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
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 56
- 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 24
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 title claims abstract description 11
- 239000002910 solid waste Substances 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 53
- 238000007740 vapor deposition Methods 0.000 claims abstract description 48
- 238000000197 pyrolysis Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000004033 plastic Substances 0.000 claims abstract description 26
- 229920003023 plastic Polymers 0.000 claims abstract description 26
- 238000002844 melting Methods 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000000746 purification Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000002485 combustion reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 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 17
- 239000002826 coolant Substances 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 15
- 239000003546 flue gas Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 10
- 230000007246 mechanism Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000004140 cleaning 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
- 238000001035 drying Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims 2
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 8
- 239000000155 melt Substances 0.000 abstract description 5
- 239000013502 plastic waste Substances 0.000 abstract description 2
- 238000005265 energy consumption 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 3
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 3
- 239000002994 raw material Substances 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
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001815 biotherapy 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
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- 230000009467 reduction Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 transition metal salts Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Carbon And Carbon Compounds (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
本发明涉及一种有机固废高聚物连续制备碳材料联产氢的系统和方法，该系统包括：熔融进料装置、热解装置、气相沉积装置、热解气纯化利用装置、燃气装置、碳产物收集装置及催化剂再生装置。该方法包括将废塑料加热熔融进入热解装置，生成的热解气通入气相沉积装置，将反应后的残余气体进行氢气分离并储存；传送带基底在装置中循环，进行气相沉积反应后冷却，在进行碳产物回收了进行催化剂的再负载和干燥，经循环后进行下一步反应。本发明形成了塑料废弃物连续制备高性能碳材料联产氢的系统，并通过热解与气相沉积过程中产生的可燃气体对系统进行部分供能，解决了传统热解方法产物收率低、能耗高的技术问题，极大地提高了能源利用率。
The present invention relates to a system and method for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers. The system comprises: a melt feeding device, a pyrolysis device, a vapor deposition device, a pyrolysis gas purification and utilization device, a gas combustion device, a carbon product collection device and a catalyst regeneration device. The method comprises heating and melting waste plastics into the pyrolysis device, passing the generated pyrolysis gas into the vapor deposition device, separating the hydrogen from the residual gas after the reaction and storing it; the conveyor belt substrate circulates in the device, cools after the vapor deposition reaction, reloads and dries the catalyst after the carbon product is recovered, and performs the next step of reaction after the cycle. The present invention forms a system for continuously preparing high-performance carbon materials and co-producing hydrogen from plastic waste, and partially powers the system with combustible gas generated during pyrolysis and vapor deposition, thereby solving the technical problems of low product yield and high energy consumption in traditional pyrolysis methods and greatly improving energy utilization.
Description
技术领域Technical Field
本发明涉及热解技术领域，尤其涉及一种有机固废高聚物连续制备碳材料联产氢的系统和方法。The present invention relates to the technical field of pyrolysis, and in particular to a system and method for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers.
背景技术Background technique
塑料被认为是自然界最难降解的物质之一，世界范围内有超过60％的废塑料采用焚烧和填埋粗放式方法处理，带来的水气土污染及占地问题不容忽视。如何实现废塑料的清洁、高值化利用成为废塑料回收利用的关键。而塑料制品富含碳、氢两种元素，常见的聚烯烃、聚苯烯类塑料所含碳元素高达80-93wt.％，氢含量8-16wt.％。废塑料裂解后生成的碳氢化合物可以作为廉价碳源用以合成碳纳米管。Plastic is considered one of the most difficult substances to degrade in nature. More than 60% of waste plastics worldwide are treated by extensive methods such as incineration and landfilling, which can not be ignored. How to achieve clean and high-value utilization of waste plastics has become the key to the recycling of waste plastics. Plastic products are rich in carbon and hydrogen. Common polyolefins and polystyrene plastics contain up to 80-93wt.% carbon and 8-16wt.% hydrogen. The hydrocarbons generated by the cracking of waste plastics can be used as a cheap carbon source to synthesize carbon nanotubes.
