Method for preparing porous ceramic microtubes loaded with carbon nanotubes and reactor device for loading carbon

Abstract

The present application relates to a kind of porous ceramic microtubule of carbon nanometer rough pipe load preparation method and its reactor equipment when loading carbon, including methane, propane, acetylene inputer, first to third regulating valve, hydrogen inputer, nitrogen or argon inputer, ceramic tube, reaction kettle, screen, heater and temperature sensor;The outlet of methane gas ware is communicated with the inlet of first regulating valve, the outlet of hydrogen inputer is communicated with the inlet of second regulating valve, the outlet of nitrogen or argon inputer is communicated with the inlet of third regulating valve;Screen is installed in reaction kettle and is divided into lower gas inlet area and upper reaction area by screen, and lower gas inlet area is communicated with upper reaction area by the mesh of screen.It has the advantage that carbon nanometer tube is grown under atmospheric pressure, carbon nanometer tube has the advantage, porosity and honeycomb ceramic specific surface are large, can be used for preparing hydrogen, removing heavy metal and other fields, processing equipment structure is compact, processing difficulty is small, and it is advantageous to popularization and other advantages.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of porous ceramic microtubule of carbon nanometer rough pipe load preparation method and its reactor equipment when being used for carbon load. BACKGROUND

[0002] At present, carbon nanotube has excellent electrical and mechanical properties, and is considered as the ideal additive phase of composite material. Carbon nanotube has great application potential in nanocomposite field as reinforcing phase and conductive phase. Carbon nanotube has very high surface area ratio, and the specific surface area of carbon nanotube is 250-3000 m 2 / g according to diameter and dispersion degree. In addition to excellent electrical conductivity and good mechanical properties, carbon nanotube is the ideal material required in electrochemical field, and is the ideal material for manufacturing electrode of electrochemical double-layer capacitor supercapacitor. Carbon nanotube has great development potential in hydrogen storage and hydrogen production application field. However, carbon nanotube grown at atmospheric pressure has imperfect crystal shape and shape, cannot completely cover honeycomb ceramic, processing equipment is relatively complex, processing technology is complicated, and processing difficulty is large, which is not conducive to popularization. SUMMARY

[0003] The present application aims to overcome the deficiencies of the prior art and provide a kind of porous ceramic microtubule of carbon nanometer rough pipe load preparation method and its reactor equipment when being used for carbon load. Carbon nanotube is grown at atmospheric pressure, and the advantages of carbon nanotube, large porosity and specific surface area of honeycomb ceramic can be used for hydrogen production, removal of heavy metals and other fields. The structure of processing equipment is compact, the processing difficulty is small, and it is conducive to popularization.

[0004] To achieve the above-mentioned purpose, the first technical solution of the technical scheme of the present application is realized

[0005] , which is a kind of porous ceramic microtubule of carbon nanometer rough pipe load preparation method, characterized by comprising:

[0006] Step one

[0007] Mixing nickel oxide or iron oxide or aluminum oxide or cerium oxide or mixture of the above materials with 3YSZ yttrium oxide

[0008] Stable zirconium oxide to obtain mixture a, and the mixing ratio is 6:4-5:5. Add pore forming agent or carbon ball to mixture b, and the weight ratio of pore forming agent or carbon ball to mixture b is 10-15%. Mixture b is extruded into shape, and sintered at 1400-1600 ℃ for 2-3 h to obtain ceramic tube with porosity of 20%±5%;

[0009] Step two

[0010] Immerse ceramic tube in slurry, and coat zirconium oxide film on the outer wall of ceramic tube;

[0011] Step three

[0012] Put the coated ceramic tube into the screen in the reactor device used for loading carbon, and heat the reactor. When the temperature of the reactor is 650-700 DEG C, open the second regulating valve to pass hydrogen into the reactor. The hydrogen enters the inner wall of the ceramic tube to perform reduction reaction for 1-1.5 hours, and nickel or iron or aluminum or cerium or the mixture of the above is generated on the inner wall of the ceramic tube. At this time, the porosity of the inner wall of the ceramic tube becomes 30-35% because the oxygen ions on the inner wall of the ceramic tube are taken away by the hydrogen.

[0013] Step four

[0014] Pass hydrogen and methane or propane or acetylene into the ceramic tube after the reduction reaction, the molar ratio of hydrogen to carbon-containing gas is 1:3-1:4, the temperature is kept at 650-700 DEG C, and the heat preservation time is 4-6 hours. Carbon nanotubes are grown on the inner wall of the ceramic tube.

[0015] Step five

[0016] Pass nitrogen or argon into the reactor to cool to normal temperature, and take out the carbon-loaded honeycomb ceramic.

[0017] In the technical solution, the hole density of the screen is one hole per 1±0.5 cm, the screen

[0018] The hole diameter of the screen is 200-250 um, and the tube diameter of the ceramic tube is 5.7-6.0 mm.

[0019] In order to achieve the above purpose, the second technical solution of the technical solution of the present application is implemented

[0020] , which is a preparation method of a carbon-loaded porous ceramic microtube, and the reactor device used for loading carbon, characterized by comprising:

[0021] a methane, propane and acetylene input device, a first regulating valve, a hydrogen input device, a second regulating valve, a nitrogen or argon input device and a third regulating valve; the outlet of the methane, propane and acetylene input device is communicated with the inlet of the first regulating valve, the outlet of the hydrogen input device is communicated with the inlet of the second regulating valve, and the outlet of the nitrogen or argon input device is communicated with the inlet of the third regulating valve; and

[0022] a ceramic tube, a reactor and a screen; the screen is installed in the reactor to divide the reactor into a lower gas inlet area and an upper reaction area, the lower gas inlet area is communicated with the upper reaction area through the mesh holes of the screen, a reaction gas inlet is arranged at the lower part of the lower gas inlet area, the reaction gas inlet is communicated with the outlets of the first regulating valve, the second regulating valve and the third regulating valve, the ceramic tube is placed on the screen and located in the upper reaction area, and the hole diameter of the ceramic tube is larger than the mesh hole diameter of the screen.

[0023] The heater is installed at the reaction kettle to heat the reaction kettle, and the probe of the temperature sensor is located in the reaction kettle to detect the temperature of the reaction kettle.

[0024] In the technical solution, the hole density of the screen is one hole per 1±0.5 cm, the hole density of the screen is 1-2 holes per 1 cm, and the hole density of the screen is 1-3 holes per 1 cm.

[0025] The pore size is 200-250 um, and the pipe diameter of the ceramic pipe is 5.7-6.0 mm.

[0026] In the technical solution, the material of the ceramic pipe is nickel oxide or iron oxide or aluminum oxide or oxygen

[0027] Cerium oxide or mixture of the above materials and 3YSZ yttrium-stabilized zirconium oxide mixture.

[0028] In the technical solution, a zirconium oxide film is coated on the outer wall of the ceramic pipe.

[0029] The advantages of the present application compared with the prior art are: carbon nanotubes are grown at atmospheric pressure, carbon nanotubes have advantages, porosity and specific surface area of honeycomb ceramic are large, can be used for preparing hydrogen, removing heavy metals and other fields, the processing equipment structure is compact, the processing difficulty is small, and it is beneficial to popularization. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a structural schematic diagram of the equipment of the present application;

[0031] Figure 2 is a top view of Figure 1 ;

[0032] Figure 3 is a sem graph after carbon of the present application is negative;

[0033] Figure 4 is another sem graph after carbon of the present application is negative. DETAILED DESCRIPTION

[0034] The specific embodiments of the present application will be further described below in combination with the drawings. It should be noted that the description of these embodiments is used to help understand the present application, but does not constitute a limitation on the present application. In addition, the technical features involved in the various embodiments of the present application described below can be combined with each other as long as they do not conflict with each other. EMBODIMENT

[0035] As shown in Figure 1 and Figure 4 , it is a method for preparing porous ceramic microtubes loaded with carbon nanometer rough tubes, which comprises the following steps:

[0036] Step one

[0037] Nickel oxide or iron oxide or aluminum oxide or cerium oxide or mixture of the above materials are mixed with 3YSZ yttrium oxide

[0038] Stable zirconium oxide is mixed to obtain mixture a, the mixing ratio is 6:4, or 5.5:4.5 or 5:5, mixture a is added to a pore-forming agent or carbon ball to obtain mixture b, the pore-forming agent or carbon ball accounts for 10% or 12.5% or 15% of the weight of mixture b, mixture b is extruded into a shape, and sintered at 1400°C or 1500°C or 1600°C for 2h or 2.5h or 3h to obtain a ceramic tube 9 with a porosity of 15% or 20% or 25%;

