CN115108546B - System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer - Google Patents
System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer Download PDFInfo
- Publication number
- CN115108546B CN115108546B CN202210454302.0A CN202210454302A CN115108546B CN 115108546 B CN115108546 B CN 115108546B CN 202210454302 A CN202210454302 A CN 202210454302A CN 115108546 B CN115108546 B CN 115108546B
- Authority
- CN
- China
- Prior art keywords
- vapor deposition
- conveyor belt
- pyrolysis
- carbon
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 title claims abstract description 12
- 239000002910 solid waste Substances 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- 238000000197 pyrolysis Methods 0.000 claims abstract description 46
- 238000007740 vapor deposition Methods 0.000 claims abstract description 45
- 238000002844 melting Methods 0.000 claims abstract description 29
- 230000008018 melting Effects 0.000 claims abstract description 29
- 239000004033 plastic Substances 0.000 claims abstract description 28
- 229920003023 plastic Polymers 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 230000001172 regenerating effect Effects 0.000 claims abstract 3
- 238000001816 cooling Methods 0.000 claims description 34
- 239000002041 carbon nanotube Substances 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 239000002826 coolant Substances 0.000 claims description 16
- 239000003546 flue gas Substances 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 230000007246 mechanism Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000013502 plastic waste Substances 0.000 abstract 1
- 238000005019 vapor deposition process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 7
- 239000003570 air Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001815 biotherapy Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 transition metal salts Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4581—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber characterised by material of construction or surface finish of the means for supporting the substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Nanotechnology (AREA)
- Combustion & Propulsion (AREA)
- Carbon And Carbon Compounds (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a system and a method for continuously preparing carbon materials and co-producing hydrogen by using organic solid waste high polymers, wherein the system comprises the following steps: the device comprises a melting feeding device, a pyrolysis device, a vapor deposition device, a pyrolysis gas purifying and utilizing device, a gas device, a carbon product collecting device and a catalyst regenerating device. The method comprises the steps of heating and melting waste plastics, feeding the waste plastics into a pyrolysis device, introducing generated pyrolysis gas into a vapor deposition device, and separating and storing residual gas after reaction by hydrogen; the conveyor belt substrate circulates in the device, is cooled after vapor deposition reaction, and is subjected to the next reaction after the carbon product is recovered, the catalyst is reloaded and dried. The invention forms a system for continuously preparing high-performance carbon materials and co-producing hydrogen by plastic waste, and partially supplies energy to the system by combustible gas generated in the pyrolysis and vapor deposition processes, thereby solving the technical problems of low product yield and high energy consumption of the traditional pyrolysis method and greatly improving the energy utilization rate.
Description
Technical Field
The invention relates to the technical field of pyrolysis, in particular to a system and a method for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers.
Background
Plastic is considered as one of the most difficult substances to degrade in nature, and over 60% of waste plastic in the world is treated by adopting a burning and landfilling rough method, so that the problems of water, air and soil pollution and occupied land are not ignored. How to realize the cleaning and high-value utilization of waste plastics becomes the key of recycling waste plastics. The plastic product is rich in two elements of carbon and hydrogen, and the carbon content of common polyolefin and polystyrene plastic is as high as 80-93wt.% and the hydrogen content is 8-16wt.%. The hydrocarbon generated after the pyrolysis of the waste plastics can be used as a cheap carbon source for synthesizing the carbon nano-tubes.
In recent years, the co-production of high-value carbon nano materials such as graphene, carbon nano tubes and the like by utilizing micromolecular carbon-containing gas generated by pyrolysis of waste plastics at high temperature is gradually developed into an advanced and economical utilization technology. Graphene and carbon nanotubes have high electron mobility, low resistivity, and excellent thermal conductivity and permeability, and have wide application prospects in the fields of energy storage and conversion, water decomposition, nano devices, environmental and green chemistry, catalysis, biosensors, biotherapy, and the like.
