CN116282009A - Preparation method of pine cone activated carbon and pine cone activated carbon - Google Patents
Preparation method of pine cone activated carbon and pine cone activated carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 235000008331 Pinus X rigitaeda Nutrition 0.000 title claims abstract description 106
- 235000011613 Pinus brutia Nutrition 0.000 title claims abstract description 106
- 241000018646 Pinus brutia Species 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 45
- 230000004913 activation Effects 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000003213 activating effect Effects 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 88
- 102000020897 Formins Human genes 0.000 claims description 44
- 108091022623 Formins Proteins 0.000 claims description 44
- 239000001569 carbon dioxide Substances 0.000 claims description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 44
- 238000001816 cooling Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- 238000007873 sieving Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- -1 transition metal salt Chemical class 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007781 pre-processing Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 59
- 239000007789 gas Substances 0.000 description 54
- 238000001179 sorption measurement Methods 0.000 description 43
- 238000003763 carbonization Methods 0.000 description 34
- 239000010453 quartz Substances 0.000 description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 239000000126 substance Substances 0.000 description 25
- 239000003575 carbonaceous material Substances 0.000 description 19
- 239000012190 activator Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 230000004807 localization Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of pine cone activated carbon and the pine cone activated carbon, which relate to the technical field of carbon processing, wherein the activated carbon in the prior art is generally chemically activated to pollute the environment, and the method comprises the following steps: mixing the pine cone with the auxiliary agent to obtain a first mixture, wherein the mixing ratio of the pine cone to the auxiliary agent is 100:1-20:1, a step of; pyrolyzing the first mixture in an oxygen-free environment at a pyrolysis temperature of 400-950 ℃; preprocessing the pyrolyzed product to obtain a pyrolytic carbon material; and (3) introducing an activating medium into the pyrolytic carbon material for activation to obtain the activated carbon. According to the preparation method of the activated carbon of the pine cone, provided by the invention, the combustible gas is generated when the activated carbon is produced by using the pyrolytic carbon obtained by pyrolyzing the waste pine cone, so that the recycling and high-value utilization of the waste pine cone are realized, meanwhile, the environmental pollution is not generated, and the obtained activated carbon has wider application scene.
Description
Technical Field
The invention relates to the technical field of carbon processing, in particular to a preparation method of pine cone activated carbon and the pine cone activated carbon.
Background
The capacitance carbon is used as a carbon material with high added value, and is a high-end product in the field of activated carbon. The novel energy storage device is widely applied to novel energy storage devices such as super capacitors and lead-carbon batteries, and further is used for docking the fields of new energy automobiles, wind power generation, high-speed rails, communication base stations, aerospace, military industry and the like. The market share of the capacitance carbon in the fields of super capacitors and lead carbon batteries in China is about 85 percent and 13 percent respectively; the capacitor carbon production process and the matched equipment have harsh conditions, the localization problem is not solved, the external dependence is extremely high, and the capacitor carbon is a key material for restricting the further development of novel energy storage appliances in China.
Worldwide, the raw materials for preparing the super capacitor carbon can be divided into three types, the first is biomass, such as coconut shell carbon with relatively high market occupation. The second category is mineral systems, including petroleum asphalt, coal asphalt, and the like. The third category is polymers such as phenolic resins. The preparation of activated carbon is divided into two major parts, namely activation and carbonization. The activation and carbonization may be performed in different orders or simultaneously. The preparation method can be classified into a chemical activation method and a physical activation method according to the activation, carbonization methods and reagents used. The chemical activation method is to select proper activator, then mix with raw material and activate directly to obtain active carbon. Can be classified into ZnCl according to the activator 2 Method, KOH method, H 3 PO 4 A method of manufacturing the same. In China, znCl 2 The activation method is the most main chemical activation method for producing active carbon, and is mainly prepared by adopting a rotary furnace or a flat plate method by taking wood dust as a raw material. H 3 PO 4 The temperature required by the method for activation is low, generally 300-350 ℃, the production cost is low, and the active carbon is produced in the United states industry mostly by adopting H 3 PO 4 A method of manufacturing the same. The physical activation method is to make the carbonized material react with the carbon material at high temperature with water vapor, carbon dioxide or oxygen and other oxidizing gas to form pores inside the material.