近年来，利用废塑料高温下热解产生的小分子含碳气体合成石墨烯、碳纳米管等高价值碳纳米材料联产氢气逐渐发展成一项先进、经济性高的利用技术。石墨烯和碳纳米管具有高电子迁移率、低电阻率以及优异的导热性和渗透性，在能量储存和转换、水分解、纳米器件、环境和绿色化学、催化、生物传感器和生物治疗等领域有广泛的应用前景。In recent years, the use of small molecular carbon-containing gases produced by high-temperature pyrolysis of waste plastics to synthesize high-value carbon nanomaterials such as graphene and carbon nanotubes and co-produce hydrogen has 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. They have broad application prospects in energy storage and conversion, water decomposition, nanodevices, environmental and green chemistry, catalysis, biosensors and biotherapy.
在现有技术中，碳纳米管的制备方式主要有电弧放电、激光烧蚀以及气相沉积等方法，其中采用电弧法和激光法所制备生成的碳纳米管纯度较低，且对原材料的形态要求较高，废弃塑料并非是该种方法制备碳纳米管的一种常规的含碳原料来源。而传统的气相沉积法中的热解方法步骤复杂，难以连续制备高性能的碳纳米管等碳材料。In the prior art, the main methods for preparing carbon nanotubes include arc discharge, laser ablation and vapor deposition. The carbon nanotubes prepared by arc method and laser method have low purity and high requirements on the morphology of raw materials. Waste plastic is not a conventional source of carbon-containing raw materials for preparing carbon nanotubes by this method. The pyrolysis method in the traditional vapor deposition method has complicated steps and it is difficult to continuously prepare high-performance carbon nanotubes and other carbon materials.
发明内容Summary of the invention
本发明目的在于针对现有技术的缺陷，提供一种连续制备碳材料联产氢的系统和方法，基于热解-沉积-再生工艺，以及传送带基底生长碳纳米管的方式，解决了传统热解方法步骤复杂、难以连续制备的问题，实现了在保证碳产物品质的同时，连续在线制备高性能碳材料。The purpose of the present invention is to address the defects of the prior art and provide a system and method for continuously preparing carbon materials and co-producing hydrogen. Based on the pyrolysis-deposition-regeneration process and the method of growing carbon nanotubes on a conveyor belt substrate, the system and method solve the problems of complex steps and difficulty in continuous preparation of traditional pyrolysis methods, and achieve continuous online preparation of high-performance carbon materials while ensuring the quality of carbon products.
为解决上述技术问题，本发明提供技术方案如下：In order to solve the above technical problems, the present invention provides the following technical solutions:
一种有机固废高聚物连续制备碳材料联产氢的系统，其特征在于：包括依次相连的熔融进料装置、热解装置、化学气相沉积装置和热解气纯化利用装置，所述化学气相沉积装置包括气相沉积炉、传送带和碳产物冷却装置，所述气相沉积炉上设置有传送带入口和传送带出口，所述碳产物冷却装置与所述传送带出口连接，所述传送带以不锈钢箔为基底，其上负载有催化剂，所述传送带能够从所述传送带入口依次进入到气相沉积炉和碳产物冷却装置内并不断向前传动，所述热解气纯化利用装置包括离心机、压缩机、氢气纯化装置和储氢罐，所述气相沉积炉上的气体出口依次连接所述离心机、压缩机、氢气纯化装置和储氢罐。A system for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers, characterized in that it includes a molten feeding device, a pyrolysis device, a chemical vapor deposition device and a pyrolysis gas purification and utilization device connected in sequence, the chemical vapor deposition device includes a vapor deposition furnace, a conveyor belt and a carbon product cooling device, the vapor deposition furnace is provided with a conveyor belt inlet and a conveyor belt outlet, the carbon product cooling device is connected to the conveyor belt outlet, the conveyor belt is based on stainless steel foil, a catalyst is loaded thereon, the conveyor belt can enter the vapor deposition furnace and the carbon product cooling device in sequence from the conveyor belt inlet and continuously drive forward, the pyrolysis gas purification and utilization device includes a centrifuge, a compressor, a hydrogen purification device and a hydrogen storage tank, the gas outlet on the vapor deposition furnace is connected to the centrifuge, the compressor, the hydrogen purification device and the hydrogen storage tank in sequence.
