CN116672987A - Device and method for preparing oligowall carbon nano tube by expandable arc discharge - Google Patents
Device and method for preparing oligowall carbon nano tube by expandable arc discharge Download PDFInfo
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- CN116672987A CN116672987A CN202310833503.6A CN202310833503A CN116672987A CN 116672987 A CN116672987 A CN 116672987A CN 202310833503 A CN202310833503 A CN 202310833503A CN 116672987 A CN116672987 A CN 116672987A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000010891 electric arc Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- 238000007790 scraping Methods 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 230000000903 blocking effect Effects 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 78
- 229910052799 carbon Inorganic materials 0.000 claims description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000004939 coking Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- PGHQEOHSIGPJOC-UHFFFAOYSA-N [Fe].[Ta] Chemical compound [Fe].[Ta] PGHQEOHSIGPJOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003870 refractory metal Substances 0.000 claims description 4
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000571 coke Substances 0.000 abstract description 15
- 239000002105 nanoparticle Substances 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000002109 single walled nanotube Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 239000000155 melt Substances 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- -1 ethylene, propylene Chemical group 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002079 double walled nanotube Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012356 Product development Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/159—Carbon nanotubes single-walled
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0875—Gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0892—Materials to be treated involving catalytically active material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
Abstract
The application belongs to the technical field of nano material preparation, and relates to a device and a method for preparing an oligowall carbon nano tube by extensible arc discharge. The device comprises: at least one synthesis unit, at least one scraping unit, at least one blocking unit, at least one collecting unit, a catalyst melt and a drive unit; the application adopts the rotary moving catalyst melt to connect the double-electrode direct current arc, can continuously prepare uniform catalyst nano particles, and the rotary moving melt and the scraping unit cooperate to remove coke attached on the surface of the catalyst melt, so as to keep the surface of the catalyst clean, thereby being beneficial to continuously preparing the uniform catalyst nano particles for growing the oligowall carbon nano tube, keeping equipment to continuously and stably grow the oligowall carbon nano tube for a long time, being particularly important for breaking through the oligowall carbon nano tube with high yield and high quality, and having great commercial value.
Description
Technical Field
The application belongs to the technical field of nano material preparation, and relates to a device and a method for preparing an oligowall carbon nano tube by extensible arc discharge.
Background
The single-wall carbon nanotube (SWCNT) is used as a typical one-dimensional nano material, has excellent mechanical, thermal and optical properties, and characteristics of huge length-diameter ratio, high specific surface area, light weight and the like, has the effects of light weight, high strength, high electric conduction, high heat conduction and the like, and has potential application prospects in the aspects of key application research and product development in the fields of wearable electric heating, electromagnetic shielding, lithium ion battery electrode materials, water filtration and purification and the like.
The most commonly used methods for preparing the oligowall carbon nanotubes are floating chemical deposition (FCCVD) and novel plasma chemical methods. As FCCVD is an economic method, the continuity of the FCCVD process is optimized for about 20 years, and the prepared initial product has high purity and high graphitization degree, but the technical problem of hundred-gram-grade single-wall carbon nanotubes produced in daily life cannot be broken through, the continuous collection of the product is uncontrollable, the ton-grade mass production is more difficult, and the application field of the product is limited. Reference nanoscales, 2019, 11, 18483-1849, chinese patent publication nos. CN109437157B, CN111348642B and CN108408716B.
In recent decades, due to the progress of plasma chemical technology, the preparation of single-wall carbon nanotubes by a plasma chemical vapor deposition method is valued by scientific research and industry, and the advantage of the plasma chemical vapor deposition is that high-quality single-wall carbon nanotubes can be prepared in a high-temperature environment, so that a new path is opened up for the industrial preparation of high-quality SWCNTs. For example, chinese patent nos. CN113860287B, CN113929084B and CN110217777a both use a single-electrode dc arc furnace, wherein the upper end is a cathode, the lower end is a graphite crucible anode, and a high-temperature plasma is formed between the cathodes by discharging to prepare a catalyst for growing single-walled carbon nanotubes. Although products with G/D ratios exceeding 70 single-walled carbon nanotubes can be obtained. However, the single-electrode direct current arc furnace has a bottom anode effect, and is difficult to continuously and stably operate.
There is another problem that a large amount of coke is generated in the reaction, coking in the reaction chamber is more and more carried out along with the reaction, the coke is enriched on the upper surface of the crucible, the coking and enrichment are easy to cause arc breakage, the arc stability is reduced, the coke is slowly fused into the melt to influence the uniformity of the components of the melt, and the activity of the catalyst prepared from the melt is greatly reduced due to the high-crystallinity carbon fused into the melt to influence the catalytic cracking to generate a product. Resulting in lower and lower SWCNT content in subsequent products, and unsustainable product growth, which seriously affects continuous stable production of the product. On the one hand, the yield gradually decreases along with the progress of the reaction, the test is stopped, the temperature is reduced to the room temperature, the coke is cleaned, and then the test is performed, so that time and labor are wasted. On the other hand, the carbon-coated iron in the initial product and the coke rich in a large amount of iron particles are gradually increased, so that the purity of the carbon tube in the initial product can be reduced, and the subsequent purification work is extremely difficult, and the industrial production of the oligowall carbon nano tube is extremely challenging.