In the prior art, the preparation method of the carbon nano tube mainly comprises methods of arc discharge, laser ablation, vapor deposition and the like, wherein the purity of the carbon nano tube prepared by adopting the arc method and the laser method is low, the morphological requirement on raw materials is high, and waste plastics are not a conventional carbon-containing raw material source for preparing the carbon nano tube by adopting the method. The pyrolysis method in the traditional vapor deposition method has complex steps, and is difficult to continuously prepare high-performance carbon materials such as carbon nanotubes.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, provides a system and a method for continuously preparing carbon materials and co-producing hydrogen, solves the problems that the traditional pyrolysis method is complex in steps and difficult to continuously prepare based on a pyrolysis-deposition-regeneration process and a mode of growing carbon nanotubes on a conveyor belt substrate, and realizes continuous online preparation of high-performance carbon materials while ensuring the quality of carbon products.
In order to solve the technical problems, the invention provides the following technical scheme:
A system for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers is characterized in that: including melt feed arrangement, pyrolysis device, chemical vapor deposition device and the pyrolysis gas purification utilization equipment that link to each other in proper order, chemical vapor deposition device includes vapor deposition stove, conveyer belt and carbon product cooling device, be provided with conveyer belt entry and conveyer belt export on the vapor deposition stove, carbon product cooling device with the conveyer belt export is connected, the conveyer belt uses the stainless steel foil as the basement, carries the catalyst on it, the conveyer belt can follow the conveyer belt entry enters into in proper order in vapor deposition stove and the carbon product cooling device and constantly forward transmission, pyrolysis gas purification utilization equipment includes centrifuge, compressor, hydrogen purification device and hydrogen storage tank, gas outlet on the vapor deposition stove connects gradually centrifuge, compressor, hydrogen purification device and hydrogen storage tank.
Further, the carbon product cooling device comprises a cooling cavity, a fan and a condenser, wherein the cooling cavity is communicated with the outlet of the conveyor belt, a cooling medium inlet and a cooling medium outlet are formed in the cooling cavity, and the cooling medium outlet is sequentially connected with the condenser, the fan and the cooling medium inlet.
Further, a carbon product collecting device is arranged at the downstream of the carbon product cooling device, the conveyor belt passes through the carbon product collecting device, and the carbon product collecting device can fall off and collect carbon products on the conveyor belt.
Further, the carbon product collecting device adopts an ultrasonic cleaning device.
Further, a catalyst regeneration device is provided downstream of the carbon product collection device, and the conveyor belt passes through the catalyst regeneration device.
Further, still include gas device, gas device includes air-fuel ratio controller, small-size combustor, first vacuum pump and second vacuum pump, melting feed arrangement includes the inner tube, sets up the outside urceolus of inner tube and sets up the inside screw conveyer of inner tube, be provided with feed inlet and discharge gate on the inner tube, the discharge gate with pyrolysis device's entry linkage, hydrogen purification device connects gradually flue gas entry on first vacuum pump, air-fuel ratio controller, small-size combustor and the urceolus, the second vacuum pump is connected with air-fuel ratio controller.
The method for continuously preparing the carbon material co-production hydrogen by using the organic solid waste high polymer is characterized by comprising the following steps of:
step 1: waste plastics are put into a melting feeding device from a feeding hole to be heated and melted;
step 2: pushing the melted material into the pyrolysis device through a spiral conveying mechanism to carry out pyrolysis reaction, and enabling gas products generated after pyrolysis to enter a vapor deposition furnace to generate carbon nanotubes on a conveyor belt substrate;
Step 3: cooling a conveyor belt from a vapor deposition furnace, taking ethanol as a medium, cleaning and separating carbon nanotubes on a conveyor belt substrate into the ethanol medium, and collecting the generated carbon nanotubes through suction filtration and separation;
step 4: supplementing and drying the catalyst on the conveyor belt substrate, and then sending the conveyor belt substrate into a vapor deposition furnace again for reaction;
Step 5: extracting residual gas after reaction in the vapor deposition furnace, and purifying and separating to obtain hydrogen and other combustible gases;
Step 6: and (2) introducing high-temperature flue gas generated by the combustion of the combustible gas into a melting feeding device to provide a heat source for melting the waste plastics in the step (1).