[0039] Step two

[0040] The ceramic tube 9 is immersed in slurry, and a zirconium oxide film is coated on the outer wall of the ceramic tube 9;

[0041] Step three

[0042] The ceramic tube 9 after coating is placed on the screen 3 in the reaction kettle 2 of the reactor device used for loading carbon, and the heater 4 is used to heat the reaction kettle 2, when the temperature of the reaction kettle 2 is at 650°C or 675°C or 700°C, the second regulating valve 8 is opened to pass hydrogen into the reaction kettle 2, the hydrogen enters the inner wall of the ceramic tube 9 to carry out reduction reaction for 1h or 1.25h or 1.5h, nickel or iron or aluminum or cerium or the mixture of the above is generated on the inner wall of the ceramic tube 9, at this time, due to the hydrogen carrying away the oxygen ions on the inner wall of the ceramic tube 9, the porosity of the inner wall of the ceramic tube 9 becomes 30% or 32.5% or 35%;

[0043] Step four

[0044] Hydrogen and methane or propane or acetylene are passed into the ceramic tube 9 after reduction reaction, the molar ratio of hydrogen to carbon-containing gas is 1:3 or 1:3.5 or 1:4, the temperature is kept at 650°C or 675°C or 700°C, and the temperature is kept for 4 hours or 5 hours or 6 hours, and carbon nanotubes grow on the inner wall of the ceramic tube 9;

[0045] Step five

[0046] Nitrogen or argon is passed into the reaction kettle 2, and the temperature is lowered to normal temperature, and the carbon-loaded honeycomb ceramic is taken out.

[0047] When used, the reaction device for loading carbon thereof comprises:

[0048] The methane, propane and acetylene inputter 5, the first regulating valve 6, the hydrogen inputter 7, the second regulating valve 8, the nitrogen or argon inputter 10 and the third regulating valve 11; the outlet of the methane, propane and acetylene inputter 5 is in communication with the inlet of the first regulating valve 6, the outlet of the hydrogen inputter 7 is in communication with the inlet of the second regulating valve 8, and the outlet of the nitrogen or argon inputter 10 is in communication with the inlet of the third regulating valve 11; and

[0049] A ceramic tube 9, a reaction vessel 2, and a screen 3 are provided. The screen 3 is installed in the reaction vessel 2, dividing it into a lower air inlet area 21 and an upper reaction area 22. The lower air inlet area 21 is connected to the upper reaction area 22 through the mesh of the screen 3. A reaction air inlet 211 is provided at the lower part of the lower air inlet area 21, and the reaction air inlet 211 is connected to the outlet of the first regulating valve 6, the outlet of the second regulating valve 8, and the outlet of the third regulating valve 11. The ceramic tube 9 is placed on the screen 3 and located in the upper reaction area 22. The aperture of the ceramic tube 9 is larger than the aperture of the screen 3.

[0050] Heater 4 and temperature sensor 1; the heater 4 is installed at the reactor 2 to heat the reactor 2, and the probe of the temperature sensor 1 is located in the reactor 2 to detect the temperature of the reactor 2.

[0051] In this embodiment, the sieve 3 has a pore density of one pore every 1 ± 0.5 cm.

[0052] The aperture is 200um, 225um, or 250um, and the diameter of the ceramic tube 9 is 5.7mm, 5.8mm, 5.9mm, or 6.0mm. Example

[0053] like Figure 1 and Figure 4 As shown, this is a method for preparing porous ceramic microtubes loaded with carbon nanotubes.

[0054] Reactor equipment used for carbon loading includes:

[0055] The system includes a methane, propane, and acetylene input device 5; a first regulating valve 6; a hydrogen input device 7; a second regulating valve 8; a nitrogen or argon input device 10; and a third regulating valve 11. The outlet of the methane, propane, and acetylene input device 5 is connected to the inlet of the first regulating valve 6; the outlet of the hydrogen input device 7 is connected to the inlet of the second regulating valve 8; and the outlet of the nitrogen or argon input device 10 is connected to the inlet of the third regulating valve 11.

