CN115505942A - Preparation method and device of carbon nano material - Google Patents
Preparation method and device of carbon nano material Download PDFInfo
- Publication number
- CN115505942A CN115505942A CN202211367195.4A CN202211367195A CN115505942A CN 115505942 A CN115505942 A CN 115505942A CN 202211367195 A CN202211367195 A CN 202211367195A CN 115505942 A CN115505942 A CN 115505942A
- Authority
- CN
- China
- Prior art keywords
- carbon
- reaction vessel
- electrochemical reaction
- reaction
- carbon dioxide
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000012429 reaction media Substances 0.000 claims abstract description 10
- 238000005204 segregation Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000007246 mechanism Effects 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000005686 electrostatic field Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims description 2
- 230000006872 improvement Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/135—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method and a device for preparing a carbon nano material, which adopt molten chloride, carbonate, fluoride and nitrate as electrochemical reaction media to prepare the carbon nano material and concretely comprise the following steps: s1, preparing an electrochemical reaction medium; s2, carrying out an electrochemical reaction process; s3, adding a carbon dioxide fluid; s4, a balanced segregation purification method. The carbon nano material is prepared through the electrochemical reaction process, and the preparation cost of the carbon nano material is greatly reduced by adopting chloride, carbonate and nitrate as main electrochemical reaction media; meanwhile, the conversion efficiency of carbon dioxide converted into elemental carbon is effectively improved through the pretreatment of the carbon dioxide gas source.
Description
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a preparation method and a device of a carbon nano material.
Background
Carbon dioxide is a main cause of greenhouse effect, and China pays more and more attention to the capture and resource utilization of carbon dioxide. The carbon dioxide is effectively recycled, so that various environmental problems caused by excessive emission of the carbon dioxide can be fundamentally solved.
The method for industrially producing the carbon nano tube always uses the CVD method, the CFB method and the like as the mainstream processes, and has the disadvantages of large production pollution, high production cost and large production energy consumption. In the prior art, massot and Novoselova respectively use an electrochemical method to reduce a molten LiF-NaF-Na2CO3 system and a molten LiCl-KCl-Na2CO3 system to obtain carbon films, douglas and the like use nickel plated with Al2O3 as an anode in 2017 to electrolyze Li2CO3 for reducing electrodes to prepare carbon nano tubes
However, in these methods, lithium salt is mainly used as a catalytically conductive substance, and the amount of lithium used is very large, and the content of lithium in the earth crust is only 0.0065%. With the development of new energy automobiles, the price of lithium salt is higher and higher, and the loss of the lithium salt leads to higher production cost of the carbon nano material. Therefore, it is very necessary to develop a production system independent of lithium salt.
Disclosure of Invention
The invention provides a method and a device for preparing a carbon nano material, which are used for solving the problems in the background technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a carbon nano material adopts molten chloride, carbonate, fluoride and nitrate as electrochemical reaction media to prepare the carbon nano material, and specifically comprises the following steps:
s1, preparing an electrochemical reaction medium: firstly, adding a certain part of mixture of chloride, carbonate, fluoride and nitrate into a reaction vessel, then adding a catalyst into the reaction vessel, heating the reaction vessel, calcining the mixture together until the mixture is molten, taking out the mixture, and uniformly compounding the mixture to serve as an electrochemical reaction mass transfer medium for later use;
s2, electrochemical reaction process: using a gas supercritical pressurizing device to pressurize and heat a carbon dioxide gas source to a supercritical state, blowing the carbon dioxide gas into an ion discharge cavity to enable supercritical carbon dioxide fluid to carry a certain charge, heating a prepared reaction vessel to a working temperature, introducing treated carbon dioxide after a mass transfer medium formed by chloride, carbonate, fluoride and nitrate, setting the depth of a reduction pole and current-voltage parameters, setting field intensity induction intensity parameters of an external magnetic field, starting to perform electrochemical reaction, wherein the electrochemical reaction lasts for about 1.5 hours, depositing a carbon material on the reduction pole of the device after the reaction is finished, and converting part of carbonate into oxide during the electrochemical reaction;
s3, adding a carbon dioxide fluid: continuously injecting charged supercritical carbon dioxide fluid into the reaction vessel while the electrochemical reaction process is carried out, so that the electrochemical reaction is continuously carried out;
s4, an equilibrium segregation purification method: when the carbon product is deposited on the reduction electrode, a part of mass transfer medium is deposited at the same time, the main components of the deposit are salt substances and carbon simple substances, the deposit is peeled off from the electrode plate by a medium-frequency heating method and then crushed to form a powdery compound, the powdery compound is re-filled into another reactor, the temperature is raised to a molten state, a temperature gradient is formed upwards from the bottom of the reactor, the temperature is gradually reduced, the carbon material can float upwards under the action of bottom crystallization according to different segregation coefficients of the materials and finally leaves a dissolved body, the floating carbon material forms a powdery and free product after the steps of re-grinding, washing, filtering, drying and the like, and the powdery and free product is a nano carbon material which comprises microstructures such as graphene, carbon nano tubes, carbon nano blocks, carbon nanospheres and the like after analysis.
As a further improvement scheme of the technical scheme: in the S1, the catalyst is transition metal oxide and chloride.
As a further improvement scheme of the technical scheme: the method of charging supercritical carbon dioxide fluid is direct ionization using electrostatic field.
As a further improvement scheme of the technical scheme: in S4, the cooling temperature gradient range of the equilibrium segregation purification method is between 10 ℃/CM and 0.1 ℃/CM.
The invention also provides a carbon nano-material preparation device, which is applied to any one of the carbon nano-material preparation methods and comprises an electrochemical reaction structure and an electrochemical reaction power supply, wherein the electrochemical reaction structure comprises a reaction vessel, the reaction vessel consists of a high-temperature reaction vessel, an oxidation electrode and a reduction electrode, and the outside of the reaction vessel consists of a magnetic field, a gas supercritical pressurizing device and a gas ionization processing device.
As a further improvement scheme of the technical scheme: the reaction vessel is made of a ceramic composite material composed of tin dioxide and other oxides.
As a further improvement scheme of the technical scheme: the outside of the reaction vessel is composed of a strong excitation electromagnet, and the magnetic field intensity range is 1000kA/m-3000kA/m.
As a further improvement scheme of the technical scheme: the reaction vessel is used as a reaction vessel for electrochemical reaction and also as an oxidation electrode in the whole electrochemical process.
As a further improvement scheme of the technical scheme: the reaction vessel comprises a heating device, a heat insulation material and a magnetic field in sequence, and the bottom of the reaction vessel is electrically connected with a cable device connected with the outside.
As a further improvement scheme of the technical scheme: the reduction pole is arranged on the top of the reaction vessel and is a movable component, and an external mechanism is responsible for controlling the depth of the reduction pole inserted into the reaction vessel.
Compared with the prior art, the invention has the beneficial effects that:
the method adopts molten chloride, carbonate and nitrate as main electrochemical reaction media, prepares the carbon nano-material through an electrochemical reaction process, and greatly reduces the preparation cost of the carbon nano-material through adopting the chloride, the carbonate and the nitrate as the main electrochemical reaction media; meanwhile, the conversion efficiency of carbon dioxide converted into simple substance carbon is effectively improved through the pretreatment of the carbon dioxide gas source.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings. The detailed description of the present invention is given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
fig. 1 is an SEM image of carbon nanotubes produced using the present method.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The invention is more particularly described in the following paragraphs with reference to the accompanying drawings by way of example. Advantages and features of the present invention will become apparent from the following description and from the claims. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of a carbon nano material, which adopts molten chloride, fluoride, carbonate and nitrate as main electrochemical reaction media to carry out electrochemical reaction to prepare the carbon nano material.
The further scheme of the scheme is that the preparation method of the carbon nano material comprises the following steps:
s1, preparing an electrochemical reaction mass, namely weighing 1 molar part of a mixture of chloride, carbonate, fluoride and nitrate, adding the mixture into a reaction vessel, weighing 0.5 molar part of a catalyst into the reaction vessel, heating the reaction vessel, calcining the mixture together until the mixture is molten (550 ℃), taking out the mixture, and uniformly compounding the mixture to serve as an electrochemical reaction mass transfer medium for later use;
s2, preparing a reaction vessel by using an electrochemical reaction structure and an electrochemical reaction power supply, wherein the reaction vessel is formed by a high-temperature reaction vessel, an oxidation electrode and a reduction electrode, and the outside of the reaction vessel is formed by a magnetic field, a gas supercritical pressurizing device and a gas ionization processing device;
and S3, in the electrochemical reaction process, a gas supercritical pressurizing device is used for pressurizing and heating a carbon dioxide gas source to a supercritical state, and the carbon dioxide gas source is blown into an ion discharge cavity to enable supercritical carbon dioxide fluid to have certain charges. And heating the prepared reaction vessel to a working temperature, and introducing the treated carbon dioxide gas after the chloride, the carbonate, the fluoride and the nitrate form a mass transfer medium. And setting the depth of the reduction pole and current and voltage parameters, and setting the field intensity induction strength parameter of the external magnetic field. The electrochemical reaction starts. The electrochemical reaction lasts for about 1.5 hours, and after the reaction is finished, the carbon material is deposited on the reduction electrode of the device. During the electrochemical reaction, partial carbonate is converted into oxide;
and S4, continuously filling the treated carbon dioxide fluid into the reaction vessel while carrying out the electrochemical reaction. These fluids continue to react with the oxide by-product of the reaction to regenerate the carbonate. The entire electrochemical reaction will continue. The carbon dioxide is conducted through a mass transfer medium, so that the electrochemical reaction is continuously generated;
s5, equilibrium segregation purification method. When the above-mentioned carbon products are deposited on the reduction electrode, a part of the mass transfer medium will also be deposited at the same time. The main components of the deposit at this time are salt substances and carbon simple substances. And stripping the deposit from the polar plate by a medium-frequency heating method, and then crushing to form a powdery compound. And (3) reloading the powdery compound into another reactor, heating to a molten state, forming a temperature gradient from the bottom of the reactor upwards, gradually cooling, wherein the temperature step is 1 ℃/CM, and according to different segregation coefficients of the materials, the carbon material can float upwards under the action of bottom crystallization and finally leave a solution. The carbon material floating at this time is subjected to the steps of re-grinding, washing with water, filtering, drying and the like to form a powdery and free product, namely the nano carbon material. The nano-scale carbon material comprises microstructures such as graphene, carbon nano-tubes, carbon nano-blocks, carbon nano-spheres and the like through analysis.
In a further aspect of the above embodiment, the reaction vessel in S2 is used as an oxidation electrode, and the material thereof is a ceramic composite material made of tin dioxide and other oxides.
In the scheme, the catalyst in the S1 is transition metal oxide and chloride, and the additive is one or more of nickel chloride, ferric chloride, cobalt chloride, nickel oxide, ferric oxide and cobalt oxide.
The further scheme of the scheme is that the external magnetic field in the S2 is formed by a strong excitation electromagnet, and the magnetic field intensity range is 1000kA/m-3000kA/m
In the further scheme of the scheme, in the process stage of gas ionization in S2, the supercritical carbon dioxide fluid is charged by using an electrostatic field for direct ionization. Also, the choice of such a dc power supply has the following points specifically indicated:
1. the voltage range of the power supply is between 1.5V and 5V, the output frequency of the power supply is high and continuously adjustable, and the range of the output frequency is between 50KHz and 300 KHz. In operation, the frequency output is also varied. The amplitude of the variation is related to the growth voltage range.
2. The power supply is designed as a reversing pulse power supply (bipolar power supply), namely an oxidation electrode and a reduction electrode can be quickly switched within a range specified by a program, and the growth of the carbon nano tube is related to the direction of the power supply.
According to a further scheme of the scheme, the reaction vessel in the S1 is used as a reaction vessel for electrochemical reaction and is also used as an oxidation electrode in the whole electrochemical process.
The further scheme of the scheme is that the cooling temperature gradient range of the equilibrium segregation purification method in the S5 is between 10 ℃/CM and 0.1 ℃/CM.
The further scheme of the scheme is that in the whole reaction device, the magnetic field is arranged at the outermost part of the reaction device, the inner layer of the magnetic field is made of heat-insulating materials, the inner layer of the magnetic field is arranged on the heating device, and the outermost part of the magnetic field is a reaction vessel. The bottom of the reaction vessel is provided with a cable device which is connected with the outside.
The further scheme of the scheme is that the reduction pole of the reaction device is arranged at the top of the device and is a movable component, and an external mechanism is responsible for controlling the depth of the reduction pole inserted into the reaction vessel.
The electrochemical reaction process mechanism of the invention is as follows:
reaction of the oxidation electrode:
[1]2O 2 -4e - ＝O 2
reaction of the reduction pole:
[2] formation of carbon:
CO32 - +4e - ＝C+3O2 -
[3] formation of carbon monoxide:
CO32 - +2e - ＝CO+2O2 -
[4] formation of carbon monoxide and carbon:
CO3 2- +3e - ＝1/2CO+1/2C+5/2O2-
the reaction of adding two poles can obtain the general reaction formula:
[5]M 2 CO3＝C(s)+O 2 +M 2 O；
[6]M 2 CO 3 ＝CO+M 2 O+1/2O 2 ；
[7]M 2 CO 3 ＝1/2CO+1/2C+M 2 O+3/4O 2 ；
absorption reaction of CO 2:
[8]M 2 O+CO 2 ＝M 2 CO 3
the electrolysis reactions [5], [6] and [7] are added with the absorption reaction [8] of CO2 to obtain the total reaction of the electrolysis unit:
[9]CO 2 ＝C+O 2 ；
[10]CO 2 ＝1/2O 2 +CO；
[11]CO 2 ＝3/4O2+1/2CO+1/2C
the invention adopts the pressurization and the charged treatment of the carbon dioxide gas source and the selective intervention of the high-frequency reversing pulse power supply, and can ensure that the chloride and the fluoride are not decomposed or are rarely decomposed when the molten chloride, carbonate, fluoride and nitrate are kept as mass transfer media in the reaction process;
according to the invention, the electrochemical reaction substance molten-state chloride, carbonate, fluoride and nitrate have very strong capture capacity on the supercritical charged carbon dioxide fluid, and after the carbon dioxide enters the supercritical fluid state, the carbon dioxide can be better mixed with the molten-state chloride, carbonate, fluoride and nitrate, so that the conversion efficiency of converting the carbon dioxide into the carbon nano material is improved.
The fluoride is introduced into the reaction system, and the fluoride can enable the transition metal catalyst to form a stable state with small-scale orientation and deposit on the reduction electrode. The stable small-scale deposition can play a great beneficial role in the catalytic process of the growth of the carbon nano tube, particularly in accurately controlling the diameter and the length-diameter ratio of the carbon nano tube.
The foregoing is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the invention in any way; one of ordinary skill in the art will readily appreciate from the disclosure that the present invention can be practiced as illustrated in the accompanying drawings and described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a carbon nano material is characterized in that molten chloride, carbonate, fluoride and nitrate are used as electrochemical reaction media to prepare the carbon nano material, and the method specifically comprises the following steps:
s1, preparing an electrochemical reaction medium: firstly, adding a certain part of mixture of chloride, carbonate, fluoride and nitrate into a reaction vessel, then adding a catalyst into the reaction vessel, heating the reaction vessel, co-calcining the mixture until the mixture is molten, taking out the mixture, and uniformly compounding the mixture to serve as an electrochemical reaction mass transfer medium for later use;
s2, electrochemical reaction process: a gas supercritical pressurizing device is used for pressurizing and heating a carbon dioxide gas source to a supercritical state, and blowing the gas into an ion discharge cavity to enable a supercritical carbon dioxide fluid to have a certain charge, a prepared reaction vessel is heated to a working temperature, a mass transfer medium formed by chloride, carbonate, fluoride and nitrate is introduced into the treated carbon dioxide gas, the depth of a reduction electrode and current and voltage parameters are set, an external magnetic field strength induction intensity parameter is set, an electrochemical reaction is started, the electrochemical reaction lasts for about 1.5 hours, after the reaction is finished, a carbon material is deposited on a reduction electrode of the device, and part of carbonate is converted into oxide in the electrochemical reaction;
s3, adding a carbon dioxide fluid: continuously injecting charged supercritical carbon dioxide fluid into the reaction vessel while the electrochemical reaction process is carried out, so that the electrochemical reaction is continuously carried out;
s4, an equilibrium segregation purification method: when the carbon product is deposited on the reduction electrode, a part of mass transfer medium is deposited at the same time, the main components of the deposit are salt substances and carbon simple substances, the deposit is peeled off from the electrode plate by a medium-frequency heating method and then crushed to form a powdery compound, the powdery compound is re-filled into another reactor, the temperature is raised to a molten state, a temperature gradient is formed upwards from the bottom of the reactor, the temperature is gradually reduced, the carbon material can float upwards under the action of bottom crystallization according to different segregation coefficients of the materials and finally leaves a dissolved body, the floating carbon material forms a powdery and free product after the steps of re-grinding, washing, filtering, drying and the like, and the powdery and free product is a nano carbon material which comprises microstructures such as graphene, carbon nano tubes, carbon nano blocks, carbon nanospheres and the like after analysis.
2. The method according to claim 1, wherein in S1, the catalyst is transition metal oxide or chloride.
3. The method for preparing carbon nano-material according to claim 1, wherein the supercritical carbon dioxide fluid is charged by direct ionization using electrostatic field.
4. The method as claimed in claim 1, wherein the cooling temperature gradient of the equilibrium segregation purification process in S4 is in the range of 10 ℃/CM to 0.1 ℃/CM.
5. A carbon nanomaterial preparation device applied to the carbon nanomaterial preparation method of any one of claims 1 to 4, comprising an electrochemical reaction structure and an electrochemical reaction power supply, wherein the electrochemical reaction structure comprises a reaction vessel, the reaction vessel comprises a high-temperature reaction vessel, an oxidation electrode and a reduction electrode, and the outside of the reaction vessel comprises a magnetic field, a gas supercritical pressurizing device and a gas ionization processing device.
6. The apparatus of claim 5, wherein the reaction vessel is made of a ceramic composite material comprising tin dioxide and other oxides.
7. The apparatus of claim 6, wherein the magnetic field outside the reaction vessel is formed by a strongly excited electromagnet, and the magnetic field strength is in a range of 1000kA/m to 3000kA/m.
8. The apparatus of claim 7, wherein the reaction vessel is used as a reaction vessel for electrochemical reaction and an oxidation electrode in the whole electrochemical process.
9. The carbon nanomaterial preparation apparatus according to claim 8, wherein the reaction vessel comprises a heating device, a thermal insulation material, and a magnetic field in sequence, and a cable device connected to the outside is electrically connected to the bottom of the reaction vessel.
10. The apparatus of claim 9, wherein the reduction electrode is a movable component on the top of the reaction vessel, and an external mechanism is responsible for controlling the depth of the reduction electrode inserted into the reaction vessel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211367195.4A CN115505942A (en) | 2022-11-02 | 2022-11-02 | Preparation method and device of carbon nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211367195.4A CN115505942A (en) | 2022-11-02 | 2022-11-02 | Preparation method and device of carbon nano material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115505942A true CN115505942A (en) | 2022-12-23 |
Family
ID=84513309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211367195.4A Pending CN115505942A (en) | 2022-11-02 | 2022-11-02 | Preparation method and device of carbon nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115505942A (en) |
-
2022
- 2022-11-02 CN CN202211367195.4A patent/CN115505942A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106549163B (en) | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate | |
| KR20180117191A (en) | Manufacturing method of graphene oxide nanoflurane serialization | |
| CN112421055B (en) | Preparation method and application of oxidized nitrogen-doped carbon nanotube array cluster/flexible carbon fiber material integrated electrode | |
| CN102769124B (en) | Graphene-supported octahedral nickel oxide composite material and preparation method thereof | |
| CN106925314A (en) | A kind of nickel assisted cryogenic synthesizes the method for molybdenum carbide elctro-catalyst | |
| CN107195908B (en) | A kind of foamed material composite cathode of microorganism electrolysis cell and preparation method thereof | |
| CN110902649B (en) | Method for preparing iron-nitrogen-carbon catalyst by using template | |
| CN109825846A (en) | A kind of method of molten caustic soda electrolytic regeneration waste lithium ion cell anode material | |
| CN113816368B (en) | Method for preparing graphene oxide by electrolyzing muddy graphite interlayer compound | |
| CN105386076A (en) | Improvement method for carbon nano tube preparation system based on high-temperature electrolysis of CO2 | |
| CN106976854A (en) | A kind of method for preparing carbon material | |
| CN106409520A (en) | Method for preparing electrode material of lithium-ion-mixed capacitor and application thereof | |
| CN115505942A (en) | Preparation method and device of carbon nano material | |
| CN111334818A (en) | Device for electrolytic catalytic oxidation and method for preparing 2, 5-furandicarboxylic acid | |
| CN116623193A (en) | Salt-assisted synthesis of defect-rich transition metal M-NC porous nano sheet material, and preparation method and application thereof | |
| CN106048641A (en) | Process method of electrochemically preparing Fe3+ and H2 in pair | |
| CN110148742A (en) | A kind of lithium ion battery cementite/carbon ultrathin nanometer sheet combination electrode material preparation process | |
| CN110422839B (en) | Synthetic method of graphene | |
| Kang et al. | Hydrogen-treated spent lithium cobalt oxide as an efficient electrocatalyst for oxygen evolution | |
| CN113479868A (en) | Method for preparing graphene through bipolar electrochemical stripping of organic acid ammonium fused salt | |
| CN110902676A (en) | Preparation method of expanded graphite | |
| CN105958048B (en) | A kind of preparation method of the two poles of the earth equality of temperature simultaneous electrolysis cobalt acid lithium and metallic cobalt | |
| CN111705336A (en) | Method for recovering nickel simple substance from waste lithium battery | |
| CN113816433B (en) | Method for preparing porous ferroferric oxide with adjustable pore diameter by using iron-containing solid waste acid immersion liquid | |
| CN114572973B (en) | Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method |
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 |