Further, the melting temperature of the waste plastics in the step 1 is 150-200 ℃, the pyrolysis reaction temperature of the pyrolysis device in the step 2 is 500-800 ℃, the reaction temperature in the vapor deposition furnace is 800 ℃, and the temperature of high-temperature flue gas generated by the combustion of combustible gas in the step 6 is 300-400 ℃.
Compared with the prior art, the invention has the beneficial effects that: 1. the system for preparing the high-quality carbon nanotube fiber by adopting continuous melting and feeding and pyrolysis-vapor deposition coupling of the waste plastics can generate byproduct gases including hydrogen, methane, carbon monoxide and the like while generating the high-quality carbon nanotubes, and the hydrogen can be separated and purified, so that the aim of co-producing the hydrogen is fulfilled. 2. After separating and purifying hydrogen, the byproduct gas generated by the system is also remained with combustible gases such as methane, carbon monoxide and the like, and the combustible gases generated in the reaction are used for supplying energy to the system part, so that a system for continuously producing high-performance carbon materials and co-producing hydrogen by using plastic wastes is formed, the energy utilization rate is greatly improved, and the purposes of energy conservation and emission reduction are achieved. 3. The invention provides a reactor for preparing carbon nano tube materials by two-section continuous on-line pyrolysis-vapor deposition, which is characterized in that pyrolysis and vapor deposition steps are respectively carried out in two-section reaction furnaces, and the processes of carbon material generation, cooling, collection and substrate recycling are integrated in a conveyor belt substrate mode, so that the continuous on-line preparation of the carbon nano materials is realized, and the operation steps are greatly simplified.
Drawings
FIG. 1 is a schematic diagram of a system for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers;
Wherein: 1-a screw conveying mechanism; 2-a melt feed apparatus; 3-a feed inlet; 4-a first vacuum pump; 5-small burner; 6-an air-fuel ratio controller; 7-a hydrogen storage tank; 8-a hydrogen purification device; 9-a compressor; 10-a centrifuge; 11-gas outlet; 12. a conveyor belt; 13-a second vacuum pump; 14-a catalyst regeneration device; 15-carbon product collection means; 16-fans; 17-a condenser; 18-a cooling chamber; 19-a vapor deposition furnace; 20-a pyrolysis device; 21-a discharge hole.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described in detail with reference to the drawings, which are provided for the purpose of illustrating the present invention only and are not to be construed as limiting the scope of the present invention.