The pine cone is the seed of the pine branch in China, pine seeds are arranged in the pine branch after the pine branch is ripe, and a large number of waste pine cones which are easy to collect are generated in the pine seed processing process. There are related efforts to prepare activated carbon by chemically activating waste pine cones. However, chemical activation is highly corrosive to equipment and pollutes the environment, and the application of the activated carbon prepared by the method is limited because of the residual chemical activator in the activated carbon. At present, no related work for preparing the activated carbon by physically activating the waste pine cone exists.
Disclosure of Invention
The invention aims to provide a preparation method of pine cone active carbon, which adopts a low-temperature physical method to prepare, and solves the problems of residual chemicals and environmental pollution of chemical method manufacturing.
In order to solve the above problems, a first aspect of the present invention provides a method for preparing activated carbon of pine cone, comprising:
mixing the pine cone with the auxiliary agent to obtain a first mixture, wherein the mass mixing ratio of the pine cone to the auxiliary agent is 100:1-20:1, the auxiliary agent is transition metal salt;
the first mixture is subjected to an oxygen-free environment at 10deg.C for min -1 Heating to pyrolysis temperature at 400-950 deg.c for 1 hr;
grinding and sieving the pyrolyzed product to obtain a pyrolytic carbon material with the particle diameter less than or equal to 50 mm;
introducing an activating medium into the pyrolytic carbon material for activation, and after activation, performing activation at 10 ℃ for min -1 And (3) cooling to room temperature to obtain the active carbon.
Optionally, the pyrolysis temperature is 400 ℃ to 650 ℃.
Optionally, the oxygen-free environment is a vacuum or protective atmosphere environment.
Optionally, an optionalThe transition metal salt is Co (NO) 3 ) 2 、Fe(NO 3 ) 3 、Cr(NO 3 ) 3 、H 2 PtCl 6 、Cu(NO 3 ) 2 、Mn(NO 3 ) 2 、AgNO 3 、Ni(NO 3 ) 2 And Zn (NO) 3 ) 2 Any one of the following.
Alternatively, the transition metal salt is Co (NO 3 ) 2 、Fe(NO 3 ) 3 、Cr(NO 3 ) 3 、H 2 PtCl 6 And Zn (NO) 3 ) 2 One of them.
Optionally, the activating medium is one or a mixture of any more of water vapor, oxygen and carbon dioxide.
Optionally, the pyrolytic carbon material is activated by introducing an activating medium into the pyrolytic carbon material:
at 10 ℃ for min -1 The temperature is adjusted to an activation temperature of 400-700 ℃.
Optionally, the activated medium is introduced into the pyrolytic carbon material for 30-300 minutes.
Optionally, the mass ratio of the activating medium to the pyrolytic carbon material is 2:1-3.5:1.
In another aspect, the invention provides a pine cone activated carbon prepared by the preparation method of the pine cone activated carbon.
The technical scheme of the invention has the following beneficial technical effects:
according to the preparation method of the activated carbon of the pine cone, combustible gas (carbon monoxide and hydrogen) is generated when the activated carbon is produced by using pyrolytic carbon obtained by pyrolyzing the waste pine cone, so that the recycling and high-value utilization of the waste pine cone are realized, the economic benefit is improved, and a new development space is provided for the waste pine cone pyrolytic treatment industry; in the practical application process, the preparation method provided by the invention does not use a chemical activating agent, adopts one or more of water vapor oxygen and carbon dioxide as an activating medium, protects the environment, reduces the corrosion to equipment, prolongs the service life of the equipment, has simple process flow, reduces investment cost, improves production efficiency and is beneficial to industrialized application.
Drawings
FIG. 1 is a flow chart of a preparation method of the pine cone activated carbon provided by the invention;
FIG. 2 is a graph of the X-ray photoelectron spectrum analysis of the pine cone-derived activated carbon material prepared in example 4;
FIG. 3 is a graph showing the nitrogen adsorption and desorption of the pine cone-derived activated carbon material prepared in example 4;
FIG. 4 is an X-ray diffractometer spectrum of the pine cone derived activated carbon material prepared in example 4;
FIG. 5 is an adsorption isotherm of p-toluene and methanol at 298K for the pine cone derived activated carbon material prepared in example 4;
FIG. 6 is a cyclic voltammogram of the pine cone derived activated carbon material prepared in example 4 in 1.0mol/L tetraethylammonium tetrafluoroborate/acetonitrile electrolyte;
fig. 7 is a graph showing the relationship between specific capacitance and discharge current density of the pine cone-derived activated carbon material and commercial activated carbon material prepared in example 4.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Specific examples and comparative examples are provided below to illustrate in detail the methods provided by the present invention.