Disclosure of Invention
The application discloses a device and a method for preparing an oligowall carbon nano tube by extensible arc discharge, which are used for solving any one of the above and other potential problems in the prior art.
In order to solve the problems existing in the prior art, the application adopts the following technical scheme: an apparatus for scalable arc discharge preparation of oligowall carbon nanotubes, the apparatus comprising: furnace body, preheater, conveyer and collection unit, its characterized in that, the device still includes: at least one synthesis unit, at least one scraping unit, at least one blocking unit, a catalyst melt and a drive unit;
the separation unit is arranged in the furnace body to separate the furnace body into a left chamber and a right chamber, the scraping unit is arranged at the upper end of the left chamber, the synthesis unit is arranged at the upper end of the right chamber, and the catalyst melt is horizontally arranged in the furnace body and is positioned below the scraping unit and the synthesis unit;
the driving unit is arranged outside one side of the furnace body, fixedly connected with one end of the catalyst melt arranged in the furnace body through a connecting shaft and used for driving the catalyst melt to rotate and stretch;
the catalyst auxiliary agent conveyor and the preheater are arranged at the top of the outer side of the furnace body and are connected with the synthesis unit;
the collecting units are respectively arranged below the synthesizing unit and the scraping unit, and are connected with the bottom of the furnace body.
Further, the synthesizing unit includes: a hollow cathode electrode gun, a hollow anode electrode gun, a hollow graphite electrode and carbon source mixed gas injection tube;
the collecting unit divide into first collecting chamber, mainly retrieves the carbon nanotube product of oligo wall, mainly retrieves the second collecting chamber of coke, first collecting chamber be located under the synthetic unit, the second collecting chamber be located under the scraping unit, the collecting chamber all is equipped with the transition room, when the collecting chamber collects the product more, under the experimental condition of incessantly, usable transition room shifts out the collecting chamber with the product for collect the product in succession, extension reaction time.
One ends of the hollow cathode electrode gun and the hollow anode electrode gun are inserted into the furnace body from the top of the furnace body, and a certain distance is reserved between the hollow cathode electrode gun and the hollow anode electrode gun; the other ends of the hollow cathode electrode gun and the hollow anode electrode gun are respectively connected with the preheater and the conveyor;
further, the carbon source mixed gas injection pipe is arranged between the hollow cathode electrode gun and the hollow anode electrode gun and is connected with the preheater.
Further, the scraping unit includes: the device comprises a first arc scraper, a second arc scraper, a first driving motor, a second driving motor and a controller;
the first driving motor and the second driving motor are arranged at the top of the furnace body and are respectively connected with the first arc scraper and the second arc scraper through connecting shafts, and the controller is respectively connected with the first driving motor and the second driving motor.
Further, the blocking unit is a plate with a round hole in the middle, the center of the round hole is concentric with the catalyst melt, one end of the plate is fixedly connected with the top of the furnace body, and the distance d between the end of the other end and the surface of the catalyst melt is 10-100mm;
the middle round hole plate is made of refractory metal tungsten, tantalum-iron alloy, magnesium-carbon material, corundum material or graphite.
Furthermore, the middle round hole plate is made of refractory metal tungsten, tantalum-iron alloy, magnesium-carbon material, corundum material or graphite.
Further, the catalyst melt is a hollow metal cylinder with the diameter not smaller than 30cm, and a cooling unit is arranged inside the hollow metal cylinder;
further, the electrode center distance D between the hollow cathode and the anode electrode is 50-350mm.
Further, the catalyst melt is an iron-containing compound or a mixture, is used for conducting a parallel hollow cathode electrode and a hollow anode electrode to form a plasma arc, and is pressed into a cylinder shape by pressing, and comprises at least one of nickel, cobalt, iron carbide, iron carboxyl, carbonyl iron, cobalt, nickel alloy, tungsten, tantalum, rhenium, molybdenum, yttrium, lanthanum and dysprosium.
Another object of the present application is to provide a method for preparing single-walled carbon nanotubes using the above apparatus, which specifically comprises the following steps:
s1) placing the cocatalyst in a conveyor, and introducing inert gas to empty the furnace body;
s2) starting a plasma arc to be conducted through the catalyst melt, starting a driving unit to enable the catalyst melt to rotate and stretch, and starting a preheater to preheat the mixed gas and the carbon source mixed gas;
s3) quantitatively introducing a catalyst auxiliary agent into the furnace body through the hollow cathode and the anode electrode by a conveyor, enabling the catalyst auxiliary agent to meet a locally molten catalyst melt through an electric arc area, further limiting the length of a nano catalyst evaporated from the catalyst melt by the catalyst auxiliary agent, preparing catalyst particles with the size of 0.5-6 nanometers, introducing carbon source mixed gas and the prepared catalyst nano particles, and performing catalytic pyrolysis to generate an oligowall carbon nano tube under the action of electric arc, wherein the oligowall carbon nano tube falls into a first collecting chamber;
s4) when the rotating and stretching direction of the catalyst melt is far away from the cathode and the anode along with the reaction, lifting the first arc-shaped scraper, pressing down the second arc-shaped scraper to enable coking attached to the surface of the melt to fall into the second collecting chamber, pressing down the first arc-shaped scraper when the rotating and stretching direction of the catalyst melt is close to the cathode and the anode, lifting up the second arc-shaped scraper to enable coke attached to the surface of the rotating melt to fall into the second collecting chamber, enabling the catalyst melt to be kept in a clean state all the time, and being beneficial to continuously generating catalyst nano particles for continuous growth.