[0056] A ceramic tube 9, a reaction vessel 2, and a screen 3 are provided. The screen 3 is installed in the reaction vessel 2, dividing it into a lower air inlet area 21 and an upper reaction area 22. The lower air inlet area 21 is connected to the upper reaction area 22 through the mesh of the screen 3. A reaction air inlet 211 is provided at the lower part of the lower air inlet area 21, and the reaction air inlet 211 is connected to the outlet of the first regulating valve 6, the outlet of the second regulating valve 8, and the outlet of the third regulating valve 11. The ceramic tube 9 is placed on the screen 3 and located in the upper reaction area 22. The aperture of the ceramic tube 9 is larger than the aperture of the screen 3.

[0057] The heater 4 is installed at the reaction kettle 2 to heat the reaction kettle 2, and the probe of the temperature sensor 1 is located in the reaction kettle 2 to detect the temperature of the reaction kettle 2.

[0058] In operation, the process is as follows:

[0059] Step one

[0060] The nickel oxide or iron oxide or aluminum oxide or cerium oxide or mixture of the above materials is mixed with 3YSZ yttrium oxide

[0061] The stable zirconium oxide is mixed to obtain a mixture a, the mixing ratio is 6:4 or 5.5:4.5 or 5:5, the mixture a is added with a pore-forming agent or carbon balls to obtain a mixture b, the pore-forming agent or carbon balls account for 10% or 12.5% or 15% of the weight of the mixture b, the mixture b is extruded into a shape, and sintered at 1400℃ or 1500℃ or 1600℃ for 2h or 2.5h or 3h to obtain a ceramic tube 9 with a porosity of 15% or 20% or 25%;

[0062] Step two

[0063] The ceramic tube 9 is immersed in slurry, and a zirconium oxide film is coated on the outer wall of the ceramic tube 9;

[0064] Step three

[0065] The ceramic tube 9 after coating is placed on the screen 3 in the reactor device for loading carbon, and the heater 4 heats the reaction kettle 2, when the temperature of the reaction kettle 2 is at 650℃ or 675℃ or 700℃, the second adjusting valve 8 is opened to pass hydrogen into the reaction kettle 2, the hydrogen enters the inner wall of the ceramic tube 9 to carry out reduction reaction for 1h or 1.25h or 1.5h, and nickel or iron or aluminum or cerium or the mixture is generated on the inner wall of the ceramic tube 9, at this time, due to the hydrogen carrying away the oxygen ions on the inner wall of the ceramic tube 9, the porosity of the inner wall of the ceramic tube 9 becomes 30% or 32.5% or 35%

[0066] Step four

[0067] Hydrogen and methane or propane or acetylene are passed into the ceramic tube 9 after reduction reaction, the molar ratio of hydrogen to carbon-containing gas is 1:3 or 1:3.5 or 1:4, the temperature is kept at 650℃ or 675℃ or 700℃, and the temperature is kept for 4h or 5h or 6h, and carbon nanotubes grow on the inner wall of the ceramic tube 9;

[0068] Step five

[0069] Nitrogen or argon is passed into the reaction kettle 2 to cool to room temperature, and the carbon-loaded honeycomb ceramic is taken out.

[0070] In this embodiment, the screen 3 has a hole density of one every 0.5cm or 1cm or 1.5cm

[0071] The pore size of the screen 3 is 200um or 225um or 250um, and the tube diameter of the ceramic tube 9 is 5.7mm or 5.8mm or 5.9mm or 6.0mm.

[0072] In this embodiment, the material of the ceramic tube 9 is nickel oxide or iron oxide or aluminum oxide or

[0073] cerium oxide or a mixture of the above materials and 3YSZ yttrium-stabilized zirconium oxide mixture.

[0074] In this embodiment, the outer wall of the ceramic tube 9 is coated with a zirconium oxide film.

[0075] The above detailed description of the embodiments of the present application is made in conjunction with the accompanying drawings, but the present application is not limited to the described embodiments. For those of ordinary skill in the art, various changes, modifications, replacements and variations of the embodiments without departing from the principles and purposes of the present application still fall within the protection scope of the present application.