Example 1
Mixing pinecone with Co (NO) 3 ) 2 Mixing according to the proportion of 20:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the tube furnace temperature was maintained at 10℃for a minute in a nitrogen atmosphere -1 The temperature rise rate of (2) is increased to 600 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 20mm;
switching nitrogen gas into carbon dioxide gas, wherein the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2.5:1, and simultaneously, the temperature of the tube furnace is 10 percent 。 C min -1 The cooling rate of (2) is reduced to 400 ℃, and the activation is carried out for 1h in a carbon dioxide atmosphere.
Then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material. In the embodiment, the corrosion problem to equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Co (NO 3 ) 2 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 765m 2 The adsorption capacity of toluene per gram was 850mg/g, the adsorption capacity of methanol was 820mg/g, and the electrochemical capacity was 70F/g.
Example 2
Mixing pinecone with Co (NO) 3 ) 2 Mixing according to the proportion of 50:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is reduced in vacuum at 10 ℃ for min -1 The temperature rising rate of (2) is increased to 400 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 30mm;
inputting a mixed gas of carbon dioxide and oxygen into a tube furnace, wherein the mixing ratio is 1:1, the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2:1, and simultaneously, the temperature of the tube furnace is 10 ℃ for min -1 The temperature rise rate of (2) is raised to 500 ℃, and the mixture of carbon dioxide and oxygen is activated for 1h.
Then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Co (NO 3 ) 2 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 1423m 2 The adsorption amount of toluene per gram was 1036mg/g, the adsorption amount of methanol was 950mg/g, and the electrochemical capacity was 106F/g.
Example 3
Mixing pinecone with Co (NO) 3 ) 2 Mixing according to the proportion of 100:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is kept in argon atmosphere at 10 ℃ for min -1 The temperature rise rate of (2) is increased to 500 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 40mm;
argon gas is switched into mixed gas of carbon dioxide gas and steam, the mixing ratio is 1:1, the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2.5:1, and the temperature of the tubular furnace is 10 ℃ for min at the same time -1 The temperature rise rate of (2) was increased to 650 ℃, and the mixture was activated in a mixed gas of carbon dioxide and water vapor for 1 hour.
Then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, by adopting a physical activation method, the method solves the problems ofCorrosion problem of equipment, meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Co (NO 3 ) 2 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the activated carbon obtained in this example was 2333m 2 The adsorption capacity of toluene per gram was 1356mg/g, the adsorption capacity of methanol was 1420mg/g, and the electrochemical capacity was 115F/g.
Example 4
Mixing pinecone with Fe (NO) 3 ) 3 Mixing according to the proportion of 20:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the tube furnace temperature was maintained at 10℃for a minute in a nitrogen atmosphere -1 The temperature rise rate of (2) is increased to 650 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 5mm;
switching nitrogen gas into mixed gas of steam gas, oxygen and carbon dioxide, wherein the mixing ratio is 1:1:1, the mass ratio of the steam gas to the pyrolytic carbon material is 3.5:1, and simultaneously, the temperature of the tube furnace is controlled at 10 ℃ for min -1 The temperature rise rate of (2) is raised to 700 ℃, and the mixture is activated for 1h in the mixed gas of vapor gas, oxygen and carbon dioxide.
Then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Fe (NO) 3 ) 3 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 2612m 2 The adsorption capacity of toluene per gram was 1832mg/g, the adsorption capacity of methanol was 1530mg/g, and the electrochemical capacity was 138F/g.
Example 5
Mixing pinecone with Fe (NO) 3 ) 3 Mixing according to the proportion of 50:1, placing in a quartz boat,transferring it into a tube furnace;
the temperature of the tube furnace is reduced in vacuum at 10 ℃ for min -1 The temperature rise rate of (2) is increased to 650 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 20mm;
introducing a mixed gas of carbon dioxide gas and steam into a tube furnace, wherein the mixing ratio is 3:1, the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2:1, and simultaneously, the temperature of the tube furnace is 10 ℃ for min -1 The temperature reduction rate of (2) is reduced to 500 ℃, and the mixture of carbon dioxide gas and water vapor is activated for 1h. Then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Fe (NO) 3 ) 3 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example is 1250m 2 The adsorption amount of toluene per gram was 920mg/g, the adsorption amount of methanol was 890mg/g, and the electrochemical capacity was 101F/g.
