CN115364811A - Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof - Google Patents

Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof Download PDF

Info

Publication number
CN115364811A
CN115364811A CN202211015644.9A CN202211015644A CN115364811A CN 115364811 A CN115364811 A CN 115364811A CN 202211015644 A CN202211015644 A CN 202211015644A CN 115364811 A CN115364811 A CN 115364811A
Authority
CN
China
Prior art keywords
sponge
petroleum asphalt
nano sponge
petroleum
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211015644.9A
Other languages
Chinese (zh)
Inventor
郝华睿
纪骞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yulin University
Original Assignee
Yulin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yulin University filed Critical Yulin University
Priority to CN202211015644.9A priority Critical patent/CN115364811A/en
Publication of CN115364811A publication Critical patent/CN115364811A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/204—Keeping clear the surface of open water from oil spills

Abstract

The invention discloses petroleum asphalt nano sponge base macroporous carbon, a preparation method and application thereof, and belongs to the technical field of oil pollution treatment materials. The petroleum asphalt nano sponge base macroporous carbon is prepared by the following steps: adding petroleum asphalt into trichloromethane or petroleum ether to obtain a soaking solution; placing the pretreated nano sponge in a soaking solution until the nano sponge is saturated in adsorption, and drying to completely volatilize chloroform or petroleum ether to obtain a sponge containing a petroleum asphalt coating; heating the sponge containing the petroleum asphalt coating to 600-700 ℃ in a nitrogen atmosphere, and performing high-temperature carbonization to obtain the petroleum asphalt nano sponge-based macroporous carbon. The petroleum asphalt nano sponge base macroporous carbon is green, pollution-free and recyclable.

Description

Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof
Technical Field
The invention relates to the technical field of oil pollution treatment materials, in particular to petroleum asphalt nano sponge-based macroporous carbon and a preparation method and application thereof.
Background
Ocean oil leakage and oil spill frequently occur in the oil exploitation and transportation process. In the oil was revealed and the toxic substance enters into the ocean, caused very big hidden danger to marine life's life safety, secondly marine life circle will also receive the influence, and marine ecosystem suffers fatal destruction. Meanwhile, the frequent occurrence of oil spillage events can also cause heavy energy and resource losses. Therefore, a material is urgently needed to solve the situation of oil pollution, improve the marine ecosystem and promote the ecological balance of the biosphere.
The oil absorption mechanism of the traditional oil absorption material comprises a absorption type, a gel type and a absorption gel composite type. Oil-absorbing materials having a porous structure are mostly of the absorption type, and absorb oil and hold it between pores by capillary force via gaps and pores existing on the surface of the material. The oil absorption material has the characteristics of high oil absorption speed and poor oil retention. Therefore, the traditional oil absorption materials have been shifted to novel oil absorption materials, and the high oil absorption materials can be generally classified into acrylates, methacrylates and olefins according to different monomers. But the high oil absorption resin can not be recycled after oil absorption and can not be recycled. The existing oil absorption material has high cost, high oil absorption and super-hydrophobic properties which can not be simultaneously met, and the existing oil absorption material can not be recycled.
The porous carbon material is a carbon material with pore structures of different sizes, and the pore diameter of the porous carbon material can be adjusted according to the requirements of practical application, so that the size of the porous carbon material can be between nano micropores and micro macropores. The porous carbon material has the characteristics of a carbon material, such as high chemical stability, good conductivity, low price and the like; the pore structure has the advantages of large specific surface area, controllable pore structure, adjustable pore diameter and the like. The porous carbon material is widely applied to relevant categories such as gas separation, water purification, chromatographic analysis and the like. According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), porous carbon materials can be classified into three categories according to their pore diameters: micropores (less than 2 nm); mesopores (2-50 nm) and macropores (greater than 50 nm). Porous carbon materials are classified into disordered porous and ordered porous according to their constitution.
Compared with the common oil absorption material, the macroporous carbon has high hydrophobicity and high oil absorption, and the material has good flame retardant property, so that the absorbed oil is removed by the macroporous carbon after oil absorption through combustion, and the macroporous carbon is recycled. It is necessary to research an oil absorption material which can treat oil pollution with high efficiency and has good adsorption effect. However, in the prior art, when the sponge is modified, octadecyltrichlorosilane is mostly adopted, the solution reacts violently with water and releases toxic gas, and when a sponge oil absorption experiment is performed, the atmospheric environment is polluted.
Disclosure of Invention
Aiming at the problems, the invention discloses petroleum asphalt nano sponge based macroporous carbon, a preparation method and application thereof.
The first purpose of the invention is to provide a preparation method of petroleum asphalt nano sponge-based macroporous carbon, which comprises the following steps:
step 1, adding petroleum asphalt into trichloromethane or petroleum ether to obtain a soak solution;
step 2, placing the pretreated nano sponge in a soaking solution until the nano sponge is saturated in adsorption, and drying the nano sponge to completely volatilize chloroform or petroleum ether to obtain a sponge containing a petroleum asphalt coating;
and 3, heating the sponge containing the petroleum asphalt coating to 600-700 ℃ in an inert gas atmosphere, and performing high-temperature carbonization to obtain the petroleum asphalt nano sponge-based macroporous carbon.
Preferably, in step 1, the concentration of the soaking solution is 0.003-0.009g/mL.
Preferably, in the step 1, after adding the petroleum asphalt into the petroleum ether, shaking for 35-40min at a constant temperature of 0-20 ℃ to obtain a soaking solution.
