CN115893409A - Method for preparing meso-microporous biomass super-activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex - Google Patents
Method for preparing meso-microporous biomass super-activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex Download PDFInfo
- Publication number
- CN115893409A CN115893409A CN202211326887.4A CN202211326887A CN115893409A CN 115893409 A CN115893409 A CN 115893409A CN 202211326887 A CN202211326887 A CN 202211326887A CN 115893409 A CN115893409 A CN 115893409A
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- biomass
- phosphoric anhydride
- microporous
- copper
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002028 Biomass Substances 0.000 title claims abstract description 34
- 230000004913 activation Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 239000012190 activator Substances 0.000 claims abstract description 20
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims description 8
- 150000004699 copper complex Chemical class 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 125000003275 alpha amino acid group Chemical group 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000001994 activation Methods 0.000 abstract description 23
- 230000003213 activating effect Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011033 desalting Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation, which comprises the following steps: sieving a biomass raw material, drying to constant weight, mixing with phosphoric anhydride and a complex copper activator, and performing ultrasonic treatment to obtain a mixture; drying the mixture, and activating at high temperature in a carbon dioxide atmosphere to obtain a carbide; and cooling the carbide to room temperature, washing with deionized water, and drying to obtain the meso-microporous biomass super activated carbon. Compared with the prior art, the invention has the following beneficial effects: 1. the adopted phosphoric anhydride and the complexing copper activator can simultaneously improve the specific surface area and the surface modification functional group of the super activated carbon, thereby improving the adsorption performance of the super activated carbon; 2. the ultrasonic treatment can accelerate the mass transfer between the biomass raw material and the activating agent, thereby greatly shortening the activation time; 3. the sample is directly transferred to a high-temperature activation temperature environment from room temperature without a heating process and an intermediate carbonization process, so that the preparation steps are simplified, and continuous production can be realized.
Description
Technical Field
The invention relates to a method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation, and belongs to the technical field of porous carbon preparation.
Background
The super activated carbon has a specific surface area of more than 2000m 2 A porous carbon material per gram. Compared with the traditional activated carbon, the activated carbon has larger specific surface area and pore volume, is considered as a high-performance strategic raw material, and has huge application value in the aspects of energy storage, environmental management, seawater desalination, sewage treatment and the like. At present, the preparation method of the super activated carbon mainly comprises three methods, namely a physical activation method, a chemical activation method and a physical-chemical combined activation method. Among them, most of the activated carbon produced by physical activation is microporous activated carbon, which has insufficiently developed mesopores and unsatisfactory adsorption performance. Use of KOH and ZnCl in chemical activation processes 2 The activator is easy to prepare the product with the specific surface area of more than 3000m 2 The activator has serious corrosion to equipment, and the intermediate product is inflammable and explosive, has larger danger, and is difficult to be applied to industrialized mass production. Compared with the two activation methods, the physical-chemical combined activation method can simultaneously obtain higher specific surface area and pore volume, but the method generally has the problems of complex operation process, long preparation time, low performance of finished products and the like, so that a new method needs to be found to simplify the activation process, shorten the activation time and simultaneously improve the adsorption performance of the super activated carbon.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing meso-microporous biomass super activated carbon.
The invention is realized by the following technical scheme:
the invention provides a method for preparing meso-microporous biomass super activated carbon based on combined activation of carbon dioxide-phosphoric anhydride-copper complex, which comprises the following steps:
sieving a biomass raw material, drying to constant weight, mixing with phosphoric anhydride and a complex copper activator, and performing ultrasonic treatment to obtain a mixture;
drying the mixture, and then performing carbon activation in a carbon dioxide atmosphere to obtain a carbide;
cooling the carbide to room temperature, washing with deionized water, and drying to obtain the meso-microporous biomass super activated carbon
Preferably, the flow rate of the carbon dioxide is 50 to 150mL/min.
Preferably, the mass fraction of the phosphoric anhydride activator is 40 to 60wt%.
Preferably, the impregnation ratio of the biomass raw material and the phosphoric anhydride activator is 1:1-3.
Preferably, the carbon activation temperature is 650-850 ℃.
Preferably, the impregnation ratio of the biomass raw material and the complex copper activator is 1.25-25.
Preferably, the concentration of the complexing copper activator is 0.05-1 mol/L.
Preferably, the ultrasonic treatment frequency is 40-60 kHz, and the power is 200-600W.
Preferably, the biomass material is coconut shell.
The realization principle of the invention is as follows:
at high temperature, the carbon dioxide and the carbon carry out elimination reaction, the carbon matrix is corroded, the surface of the inner microcrystal is exposed and further reacts with the carbon dioxide, and a huge specific surface area is formed; phosphoric anhydride can catalytically crack the biopolymer in coconut shell at high temperature, and link biopolymer fragments through cyclization and condensation reactions to form phosphate and polyphosphate, and after the phosphate and polyphosphate are removed, a rich meso-microporous structure can be formed. The complex copper can be decomposed at high temperature and can be subjected to oxidation reaction with the carbon surface, so that the copper is dispersed on the surface and in pores of the activated carbon in the form of compound molecules, the content of surface functional groups is increased, and the number of internal micropores is increased. Therefore, the carbon dioxide-phosphoric anhydride-complex copper ion combined activation method is adopted to prepare the biochar, so that the specific surface area of the super activated carbon can be increased, and the chemical property of the surface can be improved, thereby obtaining the meso-microporous biomass super activated carbon with ultrahigh adsorption property.
