CN110550618A - Device and method for recovering tail gas of CVI/CVD (chemical vapor deposition/chemical vapor deposition) process - Google Patents
Device and method for recovering tail gas of CVI/CVD (chemical vapor deposition/chemical vapor deposition) process Download PDFInfo
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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- C01B2203/1258—Pre-treatment of the feed
Abstract
The invention discloses a device and a method for recovering tail gas of a CVI/CVD (chemical vapor deposition/chemical vapor deposition) process, which comprise cooling and filtering equipment, a vacuum pump, an isothermal cracking furnace and post-stage comprehensive treatment equipment, wherein the cooling and filtering equipment comprises a circulating liquid cooling module, an oil filter and a drying filter; the bottom in the isothermal cracking furnace is provided with a preheating zone module, and an isothermal zone module is arranged above the preheating zone module. The preheating zone module is a multilayer labyrinth graphite plate. The lower part of the isothermal zone module is a delay buffer zone, the upper part of the isothermal zone module is an isothermal zone upper cavity, the isothermal zone upper cavity is provided with a multilayer graphite plate structure, an activated carbon growth structure is arranged on the graphite plate, and the surface of the activated carbon growth structure is loaded with a carbon black catalyst. The top of the isothermal cracking furnace is a gas outlet which is connected with post-stage comprehensive treatment equipment through a pipeline. The post-integrated processing equipment comprises a pressure swing separator and a solid filter. The device and the method for recovering the tail gas of the CVI/CVD process have high treatment efficiency, good safety performance and high ecological environment friendliness.
Description
Technical Field
The invention relates to an industrial tail gas treatment device and method, in particular to a CVI/CVD process tail gas recovery device and method.
Background
People pay more and more attention to environmental protection, and the call for green energy is higher and higher, so how to recycle waste in industrial production, changing waste into valuables becomes a crucial part in the whole industrial system, and the environmental protection field is receiving more and more attention. The invention mainly aims at the market demand of the carbon/carbon composite material, and the efficient utilization of the alkane tail gas in the production process of the carbon/carbon composite material is mainly considered. The carbon/carbon composite material has excellent performances of high temperature resistance, high specific strength, high specific modulus and the like, and has wide application prospects in the fields of photovoltaic monocrystalline silicon production, airplane brake discs, automobile brake discs, high-speed rail pantograph, high-speed rail brake discs and the like. At present, the carbon/carbon composite material is taken as an ideal graphite material substitute to promote the rapid development of the industry. However, the utilization rate of the source gas in the preparation process of the carbon/carbon material is low, and is only about 10%. And the tail gas is directly burned or treated by water vapor, so that a large amount of greenhouse gases are generated. The invention can recycle CVI/CVD process tail gas, changes waste into valuable, and completely converts the CVI/CVD process tail gas into clean hydrogen energy and nano carbon materials with wide application.
Disclosure of Invention
the invention aims to solve the problems in the prior art and provides a device and a method for recovering tail gas of a CVI/CVD (chemical vapor deposition) process
The technical scheme of the invention is that the device for recovering tail gas of a CVI/CVD process comprises cooling filtering equipment, a vacuum pump, an isothermal cracking furnace and post-stage comprehensive treatment equipment, wherein the cooling filtering equipment comprises a circulating liquid cooling module, an oil filter and a drying filter; the vacuum pump is arranged between the cooling filtering equipment and the isothermal cracking furnace; a preheating zone module is arranged at the bottom in the isothermal cracking furnace, and an isothermal zone module is arranged above the preheating zone module; the preheating zone module is a multilayer labyrinth graphite plate; the lower part of the isothermal zone module is a delay buffer zone, the upper part of the isothermal zone module is an isothermal zone upper cavity, the isothermal zone upper cavity is provided with a multilayer graphite plate structure, an activated carbon growth structure is arranged on the graphite plate, and the surface of the activated carbon growth structure is loaded with a carbon black catalyst; the top of the isothermal cracking furnace is a gas outlet, and the gas outlet is connected with post-stage comprehensive treatment equipment through a pipeline; the post-stage comprehensive treatment equipment comprises a pressure swing separator and a solid filter.
Preferably, the time delay buffer zone is of a funnel-shaped graphite structure, and the bottom of the funnel-shaped graphite structure is provided with an isothermal zone inlet and a graphite pipe inserted into the bottom of the funnel-shaped graphite structure.
preferably, the hydrogen after the post-processing equipment is input into a hydrogen-oxygen fuel cell.