Further, the S1) catalyst auxiliary agent is thiophene, dimethyl sulfoxide, carbon disulfide, sulfur powder, hydrogen sulfide, sulfur dioxide, ferrous sulfide, methanesulfonic acid, ferrous sulfate, tungsten sulfide, manganese sulfide, molybdenum sulfide or other sulfur-containing compounds or mixtures;
further, the number of revolutions of the catalyst melt in S1) is 6 to 360 revolutions per minute, the catalyst melt stretches no more than 100 times per minute, and the stretching distance is no less than 100mm.
Further, the preheating temperature of the carbon source mixed gas in the step S2) is 200-550 ℃; the synthesis unit is heated to 600-1600 ℃;
further, the mixed gas in the S2) is mixed gas of inert gas, reducing gas and water vapor, wherein the volume of the inert gas accounts for 20-65%, the volume of the reducing gas accounts for 30-65%, and the balance is water vapor; the carbon source mixed gas comprises carbon source gas, reducing gas and trace oxygen, wherein the volume ratio of the carbon source gas is 15-55%; the reducing gas is 30-84%, and the rest is oxygen.
For the process, the inert gas is selected from at least one of argon, nitrogen, helium, preferably argon; the reducing gas is at least one of hydrogen, carbon monoxide and ammonia.
The carbon source gas is preferably natural gas, methane, ethane, propane, butane, pentane, hexane, ethylene, propylene, aliphatic hydrocarbons, hydrocarbons having 1 to 10 carbon atoms, monocyclic or bicyclic aromatic hydrocarbons having condensed or isolated rings, and olefins C x H 2x Where x is 2, 3 or 4, the other gaseous hydrocarbons have at least one of a hydrocarbon with a high saturated vapor pressure, ethanol, anthracene or anthracene oil vapor.
The application has the beneficial effects that: by adopting the technical scheme, the device provided by the application adopts the rotating moving catalyst melt with the double scrapers to connect the double electrode direct current arc, catalyst nano particles with uniform size can be prepared continuously for preparing the oligowall carbon nano tube, the double scrapers in a low temperature area cooperate to remove coke enriched on the surface of the catalyst melt, the surface of the catalyst melt is kept clean, the catalyst is prevented from being deactivated by coking, and the uniform catalyst nano particles can be prepared continuously for growing the oligowall carbon nano tube. The coking materials fall into the coke collecting chamber at the lower end as much as possible through the scraping unit, and the lighter carbon nano materials fall into the product collecting chamber along with the airflow, so that the preliminary separation of products is realized, the pollution of the products by the coke rich in a large amount of iron particles is avoided, and the purity of the primary products is improved.
The cooling device is arranged in the catalyst melt to ensure that the rotating and moving catalyst melt always keeps local melting, large liquid drops are not formed and drop, the shape of the cylindrical melt is kept relatively stable, uniform nano catalyst particles are prepared, and the rotating and moving melt can compensate the temperature uniformity of the reaction melt caused by 2 times of the difference between the temperatures of the cathode and the anode of the double direct current electrodes.
The double electrodes can provide more high-temperature reaction regions for growth, and the bottomless anode effect can prolong the reaction time, improve the preparation efficiency, increase the productivity and achieve 1kg per hour.
The introduced trace water vapor and oxygen can play a role in etching and coking to a certain extent. Reduces the influence of coking accumulation on an air flow field, a thermal field and the preparation of a uniform catalyst so as to achieve the purpose of continuous and stable growth. Preparation of the product average Raman I G /I D Carbon nanotubes with high crystallinity of 45 or more and continuous stabilization time exceeding 100h.
The furnace body containing a long rotary movable catalyst melt can be additionally provided with a multi-combination unit, a scraping unit, a collecting unit and a blocking unit, so that the purpose of expanding the production unit is realized. Each group of production units grows 1kg per hour, 10kg per day can be produced, 3 production units can produce 30kg per day, and theoretically 34 days of productivity can reach ton-level preparation, so that the preparation of the oligoarm carbon nanotubes can break through ton-level production.