Fig. 1 shows a specific embodiment of a system for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers, which comprises:
A melting and feeding device 2 for heating and melting the waste plastics;
The pyrolysis device 20 is used for carrying out catalytic pyrolysis on molten waste plastics, and is provided with a material inlet, a pyrolysis gas outlet and a slag discharge port, wherein the material inlet is communicated with a discharge port 21 of the melting feeding device 2, and the pyrolysis gas outlet is connected with a runner pipe and leads to the vicinity of a substrate of the conveyor belt 12 in the vapor deposition furnace 19;
The vapor deposition device comprises a vapor deposition furnace 19, a conveyor belt 12 and a carbon product cooling device, wherein the vapor deposition furnace 19 is provided with a conveyor belt inlet and a conveyor belt outlet, the carbon product cooling device is connected with the conveyor belt outlet, the conveyor belt 12 takes stainless steel foil as a substrate, a catalyst is loaded on the conveyor belt 12, the conveyor belt 12 can enter the vapor deposition furnace 19 and the carbon product cooling device in sequence from the conveyor belt inlet and continuously drive forwards, the vapor deposition device is used for carrying out vapor deposition reaction on gas products generated after pyrolysis of molten waste plastics to generate carbon nanotubes, and the travelling direction of the conveyor belt 12 and the direction of pyrolysis gas flow are opposite to each other so as to improve the reaction rate;
the carbon product cooling device comprises a cooling cavity 18, a fan 16 and a condenser 17, wherein the cooling cavity 18 is communicated with a conveyor belt outlet, a cooling medium inlet and a cooling medium outlet are formed in the cooling cavity 18, the cooling medium outlet is sequentially connected with the condenser 17, the fan 16 and the cooling medium inlet, the carbon product cooling device is used for cooling generated carbon nanotube products, nitrogen is used as a cooling medium, the nitrogen is circulated through the fan 16, and the cooling medium is cooled through the condenser 17;
the pyrolysis gas purifying and utilizing device comprises a centrifugal machine 10, a compressor 9, a hydrogen purifying device 8 and a hydrogen storage tank 7, wherein a gas outlet of a gas outlet 19 on a vapor deposition furnace is sequentially connected with the centrifugal machine 10, the compressor 9, the hydrogen purifying device 8 and the hydrogen storage tank 7 and is used for carrying out hydrogen purification and combustible gas separation on residual gas after vapor deposition reaction;
the fuel gas device comprises an air-fuel ratio controller 6, a small combustor 8, a first vacuum pump 4 and a second vacuum pump 13, and the obtained combustible gas (mainly methane, carbon monoxide and the like) separated by the hydrogen purification device 8 is used as fuel, and high-temperature flue gas generated by combustion is conveyed to the melting and feeding device 2 to be used as a heat source for melting waste plastics;
A carbon product collecting device 15 disposed downstream of the carbon product cooling device, the conveyor belt 12 coming out of the carbon product cooling device passing through the carbon product collecting device 15, the carbon product collecting device 15 being capable of shedding and collecting carbon products deposited on the conveyor belt 12;
the catalyst regeneration device 14, the conveyor belt 12 coming out of the carbon product collecting device 15 passes through the catalyst regeneration device 14, and is used for reloading and drying the catalyst on the substrate of the conveyor belt 12 after the carbon product is cleaned and stripped.
The structure of the melting feeding device 2 comprises an inner cylinder and an outer cylinder sleeved outside the inner cylinder, wherein a feeding hole 3 is formed in the inner cylinder, a flue gas inlet connected with a flue gas outlet of the small combustor 5 is formed in the outer cylinder, and a flue gas flow channel is formed between the outer cylinder and the inner cylinder; the inner cylinder is internally provided with a spiral conveying mechanism 1, in particular to a spiral auger, and one end of the spiral auger is driven by a motor. The melting feeding device 2 is of a double-layer cylinder (pipe) structure, high-temperature smoke circulates between the outer cylinder and the inner cylinder, materials are conveyed in the inner cylinder, and waste plastics and the smoke indirectly transfer heat through the cylinder wall.
The structure of the vapor deposition furnace 19 further comprises an insulating layer and a flow pipe, wherein the flow pipe is used for directly conveying the pyrolyzed gas products to the vicinity of the substrate of the conveyor belt 12, and the insulating layer can ensure the self-maintenance of the carbon deposition reaction temperature.
The carbon product collecting device 15 is an ultrasonic cleaning device with two open ends, ethanol is used as a medium, the conveying belt 12 conveyed in is subjected to ultrasonic oscillation cleaning, so that carbon products fall off from a substrate, and the carbon products are separated from the medium through suction filtration.
As shown in fig. 1, the hydrogen purification device 8 is provided with a gas inlet, an upper outlet for separating high purity hydrogen, and a lower outlet for separating residual pyrolysis gas, the upper outlet is connected to the hydrogen storage tank 7, and the lower outlet is connected to the small burner 5 through the air-fuel ratio controller 6. The pyrolysis gas inlet of the hydrogen purification device 8 is connected with the gas outlet 11 of the vapor deposition furnace 19, and a centrifugal machine 10 and a compressor 9 are sequentially connected on a connecting pipeline. The hydrogen purification device 8 is provided with an upper outlet, a middle outlet and a lower outlet, the uppermost outlet is a separated high-purity hydrogen outlet, and the outlet is connected with the hydrogen storage tank 7; the middle and lower outlets are used for discharging residual pyrolysis gas into the air-fuel ratio controller 6, and the exhaust pipe is provided with a first vacuum pump 4, and the compressor 9 and the first vacuum pump 4 ensure the hydrogen separation and purification effect.
The two inlets of the air-fuel ratio controller 6 are respectively connected with a residual gas outlet of the hydrogen purification device and air, and combustible gas and air are respectively introduced into the air-fuel ratio controller 6 through the first vacuum pump 4 and the second vacuum pump 13, and the air-fuel ratio controller 6 is connected with the small combustor 5 in series and is used for controlling the proportion of the air and the combustible gas.
The catalyst in the vapor deposition furnace 19 is preferably a powder catalyst prepared by mixing inexpensive transition metal salts with an alcohol solution, drying, and annealing at high temperature under an air atmosphere. Inexpensive transition metals include, but are not limited to, one or more of iron, cobalt, nickel; the annealing temperature ranges from 800 ℃ to 850 ℃.
Preferably, the outside of the melt feeder 2, the vapor deposition furnace 19 and the catalyst regeneration device 14 is provided with a heat insulating layer.
The method for continuously preparing the carbon material and co-producing the hydrogen by using the organic solid waste high polymer comprises the following steps:
step 1: waste plastic raw materials are put into a melting and feeding device 2 from a feeding hole 3 for heating and melting, a heat source required by the melting and feeding device 2 is provided by a mode of indirect heat transfer of high-temperature flue gas generated by burning methane, carbon monoxide and other gases in a small combustor 5, and the melting temperature of the waste plastic is 150-200 ℃;
Step 2: the melted materials are pushed into a pyrolysis device 20 to carry out pyrolysis reaction by a screw conveying mechanism 1, a catalyst is not needed in the step, a needed heat source is provided in an electric heating mode, and the pyrolysis temperature is 500-800 ℃; the gas product generated after pyrolysis is introduced into the gas deposition furnace 19 to react nearby the substrate of the conveyor belt 12 through a flow pipe, the reaction temperature is 800 ℃, and the deposition reaction of the carbon nano tube is exothermic, and the outer side of the gas deposition furnace 19 is provided with a heat preservation layer, so that the step does not need a heat source, and the self-maintenance of the temperature can be realized; the catalyst was pre-supported on the surface of the substrate of the conveyor belt 12, and the solid product produced after the reaction was about 40% by weight of the charge, and the proportion of hydrogen in the residual non-condensable gas was about 70%;
Step 3: the reacted conveyor belt 12 immediately enters a carbon product cooling device for cooling, the cooling medium is nitrogen, the cooling medium is indirectly cooled by an external condenser 17, and the temperature of the cooled carbon product is 50-100 ℃; the generated carbon nanotubes are conveyed to a carbon product collecting device 15 for collection and utilization, and the carbon product collecting device 15 breaks away and collects carbon products from the substrate of the conveyor belt 12 by ultrasonic oscillation;
step 4: the conveyor belt 12 after oscillation cleaning enters a catalyst regeneration device 14 for reloading the catalyst, and enters a vapor deposition furnace 19 for reaction after drying;
step 5: residual gas in the vapor deposition furnace 19 enters the hydrogen purification device 8 after passing through the centrifugal machine 10 and the compressor 9 to separate high-purity hydrogen and is stored in the hydrogen storage tank 7;
step 6: the combustible gas (mainly comprising methane and carbon monoxide) in the residual gas enters the small burner 5 for combustion after the proportion of the combustible gas to the air is regulated by the air-fuel ratio controller 6, the discharged high-temperature flue gas is introduced between the inner cylinder and the outer cylinder of the melting feeding device 2 from the flue gas inlet and is used as a heating and melting heat source, and the temperature of the high-temperature flue gas is 300-400 ℃.
The embodiment builds a continuous preparation process of spiral melting continuous feeding and a pyrolysis and vapor deposition coupling method, adopts high-temperature flue gas to melt waste plastics, adopts a system for preparing carbon nanotubes in a segmented mode through pyrolysis and vapor deposition reaction, continuously and efficiently prepares the carbon nanotubes, and realizes high-value recycling of the waste plastics.
The foregoing detailed description will set forth only for the purposes of illustrating the general principles and features of the invention, and is not meant to limit the scope of the invention in any way, but rather should be construed in view of the appended claims.
Claims (3)
1. A system for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers is characterized in that: the device comprises a melting feeding device (2), a pyrolysis device (20), a chemical vapor deposition device and a pyrolysis gas purifying and utilizing device which are sequentially connected, wherein the chemical vapor deposition device comprises a vapor deposition furnace (19), a conveyor belt (12) and a carbon product cooling device, a conveyor belt inlet and a conveyor belt outlet are formed in the vapor deposition furnace (19), the carbon product cooling device is connected with the conveyor belt outlet, the conveyor belt (12) takes stainless steel foil as a substrate, a catalyst is loaded on the stainless steel foil, the conveyor belt (12) can sequentially enter the vapor deposition furnace (19) and the carbon product cooling device from the conveyor belt inlet and continuously forwards drive the vapor deposition furnace (19) and the carbon product cooling device, the pyrolysis gas purifying and utilizing device comprises a centrifugal machine (10), a compressor (9), a hydrogen purifying device (8) and a hydrogen storage tank (7), and a gas outlet on the vapor deposition furnace (19) is sequentially connected with the centrifugal machine (10), the compressor (9), the hydrogen purifying device (8) and the hydrogen storage tank (7);
the carbon product cooling device comprises a cooling cavity (18), a fan (16) and a condenser (17), wherein the cooling cavity (18) is communicated with the outlet of the conveyor belt, a cooling medium inlet and a cooling medium outlet are formed in the cooling cavity (18), and the cooling medium outlet is sequentially connected with the condenser (17), the fan (16) and the cooling medium inlet;
Further comprising a carbon product collection device (15), the carbon product collection device (15) being arranged downstream of the carbon product cooling device, the conveyor belt (12) passing through the carbon product collection device (15), the carbon product collection device (15) being capable of shedding and collecting carbon products on the conveyor belt (12);
The carbon product collecting device (15) adopts an ultrasonic cleaning device, a catalyst regenerating device (14) is arranged at the downstream of the carbon product collecting device (15), and the conveyor belt (12) passes through the catalyst regenerating device (14);
Still include gas device, gas device includes air-fuel ratio controller (6), small-size combustor (5), first vacuum pump (4) and second vacuum pump (13), melting feed arrangement (2) are in including inner tube, setting the outside urceolus of inner tube and setting are in screw conveying mechanism (1) inside the inner tube, be provided with feed inlet (3) and discharge gate (21) on the inner tube, discharge gate (21) with the entry linkage of pyrolysis device (20), hydrogen purification device (8) connect gradually flue gas entry on first vacuum pump (4), air-fuel ratio controller (6), small-size combustor (5) and the urceolus, second vacuum pump (13) are connected with air-fuel ratio controller (6).