Preferably, the activated carbon growth structure is a densely arranged activated carbon column.
preferably, the activated carbon growth structure is an activated carbon sheet arranged in a radiation manner.
Preferably, the activated carbon growth structure is a spirally arranged carbon felt structure.
Preferably, cooling filtration equipment still includes the oil groove, oil groove and oil filter UNICOM, the oil groove afterbody is provided with the butterfly valve.
A method for recovering tail gas of a CVI/CVD process comprises the following steps:
Cooling and filtering: tail gas of the CVI/CVD process enters cooling and filtering equipment through a tail gas inlet, and is cooled and filtered through a circulating liquid cooling module, an oil filter and a drying filter;
A cracking step: the tail gas after temperature reduction and filtration enters an isothermal cracking furnace and firstly passes through a multilayer labyrinth graphite plate preheating zone module positioned at the bottom of the isothermal cracking furnace; the preheated gas passes through a delay buffer area and a cavity on an isothermal area, and is subjected to full cracking reaction;
And (3) post-stage comprehensive treatment: hydrogen generated by the cracking reaction enters post-stage comprehensive treatment equipment through a gas outlet which is positioned at the top of the isothermal cracking furnace; respectively passing through a pressure swing separator and a solid filter.
Preferably, the isothermal zone module has a temperature of 750 ℃.
Preferably, a catalyst is arranged in the isothermal zone, and the catalyst can be ferrocene or metallic nickel.
the invention has the advantages that: 1, cooling and filtering equipment, and reducing the damage of high-temperature tail gas to a vacuum pump. 2, adopting the isothermal zone structure design of the isothermal cracking furnace containing the delay buffer zone to prolong the retention time of hydrocarbon gas and promote full cracking deposition. 3, a stable reaction environment is provided, the temperature of each position in the isothermal cracking furnace is more uniform, and the reaction temperature is easier to control. The catalytic device has stable performance, safety, reliability, simple and convenient operation and easy amplification. 4, the hydrogen production gas has high purity, and the high-purity nano material is obtained.
In order to make the technical means, technical features, objects and technical effects of the present invention easily understandable, the present invention is further described below with reference to the specific drawings.
Drawings
FIG. 1 is a schematic illustration of an apparatus according to an embodiment of the present invention;
FIG. 2 is a three-dimensional isometric view of a cavity graphite plate and an activated carbon growth structure in an isothermal zone according to an embodiment of the present invention;
FIG. 3 is a three-dimensional axial view of a cavity graphite plate and an activated carbon growth structure in a mesopore in an isothermal zone according to an embodiment of the present invention;
FIG. 4 is a schematic illustration of an apparatus according to an embodiment of the present invention;
FIG. 5 is a three-dimensional isometric view of a cavity graphite plate and an activated carbon growth structure in an isothermal zone according to an embodiment of the present invention;
FIG. 6 is a three-dimensional axial view of the graphite plates and the activated carbon growth structure in the mesopores of the isothermal zone in accordance with an embodiment of the present invention;
FIG. 7 is a schematic illustration of an apparatus according to an embodiment of the present invention;
FIG. 8 is a three-dimensional isometric view of a cavity graphite plate and an activated carbon growth structure in an isothermal zone according to an embodiment of the present invention;
Fig. 9 is a three-dimensional axial view of the structure of graphite plates and activated carbon growth in the mesoporous volume in the isothermal zone according to an embodiment of the present invention.
Detailed Description
the invention relates to a tail gas treatment method of a Chemical Vapor Infiltration/Chemical Vapor Deposition (CVI/CVD) process of hydrocarbon gas, which comprises a whole set of tail gas equipment system and a treatment process. The method is suitable for treating the tail gas in the process of preparing the carbon/carbon composite material based on the CVI/CVD method, and is also suitable for treating the tail gas of other vacuum equipment.
