CN111483998A - Carbon nano tube/oxide composite material and preparation method thereof - Google Patents
Carbon nano tube/oxide composite material and preparation method thereof Download PDFInfo
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- CN111483998A CN111483998A CN201910082419.9A CN201910082419A CN111483998A CN 111483998 A CN111483998 A CN 111483998A CN 201910082419 A CN201910082419 A CN 201910082419A CN 111483998 A CN111483998 A CN 111483998A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 31
- 229910002090 carbon oxide Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 62
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 239000000376 reactant Substances 0.000 claims abstract description 48
- 239000012159 carrier gas Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000003860 storage Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 28
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 229930192474 thiophene Natural products 0.000 claims description 15
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 11
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 9
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- 238000013329 compounding Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
Abstract
The invention discloses a carbon nano tube/oxide composite material and a preparation method thereof.A storage device of a tubular reactor device is filled with an oxide precursor, and a heating device is used for heating up the oxide precursor so as to ensure that the temperature of a vertical tube is raised to 1100-1350 ℃ and the temperature of a horizontal tube is raised to 800-900 ℃; the tail gas outlet of the tubular reactor device is opened, and the carbon tube reactant, water and the first carrier gas are simultaneously input through the first input port, wherein the input speed of the carbon tube reactant is 3-20 ml/h, the input speed of the water is 1-10 ml/h, and the input speed of the first carrier gas is 50-2000 sccm.
Description
Technical Field
The invention belongs to the technical field of carbon nanotube/oxide composite materials, and particularly relates to a carbon nanotube/oxide composite material and a preparation method thereof.
Background
Carbon Nanotubes (CNTs) have high strength, high conductivity, and multifunctional properties. The carbon tube is compounded with oxide with functional characteristics and the carbon tube to prepare the composite material with functional characteristics, which can be used as energy storage, photoelectric materials, sensitive materials and the like. At present, the carbon tube oxide is compounded by the prepared carbon tube and the carbon tube. The carbon tubes are difficult to disperse and uniform compounding is difficult to achieve.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a carbon nano tube/oxide composite material, the preparation method is based on a floating catalysis method, the one-step compounding is carried out on a carbon tube which grows in a floating gas phase, the uniform compounding is realized, and the preparation method has the characteristics of one step and no need of subsequent treatment for dispersing the carbon tube.
It is another object of the present invention to provide a tubular reactor apparatus for carrying out the above-mentioned preparation method.
The purpose of the invention is realized by the following technical scheme.
A tubular reactor apparatus comprising: the device comprises a vertical pipe, a horizontal pipe, a storage device and a product collecting box, wherein the vertical pipe is vertically arranged, the horizontal pipe is horizontally arranged, the bottom end of the vertical pipe is communicated with the top end of the product collecting box, a tail gas outlet is formed in the product collecting box, one end of the horizontal pipe is communicated with the side wall of the vertical pipe, the other end of the horizontal pipe is provided with a second input port, and heating devices are arranged around the vertical pipe and the horizontal pipe and used for heating the vertical pipe and the horizontal pipe;
the top end of the vertical pipe is closed and is provided with a first input port;
storage device is a sealed jar body storage device installs the first zone of heating that is used for this storage device heating outward, the second input port pass through the pipeline with storage device intercommunication storage device is last to be formed with a third input port.
In the above technical solution, the method further comprises: the first T-shaped pipe is composed of a first vertical pipe and a first transverse pipe, one end of the first transverse pipe is communicated with the side wall of the first vertical pipe, so that the first T-shaped pipe is provided with three mutually communicated ports, and one port of the first T-shaped pipe is communicated with the first input port.
In the above technical solution, the method further comprises: and a second T-shaped pipe with the same structure as the first T-shaped pipe, wherein one port of the second T-shaped pipe is communicated with the third input port.
In the above technical solution, the heating device installed around the vertical pipe is a second heating layer.
In the above technical scheme, the heating device installed around the horizontal pipe is a third heating layer.