进一步的，所述碳产物冷却装置包括冷却腔、风机和冷凝器，所述冷却腔与所述传送带出口连通，冷却腔上设置有冷却介质入口和冷却介质出口，所述冷却介质出口依次连接所述冷凝器、风机和冷却介质入口。Furthermore, the carbon product cooling device includes a cooling chamber, a fan and a condenser, the cooling chamber is connected to the conveyor belt outlet, and a cooling medium inlet and a cooling medium outlet are provided on the cooling chamber, and the cooling medium outlet is connected to the condenser, the fan and the cooling medium inlet in sequence.
进一步的，还包括碳产物收集装置，所述碳产物收集装置设置在所述碳产物冷却装置的下游，所述传送带穿过碳产物收集装置，碳产物收集装置能够脱落并收集传送带上的碳产物。Furthermore, it also includes a carbon product collecting device, which is arranged 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 the carbon products on the conveyor belt.
进一步的，所述碳产物收集装置采用超声清洗装置。Furthermore, the carbon product collecting device adopts an ultrasonic cleaning device.
进一步的，在所述碳产物收集装置的下游设置有催化剂再生装置，所述传送带从所述催化剂再生装置中穿过。Furthermore, a catalyst regeneration device is provided downstream of the carbon product collecting device, and the conveyor belt passes through the catalyst regeneration device.
进一步的，还包括燃气装置，所述燃气装置包括空燃比控制器、小型燃烧器、第一真空泵和第二真空泵，所述熔融进料装置包括内筒、设置在所述内筒外部的外筒和设置在所述内筒内部的螺旋输送机构，所述内筒上设置有进料口和出料口，所述出料口与所述热解装置的入口连接，所述氢气纯化装置依次连接所述第一真空泵、空燃比控制器、小型燃烧器和外筒上的烟气入口，所述第二真空泵与空燃比控制器相连接。Furthermore, it also includes a gas device, which includes an air-fuel ratio controller, a small burner, a first vacuum pump and a second vacuum pump. The molten feeding device includes an inner cylinder, an outer cylinder arranged outside the inner cylinder and a spiral conveying mechanism arranged inside the inner cylinder. The inner cylinder is provided with a feed port and a discharge port, and the discharge port is connected to the inlet of the pyrolysis device. The hydrogen purification device is connected to the first vacuum pump, the air-fuel ratio controller, the small burner and the flue gas inlet on the outer cylinder in sequence, and the second vacuum pump is connected to the air-fuel ratio controller.
一种有机固废高聚物连续制备碳材料联产氢的方法，利用上述的连续制备碳材料联产氢的系统，其特征在于，包括如下步骤：A method for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers, using the above-mentioned system for continuously preparing carbon materials and co-producing hydrogen, is characterized by comprising the following steps:
步骤1：将废塑料从进料口投入到熔融进料装置中进行加热熔融；Step 1: Put the waste plastics from the feed port into the melting feed device for heating and melting;
步骤2：熔融后的物料经由螺旋输送机构推动进入所述热解装置中进行热解反应，热解后产生的气体产物进入气相沉积炉中，在传送带基底上生成碳纳米管；Step 2: The molten material is pushed into the pyrolysis device via a screw conveying mechanism for pyrolysis reaction, and the gas product generated after pyrolysis enters the vapor deposition furnace to generate carbon nanotubes on the conveyor belt substrate;
步骤3：对从气相沉积炉中出来的传送带经过冷却后，以乙醇为介质，将传送带基底上的碳纳米管清洗分离到乙醇介质中，并经过抽滤分离，收集到生成的碳纳米管；Step 3: After cooling the conveyor belt coming out of the vapor deposition furnace, the carbon nanotubes on the conveyor belt substrate are washed and separated into the ethanol medium using ethanol as a medium, and the generated carbon nanotubes are collected by suction filtration and separation;
步骤4：对传送带基底上的催化剂进行补充和干燥，之后再次送入气相沉积炉中进行反应；Step 4: replenish and dry the catalyst on the conveyor belt substrate, and then send it into the vapor deposition furnace again for reaction;
步骤5：抽出气相沉积炉中反应后的残余气体，并进行提纯和分离得到氢气和其他可燃气体；Step 5: extracting the residual gas after the reaction in the vapor deposition furnace, and purifying and separating it to obtain hydrogen and other combustible gases;
步骤6：将所述可燃气体燃烧产生的高温烟气通入熔融进料装置中，为所述步骤1中废塑料的熔融提供热源。Step 6: The high-temperature flue gas generated by the combustion of the combustible gas is introduced into the melting feed device to provide a heat source for the melting of the waste plastics in step 1.