Claims

1. A method for preparing a porous ceramic microtubule loaded with carbon nanoribbons, characterized in that The method comprises the following steps: Step one Mixing nickel oxide or iron oxide or aluminum oxide or cerium oxide or mixture of the above materials with 3YSZ yttrium oxide Stable zirconium oxide is mixed to obtain mixture a, the mixing ratio is 6:4-5:5, mixture a is added to a pore-forming agent or carbon ball to obtain mixture b, the pore-forming agent or carbon ball accounts for 10-15% of the weight of mixture b, mixture b is extruded into a shape, and is sintered at 1400-1600 ℃ for 2-3 h to obtain a ceramic tube (9) with a porosity of 20%±5%; Step two The ceramic tube (9) is immersed in slurry, and a zirconium oxide film is coated on the outer wall of the ceramic tube (9); Step three The ceramic tube (9) after coating is placed on the screen (3) in the reaction kettle (2) in the reactor device for loading carbon, the heater (4) is used to heat the reaction kettle (2), when the temperature of the reaction kettle (2) is 650-700 ℃, the second adjusting valve (8) is opened to pass hydrogen into the reaction kettle (2), the hydrogen enters the inner wall of the ceramic tube (9) to perform reduction reaction for 1-1.5 h, nickel or iron or aluminum or cerium or the mixture is generated on the inner wall of the ceramic tube (9), at this time, the hydrogen carries away oxygen ions on the inner wall of the ceramic tube (9), and the porosity of the inner wall of the ceramic tube (9) becomes 30%-35%; Step four Hydrogen and methane or propane or acetylene are passed into the ceramic tube (9) after reduction reaction, the molar ratio of hydrogen to carbon-containing gas is 1:3-1:4, the temperature is kept at 650-700 ℃, and the temperature is kept for 4-6 h, and carbon nanotubes grow on the inner wall of the ceramic tube (9); Step five Nitrogen or argon is passed into the reaction kettle (2) to cool to room temperature, and the carbon nanometer honeycomb ceramic is taken out.

2. The method of claim 1, wherein the carbon nanoribbons are loaded into the porous ceramic microtubes by a process comprising: The screen (3) has a hole density of one hole per 1±0.5 cm, the screen (3) has a hole diameter of 200-250 um, and the ceramic tube (9) has a tube diameter of 5.7-6.0 mm. ​ 3. The method for preparing a porous ceramic microtubule loaded with carbon nanoribbons according to claim 1, wherein the reactor apparatus used for loading carbon is characterized by It comprises: The methane, propane and acetylene inputter (5), the first adjusting valve (6), the hydrogen inputter (7), the second adjusting valve (8), the nitrogen or argon inputter (10) and the third adjusting valve (11); the outlet of the methane, propane and acetylene inputter (5) is communicated with the inlet of the first adjusting valve (6), the outlet of the hydrogen inputter (7) is communicated with the inlet of the second adjusting valve (8), and the outlet of the nitrogen or argon inputter (10) is communicated with the inlet of the third adjusting valve (11); and The ceramic tube (9), the reaction kettle (2) and the screen (3); the screen (3) is installed in the reaction kettle (2) to divide the reaction kettle (2) into a lower gas inlet area (21) and an upper reaction area (22), the lower gas inlet area (21) is communicated with the upper reaction area (22) through the mesh holes of the screen (3), a reaction gas inlet (211) is arranged at the lower part of the lower gas inlet area (21), the reaction gas inlet (211) is communicated with the outlet of the first adjusting valve (6), the outlet of the second adjusting valve (8) and the outlet of the third adjusting valve (11), the ceramic tube (9) is placed on the screen (3) and located in the upper reaction area (22), and the hole diameter of the ceramic tube (9) is greater than the mesh hole diameter of the screen (3); and The heater (4) is installed at the reaction kettle (2) to heat the reaction kettle (2), and the probe of the temperature sensor (1) is located in the reaction kettle (2) to detect the temperature of the reaction kettle (2).

4. The method for preparing a porous ceramic microtubule loaded with carbon nanoribbons according to claim 3, wherein the reactor apparatus used for loading carbon is characterized by The hole density of the screen (3) is one hole per 1±0.5 cm, the hole diameter of the screen (3) is 200-250 um, and the tube diameter of the ceramic tube (9) is 5.7-6.0 mm.

5. The method for preparing a porous ceramic microtubule loaded with carbon nanoribbons according to claim 3, wherein the reactor apparatus used for loading carbon is characterized by The material of the ceramic tube (9) is nickel oxide, iron oxide, aluminum oxide, cerium oxide, or a mixture of the above materials and 3YSZ yttrium-stabilized zirconium oxide mixture.

6. The method for preparing a porous ceramic microtubule loaded with carbon nanocoil according to claim 3, wherein the reactor for loading carbon is characterized by The outer wall of the ceramic tube (9) is covered with a zirconium oxide film.

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