Example 6
Mixing pinecone with Fe (NO) 3 ) 3 Mixing according to the proportion of 100:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is reduced in vacuum at 10 ℃ for min -1 The temperature rising rate of (2) is increased to 400 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 30mm;
introducing a mixed gas of carbon dioxide gas and oxygen into a tube furnace, wherein the mixing ratio is 2.5:1, the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2:1, and simultaneously, the temperature of the tube furnace is 10 ℃ for min -1 The temperature rise rate of (2) is increased to 650 ℃, and the mixture is activated for 1h in the mixed gas of carbon dioxide and oxygen;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Fe (NO) 3 ) 3 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 1630m 2 The adsorption capacity of toluene per gram was 1223mg/g, the adsorption capacity of methanol was 1025mg/g, and the electrochemical capacity was 111F/g.
Example 7
Mixing pinecone with Cr (NO) 3 ) 3 Mixing according to the proportion of 20:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the tube furnace temperature was maintained at 10℃for a minute in a nitrogen atmosphere -1 The temperature rise rate of (2) is increased to 450 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 40mm;
switching nitrogen gas into mixed gas of carbon dioxide gas and oxygen gas, wherein the mixing ratio is 2.8:1, the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2.5:1, and simultaneously, the temperature of the tubular furnace is 10 ℃ for min -1 The temperature rise rate of (2) is increased to 550 ℃, and the mixture is activated for 1h in the mixed gas of carbon dioxide and oxygen;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Cr (NO 3 ) 3 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 1155m 2 The adsorption amount of toluene per gram was 1035mg/g, the adsorption amount of methanol was 956mg/g, and the electrochemical capacity was 103F/g.
Example 8
Mixing pinecone with Cr (NO) 3 ) 3 Mixing according to the proportion of 50:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is reduced in vacuum at 10 ℃ for min -1 The temperature rise rate of (2) is increased to 550 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 10mm;
the mixed gas of the vapor gas and the carbon dioxide is input into the tube furnace, the mixing ratio is 2.5:1, the mass ratio of the vapor gas to the pyrolytic carbon material is 2.5:1, and the temperature of the tube furnace is controlled at 10 ℃ for min at the same time -1 The temperature rise rate of (2) is raised to 700 ℃, and the mixture gas of the vapor gas and the carbon dioxide is activated for 1h;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Cr (NO 3 ) 3 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 2321m 2 The adsorption capacity of toluene per gram was 1489mg/g, the adsorption capacity of methanol was 1360mg/g and the electrochemical capacity was 117F/g.
Example 9
Mixing pinecone with Cr (NO) 3 ) 3 Mixing according to the proportion of 100:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is kept in argon atmosphere at 10 ℃ for min -1 The temperature rise rate of (2) is increased to 450 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 30mm;
switching argon gas into carbon dioxide gas, wherein the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2:1, and simultaneously, the temperature of the tube furnace is 10 ℃ for min -1 Is increased in temperature of (2)The speed is increased to 550 ℃, and the mixture is activated for 1h in a carbon dioxide atmosphere;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Cr (NO 3 ) 3 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example is 1425m 2 The adsorption capacity of toluene per gram was 1081mg/g, the adsorption capacity of methanol was 1020mg/g, and the electrochemical capacity was 106F/g.
Example 10
Mixing the pine cone with H 2 PtCl 6 Mixing according to the proportion of 20:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is reduced in vacuum at 10 ℃ for min -1 The temperature rise rate of (2) is increased to 400 ℃, and carbonization is carried out at the high temperature for 1h.
Grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 40mm;
inputting a mixed gas of carbon dioxide gas, water vapor and oxygen into a tube furnace, wherein the mixing ratio is 1:1:1, the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 3:1, and simultaneously, the temperature of the tube furnace is 10 ℃ for min -1 The temperature rise rate of (2) is increased to 600 ℃, and the mixture is activated for 1h in the mixed gas of carbon dioxide gas, water vapor and oxygen;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the physical activation method is adopted to solve the corrosion problem to equipment, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on H 2 PtCl 6 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 1365m 2 Per g, first partThe adsorption capacity of benzene was 1142mg/g, the adsorption capacity of methanol was 1050mg/g, and the electrochemical capacity was 103F/g.