进一步的，所述步骤1中废塑料的熔融温度为150℃～200℃，所述步骤2中热解装置的热解反应温度为500℃～800℃，气相沉积炉中的反应温度为800℃，所述步骤6中可燃气体燃烧产生的高温烟气温度为300℃～400℃。Furthermore, the melting temperature of the waste plastic in step 1 is 150°C to 200°C, the pyrolysis reaction temperature of the pyrolysis device in step 2 is 500°C to 800°C, the reaction temperature in the vapor deposition furnace is 800°C, and the temperature of the high-temperature flue gas generated by the combustion of the combustible gas in step 6 is 300°C to 400°C.
与现有技术相比，本发明的有益效果是：1、本发明采用的废塑料连续熔融进料、热解-气相沉积耦合制备高品质碳纳米管纤维的系统，在产生高品质碳纳米管的同时，还可以产生包括氢气、甲烷、一氧化碳等在内的副产物气体，其中的氢气可以进行分离和提纯，达到联产氢气的目的。2、本系统产生的副产物气体在经过分离提纯出氢气后，还剩余有甲烷、一氧化碳等可燃气体，利用反应中生成的可燃气体为系统部分供能，形成了塑料废弃物连续生产高性能碳材料联产氢气的系统，极大地提高了能源利用率，达到了节能减排的目的。3、本发明提出了两段式连续在线热解-气相沉积制备碳纳米管材料的反应器，将热解与气相沉积步骤分别置于两段反应炉中进行，并以传送带基底的方式集成碳材料生成、冷却、收集以及基底再利用的过程，实现了碳纳米材料的连续在线制备，大大简化了操作步骤。Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The system of the present invention for preparing high-quality carbon nanotube fibers by continuous melting feeding of waste plastics, pyrolysis-vapor deposition coupling, while producing high-quality carbon nanotubes, can also produce byproduct gases including hydrogen, methane, carbon monoxide, etc., wherein the hydrogen can be separated and purified to achieve the purpose of co-producing hydrogen. 2. After the byproduct gases produced by this system are separated and purified to produce hydrogen, combustible gases such as methane and carbon monoxide remain. The combustible gases generated in the reaction are used to power part of the system, forming a system for continuously producing high-performance carbon materials and co-producing hydrogen from plastic waste, greatly improving energy utilization and achieving the purpose of energy conservation and emission reduction. 3. The present invention proposes a two-stage continuous online pyrolysis-vapor deposition reactor for preparing carbon nanotube materials, placing the pyrolysis and vapor deposition steps in two-stage reactors respectively, and integrating the processes of carbon material generation, cooling, collection and substrate reuse in the form of a conveyor belt substrate, realizing the continuous online preparation of carbon nanomaterials, and greatly simplifying the operation steps.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明一种有机固废高聚物连续制备碳材料联产氢的系统的结构示意图；FIG1 is a schematic structural diagram of a system for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers according to the present invention;
其中：1-螺旋输送机构；2-熔融进料装置；3-进料口；4-第一真空泵；5-小型燃烧器；6-空燃比控制器；7-储氢罐；8-氢气纯化装置；9-压缩机；10-离心机；11-气体出口；12、传送带；13-第二真空泵；14-催化剂再生装置；15-碳产物收集装置；16-风机；17-冷凝器；18-冷却腔；19-气相沉积炉；20-热解装置；21-出料口。Among them: 1-screw conveying mechanism; 2-molten feeding device; 3-feeding port; 4-first vacuum pump; 5-small burner; 6-air-fuel ratio controller; 7-hydrogen storage tank; 8-hydrogen purification device; 9-compressor; 10-centrifuge; 11-gas outlet; 12, conveyor belt; 13-second vacuum pump; 14-catalyst regeneration device; 15-carbon product collection device; 16-blower; 17-condenser; 18-cooling chamber; 19-vapor deposition furnace; 20-pyrolysis device; 21-discharging port.
