cylinder method.
Example 5
A preparation method of expanded graphite comprises the following steps:
5g of natural crystalline flake graphite (80 meshes, 99% carbon content, Hongda graphite product Co., Ltd. of south villa of Qingdao), adding 2 ml of methanol, 2 ml of propanol and 4 ml of water, uniformly mixing, then directly performing suction filtration and washing for 5 times after 500 watts of ultrasound for 90 minutes, then drying for 1.5 hours at 105 ℃, and cooling to below 50 ℃ to obtain pre-expanded graphite;
transferring the pre-expanded graphite into a high-pressure kettle, adding 0.1 ml of petroleum ether, 0.2 ml of ethyl acetate and 0.2 ml of n-hexane, sealing and intercalating in the high-pressure kettle at 150 ℃ for 60 minutes, and then cooling to room temperature;
opening the autoclave cover, transferring the intercalated graphite into 1000mL glass beakers for 5 times, and respectively expanding for 40 seconds under 500 watts of microwave power to obtain the FEG of the invention;
the expansion ratio of the material is 110 times by measuring cylinder method.
Example 6
A preparation method of expanded graphite comprises the following steps:
5g of natural crystalline flake graphite (80 meshes, 99% carbon content, Hongda graphite product Co., Ltd. of south villa of Qingdao), adding 2 ml of methanol, 2 ml of propanol and 4 ml of water, uniformly mixing, then directly performing suction filtration and washing for 5 times after 500 watts of ultrasound for 90 minutes, then drying for 1.5 hours at 105 ℃, and cooling to below 50 ℃ to obtain pre-expanded graphite;
transferring the pre-expanded graphite into a high-pressure kettle, adding 0.1 ml of petroleum ether, 0.2 ml of ethyl acetate and 0.2 ml of chloroform, sealing and intercalating in the high-pressure kettle at 150 ℃ for 60 minutes, and then cooling to room temperature;
opening the autoclave cover, transferring the intercalated graphite into 1000mL glass beakers for 5 times, and respectively expanding for 40 seconds under 500 watts of microwave power to obtain the FEG of the invention;
the expansion ratio of the material is 110 times by measuring cylinder method.
Comparative example 1
A preparation method of expanded graphite comprises the following steps:
transferring 5g of natural crystalline flake graphite (80 meshes, 99% carbon content, Hongda graphite product Co., Ltd. of Nanvilla, Qingdao) into an autoclave, adding 0.1 ml of petroleum ether, 0.2 ml of ethyl acetate and 0.2 ml of chloroform, sealing and intercalating in the autoclave at 150 ℃ for 60 minutes, and then cooling to room temperature;
opening the autoclave cover, transferring the intercalated graphite into a 1000mL glass beaker for 5 times, and respectively expanding for 40 seconds under 500 watts of microwave power to obtain FEG of the invention;
the expansion ratio of the material measured by a measuring cylinder method is 145 times.
Comparative example 2
A preparation method of expanded graphite comprises the following steps:
adding 5g of ammonium persulfate into 10 ml of concentrated sulfuric acid, then adding 1g of raw material graphite, stirring for 15 minutes, then performing shake intercalation for 6 hours at room temperature, filtering, washing with distilled water to be nearly neutral, and drying to obtain the expandable graphite.
And (3) transferring the expandable graphite in the step (1) into a muffle furnace, and rapidly heating for 3 minutes at 900 ℃ to obtain the expandable graphite EG.
The expansion ratio of the material is 160 times measured by a measuring cylinder method.
Effects of the embodiment
The adsorbents prepared in examples 1 to 6 and comparative examples 1 to 2 were used in the experiment for adsorbing aromatic compounds.
The experimental method comprises the following steps: the quantitative method adopts a standard curve method and uses a least square method to calculate a regression equation. Respectively weighing two samples (0.02 g each) by using an analytical balance, adding the samples into an adsorbate solution with a certain concentration, oscillating the samples for more than 4 hours at a constant temperature of 25 ℃, filtering the samples, and measuring the absorbance of the filtrate by using an ultraviolet spectrophotometer; cyclohexane is used as a solvent and is used as a reference solution; and substituting the absorbance of the filtrate into a regression equation of a standard curve, calculating the residual concentration, further solving the adsorption capacity and taking an average value.
The results are shown in Table 1. As can be seen from the table, examples 1 to 6 have similar effects on the adsorption of benzene, pyrene, fluoranthene and chrysene, and the amounts of adsorption varied but did not differ much; the adsorption performance of comparative examples 1-2 is greatly different, and it is likely that the surface change is large. None of these expanded graphite samples adsorbed inorganic ions, dichromate.
TABLE 1 comparison of the adsorption effects of expanded graphite (unit: mg/g)
Claims (2)
1. A preparation method of expanded graphite is characterized by comprising the following steps:
(1) mixing one or more kinds of low boiling point alcohols with water, adding natural crystalline flake graphite, uniformly mixing, and performing ultrasonic treatment for 30-90 minutes; then filtering and fully washing, drying, and cooling to room temperature in a dryer to obtain pre-intercalated graphite;
(2) adding weak or nonpolar low boiling point organic compound into the pre-intercalated graphite, mixing, and sealing and heating in a high-pressure kettle for intercalation;
(3) cooling to room temperature after intercalation, and performing microwave expansion;
the low boiling point alcohols in the step (1) are methanol, ethanol and propanol;
the temperature of the high-pressure kettle in the step (2) for heating and intercalation is between the boiling point of the liquid intercalation agent and the critical temperature, and the intercalation time is 0.5-2 h; the microwave power in the step (3) is within 1000 watts, and the microwave expansion time is not more than 5 min;
the weak or non-polar low-boiling organic compound in the step (2) is one or more of benzene, toluene, xylene, n-hexane, cyclohexane, petroleum ether, ethyl acetate, dichloromethane, chloroform and carbon tetrachloride.
2. Use of the expanded graphite prepared by the method of claim 1 for adsorbing aromatic compounds.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105502360A (en) * | 2015-12-25 | 2016-04-20 | 燕山大学 | Preparation method of sulfur-free expansible graphite |
| CN106185881A (en) * | 2016-06-07 | 2016-12-07 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | A kind of method that in utilization, low-carbon (LC) Fine particle processing prepares sulphur-free expanded graphite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105502360A (en) * | 2015-12-25 | 2016-04-20 | 燕山大学 | Preparation method of sulfur-free expansible graphite |
| CN106185881A (en) * | 2016-06-07 | 2016-12-07 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | A kind of method that in utilization, low-carbon (LC) Fine particle processing prepares sulphur-free expanded graphite |
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