The use method of the tubular reactor device comprises the following steps:
1) putting a first reactant into a storage device, and heating by a heating device to ensure that the temperature of the vertical pipe and the temperature of the horizontal pipe are respectively increased;
2) opening a tail gas outlet, and simultaneously inputting a second reactant and a first carrier gas through the first input port; the first heating layer heats the storage device, and a second carrier gas is input into the storage device through the third input port.
A preparation method of a carbon nano tube/oxide composite material comprises the following steps:
1) putting an oxide precursor into a storage device of a tubular reactor device, heating by a heating device to raise the temperature of the vertical tube to 1100-1350 ℃ and the temperature of the horizontal tube to 800-900 ℃, wherein the oxide precursor is a mixture of a precursor reactant and water, and the ratio of the precursor reactant to the water is (0.1-8) in parts by volume: 1;
in the step 1), the precursor reactant is titanium tetrachloride and/or tin tetrachloride.
In the step 1), when the precursor reactant is a mixture of titanium tetrachloride and tin tetrachloride, the ratio of the titanium tetrachloride to the tin tetrachloride is 1: 1.
in the step 1), the precursor reactant is manganese nitrate.
2) Opening a tail gas outlet of the tubular reactor device, and simultaneously inputting a carbon tube reactant, water and a first carrier gas through the first input port, wherein the input speed of the carbon tube reactant is 3-20 ml/h, the input speed of the water is 1-10 ml/h, and the input speed of the first carrier gas is 50-2000 sccm, wherein the carbon tube reactant is a mixture of a carbon source, a catalyst and an additive, the carbon source is a liquid or gaseous hydrocarbon, the catalyst is a transition metal group organic salt or inorganic salt, and the additive is thiophene and/or water;
the first heating layer is heated to enable the storage device to be heated to 50-120 ℃, second carrier gas is input into the storage device through the third input port, and the input speed of the second carrier gas is 50-2000 sccm.
In the step 2), the ratio of the carbon source, the catalyst and the additive is (80-96) by mass: (1-3): (0.5 to 50).
In the step 2), the carbon tube reactant is a mixture obtained by uniformly mixing ethanol, ferrocene and thiophene, and the ratio of ethanol, ferrocene and thiophene is 93.75: 3: 0.5;
in the step 2), the ethanol, the ferrocene and the thiophene are uniformly mixed, and ultrasonic treatment is carried out for at least 10min after the ethanol, the ferrocene and the thiophene are mixed.
In the above technical solution, the first carrier gas and the second carrier gas are argon, nitrogen and/or helium.
The carbon nano tube/oxide composite material obtained by the preparation method.
Compared with the prior art, the tubular reactor device and the preparation method of the carbon nanotube/oxide composite material based on the tubular reactor device can improve the uniformity of the carbon nanotube/oxide composite material. The preparation method is based on the floating catalysis method preparation process, and the one-step compounding is carried out on the carbon tube which grows in a gas phase in a floating mode, so that the uniform compounding is realized. The preparation method has the advantages of one-step performance and no need of subsequent treatment for dispersing the carbon tube.
Drawings
FIG. 1 is a schematic diagram of the structure of a tubular reactor apparatus according to the present invention;
FIG. 2 is an optical photograph of a carbon nanotube/oxide composite material obtained in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of a carbon nanotube/oxide composite obtained in example 2 of the present invention;
FIG. 4 is a transmission electron microscope image of a carbon nanotube/oxide composite obtained in example 2 of the present invention;
FIG. 5 is a transmission electron microscope image of a carbon nanotube/oxide composite material obtained in example 3 of the present invention;
FIG. 6 is an optical photograph of a carbon nanotube/oxide composite obtained in example 4 of the present invention.