具体实施方式Detailed ways
为了加深本发明的理解，下面我们将结合附图对本发明作进一步详述，该实施例仅用于解释本发明，并不构成对本发明保护范围的限定。In order to deepen the understanding of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings. The embodiments are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention.
图1示出了一种有机固废高聚物连续制备碳材料联产氢的系统的具体实施例，包括：FIG1 shows a specific embodiment of a system for continuously preparing carbon materials and co-producing hydrogen from organic solid waste polymers, comprising:
熔融进料装置2，用于对废塑料进行加热熔融处理；The melt feeding device 2 is used for heating and melting the waste plastics;
热解装置20，用于对熔融的废塑料进行催化热解，其上设置有物料入口、热解气出口和排渣口，物料入口与熔融进料装置2的出料口21相连通，热解气出口连接流通管，通向气相沉积炉19中的传送带12基底附近；The pyrolysis device 20 is used to catalytically pyrolyze the molten waste plastics, and is provided with a material inlet, a pyrolysis gas outlet and a slag discharge port. The material inlet is connected to the discharge port 21 of the molten feeding device 2, and the pyrolysis gas outlet is connected to a flow pipe leading to the vicinity of the base of the conveyor belt 12 in the vapor deposition furnace 19;
气相沉积装置，包括气相沉积炉19、传送带12和碳产物冷却装置，气相沉积炉19上设置有传送带入口和传送带出口，碳产物冷却装置与传送带出口连接，传送带12以不锈钢箔为基底，其上负载有催化剂，传送带12能够从传送带入口依次进入到气相沉积炉19和碳产物冷却装置内并不断向前传动，气相沉积装置用于对熔融废塑料热解后生成的气体产物进行气相沉积反应生成碳纳米管，传送带12的行进方向与热解气气流的方向相向流动，以提高反应率；A vapor deposition device, comprising a vapor deposition furnace 19, a conveyor belt 12 and a carbon product cooling device. The vapor deposition furnace 19 is provided with a conveyor belt inlet and a conveyor belt outlet, the carbon product cooling device is connected to the conveyor belt outlet, the conveyor belt 12 is based on a stainless steel foil, a catalyst is loaded thereon, 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 drive forward, the vapor deposition device is used to generate carbon nanotubes by vapor deposition reaction of gas products generated after pyrolysis of molten waste plastics, and the traveling direction of the conveyor belt 12 is opposite to the direction of the pyrolysis gas flow to increase the reaction rate;
碳产物冷却装置，包括冷却腔18、风机16和冷凝器17，冷却腔18与传送带出口连通，冷却腔18上设置有冷却介质入口和冷却介质出口，冷却介质出口依次连接冷凝器17、风机16和冷却介质入口，碳产物冷却装置用于对生成的碳纳米管产物进行冷却，利用氮气作为冷却介质，通过风机16进行循环，并以冷凝器17对冷却介质进行冷却；The carbon product cooling device comprises a cooling chamber 18, a fan 16 and a condenser 17. The cooling chamber 18 is connected to the conveyor belt outlet. A cooling medium inlet and a cooling medium outlet are provided on the cooling chamber 18. The cooling medium outlet is connected to the condenser 17, the fan 16 and the cooling medium inlet in sequence. The carbon product cooling device is used to cool the generated carbon nanotube product. Nitrogen is used as a cooling medium, which is circulated through the fan 16, and the cooling medium is cooled by the condenser 17.
热解气纯化利用装置，包括离心机10、压缩机9、氢气纯化装置8和储氢罐7，气相沉积炉上19的气体出口依次连接离心机10、压缩机9、氢气纯化装置8和储氢罐7，用于对气相沉积反应后的残余气体进行氢气提纯和可燃气体分离；The pyrolysis gas purification and utilization device comprises a centrifuge 10, a compressor 9, a hydrogen purification device 8 and a hydrogen storage tank 7. The gas outlet 19 on the vapor deposition furnace is connected to the centrifuge 10, the compressor 9, the hydrogen purification device 8 and the hydrogen storage tank 7 in sequence, and is used to purify the residual gas after the vapor deposition reaction with hydrogen and separate the combustible gas;
燃气装置，包括空燃比控制器6、小型燃烧器8、第一真空泵4和第二真空泵13，利用氢气纯化装置8分离后的得到可燃气体(主要为甲烷、一氧化碳等)为燃料，并将燃烧产生的高温烟气输送至熔融进料装置2，用作废塑料熔融的热源；The gas-burning device includes an air-fuel ratio controller 6, a small burner 8, a first vacuum pump 4 and a second vacuum pump 13, which uses the combustible gas (mainly methane, carbon monoxide, etc.) separated by the hydrogen purification device 8 as fuel, and transports the high-temperature flue gas generated by the combustion to the melting feed device 2 to be used as a heat source for melting the waste plastics;
碳产物收集装置15，设置在碳产物冷却装置的下游，从碳产物冷却装置出来的传送带12穿过碳产物收集装置15，碳产物收集装置15能够脱落并收集传送带12上沉积的碳产物；A carbon product collecting device 15 is arranged downstream of the carbon product cooling device. The conveyor belt 12 coming out of the carbon product cooling device passes through the carbon product collecting device 15. The carbon product collecting device 15 can fall off and collect the carbon products deposited on the conveyor belt 12.
催化剂再生装置14，从碳产物收集装置15中出来的传送带12穿过催化剂再生装置14，用于对清洗剥离碳产物后的传送带12基底进行催化剂的再负载以及干燥。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, which is used to reload and dry the catalyst on the conveyor belt 12 substrate after cleaning and stripping the carbon product.
其中，熔融进料装置2的结构包括内筒、套设在内筒外部的外筒，内筒上设有进料口3，外筒上设有连接小型燃烧器5烟气出口的烟气入口，外筒与内筒之间形成烟气的流动通道；内筒中设有螺旋输送机构1，具体采用螺旋状绞龙，其一端由电机驱动。熔融进料装置2呈双层筒(管)状结构，外筒与内筒之间流通高温烟气，内筒中进行物料输送，废塑料与烟气通过筒壁间接传热。The structure of the melt feeding device 2 includes an inner cylinder and an outer cylinder sleeved outside the inner cylinder. The inner cylinder is provided with a feed port 3, and the outer cylinder is provided with a smoke inlet connected to the smoke outlet of the small burner 5. A smoke flow channel is formed between the outer cylinder and the inner cylinder. A spiral conveying mechanism 1 is provided in the inner cylinder, which specifically adopts a spiral auger, one end of which is driven by a motor. The melt feeding device 2 is a double-layer cylinder (tube) structure. High-temperature smoke flows between the outer cylinder and the inner cylinder, and material is transported in the inner cylinder. The waste plastic and the smoke transfer heat indirectly through the cylinder wall.
气相沉积炉19的结构还包括保温层、流通管，流通管用于将热解后的气体产物直接输送至传送带12基底附近，保温层能够保证碳沉积反应温度的自保持。The structure of the vapor deposition furnace 19 also includes a heat preservation layer and a circulation pipe. The circulation pipe is used to directly transport the gas products after pyrolysis to the vicinity of the base of the conveyor belt 12. The heat preservation layer can ensure the self-maintenance of the carbon deposition reaction temperature.
碳产物收集装置15为两端开口的超声清洗装置，以乙醇为介质，将输送进来的传送带12进行超声振荡清洗，使碳产物从基底上脱落，后续通过抽滤操作使得碳产物与介质分离。The carbon product collecting device 15 is an ultrasonic cleaning device with openings at both ends. It uses ethanol as a medium to perform ultrasonic oscillation cleaning on the conveyor belt 12 to make the carbon products fall off the substrate, and then separate the carbon products from the medium through suction filtration.
如图1所示，氢气纯化装置8上设有气体入口、用于分离高纯氢气的上部出口、用于分离残余热解气的下部出口，上部出口与储氢罐7连接，下部出口通过空燃比控制器6与小型燃烧器5连接。氢气纯化装置8的热解气入口与气相沉积炉19的气体出口11连接，连接管路上依次连接有离心机10、压缩机9。氢气纯化装置8设有上中下三处出口，最上部出口为分离后的高纯氢出口，该出口连接储氢罐7；中部、下部出口用于排出残余热解气到空燃比控制器6中，并且排气管路上设有第一真空泵4，压缩机9及第一真空泵4保证氢气分离提纯效果。As shown in FIG1 , 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 to the gas outlet 11 of the vapor deposition furnace 19, and the centrifuge 10 and the compressor 9 are connected to the connecting pipeline in sequence. The hydrogen purification device 8 is provided with three outlets, namely, upper, middle and lower. The uppermost outlet is the outlet for high-purity hydrogen after separation, which is connected to the hydrogen storage tank 7; the middle and lower outlets are used to discharge the residual pyrolysis gas into the air-fuel ratio controller 6, and the exhaust pipeline is provided with a first vacuum pump 4. The compressor 9 and the first vacuum pump 4 ensure the hydrogen separation and purification effect.
空燃比控制器6的两个入口分别连接氢气纯化装置的残余气体出口以及空气，可燃气体和空气分别通过第一真空泵4和第二真空泵13通入空燃比控制器6中，空燃比控制器6与小型燃烧器5串联，用于控制空气、可燃气体的比例。The two inlets of the air-fuel ratio controller 6 are respectively connected to the residual gas outlet of the hydrogen purification device and the air. The 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. The air-fuel ratio controller 6 is connected in series with the small burner 5 to control the ratio of air to combustible gas.
气相沉积炉19内的催化剂优选地采用的粉末催化剂，其制备方式为廉价过渡金属盐类与醇溶液混合，烘干后于空气气氛下高温退火获得。廉价过渡金属包括但不限于铁、钴、镍中的一种或多种；退火温度范围为800℃～850℃。The catalyst in the vapor deposition furnace 19 is preferably a powder catalyst, which is prepared by mixing cheap transition metal salts with an alcohol solution, drying, and then annealing at high temperature in an air atmosphere. The cheap transition metal includes but is not limited to one or more of iron, cobalt, and nickel; the annealing temperature ranges from 800°C to 850°C.
优选地，熔融进料装置2、气相沉积炉19和催化剂再生装置14外部设有保温层。Preferably, the melt feeding device 2, the vapor deposition furnace 19 and the catalyst regeneration device 14 are provided with a heat-insulating layer outside.
应用本实施例的有机固废高聚物连续制备碳材料联产氢的方法，包括以下步骤：The method for continuously preparing carbon materials and co-producing hydrogen using organic solid waste polymers of this embodiment comprises the following steps:
步骤1：废塑料原料从进料口3投入到熔融进料装置2中进行加热熔融，熔融进料装置2所需的热源由小型燃烧器5中燃烧甲烷、一氧化碳等气体产生的高温烟气间接传热的方式提供，废塑料的熔融温度为150℃～200℃；Step 1: The waste plastic raw material is fed into the melting feed device 2 from the feed port 3 for heating and melting. The heat source required by the melting feed device 2 is provided by indirect heat transfer of high-temperature flue gas generated by burning methane, carbon monoxide and other gases in the small burner 5. The melting temperature of the waste plastic is 150°C to 200°C.
步骤2：熔融后的物料经由螺旋输送机构1推动进入热解装置20中进行热解反应，该步骤不需要催化剂，所需热源以电加热形式提供，热解温度为500℃～800℃；热解后生成的气体产物经流通管通入气相沉积炉19中的传送带12基底附近反应，反应温度为800℃，由于碳纳米管的沉积反应为放热反应，且气相沉积炉19的外侧设有保温层，因此该步骤不需要热源，可以实现温度的自保持；催化剂预先负载于传送带12的基底表面，反应后生成的固体产物约占投入物料的40％wt，氢气在残余不凝气体中的比例约为70％；Step 2: The molten material is pushed into the pyrolysis device 20 via the screw conveying mechanism 1 for pyrolysis reaction. This step does not require a catalyst, and the required heat source is provided in the form of electric heating, and the pyrolysis temperature is 500°C to 800°C; the gaseous product generated after pyrolysis is passed through the circulation pipe into the vapor deposition furnace 19 near the base of the conveyor belt 12 for reaction, and the reaction temperature is 800°C. Since the deposition reaction of carbon nanotubes is an exothermic reaction, and an insulation layer is provided on the outer side of the vapor deposition furnace 19, this step does not require a heat source and can achieve self-maintenance of temperature; the catalyst is pre-loaded on the base surface of the conveyor belt 12, and the solid product generated after the reaction accounts for about 40%wt of the input material, and the proportion of hydrogen in the residual non-condensable gas is about 70%;
步骤3：反应后的传送带12随即进入碳产物冷却装置中进行冷却，采用空冷方式冷却，冷却介质为氮气，冷却介质通过外接冷凝器17的方式进行间接冷却，冷却后的碳产物温度为50-100℃；生成的碳纳米管输送至碳产物收集装置15进行收集利用，碳产物收集装置15利用超声振荡，使碳产物从传送带12的基底上脱离并收集；Step 3: The conveyor belt 12 after the reaction is immediately cooled in the carbon product cooling device, which is cooled by air cooling. The cooling medium is nitrogen. The cooling medium is indirectly cooled by an external condenser 17. The temperature of the carbon product after cooling is 50-100°C. The generated carbon nanotubes are transported to the carbon product collecting device 15 for collection and utilization. The carbon product collecting device 15 uses ultrasonic oscillation to separate the carbon product from the base of the conveyor belt 12 and collect it.
步骤4：振荡清洗后的传送带12进入催化剂再生装置14进行催化剂的再负载，并经过干燥后再次进入气相沉积炉19中反应；Step 4: The conveyor belt 12 after vibration cleaning enters the catalyst regeneration device 14 for catalyst reloading, and after drying, enters the vapor deposition furnace 19 again for reaction;
步骤5：气相沉积炉19中的残余气体经过离心机10和压缩机9后进入到氢气纯化装置8中分离出高纯氢气并储存到储氢罐7中；Step 5: The residual gas in the vapor deposition furnace 19 passes through the centrifuge 10 and the compressor 9 and enters the hydrogen purification device 8 to separate high-purity hydrogen and store it in the hydrogen storage tank 7;
步骤6：剩余气体中的可燃气体(主要包括甲烷及一氧化碳)经过空燃比控制器6调整与空气的比例后进入小型燃烧器5中燃烧，排出的高温烟气从烟气入口通入到熔融进料装置2的内筒和外筒之间作为加热熔融的热源，高温烟气的温度为300℃～400℃。Step 6: The combustible gas in the remaining gas (mainly including methane and carbon monoxide) enters the small burner 5 for combustion after the ratio with air is adjusted by the air-fuel ratio controller 6. The discharged high-temperature flue gas is passed from the flue gas inlet into the space between the inner cylinder and the outer cylinder of the melting feed device 2 as a heat source for heating and melting. The temperature of the high-temperature flue gas is 300℃～400℃.
上述实施例构建了螺旋熔融连续进料，热解与气相沉积耦合法连续制备工艺，采用高温烟气熔融废塑料，热解与气相沉积反应分段式制备碳纳米管的系统，连续高效制备碳纳米管，实现废塑料的高值化回收利用。The above embodiment constructs a continuous preparation process of spiral melting continuous feeding, pyrolysis and vapor deposition coupling method, adopts high-temperature flue gas to melt waste plastics, and pyrolysis and vapor deposition reaction to prepare carbon nanotubes in a staged manner, so as to continuously and efficiently prepare carbon nanotubes and realize high-value recycling of waste plastics.
上述具体实施方式，仅为说明本发明的技术构思和结构特征，目的在于让熟悉此项技术的相关人士能够据以实施，但以上内容并不限制本发明的保护范围，凡是依据本发明的精神实质所作的任何等效变化或修饰，均应落入本发明的保护范围之内。The above specific implementation methods are only for illustrating the technical concept and structural features of the present invention, and the purpose is to enable relevant persons familiar with this technology to implement it. However, the above content does not limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should fall within the protection scope of the present invention.
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| CN115974058B (en) * | 2023-02-15 | 2024-04-09 | 华中农业大学 | Preparation method and system of graphene |
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| CN116333774A (en) * | 2023-04-28 | 2023-06-27 | 华中科技大学 | System and method for preparing multiple products by catalytic pyrolysis of waste plastics |
| CN119082755A (en) * | 2024-11-04 | 2024-12-06 | 浙江省生态环境监测中心(浙江省生态环境信息中心) | A device and method for producing hydrogen and sulfur by utilizing industrial organic solid waste |
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