The gaseous carbon source of the device passes through the high-temperature area of the plasma arc core, and because catalyst particles with different scales exist, a part of the gaseous carbon source is cracked in advance under the action of a large-particle catalyst to form solid high-crystallinity carbon and a high-crystallinity carbon-coated iron structure, and the lower end of a hollow electrode gun is coked and slowly covered on the surface of a melt, so that the continuous preparation of the catalyst with nanometer size can be influenced, the stability of the whole airflow field and an electric arc is further influenced, and the product generation is difficult to continue. The coking carbon can be slowly fused into the melt, so that the uniformity of the components of the melt is affected, and the activity of a catalyst prepared from the melt is greatly reduced by the fused high-crystallinity carbon, so that the catalytic cracking is affected to generate a product. Resulting in lower and lower levels of SWCNT in subsequent products, and product growth is not sustainable. Severely affecting the continuous stable production of the product.
The cathode electrode gun and the anode electrode gun in each synthesis unit follow the principle of the minimum resistance principle, and the cathode electrode gun and the anode electrode gun with the minimum resistance discharge, so the application limits the distance between each group of cathode electrode gun and anode electrode gun, and meanwhile, a scraping unit and a blocking unit are arranged between two synthesis units in the expandable production unit, and the distance is far. So that the cathodes and anodes of the multi-group synthesis units do not mutually discharge to affect the preparation of the catalyst nano particles, and the production units are mutually independent and do not mutually affect. The oligowall carbon nanotube refers to a carbon nanotube with the wall number of less than or equal to three walls, and comprises a single-wall carbon nanotube, a double-wall carbon nanotube and a three-wall carbon nanotube.
The synthesizing unit and the scraping unit are separated through the blocking unit, so that high requirements of high-temperature electric arcs on the temperature resistance of the scraping unit can be prevented, and the relative low-temperature environment of the scraping unit is maintained. On the other hand, the relatively stable air flow field and temperature field required by the synthesis unit can be ensured, and meanwhile, the product with the low wall is prevented from drifting into the scraping unit. With respect to the nanostructures obtained using the described methods and devices, they are involved in materials science, nanotechnology, plasma physics, application chemistry and many other most promising orientations, particularly in lithium ion batteries.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing an oligowall carbon nanotube by scalable arc discharge according to the present application.
Fig. 2 is a schematic diagram of the structure of the multi-synthesis unit after the expansion of the device of the present application.
Fig. 3 is a side view of a barrier unit and catalyst melt of the apparatus of the present application.
Fig. 4 is a schematic diagram of a scanning electron microscope of an oligowall carbon nanotube prepared in example 3 of the present application.
FIG. 5 is a schematic representation of thermogravimetric characterization of a tube wall carbon nanotube prepared using the apparatus of the present application in example 4 of the present application.
Fig. 6 is a schematic raman spectrum of the oligowall carbon nanotube prepared in example 3 of the present application.
Fig. 7 is a schematic diagram of a transmission electron microscope of an oligowall carbon nanotube prepared in example 3 of the present application.
FIG. 8 is a schematic representation of a transmission electron microscope of the coke product prepared in example 3 of the present application.
In the figure:
100. a furnace body; 110. a synthesizing unit; 111. a hollow cathode electrode gun; 112. a hollow anode electrode gun; 113. a hollow graphite electrode; 115. a carbon source mixed gas injection pipe; 130. a preheater; 150. a conveyor; 170. a blocking unit; 190. a driving unit; 210. a catalyst melt; 211. a cooling unit; 220. a scraping unit; 221. a first arc scraper; 222. a second arc scraper; 223. a first driving motor; 224. a second driving motor; 225. a controller; 330. a collection unit; 331. a first collection chamber; 332. a second collection chamber; 333. a transition chamber.
Detailed Description
The technical scheme of the application is further described below with reference to the accompanying drawings and specific embodiments.
In order to solve the problems existing in the prior art, the application adopts the following technical scheme: an apparatus for preparing an oligowall carbon nanotube by extensible arc discharge.
As shown in fig. 1, an apparatus for preparing oligowall carbon nanotubes by arc discharge according to the present application comprises: furnace body 100, preheater 130, conveyor 150, collection unit 330, a synthesis unit 110, a scraping unit 220, a blocking unit 170, catalyst melt 210 and drive unit 190;
wherein the scraping unit 220 and the synthesizing unit 110 are disposed at an upper end of the inside of the furnace body 100 with a certain interval, the blocking unit 170 is disposed between the scraping unit 220 and the synthesizing unit 110, and the catalyst melt 210 is disposed inside the furnace body 100 below the scraping unit 220 and the synthesizing unit 110; a side view of the barrier unit and catalyst melt is shown in fig. 3.
The driving unit 190 is disposed outside one side of the furnace body 100, and is fixedly connected to one end of the catalyst melt through a connecting shaft, so as to drive the catalyst melt 210 to rotate and move in a telescopic manner;
the catalyst promoter conveyor 150 and the preheater 130 are both connected to the synthesis unit 110.
The synthesis unit includes: a hollow cathode electrode gun 111, a hollow anode electrode gun 112, a hollow graphite electrode 113, and a carbon source mixture gas injection tube 115;
the collecting unit 330 is divided into a first collecting chamber 331, a second collecting chamber 332 for mainly recovering the carbon nano tube products with the low wall and mainly recovering the coke, the first collecting chamber is positioned under the synthesizing unit, the second collecting chamber is positioned under the scraping unit, and the collecting chambers are all provided with transition chambers 333.