Wherein, 1 is the product collecting box, 2 is the third zone of heating, 3 is horizontal pipe, 4 is the pipeline, 5 is storage device, 6 is first zone of heating, 7 is the second T-pipe, 7-1 is the horizontal pipe of second, 7-2 is the second standpipe, 8 is the first T-pipe, 8-1 is the first violently pipe, 8-2 is the first standpipe, 9 is vertical pipe, 10 is the second zone of heating, 11 is the tail gas export.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Example 1
As shown in fig. 1, the tubular reactor apparatus of the present invention comprises: the device comprises a vertical pipe 9, a horizontal pipe 3, a storage device 5, a first T-shaped pipe 8, a second T-shaped pipe 7 and a product collecting box 1, wherein the vertical pipe 9 is vertically arranged, the horizontal pipe 3 is horizontally arranged, the bottom end of the vertical pipe 9 is communicated with the top end of the product collecting box 1, a tail gas outlet 11 is formed in the product collecting box 1, one end of the horizontal pipe 3 is communicated with the side wall of the vertical pipe 9, the other end of the horizontal pipe is provided with a second input port, heating devices are arranged around the vertical pipe 9 and the horizontal pipe 3 and used for heating the vertical pipe 9 and the horizontal pipe 3, the heating devices arranged around the vertical pipe 9 are a second heating layer 10, and the heating devices arranged around the horizontal pipe 3 are a third heating layer 2.
The storage device 5 is a closed tank body, a first heating layer 6 for heating the storage device 5 is arranged outside the storage device 5, the second input port is communicated with the storage device 5 through a pipeline 4, and a third input port is formed in the storage device 5.
The top end of the vertical tube 9 is closed and is provided with a first input port;
the first t-pipe 8 is composed of a first vertical pipe 8-2 and a first horizontal pipe 8-1, one end of the first horizontal pipe 8-1 is communicated with the side wall of the first vertical pipe 8-2, so that the first t-pipe 8 has three ports which are communicated with each other, and one port of the first vertical pipe 8-2 is communicated with the first input port.
The second t-pipe 7 is identical in structure to the first t-pipe 8, namely: the second t-pipe 7 is composed of a second vertical pipe 7-2 and a second horizontal pipe 7-1, one end of the second horizontal pipe 7-1 is communicated with the side wall of the second vertical pipe 7-2, so that the second t-pipe 7 has three mutually communicated ports, and one port of the second vertical pipe 7-2 is communicated with the third input port.
The experimental operation of the following examples was carried out based on the tubular reactor apparatus of example 1.
In the following examples, the first carrier gas and the second carrier gas are both argon.
Example 2
A preparation method of a carbon nano tube/oxide composite material comprises the following steps:
1) and injecting an oxide precursor into the storage device 5 through an upper end port of the second vertical pipe 7-2, wherein the oxide precursor is a mixture of a precursor reactant and water, the ratio of the precursor reactant to the water is 0.2:1 according to the volume parts, and the precursor reactant is titanium tetrachloride. The second heating layer 10 and the third heating layer 2 are heated up, respectively, so that the temperature of the vertical tube 9 is raised to 1170 ℃ and the temperature of the horizontal tube 3 is raised to 800 ℃.
2) And opening the tail gas outlet 11, and simultaneously inputting the carbon tube reactant, water and first carrier gas through the first input port, wherein the carbon tube reactant and the water are input through the upper end port of the first vertical tube 8-2, the first carrier gas is input through the port of the first transverse tube 8-1, the input speed of the carbon tube reactant is 9ml/h, the input speed of the water is 6ml/h, and the input speed of the first carrier gas is 200 sccm. The carbon tube reactant is a mixture (yellow liquid) obtained by mixing ethanol (carbon source), ferrocene (catalyst) and thiophene (additive) and performing ultrasonic treatment for 10min, and the ratio of the ethanol to the ferrocene to the thiophene is 93.75: 3: 0.5. the carbon tube reactant enters the vertical tube 9 under the driving of the first carrier gas and is pyrolyzed in the airflow of the vertical tube 9 to form carbon tubes.
The first heating layer 6 is heated to heat the storage device 5 to 80 ℃, the oxide precursor is bubbled, a second carrier gas is input into the storage device 5 through a port of the second transverse pipe 7-1, the input speed of the second carrier gas is 200sccm, and the second carrier gas drives the steam of the oxide precursor to enter the horizontal pipe 3.