The gas introduced in the CVI/CVD process is natural gas, diluent gas argon/nitrogen, a small amount of hydrogen and propylene, so that the tail gas contains undecomposed natural gas, hydrogen, argon (or nitrogen), decomposition product tar, tar and the like, which pollute the atmosphere, and thus cannot be directly discharged into the atmosphere. Because the mixed tail gas has high temperature and directly flows through the vacuum pump, the mixed tail gas can corrode the blades and the pump body, and simultaneously, the precipitation of tar can seriously affect the stability of the pumping rate, so that the tail gas needs to be correspondingly treated before flowing through the vacuum pump.
and adding partial pressure or pressurizing equipment according to needs before the treated tail gas flows out of the vacuum pump and enters the isothermal cracking furnace. And the tail gas enters the furnace chamber from the bottom inlet of the isothermal cracking furnace, hydrocarbon gas in the tail gas is cracked under the action of high temperature and a catalyst, and the nano carbon black is deposited on the surface of the activated carbon.
the tail gas flowing out of the isothermal cracking furnace flows into a pressure swing separator 24, hydrogen is separated from the cracking tail gas by using a pressure swing adsorption separation technology, and the purity of the separated product can be more than 98%.
The methane cracking reaction does not produce greenhouse gases, and the energy consumption for producing hydrogen per mole is less than that of the traditional steam reforming method, and the purity of the hydrogen produced by the method is very high, and the method does not need excessive additional gas purification procedures, and only adds one solid filter 25 to avoid the carbon nano materials from being brought into the oxyhydrogen fuel cell 26.
It is well known that the reaction temperature, the reaction atmosphere, and the catalyst composition have a significant influence on the growth of nanocarbon. When the temperature of the constant temperature area is 750 ℃ and the catalyst is ferrocene or metallic nickel, the carbon nano tube grows on the surface of the carbon cloth.
The temperature of the constant temperature zone and the type of the catalyst on the surface of the graphite cloth can be adjusted according to the difference of hydrocarbons.
One, embodiment one
As shown in fig. 1-3, in one embodiment of the present invention,
The equipment comprises the following steps:
A CVI/CVD process tail gas recovery device comprises a cooling and filtering device 1, a vacuum pump 2, an isothermal cracking furnace 3 and a post-stage comprehensive treatment device 4, wherein the cooling and filtering device 1 comprises a circulating liquid cooling module 11, an oil filter 12 and a drying filter 13; the cooling filtration equipment still includes oil groove 14, oil groove and oil filter UNICOM 12, the oil groove afterbody is provided with butterfly valve 141 and waste oil export 142. The vacuum pump 2 is arranged between the cooling and filtering device 1 and the isothermal cracking furnace 3; a preheating zone module 31 is arranged at the bottom in the isothermal cracking furnace 3, and an isothermal zone module 32 is arranged above the preheating zone module 31; the preheating zone module 31 is a multi-layer labyrinth graphite plate 313; the lower part of the isothermal zone module 32 is a delay buffer area 321, the delay buffer area 321 is a funnel-shaped graphite structure, and the bottom of the funnel-shaped graphite structure is an isothermal zone inlet 3211 and a graphite tube 3212 inserted into the bottom of the funnel-shaped graphite structure. The upper part of the isothermal zone module 321 is an isothermal zone upper cavity 322, the isothermal zone upper cavity 322 is provided with a multilayer graphite plate structure comprising graphite plates 3221, 3223 and 3224, no middle hole is formed in the graphite plate 3223, and a middle hole 3225 is formed in the graphite plate 3224; the graphite plate is provided with activated carbon columns 3222 with densely arranged activated carbon growth structures, and the surfaces of the activated carbon columns 3222 are loaded with carbon black catalysts; the top of the isothermal cracking furnace 2 is provided with a gas outlet 33, and the gas outlet 33 is connected with the post-stage comprehensive treatment equipment 4 through a pipeline; the post-integrated processing equipment 4 includes a pressure swing separator 41 and a solids filter 42. The hydrogen treated by the post-processing equipment 4 is input into a hydrogen-oxygen fuel cell 5.
(II) an implementation step
These examples are intended to be illustrative only and not to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereto by those skilled in the art. The following example 1 is an example of the procedure:
1) The circulating liquid cooling module 11 and the oil filter 12 are started.
2) Tail gas gets into from cooling filtration equipment 1 entry, through the cooling of circulating liquid cooling module 11, gets into oil filter 12 to reduce the temperature of tail gas, adsorb macromolecules such as tar in the tail gas simultaneously. The working principle of the oil filter 12 is as follows: oil is introduced from an oil inlet 121 filtered by the oil filter 12, then reaches the top pipeline 122 through a pipeline, and is sprayed out from the small holes 123 of the top pipeline 122, the sprayed oil is in a mist shape, and the oil mist can fully cool and adsorb tail gas in the descending process. The adsorbed fuel is deposited on the bottom of the oil tank 14, and the equivalent is accumulated to some extent to open the butterfly valve 141 and discharged from the waste oil outlet 142.