Preferably, in step 2, the pretreated nanosponges are prepared according to the following steps: cutting the nano sponge, respectively soaking and washing with absolute ethyl alcohol and deionized water, and drying at 100-140 ℃ to obtain the pretreated nano sponge.
Preferably, in the step 3, the high-temperature carbonization time is 1.8-2.2h.
Preferably, in step 3, the heating rate is 4-5 ℃/min.
The second purpose of the invention is to provide the petroleum asphalt nano sponge-based macroporous carbon prepared by the preparation method.
The third purpose of the invention is to provide the application of the petroleum asphalt nano sponge-based macroporous carbon in oil pollution treatment.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the nano sponge is used as a matrix, natural graphene structure existing in petroleum asphalt is utilized, petroleum asphalt rich in asphaltene is used as an impregnating agent, petroleum asphalt nano sponge-based macroporous carbon is prepared through impregnating coating and high-temperature carbonization processes, and in the carbonization process, the petroleum asphalt coated on the surface of the nano sponge is graphitized and converted into a substance similar to graphene. The prepared material has the advantages of rich pore structure, large specific surface area, stronger surface activity, high hydrophobicity and super oleophylic property; the prepared oil absorption material is green and pollution-free, and does not react with water and oil when in use;
(2) According to the invention, the nano sponge is modified by a carbonization method, and the modified nano sponge has flame retardance and high temperature resistance and can be recycled; after being extruded, the petroleum asphalt nano sponge-based macroporous carbon is burnt to remove redundant oil products in the material, and then the petroleum asphalt nano sponge-based macroporous carbon can continuously absorb the oil products, and the product still keeps 95 percent of oil absorption performance after being repeatedly used for 25 times.
(3) The invention has the advantages of cheap raw materials, simple preparation process and convenient operation.
Drawings
Fig. 1 is a flow chart of a process for preparing petroleum asphalt nano sponge-based macroporous carbon, wherein fig. 1a is a schematic diagram of a nano sponge immersion cleaning process, and fig. 1b is a schematic diagram of a nano sponge pressing process; FIG. 1c is a schematic diagram of the drying of a nanosponge; FIG. 1d is a diagram showing the state of the nanosponges in a soaking solution; FIG. 1e is a diagram of the adsorption process of the nanosponges; FIG. 1f is the adsorption saturation diagram of nanosponges; FIG. 1g is a diagram showing a state after the nano sponge absorbs the soak solution and is volatilized and dried; FIG. 1h is a diagram showing the state of the soaked nano-sponge placed in a porcelain boat; FIG. 1i shows the state of the nanosponges after carbonization;
FIG. 2 is another flow chart of the present invention, wherein FIG. 2a is a diagram of the state of the nanosponges in soaking solution; FIG. 2b is a diagram of the adsorption process of the nanosponges; FIG. 2c is the adsorption saturation diagram of nanosponges; FIG. 2d is the state diagram of the nano sponge after absorbing the soak solution and being volatilized and dried; FIG. 2e is the state diagram of the nano sponge soaked in the porcelain boat; FIG. 2f shows the state of the nanosponges after carbonization;
FIG. 3a is a scanned image of an original nanosponge;
FIG. 3b is a scan of ANS-0 prepared in comparative example 1;
FIG. 3c is a scan of ANS-a3 prepared in example 1
FIG. 3d is a scan of ANS-a6 prepared in example 2;
FIG. 3e is a scan of ANS-a9 prepared in example 3;
FIG. 4 is a graph of static contact angle measurements for a sample;
FIG. 5 is an X-ray diffraction analysis chart, in which FIG. 5a is an X-ray diffraction analysis chart of examples 1 to 3, and FIG. 5b is an X-ray diffraction analysis chart of graphene;
FIG. 6 is a plot of the pore size distribution of the sample;
FIG. 7 is a plot of isothermal adsorption-desorption of specific surface area of a sample;
FIG. 8 is the oil absorption results of ANS-a6, wherein FIGS. 8a-f are graphs of the process of ANS-a6 absorbing vegetable oil from the water surface and FIGS. 8g-h are graphs of the absorbed oil extrusions.
FIG. 9 is a diagram of recovery of ANS-a3, wherein FIGS. 9a-c are diagrams of ANS-a3, ANS-a3 extrusion and ANS-a3 extrusion after oil absorption in sequence, and FIGS. 9d-e are diagrams of combustion and combustion sintering after ANS-a3 extrusion in sequence;
FIG. 10 is a diagram of the recovery effect of an original nano sponge, wherein FIGS. 10a-e are diagrams of oil absorption, oil absorption end, extrusion, combustion and combustion end of the original sponge in sequence;
FIG. 11 is a diagram of an oil absorption experiment of an ANS-b6 sample on a water surface, wherein FIG. 11a is a diagram of a state of the sample in water, FIG. 11b is a diagram of measured castor oil, FIG. 11c is a diagram of a state of the dyed castor oil placed in a beaker, FIG. 11d-f is a diagram of a state of the ANS-b6 sample contacting an oil product, absorbing the oil product and saturating the sample in adsorption, FIG. 11g is a diagram of a state of the ANS-b6 sample after saturation in adsorption, and FIG. 11f is a diagram of a state of the ANS-a6 sample after saturation in adsorption;
FIG. 12 is a graph showing the adsorption amounts of different oils for the samples prepared in examples 1 to 3.
Detailed Description
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.
It should be noted that the petroleum asphalt used in the present invention is obtained by crushing a commercially available petroleum asphalt with a crusher, sieving the crushed petroleum asphalt with a sieve to a particle size of 180 mesh, and storing the crushed petroleum asphalt in a sealed bag for later use.