At high temperature, titanium tetrachloride reacts with water vapor to form titanium oxide in a gas phase, the titanium oxide is directly compounded with carbon tubes in airflow to form a carbon nanotube/oxide composite material, then the carbon nanotube/oxide composite material enters a product collecting box 1 under the drive of the airflow, and tail gas formed by reaction is discharged through a tail gas outlet 11.
The carbon nanotube/oxide composite obtained in example 2 had a white fluffy cotton shape, and the optical photograph thereof is shown in fig. 2. The observation of the scanning electron microscope and the transmission electron microscope shows that the titanium oxide is uniformly coated on the surface of the carbon tube, as shown in fig. 3 and 4. The carbon tubes in the gas flow are in a dispersed state and are uniformly compounded with the titanium oxide formed by the reaction in the gas flow. Avoiding the complex carbon tube dispersion process in the traditional compounding process. Realizes one-step, high-efficiency and uniform compounding. The carbon tube/titanium oxide coaxial nano structure is obtained.
Example 3
A preparation method of a carbon nano tube/oxide composite material comprises the following steps:
1) and injecting an oxide precursor into the storage device 5 through an upper end port of the second vertical pipe 7-2, wherein the oxide precursor is a mixture of a precursor reactant and water, the ratio of the precursor reactant to the water is 0.5:1 according to the volume parts, and the precursor reactant is tin tetrachloride. The second heating layer 10 and the third heating layer 2 are heated up, respectively, so that the temperature of the vertical tube 9 is raised to 1170 ℃ and the temperature of the horizontal tube 3 is raised to 800 ℃.
2) And opening the tail gas outlet 11, and simultaneously inputting the carbon tube reactant, water and first carrier gas through the first input port, wherein the carbon tube reactant and the water are input through the upper end port of the first vertical tube 8-2, the first carrier gas is input through the port of the first transverse tube 8-1, the input speed of the carbon tube reactant is 9ml/h, the input speed of the water is 6ml/h, and the input speed of the first carrier gas is 200 sccm. The carbon tube reactant is a mixture (yellow liquid) obtained by mixing ethanol (carbon source), ferrocene (catalyst) and thiophene (additive) and performing ultrasonic treatment for 10min, and the ratio of the ethanol to the ferrocene to the thiophene is 93.75: 3: 0.5. the carbon tube reactant enters the vertical tube 9 under the driving of the first carrier gas and is pyrolyzed in the airflow of the vertical tube 9 to form carbon tubes.
The first heating layer 6 is heated to heat the storage device 5 to 80 ℃, the oxide precursor is bubbled, a second carrier gas is input into the storage device 5 through a port of the second transverse pipe 7-1, the input speed of the second carrier gas is 200sccm, and the second carrier gas drives the steam of the oxide precursor to enter the horizontal pipe 3.
At high temperature, tin tetrachloride reacts with water vapor to form tin oxide in a gas phase, the tin oxide is directly compounded with carbon tubes in air flow to form a carbon nano tube/oxide composite material, then the carbon nano tube/oxide composite material enters a product collecting box 1 under the drive of the air flow, and tail gas formed by reaction is discharged through a tail gas outlet 11.
The observation of the transmission electron microscope shows that the tin oxide is uniformly loaded on the surface of the carbon tube (figure 5). This shows that the carbon tubes in the gas phase can be directly recombined based on the gas phase recombination process realized by the process. The carbon tube grown in the gas phase is in a dispersed state, which is beneficial to loading tin oxide on the surface of the carbon tube. Compared with the subsequent tin oxide compounding, the method avoids the dispersion process of the carbon tube.
Example 4
A preparation method of a carbon nano tube/oxide composite material comprises the following steps:
1) and injecting an oxide precursor into the storage device 5 through the upper end port of the second vertical pipe 7-2, wherein the oxide precursor is a mixture of a precursor reactant and water, the ratio of the precursor reactant to the water is 0.3:1 in parts by volume, the precursor reactant is a mixture of tin tetrachloride and titanium tetrachloride, and the ratio of the tin tetrachloride to the titanium tetrachloride is 1:1 in parts by volume. The second heating layer 10 and the third heating layer 2 are heated up, respectively, so that the temperature of the vertical tube 9 is raised to 1170 ℃ and the temperature of the horizontal tube 3 is raised to 800 ℃.
2) And opening the tail gas outlet 11, and simultaneously inputting the carbon tube reactant, water and first carrier gas through the first input port, wherein the carbon tube reactant and the water are input through the upper end port of the first vertical tube 8-2, the first carrier gas is input through the port of the first transverse tube 8-1, the input speed of the carbon tube reactant is 9ml/h, the input speed of the water is 6ml/h, and the input speed of the first carrier gas is 200 sccm. The carbon tube reactant is a mixture (yellow liquid) obtained by mixing ethanol (carbon source), ferrocene (catalyst) and thiophene (additive) and performing ultrasonic treatment for 10min, and the ratio of the ethanol to the ferrocene to the thiophene is 93.75: 3: 0.5. the carbon tube reactant enters the vertical tube 9 under the driving of the first carrier gas and is pyrolyzed in the airflow of the vertical tube 9 to form carbon tubes.
The first heating layer 6 is heated to heat the storage device 5 to 80 ℃, the oxide precursor is bubbled, a second carrier gas is input into the storage device 5 through a port of the second transverse pipe 7-1, the input speed of the second carrier gas is 200sccm, and the second carrier gas drives the steam of the oxide precursor to enter the horizontal pipe 3.
At high temperature, tin tetrachloride reacts with water vapor to form tin oxide in a gas phase, titanium tetrachloride reacts with the water vapor to form titanium oxide in the gas phase, the tin oxide and the titanium oxide are directly compounded with carbon tubes in air flow to form a carbon nano tube/oxide composite material, then the carbon nano tube/oxide composite material enters a product collecting box 1 under the drive of the air flow, and tail gas formed by the reaction is discharged through a tail gas outlet 11.
An optical photograph of the carbon nanotube/oxide composite material obtained in example 4 is shown in fig. 6, and has a pale yellow fluffy cotton shape. Compared with example 1, the carbon nanotube/oxide composite material obtained in example 4 has a light yellow color due to the addition of tin oxide, unlike the white color of the carbon nanotube/oxide composite material obtained in example 1. The color of the whole product is uniform, which shows that the obtained carbon tube and tin oxide are uniformly compounded.
In the technical solution of the present invention, the technical effects consistent with the above embodiments can be achieved by changing the input speeds of the oxide precursor, the carbon tube reactant, the first carrier gas and the second carrier gas, the input speed of the carbon tube reactant, the input speed of water, and the heating temperature.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A method for preparing a carbon nano tube/oxide composite material is characterized in that,
the preparation method adopts a tubular reactor device, and the tubular reactor device comprises the following steps: the device comprises a vertical pipe (9), a horizontal pipe (3), a storage device (5) and a product collecting box (1), wherein the vertical pipe (9) is vertically arranged, the horizontal pipe (3) is horizontally arranged, the bottom end of the vertical pipe (9) is communicated with the top end of the product collecting box (1), a tail gas outlet (11) is formed in the product collecting box (1), one end of the horizontal pipe (3) is communicated with the side wall of the vertical pipe (9), the other end of the horizontal pipe is provided with a second inlet, and heating devices are arranged on the periphery of the vertical pipe (9) and the periphery of the horizontal pipe (3) and used for heating the vertical pipe (9) and the horizontal pipe (3);
the top end of the vertical pipe (9) is closed and is provided with a first input port;
the storage device (5) is a closed tank body, a first heating layer (6) used for heating the storage device (5) is installed outside the storage device (5), the second input port is communicated with the storage device (5) through a pipeline (4), and a third input port is formed in the storage device (5);
the preparation method of the carbon nano tube/oxide composite material comprises the following steps:
1) putting an oxide precursor into a storage device (5) of a tubular reactor device, and heating by a heating device to raise the temperature of the vertical tube (9) to 1100-1350 ℃ and the temperature of the horizontal tube (3) to 800-900 ℃, wherein the oxide precursor is a mixture of a precursor reactant and water, and the ratio of the precursor reactant to the water is (0.1-8) in parts by volume: 1;
2) opening a tail gas outlet (11) of the tubular reactor device, and simultaneously inputting a carbon tube reactant, water and a first carrier gas through the first input port, wherein the input speed of the carbon tube reactant is 3-20 ml/h, the input speed of the water is 1-10 ml/h, the input speed of the first carrier gas is 50-2000 sccm, the carbon tube reactant is a mixture of a carbon source, a catalyst and an additive, the carbon source is a liquid or gaseous hydrocarbon, the catalyst is a transition metal group organic salt or inorganic salt, and the additive is thiophene and/or water;
the first heating layer (6) is heated to enable the storage device (5) to be heated to 50-120 ℃, a second carrier gas is input into the storage device (5) through the third input port, and the input speed of the second carrier gas is 50-2000 sccm.
2. The method according to claim 1, wherein in the step 1), the precursor reactant is titanium tetrachloride and/or tin tetrachloride, and when the precursor reactant is a mixture of titanium tetrachloride and tin tetrachloride, the ratio of titanium tetrachloride to tin tetrachloride is 1: 1.
3. the method of claim 1, wherein in step 1), the precursor reactant is manganese nitrate.
4. The production method according to claim 2 or 3, characterized by further comprising: the first T-shaped pipe (8), the first T-shaped pipe (8) is composed of a first vertical pipe (8-2) and a first transverse pipe (8-1), one end of the first transverse pipe (8-1) is communicated with the side wall of the first vertical pipe (8-2), so that the first T-shaped pipe (8) is provided with three mutually communicated ports, and one port of the first T-shaped pipe (8) is communicated with the first input port.
5. The method of claim 4, further comprising: and a second T-shaped pipe (7) with the same structure as the first T-shaped pipe (8), wherein one port of the second T-shaped pipe (7) is communicated with the third input port.
6. The method for preparing according to claim 5, characterized in that the heating means installed around the riser (9) is a second heating layer (10); and the heating device arranged around the horizontal pipe (3) is a third heating layer (2).
7. The preparation method according to claim 6, wherein in the step 2), the ratio of the carbon source, the catalyst and the additive is (80-96) in parts by mass: (1-3): (0.5 to 50).
8. The preparation method according to claim 7, wherein in the step 2), the carbon tube reactant is a mixture obtained by uniformly mixing ethanol, ferrocene and thiophene, and the ratio of ethanol, ferrocene and thiophene is 93.75: 3: 0.5; and uniformly mixing the ethanol, the ferrocene and the thiophene, and then carrying out ultrasonic treatment for at least 10 min.
9. The method of claim 8, wherein the first and second carrier gases are argon, nitrogen and/or helium.
10. The carbon nanotube/oxide composite material obtained by the production method according to any one of claims 1 to 9.
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| WO2003066521A1 (en) * | 2002-02-07 | 2003-08-14 | Carbon Nanotech Research Institute Inc. | Method and apparatus for producing fine carbon material |
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| WO2003066521A1 (en) * | 2002-02-07 | 2003-08-14 | Carbon Nanotech Research Institute Inc. | Method and apparatus for producing fine carbon material |
| CN1982212A (en) * | 2005-12-16 | 2007-06-20 | 细美事有限公司 | Device and method for synthesizing carbon nanotube |
| CN102358939A (en) * | 2011-07-15 | 2012-02-22 | 天津大学 | Method for preparing oxide/carbon tube composite nanomaterial |
| CN102583321A (en) * | 2012-03-05 | 2012-07-18 | 天津大学 | High-specific surface area carbon nanotube/oxide composite membrane and preparation method thereof |
| US20160016143A1 (en) * | 2014-07-16 | 2016-01-21 | Korea Institute Of Energy Research | APPARATUS FOR MANUFACTURING Si-BASED NANO-PARTICLES USING PLASMA |
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