3) the exhaust gas is secondarily adsorbed and filtered by the dry filter 13 to reach the vacuum pump 2, and the gas temperature is low and does not contain tar and other substances.
4) The tail gas enters the furnace chamber from the bottom inlet 30 of the isothermal cracking furnace 3, firstly enters the preheating zone module 31, flows into the preheating zone upper cavity 312 from the graphite bottom plate hole 311 in the flowing direction of the tail gas in the preheating zone module 31 as shown in fig. 1, then rises along the channel partitioned by the multi-layer labyrinth graphite plate 313 from the preheating zone upper cavity 312 (the number of layers of the graphite plate can be increased or decreased according to different hydrocarbon gases), and finally enters the isothermal zone module 32, the temperature of the tail gas is almost the same as that of the isothermal zone, the tail gas flows into the funnel-shaped delay buffer zone 321 made of graphite from the lower bottom plate hole 3211 of the isothermal zone module 32, the bottom of the funnel is provided with a section of graphite pipe 3212 extending into the bottom of the funnel, carbon black catalyst or other light catalyst particles are arranged around the graphite pipe 3212, when the tail gas flows through the graphite pipe 3212, a negative pressure is generated above the tail gas, so that, the catalyst particles are always suspended in the area above the graphite pipe 3212, if the airflow is greater than a certain value, the catalyst particles are blown to the bottom of the graphite plate 3221 above the funnel, the catalyst particles fall into the funnel-shaped area again after impacting the bottom, the pyrolysis product carbon black or carbon nanotubes are deposited on the surfaces of the catalyst particles along with the progress of the thermal cracking reaction, and the deposited carbon black or carbon nanotubes fall off from the surfaces of the catalyst particles along with the movement of the catalyst particles and the stacking of the deposits on the surfaces of the particles, so that the solid in the area is increased, and when a certain amount is reached, the surplus carbon black or carbon nanotubes overflow out of the funnel-shaped area along the wall surface of the funnel. The tail gas flows through the funnel area and enters the upper cavity 322 of the isothermal zone along the wall surface, the upper cavity 322 of the isothermal zone is provided with a multilayer graphite plate structure, the structure comprises graphite plates 3221, 3223 and 3224, activated carbon columns 3222 are densely arranged on the graphite plate structure, carbon black catalyst is loaded on the surfaces of the activated carbon columns 3222, hydrocarbon gas in the tail gas is cracked under the action of high temperature and the catalyst, nano carbon black is deposited on the surfaces of the activated carbon, the catalytic activity of the activated carbon at the initial reaction stage is stronger than that of the carbon black, but along with the deposition, holes on the surfaces of the activated carbon are occupied by the deposited carbon and inactivated, and the carbon black still has stable catalytic efficiency. The tail gas is cracked to generate the nano carbon material and hydrogen, the nano carbon material is deposited on the surface of the activated carbon column, and when the nano carbon is deposited to a certain amount, the nano carbon falls onto the surface of the graphite plate 3221 due to the fact that gravity is larger than the surface binding force. The tail gas flows out from a gas outlet 33 at the top of the isothermal cracking furnace after layer-by-layer reaction. A large amount of hydrocarbon gas is cracked in an isothermal zone to generate deposited carbon materials and hydrogen, and the design of the isothermal zone structure of the isothermal cracking furnace mainly prolongs the retention time of the hydrocarbon gas so as to ensure that the hydrocarbon gas is fully cracked and deposited. The final tail gas (98% hydrogen) flows from gas outlet 33 into the separator for separation. The reaction temperature, the reaction atmosphere and the catalyst composition have a significant effect on the growth of nanocarbon. When the temperature of the constant temperature area is 750 ℃, and the catalyst is ferrocene or metallic nickel, the catalytic effect is optimal.
5) The separated hydrogen gas passes through a pressure swing separator 41 and a solid filter 42 and then enters the hydrogen-oxygen fuel cell 5 to generate electricity. The electric power can be used in a cooling water circulation system, thereby saving energy and improving the utilization rate.
second, embodiment two
as shown in fig. 4-6, in one embodiment of the present invention,
The equipment comprises the following steps:
A CVI/CVD process tail gas recovery device comprises a cooling and filtering device 1, a vacuum pump 2, an isothermal cracking furnace 3 and a post-stage comprehensive treatment device 4, wherein the cooling and filtering device 1 comprises a circulating liquid cooling module 11, an oil filter 12 and a drying filter 13; the cooling filtration equipment still includes oil groove 14, oil groove and oil filter UNICOM 12, the oil groove afterbody is provided with butterfly valve 141 and waste oil export 142. The vacuum pump 2 is arranged between the cooling and filtering device 1 and the isothermal cracking furnace 3; a preheating zone module 31 is arranged at the bottom in the isothermal cracking furnace 3, and an isothermal zone module 32 is arranged above the preheating zone module 31; the preheating zone module 31 is a multi-layer labyrinth graphite plate 313; the lower part of the isothermal zone module 32 is a delay buffer area 321, the delay buffer area 321 is a funnel-shaped graphite structure, and the bottom of the funnel-shaped graphite structure is an isothermal zone inlet 3211 and a graphite tube 3212 inserted into the bottom of the funnel-shaped graphite structure. The upper part of the isothermal zone module 321 is an isothermal zone upper cavity 322, the isothermal zone upper cavity 322 is provided with a multilayer graphite plate structure comprising graphite plates 3221, 3222 and 3223, no middle hole is formed in the graphite plate 3223, and a middle hole 3225 is formed in the graphite plate 3224; the graphite plate is provided with active carbon sheets 3222 with the active carbon growth structures distributed in a radial shape, and the surfaces of the active carbon sheets 3222 are loaded with carbon black catalysts; the top of the isothermal cracking furnace 2 is provided with a gas outlet 33, and the gas outlet 33 is connected with the post-stage comprehensive treatment equipment 4 through a pipeline; the post-integrated processing equipment 4 includes a pressure swing separator 41 and a solids filter 42. The hydrogen gas after the post-integrated processing device 4 is fed to the hydrogen-oxygen fuel cell 5.
(II) an implementation step
These examples are intended to be illustrative only and not to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereto by those skilled in the art. The following example 1 is an example of the procedure:
1) The circulating liquid cooling module 11 and the oil filter 12 are started.
2) Tail gas gets into from cooling filtration equipment 1 entry, through the cooling of circulating liquid cooling module 11, gets into oil filter 12 to reduce the temperature of tail gas, adsorb macromolecules such as tar in the tail gas simultaneously. The working principle of the oil filter 12 is as follows: oil is introduced from an oil inlet 121 filtered by the oil filter 12, then reaches the top pipeline 122 through a pipeline, and is sprayed out from the small holes 123 of the top pipeline 122, the sprayed oil is in a mist shape, and the oil mist can fully cool and adsorb tail gas in the descending process. The adsorbed fuel is deposited on the bottom of the oil tank 14, and the equivalent is accumulated to some extent to open the butterfly valve 141 and discharged from the waste oil outlet 142.
3) the exhaust gas is secondarily adsorbed and filtered by the dry filter 13 to reach the vacuum pump 2, and the gas temperature is low and does not contain tar and other substances.