Compared with the prior art, the invention has the following beneficial effects:
1. the adopted phosphoric anhydride and the complexing copper activator can simultaneously improve the specific surface area and the surface modification functional group of the super activated carbon, thereby improving the adsorption performance of the super activated carbon;
2. the ultrasonic treatment can accelerate the mass transfer between the biomass raw material and the activating agent, thereby greatly shortening the activation time;
3. the sample is directly transferred to a high-temperature activation temperature environment from room temperature without a temperature rise process and an intermediate carbonization process, so that the preparation steps are simplified, and continuous production can be realized.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a nitrogen adsorption and desorption curve of super activated carbon prepared by activating and non-activating activated carbon with different concentrations of activating agent under the same activating conditions.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation, which specifically comprises the following steps:
sieving coconut shells with the grain size of 0.22-0.90 mm, and drying to constant weight. Mixing coconut shells, 50wt% of sulfuric anhydride and 0.2mol/L of complex copper activator according to the mass ratio of 1. And cooling to room temperature, washing a sample obtained by carbon activation with deionized water at 40-50 ℃ until a washing liquid is neutral, and drying to obtain the meso-microporous biomass super activated carbon product. And testing the desalting performance of the prepared biomass super activated carbon by adopting a capacitance deionization method. According to the international standard, the desalting amount of most biomass activated carbon is less than or equal to 40mg/g, and the desalting amount of the biomass super activated carbon product produced by the embodiment can reach 49.3mg/g which is far higher than the international standard.
Example 2
Other experimental parameters of this example were the same as those of example 1 except that the copper activation treatment was not performed.
Comparative example 1
The other experimental parameters of this comparative example were the same as those of example 1, except that the impregnation ratio of the biomass raw material to the complex copper activator was 1.
Comparative example 2
The other experimental parameters of this comparative example were the same as those of example 1, except that the impregnation ratio of the biomass raw material to the complex copper activator was 1.
Under the condition that other experimental parameters are the same, the impregnation ratio of the biomass raw material to the complex copper activator is changed (the total impregnation time is unchanged), and the pore parameters of the prepared super activated carbon are shown in table 1.
Table 1: performance characterization results of the super activated carbon sample
Sample (I) | Specific surface area (m) 2 /g) | Total pore volume (cm) 3 /g) | Pore volume (cm) of micropores 3 /g) | Pore volume of mesopores (cm) 3 /g) |
SAC | 2617 | 2.36 | 0.87 | 1.49 |
0.05-CU-SAC | 2707 | 2.07 | 0.86 | 1.21 |
0.2-CU-SAC | 3287 | 2.38 | 1.05 | 1.33 |
1-CU-SAC | 2785 | 2.09 | 0.90 | 1.19 |
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (6)
1. A method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation is characterized by comprising the following steps:
sieving a biomass raw material, drying to constant weight, mixing with phosphoric anhydride and a complex copper activator, and performing ultrasonic treatment to obtain a mixture;
drying the mixture, and then performing carbon activation in a carbon dioxide atmosphere at 650-850 ℃ to obtain a carbide;
and cooling the carbide to room temperature, washing with deionized water, and drying to obtain the meso-microporous biomass super-activated carbon.
2. The method for preparing the meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation as claimed in claim 1, wherein the mass fraction of the phosphoric anhydride activator is 40-60wt%.
3. The method for preparing the meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation according to claim 1, wherein the impregnation ratio of the biomass raw material mixed with the phosphoric anhydride activator is 1:1-3.
4. The method for preparing meso-microporous biomass super activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation according to claim 1, wherein the copper complex activator is amino acid complex copper, phosphorus complex copper and chlorine complex copper.
5. The method for preparing the meso-microporous biomass super activated carbon based on the combined activation of carbon dioxide-phosphoric anhydride-copper complex as claimed in claim 1, wherein the concentration of the copper complex activator is 0.05-1 mol/L.
6. The method for preparing the meso-microporous biomass super activated carbon based on the combined activation of carbon dioxide-phosphoric anhydride-copper complex as claimed in claim 1, wherein the impregnation ratio of the biomass raw material and the complex copper activator is 1.25-25.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211326887.4A CN115893409B (en) | 2022-10-26 | 2022-10-26 | Method for preparing mesoporous-microporous biomass super-activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211326887.4A CN115893409B (en) | 2022-10-26 | 2022-10-26 | Method for preparing mesoporous-microporous biomass super-activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115893409A true CN115893409A (en) | 2023-04-04 |
CN115893409B CN115893409B (en) | 2024-06-28 |
Family
ID=86480504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211326887.4A Active CN115893409B (en) | 2022-10-26 | 2022-10-26 | Method for preparing mesoporous-microporous biomass super-activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115893409B (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103474253A (en) * | 2013-09-30 | 2013-12-25 | 武汉理工大学 | Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor |
CN104512891A (en) * | 2013-09-26 | 2015-04-15 | 中国钢铁股份有限公司 | Activated carbon microsphere with high specific surface area, manufacturing method thereof, electrode plate and capacitor |
CN108178141A (en) * | 2018-01-17 | 2018-06-19 | 大连理工大学 | A kind of preparation method of highly conductive, high-tap density, high specific surface micro-pore charcoal |
CN109534342A (en) * | 2019-01-18 | 2019-03-29 | 中国石油大学(华东) | The preparation method of biomass super-activated carbon |
CN109850866A (en) * | 2019-01-30 | 2019-06-07 | 青岛大学 | A kind of classifying porous carbon material and preparation method thereof for flexible super capacitor |
CN112467109A (en) * | 2020-11-27 | 2021-03-09 | 西安建筑科技大学 | Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device |
US20220259049A1 (en) * | 2020-12-23 | 2022-08-18 | Zhejiang University | Bio-oil light fraction-based bread-shaped porous activated carbon, method for preparing the same and use thereof |
-
2022
- 2022-10-26 CN CN202211326887.4A patent/CN115893409B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104512891A (en) * | 2013-09-26 | 2015-04-15 | 中国钢铁股份有限公司 | Activated carbon microsphere with high specific surface area, manufacturing method thereof, electrode plate and capacitor |
CN103474253A (en) * | 2013-09-30 | 2013-12-25 | 武汉理工大学 | Porous carbon microsphere electrode materials based on surface function functional group, preparing method of materials, super capacitor of materials, and preparing method of super capacitor |
CN108178141A (en) * | 2018-01-17 | 2018-06-19 | 大连理工大学 | A kind of preparation method of highly conductive, high-tap density, high specific surface micro-pore charcoal |
CN109534342A (en) * | 2019-01-18 | 2019-03-29 | 中国石油大学(华东) | The preparation method of biomass super-activated carbon |
CN109850866A (en) * | 2019-01-30 | 2019-06-07 | 青岛大学 | A kind of classifying porous carbon material and preparation method thereof for flexible super capacitor |
CN112467109A (en) * | 2020-11-27 | 2021-03-09 | 西安建筑科技大学 | Activated carbon material, composite material, cathode material and cathode sheet of zinc ion energy storage device and zinc ion energy storage device |
US20220259049A1 (en) * | 2020-12-23 | 2022-08-18 | Zhejiang University | Bio-oil light fraction-based bread-shaped porous activated carbon, method for preparing the same and use thereof |
Also Published As
Publication number | Publication date |
---|---|
CN115893409B (en) | 2024-06-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105480974A (en) | Preparation method of high-yield mesoporous activated carbon | |
CN110745825A (en) | Preparation method of high-performance biomass-based shaddock peel oriented activated carbon VOCs adsorbent | |
CN103466619A (en) | Method for preparing active carbon by organic alcohol or organic acid doping modification | |
CN110935428A (en) | Regenerated activated carbon combined by oxidant and pore-forming agent, and preparation method and application thereof | |
CN115410834B (en) | Method for preparing lignin-based super-carbon by catalytic activation | |
CN111186836A (en) | Preparation method of corncob-based activated carbon | |
CN113926426A (en) | Method for adsorbing phthalate pollutants in wastewater by using functionalized mesoporous carbon | |
CN111498828A (en) | Method for preparing carbon aerogel by utilizing normal-pressure drying | |
KR20190072889A (en) | Activated carbon with improved butane adsorption capacity and method of producing the same | |
CN115893409B (en) | Method for preparing mesoporous-microporous biomass super-activated carbon based on carbon dioxide-phosphoric anhydride-copper complex combined activation | |
CN113318737A (en) | Copper/porous carbon catalyst and preparation method and application thereof | |
CN117003236A (en) | Shell activated carbon and preparation method and application thereof | |
CN116573643A (en) | Mixed melting activation type preparation method of sludge biochar | |
CN114471607B (en) | Preparation method of catalyst for advanced treatment of industrial wastewater by ozone or hydrogen peroxide | |
CN105197927A (en) | Preparation method of mesoporous activated carbon | |
KR101713658B1 (en) | Process of preparing mesoporous and macroporous carbon | |
CN115124273A (en) | Carbonized internal curing agent and preparation method and application thereof | |
CN115430399A (en) | Sulfur-doped carbon material and preparation method and application thereof | |
CN112755986A (en) | Activated carbon regeneration method | |
CN106219539A (en) | A kind of preparation method of high-specific surface area hierarchical porous structure activated carbon | |
CN111072398A (en) | Preparation method of high-toughness foam carbon | |
CN104495842A (en) | Method for preparing activated carbon by partially substituting potassium hydroxide by calcium hydroxide | |
CN117205953B (en) | Nonmetal nitrogen-phosphorus co-doped porous carbon catalyst and preparation method and application thereof | |
CN110013828B (en) | Preparation method of modified activated carbon material for flue gas demercuration | |
CN113735230B (en) | Manganese oxide composite hollow cubic carbon material and preparation method and application thereof |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |