CN110668419A - Preparation method of cellular porous carbon material - Google Patents
Preparation method of cellular porous carbon material Download PDFInfo
- Publication number
- CN110668419A CN110668419A CN201911008999.3A CN201911008999A CN110668419A CN 110668419 A CN110668419 A CN 110668419A CN 201911008999 A CN201911008999 A CN 201911008999A CN 110668419 A CN110668419 A CN 110668419A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon material
- temperature
- biomass
- cellular porous
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a honeycomb porous carbon material. The biomass is used as a raw material, the raw material is instantaneously puffed and converted into an expanded three-dimensional reticular porous substance due to rapid evaporation of water in the high-temperature puffing process, and then the expanded three-dimensional reticular porous substance is carbonized at high temperature to obtain the porous carbon material. The invention utilizes the high-temperature puffing process to expand the biomass, realizes the aim of opening the pores and avoids the subsequent activation step of the porous carbon material in the preparation process. The invention is economical and environment-friendly; the obtained cellular porous carbon material has a large specific surface area, a rich pore structure and moderate pore size distribution; the prepared cellular porous carbon material has the advantage of good application prospect when being used as an electrode material of a double electric layer capacitor.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a preparation method of a cellular porous carbon material.
Background
Porous carbon materials have received much attention from people because of their controllable surface areas, multi-dimensional complex pore structures, good electrical conductivity and low cost, and are widely used in the fields of gas separation, water purification, catalytic chromatography, energy storage, photocatalysis, and the like. Compared with the traditional fossil energy, biomass has the green characteristic of rich source and reproducibility, and is widely used for preparing precursors of porous carbon materials in recent years. In the prior art, the preparation of the biomass porous carbon material is generally that a biomass raw material is carbonized at a high temperature in an inert atmosphere, and then the porous carbon material with a high specific surface area is obtained by utilizing a chemical activation process, a physical activation process or a physical-chemical activation process.
The Chinese patent application (application number: 201811482678.2) discloses 'a biomass-based hierarchical porous carbon and a preparation method thereof', the method comprises the steps of shearing and sieving a biomass raw material to 20-80 meshes, adding the biomass raw material into a double-salt system aqueous solution, stirring, carrying out low-temperature hydrothermal method pre-carbonization treatment for 5-20 h at the temperature of 180-; and then heating to 600-1000 ℃ in an inert atmosphere for carbonization and activation treatment for 0.5-8 h, carrying out acid washing, alkali washing or ultrasonic treatment on the obtained product, washing with water to neutrality, and drying to obtain the biomass-based hierarchical porous carbon. Although the method is greatly developed, the preparation process is relatively complicated by the mode of carrying out high-temperature carbonization in advance and then carrying out subsequent activation and opening; the porosity of the porous carbon material prepared by the physical activation method is low, and the preparation needs to be completed at a high temperature. The activating agent and the acid washing and alkali washing processes of the method cause serious corrosion to production equipment. Has the defects of high production energy consumption, complex wastewater and waste gas treatment and great environmental pollution.
Therefore, aiming at the problems in the prior art, the method for preparing the porous carbon material which is simple and convenient to operate, low in energy consumption and environment-friendly is urgently needed to solve the defects in the prior art and is particularly important.
Disclosure of Invention
The invention aims to provide a preparation method of a cellular porous carbon material, which avoids the defects in the prior art. The method is simple and convenient to operate, and the activation step of the porous carbon material in the subsequent preparation process is omitted. The purpose of the invention is realized by the following technical scheme, which comprises the following steps:
the method comprises the following steps: putting the biomass raw material into an oil solution, and performing high-temperature puffing on the biomass raw material to obtain puffed biomass;
step two: transferring the puffed biomass to a high-temperature tube furnace, carrying out high-temperature carbonization, and cooling to obtain a carbonized pre-product;
step three: and (3) washing the carbonized pre-product by using water, washing to remove impurities, and centrifugally drying to obtain the honeycomb porous carbon material.
Therefore, the preparation of the cellular porous carbon material is realized through the technical scheme of the invention. The cellular porous carbon material can be prepared by adopting biomass as a raw material, instantly expanding the raw material due to rapid evaporation of water in the high-temperature expansion process to convert the raw material into an expanded three-dimensional mesh porous substance, and then carbonizing the expanded three-dimensional mesh porous substance at high temperature. Compared with the prior art, the method provided by the invention has the advantages of simple operation, mild reaction conditions and capability of recycling the oil in the production process. More importantly, the method omits the subsequent activation step of the porous carbon material in the preparation process, thereby further reducing the process flow.
Preferably, the biomass feedstock is a high starch containing biomass.
Preferably, the biomass feedstock is a high protein containing biomass.
More preferably, the biomass raw material is glutinous rice, corn, millet, shrimp cracker, sweet potato powder or potato chips.
Preferably, the oil solution is vegetable oil or animal oil.
More preferably, the vegetable oil is peanut oil, soybean oil, olive oil or sesame oil.
More preferably, the animal fat is lard, mutton fat or beef tallow. Compared with vegetable oil, the animal oil has better expansion effect.
Preferably, the high temperature puffing is frying puffing. The puffing effect is utilized, and the volume and the surface area of the obtained puffed biomass are several times to dozens of times of the biomass raw material.
More preferably, the oil solution is heated at a temperature of 90 ~ 250 ℃ to expand the biomass, and the temperature is such that moisture in the biomass is vaporized and flashed.
Further, the oil solution was heated at a temperature of 120 ~ 200 ℃.
Preferably, the mass ratio of the volume of the oil to the biomass feedstock is 1: 1 ~ 200 (L: g).
Preferably, the temperature rise rate of the high-temperature carbonization is 1 ~ 20 ℃ and ∙ min-1The carbonization temperature is 600-1100 ℃, and the carbonization time is 60 ~ 180 min.
Preferably, the water is distilled water, ultrapure water or deionized water.
The second purpose of the present invention is to provide an application of the cellular porous carbon material in storage of supercapacitors, lithium ion batteries, fuel cells, adsorbents, catalyst carriers, natural gas and hydrogen.
The invention has the advantages of
The invention provides a preparation method of a honeycomb porous carbon material. According to the invention, biomass is used as a raw material, the raw material is instantly puffed and converted into an expanded three-dimensional reticular porous substance due to rapid evaporation of water in the high-temperature puffing process, and then the expanded three-dimensional reticular porous substance is carbonized at high temperature to obtain the porous carbon material. Compared with the conventional preparation method of firstly carbonizing at high temperature and then activating the biomass carbon, the method has the advantages that the biomass is expanded by utilizing the high-temperature expansion process, the purpose of opening holes is realized, and the subsequent activation step of the porous carbon material in the preparation process is avoided. Compared with the prior art, the invention also has the following advantages:
1. the utilized oil can be repeatedly utilized, and is economical and environment-friendly;
2. the prepared cellular porous carbon material has a large specific surface area, a rich pore structure and moderate pore size distribution;
3. the prepared cellular porous carbon material has good application prospect as an electrode material of a double electric layer capacitor.
Drawings
The invention is further illustrated by means of the attached drawings, the examples of which are not to be construed as limiting the invention in any way.
Fig. 1 is an SEM image of a porous carbon material prepared in example 1 of a method for preparing a honeycomb-shaped porous carbon material of the present invention;
FIG. 2 is an XRD pattern of a porous carbon material produced in example 1 of a method for producing a cellular porous carbon material of the present invention;
fig. 3 shows specific capacitance values of the porous carbon material prepared in example 1 of the method for preparing a cellular porous carbon material according to the present invention at different discharge current densities.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
One embodiment of the preparation method of the cellular porous carbon material comprises the steps of measuring 100 mL lard, heating the lard to 120 ℃, putting 5 g of glutinous rice into an oil solution, carrying out hot oil dry frying on the glutinous rice, transferring the glutinous rice with the volume increased after the frying into a high-temperature tube furnace, and carrying out ∙ min at the temperature of 5 ℃ under the Ar atmosphere-1The temperature rising rate is increased to 750 ℃, the temperature is kept for 60 min, after cooling, distilled water is used for cleaning and removing impurities, and centrifugal drying is carried out to obtain the cellular porous carbon material.
The physicochemical property characterization of the prepared porous carbon material is performed by using a scanning electron microscope and X-ray diffraction, the results are shown in figures 1 and 2, and the performance test of the supercapacitor is performed on the prepared porous carbon material, and the result is shown in figure 3. According to fig. 1, the porous carbon material prepared is honeycomb-shaped; in fig. 2, the prepared porous carbon material shows two distinct diffraction peaks, corresponding to the amorphous structure of the carbon material. Supercapacitor performance testing of cellular porous carbon materials, as shown in FIG. 3, 2A ∙ g-1The specific capacity is 294F ∙ g under the discharge current density-1，50 A∙g-1The capacitance is still 155F ∙ g-1。
Example 2
In one embodiment of the method for preparing the cellular porous carbon material, 100 mL of peanut oil is measured, the peanut oil is heated to 150 ℃, 10 g of rice is put into oil solution and is subjected to hot oil dry frying, the rice with the volume increased after the frying is transferred into a high-temperature tube furnace, and the temperature is ∙ min at 10 ℃ under Ar atmosphere-1The temperature rising rate is increased to 800 ℃, the temperature is kept for 90min, after cooling, distilled water is used for cleaning and removing impurities, and centrifugal drying is carried out to obtain the cellular porous carbon material.
Example 3
One embodiment of the preparation method of the cellular porous carbon material comprises the steps of measuring 100 mL of soybean oil, heating the soybean oil to 180 ℃, putting 15 g of shrimp slices into oil solution, carrying out hot oil dry frying on the shrimp slices, transferring the glutinous rice with the volume increased after the frying into a high-temperature tube furnace, and carrying out ∙ min at 15 ℃ under Ar atmosphere-1The temperature rising rate is increased to 850 ℃, the temperature is kept for 120min, after cooling, distilled water is used for cleaning and removing impurities, and the cellular porous carbon material is obtained through centrifugal drying.
Example 4
In one embodiment of the preparation method of the cellular porous carbon material, 100 mL of sesame oil is measured and heated to 200 ℃, 20 g of sweet potato powder is put into oil solution and is fried in hot oil, the glutinous rice with the volume increased after being fried is transferred into a high-temperature tube furnace, and the glutinous rice is ∙ min at 20 ℃ under Ar atmosphere-1The temperature rise rate is increased to 900 ℃, the temperature is kept constant for 150 min, after cooling, distilled water is used for cleaning and removing impurities, and the cellular porous carbon material is obtained through centrifugal drying.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for producing a honeycomb porous carbon material, comprising the steps of:
the method comprises the following steps: putting the biomass raw material into an oil solution, and performing high-temperature puffing on the biomass raw material to obtain puffed biomass;
step two: transferring the puffed biomass to a high-temperature tube furnace, carrying out high-temperature carbonization, and cooling to obtain a carbonized pre-product;
step three: and (3) washing the carbonized pre-product by using water, washing to remove impurities, and centrifugally drying to obtain the honeycomb porous carbon material.
2. The method for producing a cellular porous carbon material according to claim 1, characterized in that: the biomass raw material is high-starch-containing biomass.
3. The method for producing a cellular porous carbon material according to claim 1, characterized in that: the biomass raw material is glutinous rice, corn, millet, shrimp slices, sweet potato powder or chips.
4. The method for producing a cellular porous carbon material according to claim 1, characterized in that: the oil solution is vegetable oil or animal oil.
5. The method for producing a cellular porous carbon material according to claim 4, characterized in that: the animal fat is lard, mutton fat or beef tallow.
6. The method for producing a cellular porous carbon material according to claim 1, wherein the temperature of the oil solution is 90 ~ 250 ℃.
7. The method according to claim 6, wherein the temperature of the oil solution is 120 ~ 200 ℃.
8. The method according to claim 1, wherein the mass ratio of the volume of the oil solution to the biomass raw material is 1: 1 ~ 200 (L: g).
9. The method for preparing a cellular porous carbon material according to claim 1, wherein the temperature rise rate of the high-temperature carbonization is 1 ~ 20 ℃ to ∙ min-1The carbonization temperature is 600-1100 ℃, and the carbonization time is 60 ~ 180 min.
10. Use of the cellular porous carbon material according to any one of claims 1 ~ 9 in supercapacitors, lithium ion batteries, fuel cells, adsorbents, storage of natural gas or hydrogen, catalyst supports.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911008999.3A CN110668419A (en) | 2019-10-23 | 2019-10-23 | Preparation method of cellular porous carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911008999.3A CN110668419A (en) | 2019-10-23 | 2019-10-23 | Preparation method of cellular porous carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110668419A true CN110668419A (en) | 2020-01-10 |
Family
ID=69083706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911008999.3A Pending CN110668419A (en) | 2019-10-23 | 2019-10-23 | Preparation method of cellular porous carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110668419A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072702A (en) * | 2022-07-12 | 2022-09-20 | 淮北师范大学 | Method for preparing porous electromagnetic wave absorbing material by using artificial food |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817065A (en) * | 2015-04-02 | 2015-08-05 | 安徽农业大学 | Preparation method of cellular starch-based porous carbon material |
-
2019
- 2019-10-23 CN CN201911008999.3A patent/CN110668419A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817065A (en) * | 2015-04-02 | 2015-08-05 | 安徽农业大学 | Preparation method of cellular starch-based porous carbon material |
Non-Patent Citations (1)
| Title |
|---|
| 李国平等: "《粮油食品加工技术》", 31 January 2017, 重庆大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072702A (en) * | 2022-07-12 | 2022-09-20 | 淮北师范大学 | Method for preparing porous electromagnetic wave absorbing material by using artificial food |
| CN115072702B (en) * | 2022-07-12 | 2023-08-25 | 淮北师范大学 | Method for preparing porous electromagnetic wave absorbing material by using artificial food |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gopalakrishnan et al. | Ultrathin graphene-like 2D porous carbon nanosheets and its excellent capacitance retention for supercapacitor | |
| Li et al. | Green conversion of bamboo chips into high-performance phenol adsorbent and supercapacitor electrodes by simultaneous activation and nitrogen doping | |
| Zhan et al. | Preparation of highly porous activated carbons from peanut shells as low-cost electrode materials for supercapacitors | |
| Qu et al. | Converting biowaste corncob residue into high value added porous carbon for supercapacitor electrodes | |
| CN108529587B (en) | Preparation method and application of phosphorus-doped biomass graded porous carbon material | |
| Lu et al. | Preparation and application of capacitive carbon from bamboo shells by one step molten carbonates carbonization | |
| CN103011147B (en) | Method for preparing graphene through thermal reduction | |
| CN109231204B (en) | Method for preparing porous carbon by biomass step-by-step activation | |
| WO2021027100A1 (en) | Nitrogen-doped porous carbon material, preparation method therefor and use thereof | |
| CN108128773B (en) | Method for preparing electrode carbon material for electrochemical capacitor by using peanut shells | |
| AU2020101074A4 (en) | Licorice root residue-based hierarchical porous carbon, preparation method and application thereof | |
| Hu et al. | Preparation and property of N-doped porous carbon material by one-step pyrolysis of protein-rich algal biomass | |
| CN105314629A (en) | Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources | |
| CN111115629A (en) | High-specific-surface-area carbon material based on waste tobacco stems and preparation method and application thereof | |
| CN106629723A (en) | Biomass-based N, S and P-containing co-doped porous carbon and application thereof | |
| CN115231568B (en) | Graphene-like carbon nano sheet macroporous crosslinked cotton stalk biomass carbon electrode material and preparation method thereof | |
| CN109205620A (en) | A kind of carbon bionic nano material and preparation method | |
| CN112713009A (en) | Preparation method of olive shell derived supercapacitor electrode material | |
| CN112133572A (en) | Three-dimensional porous biomass carbon material used as supercapacitor and preparation method thereof | |
| CN110668419A (en) | Preparation method of cellular porous carbon material | |
| Zhu et al. | One-step chemical activation facilitates synthesis of activated carbons from Acer truncatum seed shells for premium capacitor electrodes | |
| CN109205622B (en) | Preparation method of biomass tar derived porous carbon material | |
| CN114956074A (en) | Seaweed-based three-dimensional porous carbon sieve and preparation method thereof | |
| CN111689496A (en) | Persimmon peel-based nitrogen-doped activated carbon and preparation method thereof | |
| CN112194129B (en) | Method for preparing straw-based ordered porous carbon material through hydrothermal-assisted chemical activation and application |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200110 |