4) The tail gas enters the furnace chamber from the bottom inlet 30 of the isothermal cracking furnace 3, firstly enters the preheating zone module 31, flows into the preheating zone upper cavity 312 from the graphite bottom plate hole 311, then rises along the channel partitioned by the multi-layer labyrinth graphite plate 313 (the number of layers of the graphite plate can be increased or decreased according to different hydrocarbon gases) from the preheating zone upper cavity 312 as shown in fig. 4, and finally enters the isothermal zone module 32, at the moment, the temperature of the tail gas has no little difference with the temperature of the isothermal zone, the tail gas flows into the funnel-shaped delay buffer zone 321 made of graphite from the bottom plate hole 3211 of the isothermal zone module 32, a section of graphite pipe 3212 extending into the bottom of the funnel is arranged at the bottom of the funnel, carbon black catalyst or other light catalyst particles are arranged around the graphite pipe 3212, when the tail gas flows through the graphite pipe 3212, negative pressure is generated above the tail gas, so that the light catalyst is blown up, the catalyst particles are always suspended in the area above the graphite pipe 3212, if the airflow is greater than a certain value, the catalyst particles are blown to the bottom of the graphite plate 3221 above the funnel, the catalyst particles fall into the funnel-shaped area again after impacting the bottom, the pyrolysis product carbon black or carbon nanotubes are deposited on the surfaces of the catalyst particles along with the progress of the thermal cracking reaction, and the deposited carbon black or carbon nanotubes fall off from the surfaces of the catalyst particles along with the movement of the catalyst particles and the stacking of the deposits on the surfaces of the particles, so that the solid in the area is increased, and when a certain amount is reached, the surplus carbon black or carbon nanotubes overflow out of the funnel-shaped area along the wall surface of the funnel. The tail gas flows through the funnel area and then enters the upper cavity 322 of the isothermal zone along the wall surface, the upper cavity 322 of the isothermal zone is provided with a multilayer graphite plate structure, the structure comprises graphite plates 3221, 3223 and 3224, activated carbon sheets 3222 radially arranged on the graphite plate structure, carbon black catalyst is loaded on the surfaces of the activated carbon sheets 3222, under the action of high temperature and the catalyst, hydrocarbon gas in the tail gas is cracked, nano carbon black is deposited on the surfaces of the activated carbon, the catalytic activity of the activated carbon at the initial stage of reaction is stronger than that of the carbon black, but along with the deposition, holes on the surfaces of the activated carbon are occupied by the deposited carbon and inactivated, and the carbon black still has relatively stable catalytic efficiency at the moment. The tail gas is cracked to generate the nano carbon material and hydrogen, the nano carbon material is deposited on the surface of the active carbon sheet, and when the nano carbon is deposited to a certain amount, the nano carbon falls onto the surface of the graphite plate 3221 due to the fact that gravity is larger than the surface binding force. The tail gas flows out from a gas outlet 33 at the top of the isothermal cracking furnace after layer-by-layer reaction. A large amount of hydrocarbon gas is cracked in an isothermal zone to generate deposited carbon materials and hydrogen, and the design of the isothermal zone structure of the isothermal cracking furnace mainly prolongs the retention time of the hydrocarbon gas so as to ensure that the hydrocarbon gas is fully cracked and deposited. The final tail gas (98% hydrogen) flows from gas outlet 33 into the separator for separation. The reaction temperature, the reaction atmosphere and the catalyst composition have a significant effect on the growth of nanocarbon. When the temperature of the constant temperature area is 750 ℃, and the catalyst is ferrocene or metallic nickel, the catalytic effect is optimal.
5) the separated hydrogen gas passes through a pressure swing separator 41 and a solid filter 42 and then enters the hydrogen-oxygen fuel cell 5 to generate electricity. The electric power can be used in a cooling water circulation system, thereby saving energy and improving the utilization rate.
Third, example III
As shown in fig. 7-9, in one embodiment of the present invention,
The equipment comprises the following steps:
A CVI/CVD process tail gas recovery device comprises a cooling and filtering device 1, a vacuum pump 2, an isothermal cracking furnace 3 and a post-stage comprehensive treatment device 4, wherein the cooling and filtering device 1 comprises a circulating liquid cooling module 11, an oil filter 12 and a drying filter 13; the cooling filtration equipment still includes oil groove 14, oil groove and oil filter UNICOM 12, the oil groove afterbody is provided with butterfly valve 141 and waste oil export 142. The vacuum pump 2 is arranged between the cooling and filtering device 1 and the isothermal cracking furnace 3; a preheating zone module 31 is arranged at the bottom in the isothermal cracking furnace 3, and an isothermal zone module 32 is arranged above the preheating zone module 31; the preheating zone module 31 is a multi-layer labyrinth graphite plate 313; the lower part of the isothermal zone module 32 is a delay buffer area 321, the delay buffer area 321 is a funnel-shaped graphite structure, and the bottom of the funnel-shaped graphite structure is an isothermal zone inlet 3211 and a graphite tube 3212 inserted into the bottom of the funnel-shaped graphite structure. The upper part of the isothermal zone module 321 is an isothermal zone upper cavity 322, the isothermal zone upper cavity 322 is provided with a multilayer graphite plate structure comprising graphite plates 3221, 3223 and 3224, the graphite plates have no middle hole, and tail gas passes through the two sides; the graphite plate is provided with a carbon felt structure 3222 with the activated carbon growth structure in a spiral arrangement, and the surface of the carbon felt structure 3222 is loaded with a carbon black catalyst; the top of the isothermal cracking furnace 2 is provided with a gas outlet 33, and the gas outlet 33 is connected with the post-stage comprehensive treatment equipment 4 through a pipeline; the post-integrated processing apparatus 4 includes a pressure swing separator 41 and a solid filter 42. The hydrogen gas after the post-integrated processing device 4 is fed to the hydrogen-oxygen fuel cell 5.
(II) an implementation step
These examples are intended to be illustrative only and not to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereto by those skilled in the art. The following example 1 is an example of the procedure:
1) The circulating liquid cooling module 11 and the oil filter 12 are started.
2) Tail gas gets into from cooling filtration equipment 1 entry, through the cooling of circulating liquid cooling module 11, gets into oil filter 12 to reduce the temperature of tail gas, adsorb macromolecules such as tar in the tail gas simultaneously. The working principle of the oil filter 12 is as follows: oil is introduced from an oil inlet 121 filtered by the oil filter 12, then reaches the top pipeline 122 through a pipeline, and is sprayed out from the small holes 123 of the top pipeline 122, the sprayed oil is in a mist shape, and the oil mist can fully cool and adsorb tail gas in the descending process. The adsorbed fuel is deposited on the bottom of the oil tank 14, and the equivalent is accumulated to some extent to open the butterfly valve 141 and discharged from the waste oil outlet 142.
3) The exhaust gas is secondarily adsorbed and filtered by the dry filter 13 to reach the vacuum pump 2, and the gas temperature is low and does not contain tar and other substances.
4) the tail gas enters the furnace chamber from the bottom inlet 30 of the isothermal cracking furnace 3, firstly enters the preheating zone module 31, flows into the preheating zone upper cavity 312 from the graphite bottom plate hole 311, then rises along the channel partitioned by the multi-layer labyrinth graphite plate 313 (the number of layers of the graphite plate can be increased or decreased according to different hydrocarbon gases) from the preheating zone upper cavity 312 as shown in fig. 7, and finally enters the isothermal zone module 32, at the moment, the temperature of the tail gas has no little difference with the temperature of the isothermal zone, the tail gas flows into the funnel-shaped delay buffer zone 321 made of graphite from the bottom plate hole 3211 of the isothermal zone module 32, a section of graphite pipe 3212 extending into the bottom of the funnel is arranged at the bottom of the funnel, carbon black catalyst or other light catalyst particles are arranged around the graphite pipe 3212, when the tail gas flows through the graphite pipe 3212, negative pressure is generated above the tail gas, so that the light catalyst is blown up, the catalyst particles are always suspended in the area above the graphite pipe 3212, if the airflow is greater than a certain value, the catalyst particles are blown to the bottom of the graphite plate 3221 above the funnel, the catalyst particles fall into the funnel-shaped area again after impacting the bottom, the pyrolysis product carbon black or carbon nanotubes are deposited on the surfaces of the catalyst particles along with the progress of the thermal cracking reaction, and the deposited carbon black or carbon nanotubes fall off from the surfaces of the catalyst particles along with the movement of the catalyst particles and the stacking of the deposits on the surfaces of the particles, so that the solid in the area is increased, and when a certain amount is reached, the surplus carbon black or carbon nanotubes overflow out of the funnel-shaped area along the wall surface of the funnel. The tail gas flows through the funnel area and then enters the upper cavity 322 of the isothermal zone along the wall surface, the upper cavity 322 of the isothermal zone is provided with a multilayer graphite plate structure, the structure comprises graphite plates 3221, 3223 and 3224, a carbon felt structure 3222 spirally arranged on the graphite plate structure, a carbon black catalyst is loaded on the surface of the carbon felt structure 3222, under the action of high temperature and the catalyst, hydrocarbon gas in the tail gas is cracked, nano carbon black is deposited on the surface of active carbon, the catalytic activity of the active carbon at the initial stage of reaction is stronger than that of the carbon black, but along with the deposition, holes on the surface of the active carbon are occupied by the deposited carbon and inactivated, and the carbon black still has relatively stable catalytic efficiency at the moment. The tail gas is cracked to generate the nano carbon material and hydrogen, the nano carbon material is deposited on the surface of the carbon felt structure, and when the nano carbon is deposited to a certain amount, the nano carbon falls onto the surface of the graphite plate 3221 due to the fact that gravity is larger than the surface binding force. The tail gas flows out from a gas outlet 33 at the top of the isothermal cracking furnace after layer-by-layer reaction. A large amount of hydrocarbon gas is cracked in an isothermal zone to generate deposited carbon materials and hydrogen, and the design of the isothermal zone structure of the isothermal cracking furnace mainly prolongs the retention time of the hydrocarbon gas so as to ensure that the hydrocarbon gas is fully cracked and deposited. The final tail gas (98% hydrogen) flows from the gas outlet 33 into a separator for separation. The reaction temperature, the reaction atmosphere and the catalyst composition have a significant effect on the growth of nanocarbon. When the temperature of the constant temperature area is 750 ℃, and the catalyst is ferrocene or metallic nickel, the catalytic effect is optimal.
5) The separated hydrogen gas passes through a pressure swing separator 41 and a solid filter 42 and then enters the hydrogen-oxygen fuel cell 5 to generate electricity. The electric power can be used in a cooling water circulation system, thereby saving energy and improving the utilization rate.
in summary, the embodiments of the present invention are merely exemplary and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made according to the content of the claims of the present invention should fall within the technical scope of the present invention.
Claims (10)
1. A CVI/CVD process tail gas recovery device comprises a cooling filter device, a vacuum pump, an isothermal cracking furnace and a post-stage comprehensive treatment device, and is characterized in that the cooling filter device comprises a circulating liquid cooling module, an oil filter and a drying filter; the vacuum pump is arranged between the cooling filtering equipment and the isothermal cracking furnace; a preheating zone module is arranged at the bottom in the isothermal cracking furnace, and an isothermal zone module is arranged above the preheating zone module; the preheating zone module is a multilayer labyrinth graphite plate; the lower part of the isothermal zone module is a delay buffer zone, the upper part of the isothermal zone module is an isothermal zone upper cavity, the isothermal zone upper cavity is provided with a multilayer graphite plate structure, an activated carbon growth structure is arranged on the graphite plate, and the surface of the activated carbon growth structure is loaded with a carbon black catalyst; the top of the isothermal cracking furnace is a gas outlet, and the gas outlet is connected with post-stage comprehensive treatment equipment through a pipeline; the post-stage comprehensive treatment equipment comprises a pressure swing separator and a solid filter.
2. A CVI/CVD process off-gas recovery apparatus as claimed in claim 1, wherein the delay buffer zone is a funnel-shaped graphite structure, and the bottom of the funnel-shaped graphite structure is an isothermal zone inlet and a graphite tube inserted into the bottom of the funnel-shaped graphite structure.
3. The apparatus for recovering CVI/CVD process off-gas as claimed in claim 1, wherein the hydrogen gas after the post-integrated processing apparatus is introduced into a hydrogen-oxygen fuel cell.
4. The apparatus for recovering CVI/CVD process off-gas as claimed in claim 1, wherein the activated carbon growth structure is densely arranged activated carbon columns.
5. a CVI/CVD process off-gas recovery device according to claim 1, characterized in that the activated carbon growth structure is a radiantly arranged activated carbon sheet.
6. A CVI/CVD process off-gas recovery device according to claim 1, characterized in that the activated carbon growth structure is a spirally arranged carbon felt structure.
7. the apparatus for recovering CVI/CVD process off-gas according to claim 1, wherein the temperature-reducing filtering device further comprises an oil tank, the oil tank is communicated with the oil filter, and a butterfly valve is disposed at the tail of the oil tank.
8. A method for recovering tail gas of a CVI/CVD process comprises the following steps:
Cooling and filtering: tail gas of the CVI/CVD process enters cooling and filtering equipment through a tail gas inlet, and is cooled and filtered through a circulating liquid cooling module, an oil filter and a drying filter;
A cracking step: the tail gas after temperature reduction and filtration enters an isothermal cracking furnace and firstly passes through a multilayer labyrinth graphite plate preheating zone module positioned at the bottom of the isothermal cracking furnace; the preheated gas passes through a delay buffer area and a cavity on an isothermal area, and is subjected to full cracking reaction;
And (3) post-stage comprehensive treatment: hydrogen generated by the cracking reaction enters post-stage comprehensive treatment equipment through a gas outlet which is positioned at the top of the isothermal cracking furnace; respectively passing through a pressure swing separator and a solid filter.
9. The method of claim 8, wherein the isothermal zone module has a temperature of 750 ℃.
10. A method for recovering tail gas from CVI/CVD processes according to claim 8, wherein a catalyst is placed in the isothermal zone, and the catalyst is ferrocene or metallic nickel.
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