Example 11
Mixing the pine cone with H 2 PtCl 6 Mixing according to the proportion of 50:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the tube furnace temperature was maintained at 10℃for a minute in a nitrogen atmosphere -1 The temperature rise rate of (2) is increased to 550 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 5mm;
switching nitrogen gas into steam gas, wherein the mass ratio of the steam gas to the pyrolytic carbon material is 2.5:1, and simultaneously, the temperature of the tube furnace is 10 ℃ for min -1 The temperature rise rate of (2) is increased to 700 ℃, and the mixture is activated in vapor gas for 1h;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the physical activation method is adopted to solve the corrosion problem to equipment, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on H 2 PtCl 6 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in the embodiment is 2255m 2 The adsorption amount of toluene per gram was 1605mg/g, the adsorption amount of methanol was 1460mg/g, and the electrochemical capacity was 125F/g.
Example 12
Mixing the pine cone with H 2 PtCl 6 Mixing according to the proportion of 100:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is kept in argon atmosphere at 10 ℃ for min -1 The temperature rise rate of (2) is increased to 600 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 20mm;
argon gas is switched into carbon dioxide gas, and the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2:1, which is the same asAt the temperature of 10 ℃ for min -1 The cooling rate of (2) is reduced to 400 ℃, and the activation is carried out for 1h in a carbon dioxide atmosphere. Then at 10 ℃ for min -1 Cooling to room temperature to obtain an active carbon material;
in the embodiment, the physical activation method is adopted to solve the corrosion problem to equipment, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on H 2 PtCl 6 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in the embodiment is 980m 2 The adsorption capacity of toluene per gram was 321mg/g, the adsorption capacity of methanol was 280mg/g, and the electrochemical capacity was 65F/g.
Example 13
Mixing pine cone with Zn (NO) 3 ) 2 Mixing according to the proportion of 20:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the tube furnace temperature was maintained at 10℃for a minute in a nitrogen atmosphere -1 The temperature rising rate of (2) is increased to 400 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 30mm;
switching nitrogen gas into carbon dioxide gas, wherein the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 3:1, and simultaneously, the temperature of the tube furnace is 10 ℃ for min -1 The temperature rise rate of (2) is increased to 500 ℃, and the activation is carried out for 1h in the carbon dioxide atmosphere;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Zn (NO 3 ) 2 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 2000m 2 Per g, the adsorption capacity of toluene is 1163mg/g, the adsorption capacity of methanol is 1070mg/g, and the electrochemical electricity is realizedThe capacity is 105F/g.
Example 14
Mixing pine cone with Zn (NO) 3 ) 2 Mixing according to the proportion of 50:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is reduced in vacuum at 10 ℃ for min -1 The temperature rise rate of (2) is increased to 600 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 20mm;
carbon dioxide gas is input into the tubular furnace, the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2.8:1, and the temperature of the tubular furnace is controlled at 10 ℃ for min at the same time -1 The cooling rate of (2) is reduced to 400 ℃, and the activation is carried out for 1h in a carbon dioxide atmosphere. Then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Zn (NO 3 ) 2 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 1550m 2 The adsorption capacity of toluene per gram was 1389mg/g, the adsorption capacity of methanol was 1220mg/g, and the electrochemical capacity was 118F/g.
Example 15
Mixing pine cone with Zn (NO) 3 ) 2 Mixing according to the proportion of 100:1, placing in a quartz boat, and transferring the quartz boat into a tube furnace;
the temperature of the tube furnace is kept in argon atmosphere at 10 ℃ for min -1 The temperature rising rate of (2) is increased to 400 ℃, and the carbonization is carried out for 1h at the high temperature;
grinding and sieving are carried out after high-temperature carbonization, and the diameter of the obtained pyrolytic carbon material is 30mm;
switching argon gas into carbon dioxide gas, wherein the mass ratio of the carbon dioxide gas to the pyrolytic carbon material is 2.5:1, and simultaneously, the temperature of the tubular furnace is 10 ℃ for min -1 Is heated to 500 ℃ in a carbon dioxide atmosphereActivating for 1h;
then at 10 ℃ for min -1 Cooling to room temperature to obtain the active carbon material.
In the embodiment, the corrosion problem to the equipment is solved by adopting a physical activation method, and meanwhile, the prepared activated carbon does not retain chemical activator, has unlimited application range and is based on Zn (NO 3 ) 2 The specific surface area of the obtained activated carbon was not affected while the reaction temperature was lowered in this example. The specific surface area of the pine cone activated carbon obtained in this example was 2253m 2 The adsorption capacity of toluene per gram was 1643mg/g, the adsorption capacity of methanol was 1450mg/g, and the electrochemical capacity was 109F/g.
Comparative example 1
S1, drying the pine cone at 100-120 ℃ for 20-30 h;
s2, crushing the dried pine cone in the step S1 to a grain size of 1-3 mm to obtain pine cone particles;
s3, mixing the pine cone particles in the step S2 with potassium hydroxide according to the weight ratio of 1:1-1:4, and adding water to impregnate the pine cone particles for 20-30 h to obtain a mixed material;
s4, placing the mixed material obtained in the step S3 into a microwave oven for carbonization and activation, wherein the microwave irradiation power is 200-700W, and the microwave irradiation time is 5-10 min, so as to obtain an activated mixed material;
s5, sequentially carrying out acid washing, water washing, drying and grinding on the activated mixed material in the step S4 to obtain the activated carbon.
The specific surface area of the pine cone activated carbon obtained in comparative example 1 was 868 m 2 The adsorption capacity of toluene per gram was 265 mg/g, the adsorption capacity of methanol was 156 mg/g and the electrochemical capacitance was 55F/g.
Comparative example 2
S1, pretreatment: washing the pine cone with ethanol and clear water, drying, grinding and crushing to obtain dried pretreated pine cone powder;
s2, calcining: calcining the pine cone powder pretreated in the step S1 at 500-900 ℃ for 1-5 h, washing the calcined powder with distilled water, and drying to obtain the pine cone-based biomass activated carbon;
s3, acid treatment: and (2) soaking the pine cone based biomass activated carbon obtained in the step (S2) in a concentrated acid solvent according to the proportion of adding 1-8 g of the pine cone based biomass activated carbon into each 100ml of the solvent, placing the soaked pine cone based biomass activated carbon in an oil bath at 60-90 ℃ for stirring for 3-5 hours, taking out, washing with water to be neutral, and finally drying to obtain the porous pine cone based biomass activated carbon.
The specific surface area of the pine cone activated carbon obtained in comparative example 2 was 98 m 2 The adsorption capacity of toluene per gram was 125 mg/g, the adsorption capacity of methanol was 136 mg/g and the electrochemical capacitance was 46F/g.
Relevant experiments were carried out on the pine cone activated carbon materials prepared in examples 1 to 15 and comparative examples 1 and 2, respectively, and the results are shown in Table 1.
Table 1 comparative experiment table for active carbon of pine cone
As can be seen from the above experimental data, the inventive examples employed Fe (NO 3 ) 3 、Co(NO 3 ) 2 、H 2 PtCl 6 The active carbon of the pine cone prepared by the auxiliary agents has obvious improvement in the aspects of specific surface area, toluene adsorption capacity, methanol adsorption capacity, electrochemical capacitance and the like. Auxiliary Fe (NO) 3 ) 3 、Co(NO 3 ) 2 、H 2 PtCl 6 The catalyst can be converted into transition metal oxide or metal simple substance Pt and the like in the heat treatment process, which is beneficial to reducing the activation temperature and improving the specific surface area of the prepared active carbon, thereby improving the adsorption quantity of the p-toluene and the methanol and the performance of the super capacitor. In addition, the formed transition metal oxide and the like can also provide pseudo capacitance, so that the performance of the supercapacitor is further improved. Compared with the comparative example, the potassium hydroxide or the concentrated acid is adopted as the auxiliary agent, the obtained product has obviously improved data in all aspects, simultaneously does not generate chemical pollution, reduces the reaction temperature, has simple process flow, reduces the investment cost, improves the production efficiency and is beneficial to industrialized application.
Fig. 1 is a flow chart of a preparation method of the pine cone activated carbon.
Fig. 2 is an X-ray photoelectron spectrum total analysis spectrum of the pine cone-derived activated carbon material prepared in example 4, and it can be seen from the figure that the pine cone-derived activated carbon material mainly contains carbon and oxygen elements. The atomic percentages of carbon and oxygen were 96.3% and 3.7%, respectively.
FIG. 3 is a graph showing the adsorption and desorption of nitrogen from the pine cone-derived activated carbon material prepared in example 4, and it can be seen from FIG. 3 that the prepared pine cone-derived activated carbon material has a porous structure with a specific surface area of 2612m 2 g –1 。
FIG. 4 is an X-ray diffractometer spectrum of the pine cone derived activated carbon material prepared in example 4, showing that the prepared pine cone derived activated carbon material exhibited a broad peak at about 24 ° (interlayer spacing of about 0.37 nm), indicating its amorphous carbon structure.
Fig. 5 is an adsorption isotherm of toluene and methanol at 298K of the pine cone-derived activated carbon material prepared in example 4, and it can be seen from fig. 5 that the prepared pine cone-derived activated carbon material has excellent organic vapor adsorption performance, and adsorption amounts of toluene and methanol are 1832 and 1530mg/g, respectively.
FIG. 6 is a cyclic voltammogram of the pine cone derived activated carbon material prepared in example 4 in 1.0mol/L tetraethylammonium tetrafluoroborate/acetonitrile electrolyte, as can be seen from FIG. 6, all cyclic voltammograms exhibit a quasi-rectangular shape. The cyclic voltammogram of the pine cone derived activated carbon material still remained quasi-rectangular in shape as the scan rate was increased to 100 mV/s.
Fig. 7 is a graph showing the relationship between the specific capacitance and the discharge current density of the pine cone-derived activated carbon material and the commercial activated carbon material prepared in example 4, wherein the upper graph represents the pine cone activated carbon provided by the present invention, and the lower graph represents the commercial activated carbon, and it can be seen from fig. 7 that the pine cone-derived activated carbon material prepared by the present invention has a better rate capability, and the electrochemical capacitance of the pine cone-derived activated carbon material can still reach 138F/g even when the current density increases to 10A/g. Compared with commercial active carbon materials, the active carbon materials derived from the pine cone have better performance.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Although embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
The steps in the method of the embodiment of the invention can be sequentially adjusted, combined and deleted according to actual needs.
Claims (10)
1. The preparation method of the pine cone activated carbon is characterized by comprising the following steps:
mixing the pine cone with the auxiliary agent to obtain a first mixture, wherein the mass mixing ratio of the pine cone to the auxiliary agent is 100:1-20:1, the auxiliary agent is transition metal salt;
the first mixture is subjected to an oxygen-free environment at 10 ℃ for min -1 Heating to pyrolysis temperature at 400-950 deg.c for 1 hr;
grinding and sieving the pyrolyzed product to obtain a pyrolytic carbon material with the particle diameter less than or equal to 50 mm;
activating pyrolytic carbon material with activating medium at 10 deg.c for min -1 And (3) cooling to room temperature to obtain the active carbon.
2. The method for preparing the activated carbon of pine cone according to claim 1, wherein,
the pyrolysis temperature is 400-650 ℃.
3. The method for preparing the activated carbon of pine cone according to claim 1, wherein,
the oxygen-free environment includes a vacuum or a protective atmosphere environment.
4. The method for preparing the activated carbon of pine cone according to claim 1, wherein,
the transition metal salt is Co (NO) 3 ) 2 、Fe(NO 3 ) 3 、Cr(NO 3 ) 3 、H 2 PtCl 6 、Cu(NO 3 ) 2 、Mn(NO 3 ) 2 、AgNO 3 、Ni(NO 3 ) 2 And Zn (NO) 3 ) 2 Any one of the following.
5. The method for preparing the activated carbon of pine cone according to claim 4, wherein,
the transition metal salt is Co (NO) 3 ) 2 、Fe(NO 3 ) 3 、Cr(NO 3 ) 3 、H 2 PtCl 6 And Zn (NO) 3 ) 2 Any one of the following.
6. The method for preparing the activated carbon of pine cone according to claim 1, wherein,
the activating medium is one or a mixture of any of water vapor, oxygen and carbon dioxide.
7. The method for preparing the activated carbon of pine cone according to claim 1, wherein,
introducing an activating medium into the pyrolytic carbon material for activation to be:
at 10 ℃ min -1 The temperature is adjusted to an activation temperature of 400-700 ℃.
8. The method for preparing the activated carbon of pine cone according to claim 1, wherein,
and the time for activating the pyrolytic carbon material by introducing an activating medium is 30-300 minutes.
9. The method for preparing the activated carbon of pine cone according to claim 1, wherein,
the mass ratio of the activating medium to the pyrolytic carbon material is 2:1-3.5:1.
10. A pine cone activated carbon, characterized in that it is prepared by the preparation method of the pine cone activated carbon according to any one of claims 1 to 9.
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