2. A method for continuously preparing carbon materials and co-producing hydrogen by using organic solid waste high polymers, which is characterized by comprising the following steps:
Step 1: waste plastics are put into a melting feeding device (2) from a feeding hole (3) for heating and melting;
step 2: pushing the melted material into the pyrolysis device (20) through the spiral conveying mechanism (1) to carry out pyrolysis reaction, and enabling gas products generated after pyrolysis to enter the vapor deposition furnace (19) to generate carbon nanotubes on the substrate of the conveyor belt (12);
Step 3: cooling a conveyor belt (12) from a vapor deposition furnace (19), taking ethanol as a medium, cleaning and separating carbon nanotubes on a substrate of the conveyor belt (12) into the ethanol medium, and collecting the generated carbon nanotubes through suction filtration and separation;
step 4: replenishing and drying the catalyst on the substrate of the conveyor belt (12), and then sending the catalyst into a vapor deposition furnace (19) again for reaction;
step 5: residual gas after reaction in the vapor deposition furnace (19) is extracted, purified and separated to obtain hydrogen and other combustible gases;
Step 6: and (2) introducing high-temperature flue gas generated by the combustion of the combustible gas into a melting feeding device (2) to provide a heat source for melting the waste plastics in the step (1).
3. The method for continuously preparing carbon materials and co-producing hydrogen by using the organic solid waste high polymer according to claim 2, which is characterized in that: the melting temperature of waste plastics in the step1 is 150-200 ℃, the pyrolysis reaction temperature of the pyrolysis device (20) in the step 2 is 500-800 ℃, the reaction temperature in the vapor deposition furnace (19) is 800 ℃, and the temperature of high-temperature flue gas generated by the combustion of combustible gas in the step 6 is 300-400 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210454302.0A CN115108546B (en) | 2022-04-27 | 2022-04-27 | System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer |
| PCT/CN2022/132801 WO2023207044A1 (en) | 2022-04-27 | 2022-11-18 | System and method for continuously preparing carbon material and co-producing hydrogen from organic solid waste polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210454302.0A CN115108546B (en) | 2022-04-27 | 2022-04-27 | System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115108546A CN115108546A (en) | 2022-09-27 |
| CN115108546B true CN115108546B (en) | 2024-08-06 |
Family
ID=83326554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210454302.0A Active CN115108546B (en) | 2022-04-27 | 2022-04-27 | System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115108546B (en) |
| WO (1) | WO2023207044A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115108546B (en) * | 2022-04-27 | 2024-08-06 | 东南大学 | System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer |
| CN115974058B (en) * | 2023-02-15 | 2024-04-09 | 华中农业大学 | Preparation method and system of graphene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105531226A (en) * | 2013-09-30 | 2016-04-27 | 日本瑞翁株式会社 | Method for producing carbon nanostructure, and carbon nanotube |
| CN107934938A (en) * | 2017-12-06 | 2018-04-20 | 武汉光谷环保科技股份有限公司 | The method that two-phase method catalytic pyrolysis waste plastic prepares carbon nanotubes |
| CN113457575A (en) * | 2021-06-07 | 2021-10-01 | 东南大学 | System and method for preparing carbon nanofibers and hydrogen through microwave continuous pyrolysis |
| CN114031068A (en) * | 2021-11-16 | 2022-02-11 | 东南大学 | High-yield preparation of carbon nano tube and hydrogen based on mesh catalyst and regeneration method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168656C (en) * | 2000-04-13 | 2004-09-29 | 中国科学院成都有机化学研究所 | Moving-bed catalytic cracking process for continuously preparing nm carbon tubes |
| JP7176126B1 (en) * | 2018-08-16 | 2022-11-21 | ニー アン ポリテクニック | Process and Apparatus for Synthesizing Multiwalled Carbon Nanotubes from High Polymer Waste |
| CN109336096B (en) * | 2018-10-19 | 2023-09-26 | 深圳市纳设智能装备有限公司 | Equipment for open type continuous growth of carbon nano material and preparation method |
| CN111621315A (en) * | 2020-05-29 | 2020-09-04 | 广州维港环保科技有限公司 | Pyrolysis process system for recycling waste plastics |
| CN114180555B (en) * | 2021-11-04 | 2023-02-03 | 华中科技大学 | Carbon nanotube preparation system and method using waste plastics as raw materials |
| CN114068958B (en) * | 2021-11-16 | 2023-12-08 | 东南大学 | Method for preparing carbon nano tube by catalytic pyrolysis of waste plastics and applying carbon nano tube to low-temperature fuel cell |
| CN115108546B (en) * | 2022-04-27 | 2024-08-06 | 东南大学 | System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer |
-
2022
- 2022-04-27 CN CN202210454302.0A patent/CN115108546B/en active Active
- 2022-11-18 WO PCT/CN2022/132801 patent/WO2023207044A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105531226A (en) * | 2013-09-30 | 2016-04-27 | 日本瑞翁株式会社 | Method for producing carbon nanostructure, and carbon nanotube |
| CN107934938A (en) * | 2017-12-06 | 2018-04-20 | 武汉光谷环保科技股份有限公司 | The method that two-phase method catalytic pyrolysis waste plastic prepares carbon nanotubes |
| CN113457575A (en) * | 2021-06-07 | 2021-10-01 | 东南大学 | System and method for preparing carbon nanofibers and hydrogen through microwave continuous pyrolysis |
| CN114031068A (en) * | 2021-11-16 | 2022-02-11 | 东南大学 | High-yield preparation of carbon nano tube and hydrogen based on mesh catalyst and regeneration method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023207044A1 (en) | 2023-11-02 |
| CN115108546A (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115108546B (en) | System and method for continuously preparing carbon material and co-producing hydrogen by using organic solid waste high polymer | |
| CN113457575B (en) | System and method for preparing carbon nanofibers and hydrogen through microwave continuous pyrolysis | |
| JP5706294B2 (en) | Catalytic reactor | |
| CN101412915A (en) | Interior heating type method for continuously preparing coal gas by pyrolysis and gasification of biomass and pyrolysis gasification furnace | |
| CN112142038A (en) | Carbon nanotube batch preparation system with tail gas waste heat recycling device | |
| CN114180555B (en) | Carbon nanotube preparation system and method using waste plastics as raw materials | |
| CN112961695A (en) | Solid waste anaerobic pyrolysis and high-temperature melting treatment process and system | |
| CN101407320B (en) | Vertical reaction device for preparing nano carbon fibre in batch | |
| JP4869300B2 (en) | Nanocarbon production equipment | |
| CN108219852A (en) | The gasification reactor apparatus and its producing gas method of microwave-heating biomass | |
| CN101812309B (en) | Method for preparing coal-based carbonized material used for preparing active carbon | |
| JP5117252B2 (en) | Nanocarbon and carbide continuous production equipment | |
| CN110747010A (en) | Self-produced gas combustion linkage type pyrolysis gasification device | |
| CN113405367B (en) | Lithium battery recycling powder reduction equipment and ternary lithium battery recycling powder reduction method | |
| CN102115672B (en) | Reaction furnace device for decomposing substances to be treated by utilizing high temperature steam and heat source | |
| CN212833623U (en) | Pyrolysis gas recycling reaction device | |
| CN201313818Y (en) | Vertical reaction device for massive preparation of nano-carbon fiber | |
| CN110127664B (en) | Equipment and method for automatically and continuously producing carbon nano tube by using fixed bed | |
| CN210974536U (en) | Side-draft type oxygen-free medium-temperature pyrolysis furnace | |
| CN110746992A (en) | Side-draft type oxygen-free medium-temperature pyrolysis furnace | |
| CN206278924U (en) | The system for preparing calcium carbide | |
| CN110747009A (en) | Updraft type pyrolysis gasification system | |
| KR101704767B1 (en) | Gasifier having circulation structure of thermal decomposition gas | |
| CN220867333U (en) | Device for preparing biochar and pyrolysis oil by biomass continuous pyrolysis | |
| CN110669537B (en) | Carbon-fertilizer co-production system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |