CN112142038A - Carbon nanotube batch preparation system with tail gas waste heat recycling device - Google Patents
Carbon nanotube batch preparation system with tail gas waste heat recycling device Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01B32/159—Carbon nanotubes single-walled
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a carbon nano tube batch preparation system with a tail gas waste heat recycling device, which consists of a low-temperature furnace, a carbon nano tube high-temperature growth furnace, a two-stage cyclone separator and a tail gas heat conduction oil heat exchanger. And after heating and gasifying the liquid-phase carbon source and the solid catalyst in a low-temperature furnace, blowing the gasified liquid-phase carbon source and the solid catalyst into a high-temperature growth furnace by carrier gas to generate a carbon nano tube generation reaction, blowing the generated carbon nano tube into a two-stage cyclone separator by the carrier gas through the upper part of a hearth to perform filtration and separation, purifying the separated carbon nano tube, packaging and transporting the purified carbon nano tube, feeding the residual high-temperature tail gas into a tail gas heat-conducting oil heat exchanger to transfer heat to heat-conducting oil, and heating the heat. The invention combines the carbon nano tube manufacturing system with the tail gas waste heat recovery and utilization device for the first time, so that the heat of the tail gas is reasonably utilized to the maximum extent, and the energy is saved. The invention can realize the manufacture of various carbon nano tubes by controlling the raw materials and the temperature, and the product types are diversified.
Description
Technical Field
The invention belongs to the field of carbon nanotube manufacturing, and particularly relates to a batch preparation system of carbon nanotubes with a tail gas waste heat recycling device.
Background
1991 Japanese expert Iijima et al, after the first discovery of carbon nanotube molecules, have attracted great attention from the scientific community. Carbon nanotubes, as a novel carbonaceous material, have many excellent properties, such as: the breaking strength is high and is about 100 times of that of steel, and the tensile strength range of a single carbon nanotube is 10-100GPa, so that the carbon nanotube is one of the materials with the highest mechanical strength. The heat conductivity is strong, about 5 times of the heat conductivity of copper, and the axial heat conductivity of a single-walled carbon nanotube is 3500W/(m.K), which is much higher than that of carbonaceous materials such as graphite. The conductivity is strong, and the conductivity can reach about 10000 times of that of common conductive metal copper.
The laboratory preparation of carbon nanotubes usually employs a chemical vapor deposition method (CVD method), and the reaction principle is that solid catalyst particles and a liquid-phase carbon source are first heated to gasification, and then a nano-scale gaseous catalyst, a gaseous carbon source, a carrier gas and the like are mixed and heated to the carbon nanotube generation temperature, usually 600-1200 ℃, and the carbon nanotube generation reaction starts to occur. The chemical vapor deposition method can realize the generation of the carbon nano tube by high-temperature heating under normal pressure, has low cost of raw materials and simple and convenient operation of equipment, can realize the production of multi-wall or single-wall carbon nano tubes by controlling the types of carbon sources, catalysts and carrier gases, and is the preparation method which can realize the most industrialized production. However, the scale-up of laboratory equipment to the industrial process has many problems, such as that the batch continuous production cannot be realized by adopting a tubular furnace to perform the reaction in a laboratory, and how to realize the continuity of the investment of carbon sources and catalysts. And the global production of the carbon nano tube is mainly from future carbon companies in Germany and Japanese Showa electrician companies, and China does not realize autonomous mass production. Therefore, how to realize continuous mass production of the carbon nano tube and improvement of the process technology in China becomes a significant problem concerned in the field of carbon nano tube manufacturing at present.
The carbon source used in the carbon nanotube formation reaction is usually a hydrocarbon compound of C, H elements such as methane and benzene, and an organic compound of C, H, O elements such as ethanol. Gaseous carbon source at temperatureCO and a small amount of CO can be decomposed after the temperature is heated to 500 DEG C2A small amount of amorphous carbon and a large amount of H2. According to zingiberamine available at university of Zhejiang, thermodynamic analysis is performed on the reaction process, so that the reaction mainly occurring after 700K is obtained is the generation reaction of CO, so that the gas-phase carbon source is actually CO decomposed at high temperature, CO is adsorbed on the surface of the nano-scale metal catalytic particles, carbon is generated by catalytic pyrolysis, the carbon is diffused on the surface of the catalyst particles and is deposited to separate out carbon nanotubes, and the growth is stopped when the catalyst particles are completely wrapped by carbon and lose activity. CO is decomposed into amorphous carbon and CO by heating2However, amorphous carbon can be converted to CO and H by the water gas reaction at high temperature with the addition of deionized water2And the generation of impurities is reduced. Thus, it can be obtained that H is mainly contained in the off-gas after the reaction is completed2Only contains a small amount of unreacted CO and CO2And the proportion of the three components can be controlled by the selection of raw materials. From H2The temperature of the high-temperature tail gas mainly reaches 900-2With CO, CO2The mixed gas can also be applied to industrial combustion, and the mixed gas of the three is a common industrial raw material for producing propylene and an iron-making process.
In the face of increasingly severe environmental problems, energy conservation and emission reduction become a long-term strategy for realizing sustainable development, at present, after the manufacturing process of the carbon nano tube is finished, tail gas is naturally cooled to room temperature and then is directly discharged into the environment, and the part of tail gas is discharged into the environment, so that not only can a large amount of heat be wasted, but also the pollution to the production environment can be caused. For example, chinese patent "a method for treating tail gas in mass production of carbon nanotubes" (patent No. CN201410010726.3) discloses a method for recycling tail gas in mass production of carbon nanotubes, but the target gas is obtained through a condensing and filtering system, the heat of high-temperature tail gas still cannot be utilized, and maximum utilization of energy is not achieved, and the addition of a tail gas treatment device to the original preparation system would result in higher cost, and neither increase economic benefits nor save energy. Therefore, the device can recover the waste heat of the high-temperature tail gas and recycle the waste heat, can simultaneously reduce the heat waste and the pollution caused by the tail gas discharged into the environment, and achieves the aims of energy conservation and emission reduction.
Disclosure of Invention
The invention aims to solve the problems in the existing preparation system, provides a carbon nano tube batch preparation system with a tail gas waste heat recycling device, can realize batch production of carbon nano tubes, can reasonably utilize the waste heat of residual gas after product synthesis reaction, reduces energy waste, continuously collects tail gas after waste heat recovery for subsequent utilization, and realizes the purposes of energy conservation and emission reduction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon nanotube batch preparation system with a tail gas waste heat recycling device comprises a low-temperature furnace, a high-temperature growth furnace, a two-stage cyclone separator and a tail gas heat conduction oil heat exchanger; wherein, the bottom of the high temperature growth furnace is provided with a first carrier gas and protective gas inlet, the bottom of the low temperature furnace is provided with a second carrier gas and protective gas inlet, the side wall of the low temperature furnace is provided with a solid catalyst hopper extending into the low temperature furnace, the bottom is provided with a temperature thermocouple and a carbon source injection device extending into the low temperature furnace, the side wall of the low temperature furnace is circumferentially provided with a plurality of heat conducting oil heating pipes, the outlet of the low temperature furnace is communicated with the inlet of the high temperature growth furnace, the outlet of the high temperature growth furnace is communicated with the inlet of the two-stage cyclone separator, the tail gas heat conducting oil heat exchanger is provided with a flue gas inlet, a flue gas outlet, a heat conducting oil inlet and a heat conducting oil outlet, the outlet of the two-stage cyclone separator is communicated with the flue gas inlet of the heat conducting oil heat exchanger, the outlet of the heat conducting oil heating pipe is communicated to the heat conducting oil inlet of the tail gas heat conducting oil heat exchanger.
The further improvement of the invention is that the low-temperature furnace is used for introducing a catalyst precursor, a gas-phase or liquid-phase carbon source and a growth promoter which are required for generating the carbon nano tube into the furnace and heating to a set temperature, so that solid and liquid in the low-temperature furnace are completely gasified but do not reach the temperature at which the high-temperature decomposition reaction of the carbon source and the catalyst begins to occur, the heating temperature of the low-temperature furnace is 150-250 ℃, a heating pipe flowing heat-conducting oil is wound on the outer wall of the low-temperature furnace to provide a heat source for heating the low-temperature furnace, and gasified catalyst gas and the carbon source are mixed and then enter the next-stage high-temperature growth.
The invention is further improved in that along with the temperature rise, carbon source and catalyst gas introduced into the high-temperature growth furnace from the low-temperature furnace start to generate carbon nanotube generation reaction under the action of carrier gas, the finished product of the carbon nanotube gradually fills the whole high-temperature growth furnace, the formed carbon nanotube is blown out of the furnace from the upper part of a hearth by the carrier gas blown in from the bottom and enters a two-stage cyclone separator, the heating temperature of the high-temperature growth furnace is 800 plus materials, 1200 ℃, and the heating mode is electric heating or gas heating.
The invention is further improved in that the two-stage cyclone separator comprises a first-stage cyclone separator and a second-stage cyclone separator which are sequentially communicated, the two-stage continuous gas-solid separation is carried out on the carbon nano tube crude product blown out from the high-temperature growth furnace, the separated high-temperature carbon nano tube finished product is cooled and then purified, and then the carbon nano tube finished product can be packaged and transported, the separated high-temperature tail gas is introduced into the tail gas heat-conducting oil heat exchanger, and the rest heat is utilized subsequently.
The invention has the further improvement that the carbon nano tube product passes through the two-stage cyclone separator after being generated, 95 percent of finished product is filtered and separated after passing through the first-stage cyclone separator, and more than 99 percent of finished product is subjected to gas-solid separation after passing through the second-stage cyclone separator.
The invention has the further improvement that the tail gas heat-conducting oil heat exchanger transfers the heat of the high-temperature tail gas separated by the two-stage cyclone separator to the organic heat carrier with large heat exchange coefficient and small heat exchange loss, and recovers the waste heat of the organic heat carrier, and the selected organic heat carrier is heat-conducting oil; the internal part of the heat conduction oil heat exchanger is divided into a high-temperature tail gas channel and a heat conduction oil channel, the heat conduction oil flows in the pipe, the high-temperature tail gas flows outside the pipe, the flowing form is a counter flow, the high-temperature tail gas separated by the cyclone separator enters the tail gas heat conduction oil heat exchanger and transfers heat to the heat conduction oil in the pipe, the heat conduction oil absorbs heat and rises temperature and then flows out of the heat exchanger, the heat conduction oil flows into the circumferential heat conduction oil heating pipe on the side wall of the low-temperature furnace under the action of the heat conduction oil circulating pump and transfers the heat into the low-temperature furnace, the recovered waste heat is utilized to provide heat for.
The invention has the further improvement that the temperature of the high-temperature tail gas can be reduced to the environmental temperature after the high-temperature tail gas passes through the tail gas heat-conducting oil heat exchanger, and most of the tail gas after the carbon nano tube generation reaction is finished consists of H2Composition containing only small amounts of CO and CO2The low-temperature tail gas discharged after the heat exchanger is compressed and collected, and is used in industrial combustion or used as a raw material in chemical industry.
The invention has the further improvement that a heat-conducting oil expansion tank and a heat-conducting oil temperature measuring instrument are arranged on an external heat-conducting oil pipeline of the tail gas heat-conducting oil heat exchanger; the heat conducting oil expansion tank is used for storing the expansion amount after the heat conducting oil is heated, discharging steam and dehydrating when new oil is heated, adding the new oil and a supplementing device when the heat conducting oil is reduced; the heat conducting oil thermodetector is used for measuring whether the temperature of the heated heat conducting oil reaches a target temperature or not and whether the temperature of the heated heat conducting oil exceeds the target temperature or not.
The further improvement of the invention is that the carrier gas or the protective gas in the low-temperature furnace and the high-temperature growth furnace are blown in from the bottom, the bottom parts in the two hearths are provided with air distribution plates with small holes, so that the solid particles in the furnaces are prevented from falling to block air inlets, the gas is uniformly fed in the furnaces, and the flow rate of the carrier gas and the protective gas is 0.1-0.5 m/s.
The invention is further improved in that the carbon source used is a liquid or gas carbon source, the catalyst used is a solid metal catalyst, the growth promoter used is a sulfur-containing compound such as thiophene, and the sulfur-containing compound can be mixed with the carbon source and contained in a container, the mixing ratio of the sulfur-containing compound to the carbon source is 0.5:99.5-5:95, and the growth promoter is optionally added or not added according to the situation; the protective gas used is argon or nitrogen, and the carrier gas used is hydrogen or argon.
The invention has at least the following beneficial technical effects:
1. the invention reforms the laboratory device for manufacturing the carbon nano tube by the chemical vapor deposition method into an industrialized batch preparation system, the preparation system of the carbon nano tube is divided into a low-temperature furnace and a high-temperature growth furnace, the heating temperature of the low-temperature furnace is 150-.
2. The device can realize the manufacture of single-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanotube fibers by controlling raw materials, temperature and the like, and has diversified product types. For example, when the carbon source used is ethanol, the carrier gas is hydrogen, the catalyst is a ferrocene metal catalyst, and the heating temperature of the high-temperature growth furnace is 1180 ℃, the carbon nanotube fiber can be manufactured; when the carbon source is benzene, the carrier gas is argon, the catalyst is ferrocene metal catalyst, and the heating temperature of the high-temperature furnace is 650-950 ℃, the manufacture of the single-walled carbon nanotube can be realized.
3. The carbon nanotube manufacturing system is combined with the tail gas waste heat recovery and utilization device, high-temperature tail gas has high heat after the carbon nanotube reaction is finished, heat conducting oil is used as an organic heat carrier, the heat is recovered, and the waste heat is utilized to the gasification heating process of a carbon source and a catalyst, so that the heat of the tail gas is utilized reasonably to the maximum extent, and the purpose of saving energy is achieved.
4. The temperature of the high-temperature tail gas after waste heat recovery is reduced to the environmental temperature, most of the gas in the tail gas is H2 and only contains a small amount of CO and CO2, and the part of the normal-temperature normal-pressure tail gas can be reused for industrial combustion or used as an industrial raw material for continuous utilization, and the purpose of emission reduction can be achieved by collecting the part of the normal-temperature normal-pressure tail gas.
Drawings
Fig. 1 is a schematic view of a batch carbon nanotube production system with a tail gas waste heat utilization and recovery device according to the present invention.
Description of reference numerals:
1-temperature thermocouple in the hearth; 2-a solid catalyst hopper; 3-a carbon source injection device; 4-high temperature growth furnace; 5-a first-stage cyclone separator; 6-a secondary cyclone separator; 7-tail gas heat conducting oil heat exchanger; 8-a heat transfer oil circulating pump; 9-first carrier gas and shielding gas inlet; 10-circulation heat conducting oil flow adjusting device; 11-second carrier gas and shielding gas inlet; 12-a heat conducting oil heating pipe; 13-a heat conducting oil expansion tank; 14-heat conducting oil thermodetector; 15-carbon nanotube collection device.
Detailed Description
The invention is further described below with reference to the figures and examples.
As shown in fig. 1, the system for batch preparation of carbon nanotubes with a tail gas waste heat recovery and reuse device provided by the invention comprises a low-temperature furnace, a carbon nanotube high-temperature growth furnace, two-stage cyclone separators and a tail gas heat conduction oil heat exchanger. A first carrier gas and protective gas inlet 9 is arranged at the bottom of the high-temperature growth furnace 4, a second carrier gas and protective gas inlet 11 is arranged at the bottom of the low-temperature furnace, a solid catalyst hopper 2 extending into the low-temperature furnace is arranged on the side wall of the low-temperature furnace, a temperature thermocouple 1 and a carbon source injection device 3 extending into the low-temperature furnace are arranged at the bottom of the low-temperature furnace, a plurality of heat-conducting oil heating pipes 12 are arranged on the periphery of the side wall of the low-temperature furnace, an outlet of the low-temperature furnace is communicated with an inlet of the high-temperature growth furnace 4, an outlet of the high-temperature growth furnace 4 is communicated with an inlet of a two-stage cyclone separator, a flue gas inlet, a flue gas outlet, a heat-conducting oil inlet and a heat-conducting oil outlet are arranged on the tail gas heat-conducting oil heat exchanger 7, an outlet of the two-stage cyclone, the outlet of the heat conducting oil heating pipe 12 is communicated to the heat conducting oil inlet of the tail gas heat conducting oil heat exchanger 7. A heat conducting oil expansion tank 13 and a heat conducting oil temperature measuring instrument 14 are arranged on an outer heat conducting oil pipeline of the tail gas heat conducting oil heat exchanger 7; the heat conducting oil expansion tank 13 is used for storing the expansion amount after the heat conducting oil is heated, discharging steam and dehydrating when new oil is heated, adding the new oil and a supplementing device when the heat conducting oil is reduced; the heat transfer oil temperature measuring instrument 14 is used for measuring whether the temperature of the heated heat transfer oil reaches a target temperature or not and whether the temperature exceeds the target temperature or not.
The low-temperature furnace is used for heating a mixture of a liquid carbon source and a growth promoter and a solid catalyst to gasification, mixing and then putting in a furnaceIntroducing the carbon nano tube into the next-stage high-temperature growth furnace under the action of carrier gas to play a role in preprocessing reaction raw materials, wherein the heating mode of the low-temperature furnace is heating by utilizing a heating pipe wound on the outer wall of the furnace, and the heating temperature is 150-250 ℃. The carbon nanotube generating reaction occurs in the high temperature growth furnace of the carbon nanotube, the heating temperature is 600-1200 ℃, after the carbon source and the catalyst gas in the upper stage furnace are introduced into the high temperature reaction furnace, the high temperature decomposition of the carbon source occurs at first, the amorphous carbon and H are decomposed2O、CO、H2、CO2And the compounds are continuously heated, the gas phase catalyst decomposes nano-scale catalyst particles, the growth promoter decomposes atomic-scale particles, the nano-scale catalyst particles and the catalyst particles are combined to form composite catalyst particles, the growth reaction of the carbon nano-tubes starts to be carried out on the surface and the inside of the carbon nano-tubes, the formed carbon nano-tubes gradually fill the inside of the whole high-temperature furnace, the carrier gas introduced from the bottom can blow the carbon nano-tube products out of the hearth from an outlet at the top of the hearth, and the carbon nano-tube products are introduced into a two-stage cyclone. The coarse filtration of products is carried out in the first-stage cyclone separator, 95% gas-solid separation can be realized, the second-stage cyclone separator is then introduced for fine filtration, about 99% gas-solid separation can be realized, the separated carbon nanotubes are subjected to subsequent processing and purification, then the carbon nanotubes can be packaged and transported out of a factory, and the residual high-temperature tail gas enters the tail gas heat conduction oil heat exchanger 7 to transfer heat to heat conduction oil. The tail gas heat conduction oil heat exchanger 7 is internally provided with a tail gas channel and a heat conduction oil pipe, the temperature is reduced to the ambient temperature after the heat exchange between the tail gas and the heat conduction oil is completed, and the tail gas heat conduction oil heat exchanger mainly comprises H2And small amounts of CO and CO2The heat conduction oil flows out of the heat conduction oil pipe outside the low-temperature furnace and then returns to the tail gas heat conduction oil heat exchanger 7 for reheating, and the heat conduction oil can be recycled. The thermocouple 1 for monitoring the temperature in the furnace is arranged on the low-temperature furnace, when the temperature in the furnace is too high and is about to exceed the decomposition temperature of a carbon source and a catalyst, the heat conduction oil entering the heating pipe can be reduced by adjusting the circulating heat conduction oil flowmeter 10, the heat absorption in the furnace in unit real time is reduced, and the purpose of controlling the temperature is achieved. Such as the decomposition temperature of ethanolThe temperature is 300 ℃, the temperature needs to be controlled when the temperature is 250 ℃, the circulation flow of the heat conduction oil entering the heat conduction pipe can be reduced through the flow adjusting device 10 on the heat conduction oil pipeline, the heat absorbed by the low-temperature furnace in unit time is reduced, and the temperature in the hearth of the low-temperature furnace can be controlled.
The carbon source used is a liquid or gaseous carbon source such as benzene, ethanol, methane, etc.; the catalysts used are solid metal catalysts, e.g. ferrocene, NiBase catalysts, etc.; the growth promoter is sulfur-containing compound such as thiophene, and can be mixed with carbon source and contained in a container, the mixing ratio of the growth promoter to the carbon source is 0.5:99.5-5:95, and the growth promoter is optionally added or not added according to the situation; the protective gas used is argon or nitrogen, and the carrier gas used is hydrogen or argon.
In addition, the production of different types of carbon nanotubes can be realized by changing the types of carbon sources, controlling the growth temperature and the like, and products can be single-walled carbon nanotubes, multi-walled carbon nanotubes and carbon nanotube fibers.
During actual work, firstly opening the second carrier gas and protective gas inlet 11 and the first carrier gas and protective gas inlet 9 at the bottom of the low-temperature furnace and the high-temperature growth furnace, introducing protective gas, and exhausting air in the device. Then opening the high-temperature growth furnace to gradually heat the high-temperature growth furnace to a set reaction temperature, introducing the heated high-temperature protective gas into a tail gas heat-conducting oil heat exchanger 7 after passing through a two-stage cyclone separator, heating the heat-conducting oil from room temperature to a set temperature of about 200 ℃ after being heated, then introducing the heated high-temperature protective gas into a low-temperature furnace external heat-conducting oil heating pipe 12, gradually raising the temperature of the low-temperature furnace to about 180 ℃, opening a catalyst feed inlet 2 at the upper part of the low-temperature furnace, adding a solid catalyst, simultaneously introducing a mixture of a gaseous or liquid carbon source and a growth promoter, heating, gasifying and mixing the mixture, then introducing the mixture into. During the reaction process, high-temperature tail gas continuously enters the tail gas heat-conducting oil heat exchanger 7, and the heat of the tail gas heat-conducting oil heat exchanger 7 keeps the temperature of heat-conducting oil flowing out of the tail gas heat-conducting oil heat exchanger at about 200 ℃.
The tail gas heat conduction oil heat exchanger 7 is a shell-and-tube heat exchanger, the design size is 1.0-1.5m long, 0.3-0.4m wide and 0.4-0.6m high, the arrangement mode of the internal heat conduction oil pipeline is that three rows of serpentine coils are arranged in parallel, each row of pipelines is formed by six pipes with the length of 1.0m in a serpentine connection mode, and the pipe diameter of each pipeline is 0.03 m. The adopted heat conduction oil can be LQC-320 series heat conduction oil, 30L of normal temperature and normal pressure heat conduction oil is injected through a heat conduction oil expansion tank when the tail gas heat conduction oil heat exchanger is started, the flow of carrier gas introduced into the high-temperature growth furnace is 70L/h when the tail gas heat conduction oil heat exchanger is started, the heat of the high-temperature carrier gas is utilized to heat the heat conduction oil to the set temperature of about 200 ℃, and the temperature rise time is 2-3 h. When the temperature of the heat conduction oil rises to about 200 ℃, the temperature of the low-temperature furnace rises to about 180 ℃ of the gasification temperature of the catalyst, the solid catalyst and the carbon source gas are started to be added, the subsequent reaction starts to occur, the circulation flow of the heat conduction oil is set to be 3-5L/h, the temperature of the heat conduction oil leaving the tail gas heat conduction oil heat exchanger 7 is about 200 ℃, and the temperature of the heat conduction oil returning to the tail gas heat conduction oil heat exchanger 7 is about 150-.
The low-temperature furnace is a cylindrical heating furnace, and the inner wall surface of the furnace is wound with a heat conduction oil pipe. The size of the low-temperature furnace is 0.4-0.6m in diameter and 1.2-1.6m in height, and a heat-conducting oil pipe with the total length of 6-10m and the diameter of 3cm is wound along the wall surface.
Example 1
When the target product is the carbon nano tube fiber, the used carbon source is liquid ethanol, the growth promoter is thiophene, the mixing ratio of the ethanol to the thiophene is 99.2:0.8, and the rate of introducing the ethanol into the low-temperature reaction furnace is 1-1.5L/min; the used solid catalyst is ferrocene, 1-3kg is added at the beginning of the reaction, and then supplementary feeding is carried out at the speed of 80-120 g/h; the used protective gas is argon, and air is introduced into the low-temperature furnace and the high-temperature growth furnace at the speed of 0.2m/s after the reaction begins; the used carrier gas is hydrogen, the gas introducing speed of the protective gas in the low-temperature furnace is 0.2m/s, and the gas introducing speed of the protective gas in the high-temperature growth furnace is 0.15 m/s; the heating temperature of the low-temperature furnace is 150-. The yield of the carbon nano tube fiber can reach 10-15 kg/h.
Example 2
When the target product is the single-walled carbon nanotube, the used carbon source is liquid benzene, the growth promoter is thiophene, the mixing ratio of the benzene to the thiophene is 99:1-95:5, and the rate of introducing the benzene into the low-temperature reaction furnace is 1-1.5L/min; the used solid catalyst is ferrocene, 1-3kg is added at the beginning of the reaction, and then supplementary feeding is carried out at the speed of 80-120 g/h; the used carrier gas and protective gas are argon, the gas introducing speed of the carrier gas and the protective gas in the low-temperature growth furnace is 0.15m/s, and the gas introducing speed of the carrier gas and the protective gas in the high-temperature growth furnace is 0.1 m/s; the heating temperature of the low-temperature furnace is 150-200 ℃, the ferrocene starts to be gasified at 185 ℃, and the heating temperature of the high-temperature growth furnace is 650-950 ℃. The yield of the single-walled carbon nano-tube can reach 9-14 kg/h.
Claims (10)
1. A carbon nanotube batch preparation system with a tail gas waste heat recycling device is characterized by comprising a low-temperature furnace, a high-temperature growth furnace (4), a two-stage cyclone separator and a tail gas heat conduction oil heat exchanger (7); the bottom of the high-temperature growth furnace (4) is provided with a first carrier gas and protective gas inlet (9), the bottom of the low-temperature furnace is provided with a second carrier gas and protective gas inlet (11), the side wall of the low-temperature furnace is provided with a solid catalyst hopper (2) extending into the low-temperature furnace, the bottom of the low-temperature furnace is provided with a temperature thermocouple (1) and a carbon source injection device (3) extending into the low-temperature furnace, the periphery of the side wall of the low-temperature furnace is provided with a plurality of heat conduction oil heating pipes (12), the outlet of the low-temperature furnace is communicated to the inlet of the high-temperature growth furnace (4), the outlet of the high-temperature growth furnace (4) is communicated to the inlet of the two-stage cyclone separator, the tail gas heat conduction oil heat exchanger (7) is provided with a flue gas inlet, a flue gas outlet, a heat conduction oil inlet and a heat conduction oil outlet, the outlet of the two-stage cyclone The quantity adjusting device (10) is communicated to an inlet of the heat conducting oil heating pipe (12), and an outlet of the heat conducting oil heating pipe (12) is communicated to a heat conducting oil inlet of the tail gas heat conducting oil heat exchanger (7).
2. The system for the batch preparation of carbon nanotubes with the tail gas waste heat recycling device as claimed in claim 1, wherein the low temperature furnace is used for introducing the catalyst precursor, the gas phase or liquid phase carbon source and the growth promoter required for the generation of the carbon nanotubes into the furnace and heating to a set temperature, so that the solid and liquid are completely gasified but do not reach the temperature at which the high temperature decomposition reaction of the carbon source and the catalyst begins to occur, the heating temperature of the low temperature furnace is 150-.
3. The system for preparing carbon nanotubes in batches with a tail gas waste heat recovery and recycle device according to claim 1, characterized in that along with the temperature rise, the carbon source and the catalyst gas introduced from the low-temperature furnace into the high-temperature growth furnace under the action of the carrier gas start to generate the carbon nanotube generation reaction, the carbon nanotube finished product gradually fills the whole high-temperature growth furnace (4), the formed carbon nanotubes are blown out of the furnace from the upper part of the hearth by the carrier gas blown in from the bottom and enter the two-stage cyclone separator, the heating temperature of the high-temperature growth furnace (4) is 800-.
4. The carbon nanotube batch preparation system with the tail gas waste heat recycling device according to claim 1, wherein the two-stage cyclone separator comprises a first-stage cyclone separator (5) and a second-stage cyclone separator (6) which are sequentially communicated, two-stage continuous gas-solid separation is performed on a carbon nanotube crude product blown out from the high-temperature growth furnace (4), the separated high-temperature carbon nanotube finished product is cooled and subjected to subsequent purification processing, packaging and transportation can be performed, the separated high-temperature tail gas is introduced into a tail gas heat conduction oil heat exchanger (7), and the rest heat is subsequently utilized.
5. The carbon nanotube batch preparation system with the tail gas waste heat recovery and reuse device according to claim 4, wherein after being generated, the carbon nanotube product passes through a two-stage cyclone separator, and after passing through a first-stage cyclone separator (5), 95% of finished product is filtered and separated, and after passing through a second-stage cyclone separator (6), more than 99% of finished product is subjected to gas-solid separation.
6. The carbon nanotube batch preparation system with the tail gas waste heat recycling device according to claim 1, wherein the tail gas heat conduction oil heat exchanger (7) transfers heat of high-temperature tail gas separated by the two-stage cyclone separator to an organic heat carrier with a large heat exchange coefficient and a small heat exchange loss to recycle waste heat of the organic heat carrier, and the selected organic heat carrier is heat conduction oil; the internal part of the heat conduction oil heat exchanger is divided into a high-temperature tail gas channel and a heat conduction oil channel, heat conduction oil flows in a pipe, the high-temperature tail gas flows outside the pipe in a countercurrent mode, the high-temperature tail gas separated by the cyclone separator enters a tail gas heat conduction oil heat exchanger (7) and transfers heat to heat conduction oil in the pipe, the heat conduction oil absorbs heat and rises temperature and then flows out of the heat exchanger, the heat conduction oil flows into a circumferential heat conduction oil heating pipe (12) on the side wall of the low-temperature furnace under the action of a heat conduction oil circulating pump (8), the heat is transferred into the low-temperature furnace, recovered waste heat is utilized to provide heat for gasification of the solid catalyst, the heat conduction.
7. The carbon nanotube batch preparation system with tail gas waste heat recovery and reuse device according to claim 6, wherein the temperature of the high-temperature tail gas is reduced to ambient temperature after passing through the tail gas heat transfer oil heat exchanger (7), and most of the tail gas after the carbon nanotube generation reaction is finished is H2Composition containing only small amounts of CO and CO2The low-temperature tail gas discharged after the heat exchanger is compressed and collected, and is used in industrial combustion or used as a raw material in chemical industry.
8. The carbon nanotube batch preparation system with the tail gas waste heat recycling device according to claim 1, wherein a heat conducting oil expansion tank (13) and a heat conducting oil temperature measuring instrument (14) are arranged on an external heat conducting oil pipeline of the tail gas heat conducting oil heat exchanger (7); the heat conducting oil expansion tank (13) is used for storing the expansion amount after the heat conducting oil is heated, discharging steam and dehydrating when new oil is heated, adding the new oil and a supplementing device when the heat conducting oil is reduced; the heat conducting oil thermodetector (14) is used for measuring whether the temperature of the heated heat conducting oil reaches a target temperature or not and whether the temperature of the heated heat conducting oil exceeds the target temperature or not.
9. The system for mass production of carbon nanotubes with a tail gas waste heat recovery and reuse device according to claim 1, wherein the carrier gas or the shielding gas in the low temperature furnace and the high temperature growth furnace (4) is blown in from the bottom, the bottom in both chambers is equipped with a wind distribution plate with small holes to prevent the solid particles in the furnace from falling down and blocking the air inlet, and the gas is uniformly fed into the furnace, and the flow rate of the carrier gas and the shielding gas is 0.1-0.5 m/s.
10. The system for the batch preparation of the carbon nanotubes with the tail gas waste heat recycling device according to claim 1, wherein the carbon source is a liquid or gaseous carbon source, the catalyst is a solid metal catalyst, the growth promoter is a sulfur-containing compound such as thiophene, and the sulfur-containing compound and the carbon source can be mixed and contained in a container, the mixing ratio of the carbon source to the growth promoter is 0.5:99.5-5:95, and the growth promoter is optionally added or not added according to the situation; the protective gas used is argon or nitrogen, and the carrier gas used is hydrogen or argon.
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