The invention uses two methods to prepare petroleum asphalt nano sponge-based macroporous carbon, the first method uses petroleum asphalt as a dip-coating reagent, uses chloroform solution capable of dissolving petroleum asphalt as a solvent, uses nano sponge with an original porous structure as a template, the preparation process is shown in figure 1, and the preparation process comprises the steps of sequentially carrying out dip-washing (figure 1 a), pressing (figure 1 b), drying (figure 1 c), soaking and adsorbing until saturation (figures 1 d-f), drying (figure 1 g), and then placing in a porcelain boat for carbonization (figures 1 h-i). The material prepared by the method using trichloromethane as a solvent is collectively called ANS-a.
The second method is to use petroleum asphalt as a dip-coating reagent, use petroleum ether solution which is difficult to dissolve asphalt as a solvent, dissolve the petroleum asphalt by ultrasonic dispersion, use nano sponge with original porous structure as a template, and prepare the nano sponge with the preparation process shown in figure 2, soaking and adsorbing the pretreated nano sponge in the petroleum asphalt/petroleum ether solution (figure 2 a) until saturation (figure 2 b-c), drying (figure 2 d), and then putting the nano sponge in a porcelain boat for carbonization (figure 2 e-f). The material prepared by the method using petroleum ether as a solvent is collectively called ANS-b.
Example 1
Firstly, selecting commercially available Nano Sponge (NS), cutting into required sizes (4 cm in length, 2.5cm in width and 2cm in height), respectively rinsing in absolute ethyl alcohol and deionized water for 3-5 times by using a soaking-pressing method, putting into an electrothermal blowing drying oven, and drying at 140 ℃ for more than 8 hours.
And secondly, adding the petroleum asphalt into the trichloromethane solution to prepare the petroleum asphalt/trichloromethane solution with the concentration of 0.003 g/mL.
And thirdly, soaking the dried sponge small blocks into a petroleum asphalt/trichloromethane solution, and sealing and storing for more than 6 hours by using a preservative film until the petroleum asphalt/trichloromethane solution is adsorbed and saturated by the sponge. And finally, taking out the sponge with saturated adsorption from the solution, putting the sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for 18 hours, uniformly coating petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of volatilizing the trichloromethane, putting the sponge with the petroleum asphalt coating into a high-temperature-resistant porcelain boat for high-temperature carbonization through a high-temperature tube furnace after the trichloromethane solution is completely volatilized, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere and keeping for 2 hours, thereby obtaining black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon, which is marked as ANS-a3.
Example 2
Firstly, selecting commercially available Nano Sponge (NS) to be cut into required sizes (length is 4cm, width is 2.5cm and height is 2 cm), respectively rinsing in absolute ethyl alcohol and deionized water for 3-5 times by using a soaking-pressing method, putting the materials into an electrothermal blowing drying oven, and drying for more than 8 hours at 140 ℃.
And secondly, adding the petroleum asphalt into the trichloromethane solution to prepare the petroleum asphalt/trichloromethane solution with the concentration of 0.006 g/mL.
And thirdly, soaking the dried sponge small blocks into a petroleum asphalt/trichloromethane solution, and sealing and storing for more than 6 hours by using a preservative film until the petroleum asphalt/trichloromethane solution is adsorbed and saturated by the sponge. And finally, taking out the sponge with saturated adsorption from the solution, putting the sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for 18h, uniformly coating petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of volatilizing the trichloromethane, putting the sponge with the petroleum asphalt coating into a high-temperature-resistant porcelain boat for high-temperature carbonization through a high-temperature tube furnace after the trichloromethane solution is completely volatilized, heating to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere and keeping for 2h to obtain black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon, wherein the black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon is marked as ANS-a6.
Example 3
Firstly, selecting commercially available Nano Sponge (NS) to be cut into required sizes (length is 4cm, width is 2.5cm and height is 2 cm), respectively rinsing in absolute ethyl alcohol and deionized water for 3-5 times by using a soaking-pressing method, putting the materials into an electrothermal blowing drying oven, and drying for more than 8 hours at 140 ℃.
And secondly, adding the petroleum asphalt into the trichloromethane solution to prepare the petroleum asphalt/trichloromethane solution with the concentration of 0.009g/mL.
And thirdly, soaking the dried sponge small blocks into a petroleum asphalt/trichloromethane solution, and sealing and storing for more than 6 hours by using a preservative film until the petroleum asphalt/trichloromethane solution is adsorbed and saturated by the sponge. And finally, taking out the sponge with saturated adsorption from the solution, putting the sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for 18h, uniformly coating petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of volatilizing the trichloromethane, putting the sponge with the petroleum asphalt coating into a high-temperature-resistant porcelain boat for high-temperature carbonization through a high-temperature tube furnace after the trichloromethane solution is completely volatilized, heating to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere and keeping for 2h to obtain black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon, wherein the black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon is marked as ANS-a9.
Example 4
Firstly, cutting the nano sponge into the size of (3 cm multiplied by 4cm multiplied by 5 cm). And then, washing with absolute ethyl alcohol, removing the ethanol liquid in an extrusion mode, repeatedly washing for 3-4 times, then washing with deionized water for 3-4 times, removing the cleaning liquid in an extrusion mode again, then placing the cleaning liquid in an electrothermal blowing drying box, and drying for more than 8 hours at the temperature of 140 ℃.