Wherein one ends of the hollow cathode electrode gun 111 and the hollow anode electrode gun 112 are inserted into the furnace body from the top of the furnace body 100, and a certain distance is formed between the hollow cathode electrode gun 111 and the hollow anode electrode gun 112; the other ends of the hollow cathode electrode gun and the hollow anode electrode gun are respectively connected with the preheater 130 and the conveyor 150;
the carbon source mixture gas injection pipe 115 is disposed between the hollow cathode electrode gun 111 and the hollow anode electrode gun 112, and is connected to the preheater 130.
The scraping unit 220 includes: a first arc blade 221, a second arc blade 222, a first driving motor 223, a second driving motor 224, and a controller 225;
wherein, the first driving motor 223 and the second driving motor 224 are disposed at the top of the furnace body 100 and are respectively connected with the first arc-shaped scraper 221 and the second arc-shaped scraper 222 through connecting shafts, and the controller 225 is respectively connected with the first driving motor and the second driving motor.
The blocking unit 170 is a middle circular hole plate, the center of the circle is concentric with the catalyst melt 210, one end of the middle circular hole plate is fixedly connected with the top of the furnace body, and the distance d between the end of the other end of the middle circular hole plate and the surface of the catalyst melt 210 is 10-100mm;
the middle round hole plate is made of refractory metal tungsten, tantalum-iron alloy, magnesium-carbon material, corundum material or graphite. A side view of the barrier unit and catalyst solution is shown in fig. 3.
The catalyst melt 210 is a hollow metal cylinder with the diameter not smaller than 30cm, and a cooling unit 211 is arranged inside the hollow metal cylinder; the electrode core distance D of the hollow cathode and the anode electrode is 50-350mm.
The catalyst melt 210 is an iron-containing compound or mixture for forming a plasma arc between two parallel sets of electrodes, and is formed into a cylindrical shape by pressing, and comprises at least one of nickel, cobalt, iron carbide, iron carboxyl, iron carbonyl, cobalt, nickel alloy, tungsten, tantalum, rhenium, molybdenum, yttrium, lanthanum, and dysprosium.
As shown in fig. 2, the structure of the expanded multi-synthesis unit of the device of the present application is schematically shown, the device adopts 3 synthesis units 110 and 3 scraping units 220 which are sequentially equidistantly arranged, a blocking unit 170 is disposed between each synthesis unit 110 and each scraping unit 220, the 3 synthesis units 110 share one catalyst melt 210, a collection unit 330 is disposed below each synthesis unit 110 and each scraping unit 220, and a transition chamber 333 is disposed at the bottom of each collection unit 330.
Another object of the present application is to provide a method for preparing single-walled carbon nanotubes using the above apparatus, which specifically comprises the following steps:
s1) placing the cocatalyst in a conveyor 150, and introducing inert gas to empty the furnace body 100;
s2) starting a plasma arc to be conducted through the catalyst melt 210, starting the driving unit 190 to rotate and stretch the catalyst melt, and starting the preheater 130 to preheat the mixed gas and the carbon source mixed gas;
s3) quantitatively introducing a catalyst auxiliary agent into the furnace body through the hollow cathode electrode gun 111 and the hollow anode electrode 112 by the conveyor 150, wherein the catalyst auxiliary agent meets the locally molten catalyst melt 210 through an electric arc area, the length of a nano catalyst evaporated from the catalyst melt is further limited by the catalyst auxiliary agent, the nano catalyst is used for preparing catalyst particles of 0.5-6 nanometers, and the carbon source mixed gas and the prepared catalyst nano particles are subjected to catalytic pyrolysis under the action of electric arc to generate oligowall carbon nano tubes which fall into the first collecting chamber 331;
s4) when the rotation and expansion direction of the catalyst melt 210 is far away from the cathode and the anode along with the reaction, the first arc-shaped scraper 221 is lifted, the second arc-shaped scraper 222 is pressed down, so that coking adhering to the surface of the melt is scraped off and falls into the second collecting chamber 332, when the rotation and expansion direction of the catalyst melt is close to the cathode and the anode, the first arc-shaped scraper 221 is pressed down, the second arc-shaped scraper 222 is lifted, so that coke adhering to the surface of the rotating melt falls into the second collecting chamber, the catalyst melt is kept in a clean state all the time, and continuous generation of catalyst nano particles for continuous growth is facilitated.
The S1) catalyst auxiliary agent is thiophene, dimethyl sulfoxide, carbon disulfide, sulfur powder, hydrogen sulfide, sulfur dioxide, ferrous sulfide, methanesulfonic acid, ferrous sulfate, tungsten sulfide, manganese sulfide, molybdenum sulfide or other sulfur-containing compounds or mixtures;
the number of revolutions of the catalyst melt 210 in S1) is 6-360 revolutions per minute, the catalyst melt stretches no more than 100 times per minute, and the stretching distance is no less than 100mm.
The preheating temperature of the carbon source mixed gas in the S2) is 200-550 ℃; the synthesis unit 110 is heated to 600-1600 ℃;
the mixed gas in the S2) is mixed gas of inert gas, reducing gas and water vapor, wherein the volume of the inert gas accounts for 20-65%, the volume of the reducing gas accounts for 30-65%, and the balance is water vapor; the carbon source mixed gas comprises carbon source gas, reducing gas and trace oxygen, wherein the volume ratio of the carbon source gas is 15-55%; the reducing gas is 30-84%, and the rest is oxygen.
For the process, the inert gas is selected from at least one of argon, nitrogen, helium, preferably argon; the reducing gas is at least one of hydrogen, carbon monoxide and ammonia.
The carbon source gas is preferably natural gas, methane, ethane, propane, butane, pentane, hexane, ethylene, propylene, aliphatic hydrocarbons, hydrocarbons having 1 to 10 carbon atoms, monocyclic or bicyclic aromatic hydrocarbons having condensed or isolated rings, and olefins C x H 2x Where x is 2, 3 or 4, the other gaseous hydrocarbons have at least one of a hydrocarbon with a high saturated vapor pressure, ethanol, anthracene or anthracene oil vapor.
Example 1
Firstly, putting a cocatalyst thiophene into a conveyor, and introducing inert gas argon to empty a furnace body; then the plasma arc was started and heated to 960 ℃ by catalyst melt conduction, the hollow cathode and anode electrode core distance D being 120mm. The catalyst melt is a hollow metal cylinder containing iron and dysprosium, the diameter is 20cm, a cooling unit is arranged inside the hollow metal cylinder, the rotation number of the catalyst melt is 60 revolutions per minute, the catalyst melt stretches for 10 times per minute, and the stretching distance is 280mm.
Starting a preheater to preheat the mixed gas and the carbon source mixed gas, wherein the preheating temperature of the carbon source mixed gas is 350 ℃; the mixed gas is a mixed gas of inert gas, reducing gas and water vapor, wherein the inert gas is 65% of argon by volume, the reducing gas is 33% of hydrogen by volume, and the balance is water vapor. The carbon source mixed gas contains carbon source gas, reducing gas and trace oxygen, wherein the carbon source gas is natural gas with the volume ratio of 55.5%, the reducing gas is carbon monoxide with the volume ratio of 44%, and the other is oxygen.
The separation unit is a middle round hole plate made of tungsten, the center of the circle is concentric with the catalyst melt, and the distance d from the surface of the catalyst melt is 60mm. Catalyst particles of 0.5-6 nanometers are prepared, carbon source mixed gas and the prepared catalyst nano particles are introduced, and the catalyst nano particles are catalytically cracked under the action of an electric arc to generate the oligowall carbon nano tubes which fall into a first collecting chamber. When the direction of rotation and extension of the catalyst melt is far away from the cathode and the anode, the first arc-shaped scraper is lifted, the second arc-shaped scraper is pressed down, coking attached to the surface of the melt is scraped and falls into the second collecting chamber, when the direction of rotation and extension of the catalyst melt is close to the direction of the cathode and the anode, the first arc-shaped scraper is pressed down, the second arc-shaped scraper is lifted, coke attached to the surface of the rotating melt falls into the second collecting chamber, the catalyst melt is kept in a clean state all the time, and continuous generation of catalyst nano particles for continuous growth is facilitated.
From Table 2, it can be seen that the average I of the initial product obtained in example 1 G /I D The ratio is 35, the residual TG of the product is 47.6%, the initial product yield of the oligowall carbon nano tube is 0.73kg/h, and the continuous reaction time can reach 198 hours.
The device and the method can be beneficial to realizing continuous and effective obtaining of macro-quantity of the oligowall carbon nanotubes for a long time. Meanwhile, the method has similar effects on other similar reactors and has certain universality.
The Raman spectroscopy, thermogravimetric characterization method, scanning electron microscopy and energy dispersion X-ray spectrum characterization method, transmission electron microscopy characterization method and ultraviolet visible near infrared absorption spectrum characterization method standards of the high-quality oligowall carbon nanotube sample are disclosed in GB/T32871-2016, GB/T24490-2009, GB/T32869-2016, GB/T30134-2014 and GB/T39114-2020. The test protocols are described with reference to table 1.
Table 1 test protocol
| Technical specification of | Unit (B) | Evaluation method |
| Carbon tube content | wt％ | TEM，EDX，TGA |
| Number of carbon nanotube walls | / | TEM，EDX，TGA |
| Diameter of carbon nanotube | nm | Raman，TEM，NIR-Vis |
| I G /I D Ratio of | / | Raman |
| Specific surface area | m 2 /g | BET |
Example 2
The device and the process method of the embodiment 1 are characterized in that the cocatalyst is manganese sulfide, the furnace body is heated to 1160 ℃, and the electrode center distance D between the hollow cathode and the anode electrode is 280mm. The catalyst melt comprised a hollow metal cylinder of iron and molybdenum with a diameter of 30cm, a number of revolutions of the catalyst melt of 120 revolutions per minute, a telescoping distance of 360mm and 30 revolutions per minute. The preheating temperature of the carbon source mixed gas is 450 ℃, the mixed gas is that inert gas accounts for 35% of argon in volume, reducing gas accounts for 43% of hydrogen in volume, and the balance is water vapor. The carbon source gas in the carbon source mixed gas is methane with the volume ratio of 45%, the reducing gas is carbon monoxide with the volume ratio of 54%, and the other is oxygen. The separation unit is a middle round hole plate made of tantalum, and the distance d of the surface of the catalyst melt is 50mm.
From Table 2, it can be seen that the average I of the initial product obtained in example 2 G /I D The ratio is 48, the residual TG of the product is 35.3%, the initial product yield of the oligowall carbon nano tube is 0.89kg/h, and the continuous reaction time can reach 268 hours and exceeds 10 days.
Example 3
The apparatus and process used in example 2 was distinguished in that the promoter was methanesulfonic acid and the furnace was heated to 1550 ℃. The catalyst melt comprised a hollow metal cylinder of iron, nickel and yttrium with an outer diameter of 60cm and a number of revolutions per minute of the catalyst melt of 180 revolutions per minute.
The preheating temperature of the carbon source mixed gas is 550 ℃; the mixed gas is inert gas, the argon volume ratio is 40%, the reducing gas is hydrogen volume ratio is 55%, and the rest is water vapor. The carbon source mixed gas comprises carbon source gas, reducing gas and trace oxygen, wherein the carbon source gas is propylene, and the volume ratio of the carbon source gas to the propylene is 35.5%; the reducing gas is carbon monoxide with a volume ratio of 64%. The separation unit is a middle round hole plate made of corundum, and the distance d of the surface of the catalyst melt is 30mm.
FIG. 6 shows that the sample obtained in example 3 has a distinct and sharp RBM characteristic absorption peak at 180cm-1, i.e., the product contains single-walled carbon nanotubes, and the product I is calculated under the test condition of excitation wavelength of 532nm G /I D The ratio is 62, namely the prepared product contains high-quality single-wall carbon nanotubes, 21.8% of TG residues of the initial product are obtained from table 2, the surface impurities of the sample of example 3 are less as seen from a scanning electron microscope of fig. 4, the surface impurities are consistent with the characterization result of TG residues, the transmission electron microscope characterization of the prepared product of example 3 of fig. 7 shows that the product also contains obvious double-wall carbon nanotubes, and the transmission electron microscope characterization of the coked product collected by example 3 is shown that the coked product is mainly carbon spheres with the diameter of 50-300 nm. The initial product yield of the carbon nano tube with the oligowall is 1.1kg/h, the continuous reaction time can reach 267 hours, and the method is also suitable for the preparation of the nano tube with the oligowallOver 10 days.
Example 4
The apparatus and process used in example 3 was distinguished in that the promoter was methanesulfonic acid and the furnace was heated to 1350 ℃. The catalyst melt comprised a hollow metal cylinder of iron and lanthanum with an outer diameter of 40cm of catalyst melt and a number of revolutions per minute of catalyst melt of 240 revolutions per minute. Telescoping was performed 6 times per minute, with a telescoping distance of 500mm. The separation unit is a middle round hole plate made of magnesium carbon material, and the distance d of the surface of the catalyst melt is 15mm.
From FIG. 5, the product TG characterization of example 4 gave a residue of 19.5%, from which Table 2 the average I of the initial product obtained in example 4 can be seen G /I D The ratio is 65, the initial product yield of the oligowall carbon nano tube is 1.2kg/h, and the continuous reaction time can reach 245 hours and exceeds 10 days.
Example 5
The process of example 3 is adopted, except that the furnace body containing a long rotary movable catalyst melt is additionally provided with 3 combination units, a scraping unit, a collecting unit and a blocking unit, so that the purpose of the expandable production unit is realized, and the expandable production unit is shown in a form shown in figure 2. From Table 2, it can be seen that the average I of the initial product obtained in example 5 G /I D The ratio is 56, the product TG residue is 17.8%, the initial product yield of the oligowall carbon nano tube is 3.2kg/h, and calculated according to 10 hours of daily work, 3 production units can produce more than 30kg per day, and theoretically, the production capacity can reach ton-level preparation within 32 days, so that the oligowall carbon nano tube can break through ton-level production preparation, and the future can be expected.
Table 2 product index in examples
The above description of embodiments is only for aiding in the understanding of the method of the present application and its core ideas; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a preset error range, substantially achieving the technical effect. The description hereinafter sets forth a preferred embodiment for practicing the application, but is not intended to limit the scope of the application, as the description is given for the purpose of illustrating the general principles of the application. The scope of the application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as limited to other embodiments, and is capable of numerous other combinations, modifications and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein, either as a result of the foregoing teachings or as a result of the knowledge or technology of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the application are intended to be within the scope of the appended claims.
Claims (10)
1. An apparatus for scalable arc discharge preparation of oligowall carbon nanotubes, the apparatus comprising: furnace body, preheater, conveyer and collection unit, its characterized in that, the device still includes: at least one synthesis unit, at least one scraping unit, at least one blocking unit, a catalyst melt and a drive unit;
the separation unit is arranged in the furnace body to separate the furnace body into a left chamber and a right chamber, the scraping unit is arranged at the upper end of the left chamber, the synthesis unit is arranged at the upper end of the right chamber, and the catalyst melt is horizontally arranged in the furnace body and is positioned below the scraping unit and the synthesis unit;
the driving unit is arranged outside one side of the furnace body, fixedly connected with one end of the catalyst melt arranged in the furnace body through a connecting shaft and used for driving the catalyst melt to rotate and stretch;
the catalyst auxiliary agent conveyor and the preheater are arranged at the top of the outer side of the furnace body and are connected with the synthesis unit;
the collecting units are respectively arranged below the synthesizing unit and the scraping unit, and are connected with the bottom of the furnace body.
2. The apparatus according to claim 1, wherein the synthesizing unit comprises: a hollow cathode electrode gun, a hollow anode electrode gun, a hollow graphite electrode and carbon source mixed gas injection tube;
one ends of the hollow cathode electrode gun and the hollow anode electrode gun are inserted into the furnace body from the top of the furnace body, and a certain distance is reserved between the hollow cathode electrode gun and the hollow anode electrode gun; the other ends of the hollow cathode electrode gun and the hollow anode electrode gun are respectively connected with the preheater and the conveyor;
the carbon source mixed gas injection pipe is arranged between the hollow cathode electrode gun and the hollow anode electrode gun and is connected with the preheater;
the polar center distance D between the hollow cathode electrode gun and the hollow anode electrode gun is 50-350mm.
3. The device according to claim 1, wherein the scraping unit comprises: the device comprises a first arc scraper, a second arc scraper, a first driving motor, a second driving motor and a controller;
the first driving motor and the second driving motor are arranged at the top of the furnace body and are respectively connected with the first arc scraper and the second arc scraper through connecting shafts, and the controller is respectively connected with the first driving motor and the second driving motor.
4. The device according to claim 1, wherein the blocking unit is a plate with a round hole in the middle, the center of the round hole is concentric with the catalyst melt, one end of the plate is fixedly connected with the top of the furnace body, and the distance d between the end of the other end and the surface of the catalyst melt is 10-100mm;
the middle round hole plate is made of refractory metal tungsten, tantalum-iron alloy, magnesium-carbon material, corundum material or graphite.
5. The apparatus according to claim 2, wherein the catalyst melt is a hollow metal cylinder having a diameter of not less than 30cm, and a cooling unit is provided inside the hollow metal cylinder;
the catalyst melt is an iron-containing compound or mixture.
6. A method for preparing oligowall carbon nanotubes using the apparatus according to any one of claims 1-5, characterized in that the method comprises in particular the following steps:
s1) placing the cocatalyst in a conveyor, and introducing inert gas to empty the furnace body;
s2) starting a plasma arc to be conducted through the catalyst melt, starting a driving unit to enable the catalyst melt to rotate and stretch, and starting a preheater to preheat the mixed gas and the carbon source mixed gas;
s3) a certain amount of catalyst auxiliary agent enters the furnace body through the hollow cathode and the anode electrode, and meanwhile, the preheated carbon source mixed gas enters the furnace body;
the catalyst auxiliary agent is subjected to arc area and catalyst melt meeting, evaporated under the action of arc to obtain catalyst particles of 0.5-6 nanometers, and then the catalyst particles are mixed with a carbon source gas after catalytic pyrolysis to generate an oligowall carbon nanotube product;
s4) starting a scraping unit to scrape off the coking attached to the surface of the catalyst melt.
7. The method according to claim 6, wherein the S1) catalyst promoter is thiophene, dimethyl sulfoxide, carbon disulfide, sulfur powder, hydrogen sulfide, sulfur dioxide, ferrous sulfide, methanesulfonic acid, ferrous sulfate, tungsten sulfide, manganese sulfide, molybdenum sulfide or other sulfur-containing compounds or mixtures.
8. The method of claim 6, wherein the number of revolutions of the catalyst melt in S2) is from 6 to 360 revolutions per minute, the catalyst melt stretches no more than 100 times per minute, and the stretching distance is no less than 100mm.
9. The method according to claim 6, wherein the carbon source mixture preheating temperature in S2) is 200 to 550 ℃; the synthesis unit is heated to 600-1600 ℃.
10. The method according to claim 6, wherein the mixed gas in S2) comprises a mixed gas of inert gas, reducing gas and water vapor, wherein the inert gas accounts for 20-65% by volume, the reducing gas accounts for 30-65% by volume, and the balance is water vapor;
the carbon source mixed gas comprises carbon source gas, reducing gas and oxygen, wherein the volume ratio of the carbon source gas is 15-55%; the reducing gas is 30-84%, and the rest is oxygen.
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| CN202310833503.6A CN116672987A (en) | 2023-07-07 | 2023-07-07 | Device and method for preparing oligowall carbon nano tube by expandable arc discharge |
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| CN202310833503.6A CN116672987A (en) | 2023-07-07 | 2023-07-07 | Device and method for preparing oligowall carbon nano tube by expandable arc discharge |
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