And secondly, adding the petroleum asphalt into the petroleum ether solution to obtain the petroleum asphalt/petroleum ether solution with the concentration of 0.003g/mL, wherein the asphalt cannot be dissolved in the petroleum ether solution, so the petroleum asphalt/petroleum ether solution is uniformly mixed by a water bath constant-temperature oscillator and oscillating for 35min at the temperature of 20 ℃.
And thirdly, immersing the dried sponge small blocks in petroleum asphalt/petroleum ether solution, placing the sponge small blocks into a beaker for sealing for more than 6 hours, taking out the nano sponge from the solution after the sponge adsorbs the petroleum asphalt/petroleum ether solution to be saturated, placing the nano sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for more than 18 hours, uniformly coating the petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of completely volatilizing the petroleum ether, placing the sponge coated with the petroleum asphalt into a high-temperature resistant porcelain boat for high-temperature carbonization through a high-temperature tube furnace after the petroleum ether solution is completely volatilized, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere and keeping for 2 hours to prepare black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon marked as ANS-b3.
Example 5
Firstly, cutting the nano sponge into the size of (3 cm multiplied by 4cm multiplied by 5 cm). And then, washing with absolute ethyl alcohol, removing the ethanol liquid in an extrusion mode, repeatedly washing for 3-4 times, then washing with deionized water for 3-4 times, removing the cleaning liquid in an extrusion mode again, then placing the cleaning liquid in an electrothermal blowing drying box, and drying for more than 8 hours at the temperature of 140 ℃.
And secondly, adding the petroleum asphalt into the petroleum ether solution to obtain the petroleum asphalt/petroleum ether solution with the concentration of 0.006g/mL, wherein the asphalt cannot be dissolved in the petroleum ether solution, so the petroleum asphalt/petroleum ether solution is uniformly mixed by a water bath constant-temperature oscillator and oscillating for 35min at the temperature of 20 ℃.
Immersing the dried sponge small blocks in petroleum asphalt/petroleum ether solution, sealing the sponge small blocks in a beaker for more than 6 hours, taking out the nano sponge from the solution after the sponge adsorbs the petroleum asphalt/petroleum ether solution to saturation, putting the nano sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for more than 18 hours, uniformly coating the petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of completely volatilizing the petroleum ether, putting the sponge with the petroleum asphalt coating into a high-temperature-resistant porcelain boat after the petroleum ether solution is completely volatilized, performing high-temperature carbonization through a high-temperature tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere and keeping for 2 hours to prepare black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon, which is marked as ANS-b6.
Example 6
Firstly, cutting the nano sponge into the size of (3 cm multiplied by 4cm multiplied by 5 cm). And then, washing with absolute ethyl alcohol, removing the ethanol liquid in an extrusion mode, repeatedly washing for 3-4 times, then washing with deionized water for 3-4 times, removing the cleaning liquid in an extrusion mode again, then placing the cleaning liquid in an electrothermal blowing drying box, and drying for more than 8 hours at the temperature of 140 ℃.
And secondly, adding the petroleum asphalt into the petroleum ether solution to obtain the petroleum asphalt/petroleum ether solution with the concentration of 0.009g/mL, wherein the asphalt cannot be dissolved in the petroleum ether solution, so the petroleum asphalt/petroleum ether solution is uniformly mixed by a water bath constant-temperature oscillator and oscillating for 35min at the temperature of 20 ℃.
And thirdly, immersing the dried sponge small blocks in petroleum asphalt/petroleum ether solution, placing the sponge small blocks into a beaker for sealing for more than 6 hours, taking out the nano sponge from the solution after the sponge adsorbs the petroleum asphalt/petroleum ether solution to be saturated, placing the nano sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for more than 18 hours, uniformly coating the petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of completely volatilizing the petroleum ether, placing the sponge coated with the petroleum asphalt into a high-temperature resistant porcelain boat for high-temperature carbonization through a high-temperature tube furnace after the petroleum ether solution is completely volatilized, heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere and keeping for 2 hours to prepare black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon marked as ANS-b9.
Example 7
Firstly, cutting the nano sponge into the size of (3 cm multiplied by 4cm multiplied by 5 cm). And then washing with absolute ethyl alcohol, removing the ethyl alcohol liquid in an extrusion mode, repeatedly washing for 3-4 times, then washing with deionized water for 3-4 times, removing the cleaning liquid in an extrusion mode again, then putting into an electrothermal blowing drying oven, and drying at 100 ℃ for more than 10 hours.
And secondly, adding the petroleum asphalt into the petroleum ether solution to obtain the petroleum asphalt/petroleum ether solution with the concentration of 0.006g/mL, wherein the asphalt cannot be dissolved in the petroleum ether solution, so the petroleum asphalt/petroleum ether solution is uniformly mixed by a water bath constant-temperature oscillator and oscillating for 40min at 0 ℃.
And thirdly, immersing the dried sponge small blocks in petroleum asphalt/petroleum ether solution, placing the sponge small blocks into a beaker for sealing for more than 6 hours, taking out the nano sponge from the solution after the sponge adsorbs the petroleum asphalt/petroleum ether solution to be saturated, placing the nano sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for more than 18 hours, uniformly coating the petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of completely volatilizing the petroleum ether, placing the sponge coated with the petroleum asphalt into a high-temperature-resistant porcelain boat for high-temperature carbonization through a high-temperature tube furnace after the petroleum ether solution is completely volatilized, heating to 700 ℃ at a heating rate of 4 ℃/min in a nitrogen atmosphere, and keeping for 1.8 hours to prepare the black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon.
Example 8
Firstly, cutting the nano sponge into the size of (3 cm multiplied by 4cm multiplied by 5 cm). And then, washing with absolute ethyl alcohol, removing the ethanol liquid in an extrusion mode, repeatedly washing for 3-4 times, then washing with deionized water for 3-4 times, removing the cleaning liquid in an extrusion mode again, then placing the cleaning liquid in an electrothermal blowing drying box, and drying for more than 9 hours at 120 ℃.
And secondly, adding the petroleum asphalt into the petroleum ether solution to obtain the petroleum asphalt/petroleum ether solution with the concentration of 0.009g/mL, wherein the asphalt cannot be dissolved in the petroleum ether solution, so the petroleum asphalt/petroleum ether solution is uniformly mixed by a water bath constant temperature oscillator and oscillating for 37min at 10 ℃.
Immersing the dried sponge small blocks in petroleum asphalt/petroleum ether solution, sealing the sponge small blocks in a beaker for more than 6 hours, taking out the nano sponge from the solution after the sponge adsorbs the petroleum asphalt/petroleum ether solution to saturation, putting the nano sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for more than 18 hours, uniformly coating the petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of completely volatilizing the petroleum ether, putting the sponge with the petroleum asphalt coating into a high-temperature-resistant porcelain boat after the petroleum ether solution is completely volatilized, performing high-temperature carbonization through a high-temperature tube furnace, heating to 650 ℃ at the heating rate of 4 ℃/min in the nitrogen atmosphere and keeping for 2.2 hours to prepare the black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon.
Example 9
Firstly, selecting commercially available Nano Sponge (NS) to be cut into required sizes (length is 4cm, width is 2.5cm and height is 2 cm), respectively rinsing in absolute ethyl alcohol and deionized water for 3-5 times by using a soaking-pressing method, putting the materials into an electrothermal blowing drying oven, and drying for more than 9 hours at 120 ℃.
And secondly, adding the petroleum asphalt into the trichloromethane solution to prepare the petroleum asphalt/trichloromethane solution with the concentration of 0.003 g/mL.
And thirdly, soaking the dried sponge small blocks into a petroleum asphalt/trichloromethane solution, and sealing and storing for more than 6 hours by using a preservative film until the petroleum asphalt/trichloromethane solution is adsorbed and saturated by the sponge. And finally, taking out the sponge with saturated adsorption from the solution, putting the sponge into a fume hood (needing to be sealed and provided with an air draft device) for drying for 18h, uniformly coating petroleum asphalt on the surface layer and the inner pores of the nano sponge in the process of volatilizing the trichloromethane, putting the sponge with the petroleum asphalt coating into a high-temperature-resistant porcelain boat for high-temperature carbonization through a high-temperature tube furnace after the trichloromethane solution is completely volatilized, heating to 700 ℃ at the heating rate of 4 ℃/min in the nitrogen atmosphere and keeping for 2h, thereby obtaining the black and good-flexibility reticular petroleum asphalt nano sponge-based macroporous carbon.
Comparative example 1
The nano sponge is pretreated according to the method of the embodiment 1, then is put into a high temperature resistant porcelain boat and is carbonized at high temperature through a high temperature tube furnace, and is heated to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere and is kept for 2 hours, so that the carbonized nano sponge is obtained and marked as ANS-0.
The petroleum asphalt nano sponge-based macroporous carbon obtained by the preparation method is further discussed below.
(1) Structure of petroleum asphalt nano sponge-based macroporous carbon
TABLE 1 basic Properties of ANS-a samples
Figure BDA0003812402440000111
As shown in Table 1, the carbonized sponge retained the original topographical features but was significantly reduced in volume by about 31.7% compared to the original NS, while the sample mass was reduced to 28% -39% of the original NS mass, and the density of the sample from ANS-0, ANS-a3 to ANS-a9 was from 8.3mg/cm 3 Increased to 13.2mg/cm 3 This growth trend is associated with a dramatic increase in the concentration of petroleum pitch in the dip coating solution.
FIG. 3 is a scanning electron micrograph of a sample, wherein FIG. 3a is a raw Nanosponge (NS), FIG. 3b is ANS-0 prepared in comparative example 1, FIG. 3c is ANS-a3 prepared in example 1, FIG. 3d is ANS-a6 prepared in example 2, and FIG. 3e is ANS-a9 prepared in example 3. As can be seen from FIG. 3, the ANS-a6 sample and the original NS and ANS-a0 have the same internal morphology and have a loose and porous network structure, which indicates that the pore structure of the nanosponges is not damaged, and the samples of examples 1 to 3 retain the original internal space structure, thereby facilitating the adsorption of the material. Comparing the samples of examples 1-3 with the SEM images of NS and ANS-a0, it is clear that the skeleton of NS is relatively complete and smooth and the channels are communicated with each other, while the skeleton of ANS-a6 is deformed and the filler is present, and the filler is gradually increased and thickened along with the increase of the concentration of petroleum asphalt/chloroform, which can be inferred that the filler in the skeleton of ANS-a6 is derived from petroleum asphalt. When the concentration of the petroleum asphalt/chloroform is higher, the prepared ANS-a9 has a more complex framework structure compared with ANS-a3 and ANS-a6 prepared when the concentration is lower, and the number of film-shaped objects is obviously increased, so that the film-shaped objects are not only attached to the surface of the framework, but also filled in a pore structure.
FIG. 4 is a graph of the static contact angle measurements for the samples, and from FIG. 4 it can be seen that the contact angles for the NS sample with water and oil are both 0, which indicates that the NS backbone surface is hydrophilic-lipophilic; the NS-0 sample became hydrophobic with a contact angle increasing from 0 ° to 115.6 °, and the water droplets contacted the sponge surface and were able to maintain a shape that was not absorbed by it. When the oil contacts the surface of the sponge, the sponge can be quickly absorbed, the contact angle of the oil is 0 degrees, and the oil absorption performance is shown; this result indicates that the carbonized sponge has not only a hydrophobic surface but also an oleophilic surface. In the samples of examples 1-3, the water contact angle gradually increased with increasing concentration of petroleum pitch, from 120.26 ° to 146.88 °, significantly larger than the directly carbonized sponge. This result indicates that the addition of petroleum pitch to the dip coating solution can change the wettability of the sponge body, and as the concentration of petroleum pitch increases, the hydrophobic properties of the sample become more superior.
Fig. 5 is an X-ray diffraction analysis diagram, wherein fig. 5a is an X-ray diffraction analysis diagram of examples 1-3, and fig. 5b is an X-ray diffraction analysis diagram of graphene, and as can be seen from the graph in fig. 5, the sample shows a prominent characteristic absorption peak near 2 θ =31 °, and the peak width is narrowed and shifted slightly to the right compared with the (002) peak of the graphite structure, illustrating that the surface activity thereof is enhanced; secondly, the sample shows a weak characteristic absorption peak around 2 θ =42 °, which corresponds to the peak value of (100) of the graphite structure, and no other peak is present, which is similar to the XRD pattern of graphene, and the samples prepared in examples 1-3 all have the same XRD structure, so that it can be judged that the petroleum pitch coated on the surface of the nano sponge is graphitized in the middle of undergoing carbonization, and is crystalline and enhanced in surface activity, similar to the graphene material.
FIG. 6 is a graph showing the distribution of pore diameters, and it can be seen from FIG. 6 that the pores of the five types of sponges are mainly mesoporous (2 nm-30 nm), but have some micropores of 2nm or less, as indicated by the distribution curves of pore diameters of NS, NS-0, ANS-a3, ANS-a6, and ANS-a9. The volume of the micropores reaches 0.008cm 3 ·g -1 . The significantly larger pore volume at 2.5nm for NS shown in FIG. 6 reached a value of 0.025cm 3 ·g -1 Through carbonization and modification of the sponge by petroleum asphalt, the pore volume of the sponge can be obviously reducedCorresponding to the increase of the specific surface area, the pore volume of ANS-a9 is the smallest as can be seen from FIG. 6, which shows that the pore volume of the sponge is reduced along with the increase of the concentration of the petroleum asphalt, the specific surface area is increased, and the adsorption effect on the material is more excellent.
Fig. 7 is a graph showing the adsorption-desorption curves for specific surface area isotherms, and it can be seen from fig. 7 that isotherms of the samples prepared in examples 1 to 3 can be classified as type iii isotherms having a hysteresis loop of type H2 (b), which is characteristic of a protrusion toward the relative pressure axis and occurs when weak gas-solid phase interaction occurs on a non-porous or macroporous solid, and is not common. The specific surface area is an important characteristic for characterizing the porous carbon material, and the larger the specific surface area is, the stronger the surface effect of the material is.
(2) Oil absorption performance of petroleum asphalt nano sponge-based macroporous carbon
FIG. 8 is the oil absorption results for ANS-a6, where FIGS. 8a-f are the process of ANS-a6 absorbing vegetable oil from the water surface and FIGS. 8g-h are the absorbed oil squeeze-out. The sponge used in fig. 8 is a sample ANS-a6 which not only has a three-dimensional loose porous network structure, but also shows excellent super-hydrophobicity, and the properties all show that ANS-a6 can be used as a good oil absorption material for oil-water separation. ANS-a6 can remove oil from the surface of water. When ANS-a6 comes into contact with the vegetable oil stained red by the oil dye, as shown in FIGS. 8a-h, it can be seen that the sample ANS-a6 floats on the water surface, exhibiting high hydrophobicity and ultra-low density. When the ANS-a6 sample floats on the water surface, a large amount of adsorption can be completed within 2s, adsorption balance is achieved within 8s, the sample is moved out of the water surface, and no oil leakage phenomenon exists, so that the ANS-a6 has an excellent oil retention function. During oil absorption, the surface tension forces the ANS-a6 sponge and the oil into intimate contact. In addition, the ANS-a6 sponge which is saturated in adsorption can be squeezed by forceps in a manner shown in figure 8h to eliminate adsorbed oil, so that the oil absorption function of the sponge is recovered, but the molecular structure of the sponge is not damaged, which also shows that the ANS-a6 sponge has excellent flexibility. After the ANS-a6 sponge contacts with the oil product, the oil product can be stored in the pore canal structure of the material due to the super-oleophylic function and the unique macroporous structure, and the purpose of oil-water separation is realized. Samples ANS-a3 and ANS-a9 have the same water surface oil absorption properties as ANS-a6. The control sample ANS-0, due to its low density, also floats on the water surface absorbing oil, but also slowly absorbs water. The primary NS, when mixed with water, rapidly absorbs the water until it sinks to the bottom of the water, indicating high water absorption. Therefore, NS and NS-a0 cannot be used as oil absorbents to control oil contamination of water surfaces. The rapid adsorption of the food oil by ANS-a6 was also demonstrated when the adsorption rate of ANS-a6 was measured.
In addition to oil absorption properties, recyclability and reuse are also one of the major factors used to rate the commercial application of oil absorbing materials. FIG. 9 is a diagram of recovery of ANS-a3, wherein FIGS. 9a-c are diagrams of ANS-a3, ANS-a3 extrusion and ANS-a3 extrusion after oil absorption, and FIGS. 9d-e are diagrams of combustion and sintering post combustion after ANS-a3 extrusion. As shown in fig. 9, the sample absorbed with the vegetable oil stained red by the oily pigment was subjected to simple squeezing with tweezers to remove a part of the oil, and then to combustion to remove the remaining oil, and after the combustion and sintering, the ANS-a3 sample retained the appearance similar to that of the original material.
FIG. 10 is a diagram of the recovery effect of the original nano sponge, wherein FIGS. 10a-e are diagrams of the original sponge after absorbing oil, extruding, burning, and after burning. Compared with the original nano sponge, ANS-a3 has certain high temperature resistance and flame retardance, and ANS-a3 can remove the absorbed flammable liquid in a combustion mode to realize self recycling. Therefore, the sponge after oil removal is subjected to the oil absorption step. The ANS-a3 sample had no significant structural damage and the oil absorption properties also had an absorbency of 95%.
Selecting an ANS-b6 sample to carry out an oil absorption experiment on a water surface, firstly taking a 1000ml beaker, measuring 700ml of deionized water, putting the sample into the beaker, finding that the sample floats on the water surface (figure 11 a), measuring 5ml of castor oil by using a measuring cup (figure 11 b), dyeing the castor oil into red by using an oily pigment, pouring the red castor oil into the beaker (figure 11 c), and observing that the ANS-b6 sample floats on the water surface from figures 11d-f, and once contacting with an oil product, the oil product can be quickly absorbed until the sample is saturated in adsorption. Although the sample ANS-b6 can absorb oil, the sample body cannot float on the water surface, as shown in FIG. 11g, because when petroleum ether is used as a solvent, the petroleum ether cannot well dissolve petroleum asphalt and is volatile, so that the petroleum asphalt is adsorbed by the sponge and is not saturated and uniform enough, and the sponge needs to be taken out in time after oil absorption is completed. And the sample ANS-a6 can still float on the water surface after being adsorbed and saturated (figure 11 h), so that the method is more favorable for later-stage recycling. Sample ANS-a6, has the same water surface oil absorption behavior as ANS-a3 and ANS-a9. ANS-b3 and ANS-b9 have the same surface oil absorption behavior as ANS-b6.
FIG. 12 is a graph of the adsorption amounts of the samples prepared in examples 1 to 3 for different oils. As shown in FIG. 12, the sample ANS-a can absorb various oils (e.g., turpentine, palm oil, castor oil, cedar oil), but the samples prepared in examples 1 to 3 show different absorption capacities due to the difference in physical characteristics such as density, surface tension, etc. between the different oils. It can be seen that ANS-a6 has the best adsorption capacity, much higher than ANS-a3 and ANS-a9. Under the same mass ratio, the adsorption capacity of ANS-a6 is far higher than that of the traditional adsorption material. Compared with the high oil absorption material reported at present, the oil absorption capacity of ANS-a6 is also at a higher level, and the oil absorption capacity reaches about 125 times of the self weight. In addition, the invention uses cheap petroleum asphalt and nano sponge as raw materials, and prepares the petroleum asphalt nano sponge-based macroporous carbon by a simple process of direct carbonization, and the method is more suitable for large-scale production and application.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (8)

1. The preparation method of the petroleum asphalt nano sponge-based macroporous carbon is characterized by comprising the following steps:
step 1, adding petroleum asphalt into trichloromethane or petroleum ether to obtain a soak solution;
step 2, placing the pretreated nano sponge into a soaking solution until the nano sponge is saturated in adsorption, and drying the nano sponge to completely volatilize trichloromethane or petroleum ether to obtain a sponge containing a petroleum asphalt coating;
and 3, heating the sponge containing the petroleum asphalt coating to 600-700 ℃ in an inert gas atmosphere, and performing high-temperature carbonization to obtain the petroleum asphalt nano sponge-based macroporous carbon.
2. The method for preparing petroleum asphalt nano sponge-based macroporous carbon as claimed in claim 1, wherein in the step 1, the concentration of the soaking solution is 0.003-0.009g/mL.
3. The method for preparing petroleum asphalt nano sponge-based macroporous carbon as claimed in claim 1, wherein in the step 1, the petroleum asphalt is added into petroleum ether and then is vibrated at a constant temperature of 0-20 ℃ for 35-40min to obtain a soaking solution.
4. The preparation method of the petroleum asphalt nano sponge based macroporous carbon as claimed in claim 1, wherein in the step 2, the pretreated nano sponge is prepared according to the following steps: cutting the nano sponge, respectively soaking and washing with absolute ethyl alcohol and deionized water, and drying at 100-140 ℃ to obtain the pretreated nano sponge.
5. The method for preparing petroleum asphalt nano sponge based macroporous carbon as claimed in claim 1, wherein in the step 3, the high temperature carbonization time is 1.8-2.2h.
6. The method for preparing petroleum asphalt nano sponge based macroporous carbon as claimed in claim 1, wherein in the step 3, the heating rate is 4-5 ℃/min.
7. A petroleum asphalt nano sponge based macroporous carbon prepared by the preparation method of any one of claims 1 to 6.
8. Use of the petroleum pitch nanosponge-based macroporous carbon of claim 7 in the treatment of oil contamination.
CN202211015644.9A 2022-08-24 2022-08-24 Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof Pending CN115364811A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211015644.9A CN115364811A (en) 2022-08-24 2022-08-24 Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211015644.9A CN115364811A (en) 2022-08-24 2022-08-24 Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115364811A true CN115364811A (en) 2022-11-22

Family

ID=84067661

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211015644.9A Pending CN115364811A (en) 2022-08-24 2022-08-24 Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115364811A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544321A (en) * 2003-11-25 2004-11-10 复旦大学 Preparation method of carbon material with highly ordered nanometer hole of graphite hole wall structure
CN104300150A (en) * 2014-05-07 2015-01-21 河南中联高科新能源有限公司 Asphalt-based nanoporous carbon material, negative material thereof, and lithium ion battery
CN104987528A (en) * 2015-06-29 2015-10-21 武汉工程大学 Modification method of oleophylic and hydrophobic nano-sponge
CN106693444A (en) * 2016-12-27 2017-05-24 西南石油大学 Preparing method of reproducible super-hydrophobic graphite alkenyl oil absorption sponge
WO2017116657A1 (en) * 2015-12-28 2017-07-06 Nanotek Instruments, Inc. Graphene-Carbon Hybrid Foam
CN108212083A (en) * 2017-12-28 2018-06-29 西南石油大学 A kind of oil suction carbon sponge and preparation method thereof
CN110090631A (en) * 2019-05-27 2019-08-06 深圳市辉翰科技发展有限公司 A kind of large area charing sponge and preparation method thereof that the graphene of modifying super hydrophobicity is modified
CN113736133A (en) * 2021-09-24 2021-12-03 北京美斯顿科技开发有限公司 Graphene-based sponge and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544321A (en) * 2003-11-25 2004-11-10 复旦大学 Preparation method of carbon material with highly ordered nanometer hole of graphite hole wall structure
CN104300150A (en) * 2014-05-07 2015-01-21 河南中联高科新能源有限公司 Asphalt-based nanoporous carbon material, negative material thereof, and lithium ion battery
CN104987528A (en) * 2015-06-29 2015-10-21 武汉工程大学 Modification method of oleophylic and hydrophobic nano-sponge
WO2017116657A1 (en) * 2015-12-28 2017-07-06 Nanotek Instruments, Inc. Graphene-Carbon Hybrid Foam
CN106693444A (en) * 2016-12-27 2017-05-24 西南石油大学 Preparing method of reproducible super-hydrophobic graphite alkenyl oil absorption sponge
CN108212083A (en) * 2017-12-28 2018-06-29 西南石油大学 A kind of oil suction carbon sponge and preparation method thereof
CN110090631A (en) * 2019-05-27 2019-08-06 深圳市辉翰科技发展有限公司 A kind of large area charing sponge and preparation method thereof that the graphene of modifying super hydrophobicity is modified
CN113736133A (en) * 2021-09-24 2021-12-03 北京美斯顿科技开发有限公司 Graphene-based sponge and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
姚倩: "沥青基多孔碳材料的制备及应用性能研究", 中国优秀硕士学位论文全文数据库, no. 2018, pages 3 *

Similar Documents

Publication Publication Date Title
CN109970058B (en) Preparation method of coffee grounds matrix activated carbon
CN105647159B (en) A kind of polymer-base foam material and the preparation method and application thereof of graphene ribbon modification
CN109553098A (en) A kind of method and application preparing the foramen magnum-mesoporous carbon of high-specific surface area using salt template
Zhang et al. Superhydrophobic nanoporous polymer-modified sponge for in situ oil/water separation
Ncibi et al. Modelling single compound adsorption onto porous and non-porous sorbents using a deformed Weibull exponential isotherm
Liu et al. Eco-friendly fabrication of sponge-like magnetically carbonaceous fiber aerogel for high-efficiency oil–water separation
Li et al. Preparation of corn straw based spongy aerogel for spillage oil capture
CN107552023B (en) High-adsorption ultralight three-dimensional hierarchical pore structure carbon aerogel material for water treatment and preparation method thereof
CN108636384A (en) A kind of preparation method of greasy dirt sorbing material
CN110237830A (en) A kind of mild preparation method of environmental protection of hydrophobic oleophilic oil sponge
CN110327851A (en) Elastic graphite alkene aeroge and its preparation method and application
Liu et al. Superhydrophobic graphene aerogel beads for adsorption of oil and organic solvents via a convenient in situ sol-gel method
Zhang et al. Hybridization of Al2O3 microspheres and acrylic ester resins as a synergistic absorbent for selective oil and organic solvent absorption
CN109437147A (en) A kind of preparation method of multifunctional C foam
Zang et al. Hollow carbon fiber sponges from crude catkins: an ultralow cost absorbent for oils and organic solvents
CN103447003B (en) Multi-stage porous carbon block is as the application of the organic absorption/salvage material of oil
Zhang et al. A novel multi-wall carbon nanotubes/poly (n-butylacrylate-co-butyl methacrylate) hybrid resin: synthesis and oil/organic solvents absorption
Puccini et al. Pollutant removal from gaseous and aqueous phases using hydrochar-based activated carbon
Huang et al. Popped rice biochar and superhydrophobic SiO 2/popped rice biochar for oil adsorption
Ye et al. Fatty amines embedded carbon membranes with aligned nanochannels network: a device with extremely high photothermal conversion efficiency toward solar energy harvesting and storage
CN115364811A (en) Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof
CN113929078A (en) Preparation method of hierarchical pore type biomass carbon aerogel material
CN112897503A (en) Acid modification preparation method of biomass charcoal material with toluene adsorption effect
CN105905880B (en) A kind of method and its adsorption applications preparing porous charcoal ball by Chinese sweet gum ripening fruits
CN106994332B (en) Preparation and application of kapok fiber-based elastic foam material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination