CN116902915A - Method for preparing hydrogen-carbon nanomaterial by methane catalytic pyrolysis and integrated system and method for co-producing hydrogen-carbon nanomaterial - Google Patents
Method for preparing hydrogen-carbon nanomaterial by methane catalytic pyrolysis and integrated system and method for co-producing hydrogen-carbon nanomaterial Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 280
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 181
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 119
- 239000001257 hydrogen Substances 0.000 claims abstract description 119
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 239000002699 waste material Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 64
- 238000000746 purification Methods 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000001590 oxidative effect Effects 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000010813 municipal solid waste Substances 0.000 claims abstract description 25
- 238000005336 cracking Methods 0.000 claims abstract description 22
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 238000003860 storage Methods 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 238000000926 separation method Methods 0.000 claims description 40
- 238000011084 recovery Methods 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 238000000197 pyrolysis Methods 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000004576 sand Substances 0.000 claims description 14
- 239000002028 Biomass Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 238000000855 fermentation Methods 0.000 claims description 12
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 230000010354 integration Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000011218 binary composite Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 4
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- 229920000647 polyepoxide Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910021392 nanocarbon Inorganic materials 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
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- 239000000956 alloy Substances 0.000 description 5
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- 229910044991 metal oxide Inorganic materials 0.000 description 4
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- 229920000620 organic polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 229910001152 Bi alloy Inorganic materials 0.000 description 1
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000002546 full scan Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- 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
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
Abstract
The invention provides a method for preparing a hydrogen-carbon nanomaterial by methane catalytic pyrolysis, and an integrated system and method for co-producing the hydrogen-carbon nanomaterial. The method comprises the following steps: the gas comprising methane is subjected to catalytic cracking reaction in the presence of a catalyst to obtain hydrogen and carbon nanomaterial, and the catalytic cracking reaction is performed in the presence of an oxidizing gas. The integrated system comprises a raw material gas preparation device, a methane catalytic cracking reactor, a hydrogen purification device and a carbon nano material discharging device. The cracking reaction is carried out in the presence of oxidizing gas, so that the cracking performance is optimized, the service life of the catalyst is prolonged, and higher conversion rate is realized. The invention has the advantages of continuous production, low cost, high benefit, low energy consumption, automation and easy scale, and can recycle the waste, such as wet garbage, waste high molecular organic matters and the like, to produce the raw material gas mainly containing methane, thereby providing a brand new and ideal practical technology for the efficient recycling of the raw material gas.
Description
Technical Field
The invention relates to the technical field of preparing hydrogen-carbon nano materials by methane catalytic pyrolysis, in particular to a method for preparing hydrogen-carbon nano materials by methane catalytic pyrolysis and an integrated system and method for co-producing hydrogen-carbon nano materials.
Background
Hydrogen has the advantages of high energy density, high combustion heat value, more reserves (hydrogen is the element with the most abundant content in universe), storability, reproducibility, power generation, zero pollution, zero carbon emission and the like, so the hydrogen can be known as the final energy of 21 st century and is hopeful to solve the problems of the current energy crisis, environmental pollution and the like. Since hydrogen energy is a secondary energy source, hydrogen gas needs to be produced from a hydrogen-containing compound. Methane is the most abundant hydrocarbon and widely available (e.g., natural gas and biogas from anaerobic fermentation of wet waste), and is the most dominant feedstock for hydrogen production in industry today. At present, common hydrogen preparation methods mainly comprise methane steam reforming, methane partial oxidation, methane catalytic cracking, coal vaporization, methanol decomposition, ammonia decomposition, electrolysis of water, photocatalytic decomposition of water, biomass conversion and the like. Wherein, the hydrogen production by methane steam reforming is the largest in scale and accounts for about 50% of the world hydrogen production. However, the method has high energy consumption, high production cost and high carbon dioxide emission; the energy conversion efficiency of the partial oxidation hydrogen production of methane is low, and the production process is accompanied by carbon dioxide byproducts; coal gasification hydrogen production equipment is complex, expensive and has a large amount of pollutants and carbon dioxide byproducts; methanol decomposition and ammonia decomposition occupy most of the small and medium-scale hydrogen production markets, but the hydrogen in raw materials methanol and ammonia is derived from methane reforming or coal gasification, so the raw materials are not called clean; electrolytic water and other emerging hydrogen production processes such as photolytic water and biomass conversion are still in the primary stage, and material cost and performance remain to be perfected. The methane catalytic cracking hydrogen production technology is relatively mature, the investment scale is relatively small, pollutants such as carbon dioxide and the like are not discharged in the production process, and high-quality green hydrogen and high-added-value functional carbon nano materials can be obtained simultaneously.
In recent years, with the development of catalysts and the guidance of problems, a plurality of different types of methane cracking reactors have been reported in a large number of documents. Of these, the fixed bed type is most common, but is used only on a laboratory bench scale because continuous production techniques cannot be established. The moving bed type and the fluidized bed type are very similar, and are suitable for mass production because both can continuously add catalyst and discharge carbon nanomaterial. However, the heat transfer efficiency in the cavity of the mobile reactor is low, the catalyst covered carbon is serious, and the pipeline is easy to be blocked in the production process; the fluidized bed reactor has high heat transfer efficiency, but the contact time (reaction time) of the reaction gas and the catalyst particles is very short, and the generated carbon tube containing the active metal nano particles can be removed from the reactor in a short time, so that the catalyst utilization rate is too low, and the practical applicability is difficult. In view of the above problems, upham et al recently reported a methane cracking key technical equipment of the molten liquid metal type. The technical equipment adopts molten nickel-bismuth alloy (27:73) as a catalyst, the density difference and bubble separation effect of the carbon nano tube material generated by pyrolysis and the molten alloy ensure that the carbon material does not cover the catalyst any more, is deposited at the top end of the reactor, is beneficial to separation and extraction, and finally ensures that the technology realizes the methane conversion rate of 95% in a bubbling tower at 1065 ℃ and has production continuity. Meanwhile, the heat transfer efficiency of the molten liquid metal type is high. Therefore, the technique is considered to be suitable for application to mass production. However, this technology needs to work above 1000 ℃ (high energy consumption), and the molten alloy of atomic scale level also has a certain strong corrosiveness (high requirement on reactor quality), and further research and development optimization is still necessary.
Meanwhile, the number of wet garbage and organic polymer waste is increased, but a treatment mode of high-efficiency environment-friendly recycling is still lacking, so that the environmental pollution is aggravated for a long time, and the environmental sanitation and the production and living safety are affected. Therefore, by utilizing the integrated chain type chemical recovery method and the system thereof, the treatment modes of innocuity, reduction and reclamation can be realized, and the recovery and conversion of organic solid waste into high-purity hydrogen and high-added-value nano carbon materials are one of important paths for sustainable development of economy and society in China. The produced hydrogen can be used in the important fields of energy, chemical industry and the like, while the nano carbon material can be used for reinforcing composite materials for tires, coatings and the like, and a high-quality recycling economy mode of organic solid waste is constructed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing hydrogen-carbon nanomaterial by catalytic cracking of methane, and an integrated system and method for co-producing hydrogen-carbon nanomaterial, in which a small amount of oxidizing gas can be introduced during catalytic cracking reaction, so as to further optimize cracking performance, prolong catalyst life and achieve higher conversion rate. The invention can continuously co-produce the hydrogen-carbon nano material, has low cost, high benefit and low energy consumption, accords with the national sustainable development strategy, has the characteristics of automation and easy scale, and can further recycle the waste, such as wet garbage, waste high molecular organic matters and the like, so as to produce the raw material gas mainly comprising methane, thereby providing a brand new and ideal practical technology for the efficient recycling of the raw material gas.
To achieve the above and other related objects, a first aspect of the present invention provides a method for preparing a hydrogen-carbon nanomaterial by catalytic cracking of methane, comprising the steps of:
and carrying out catalytic cracking reaction on the gas comprising methane in the presence of a catalyst to obtain hydrogen and carbon nanomaterial, wherein the catalytic cracking reaction is carried out under the condition of introducing oxidizing gas.
The invention introduces oxidizing gas during catalytic cracking reaction, optimizes cracking performance, prolongs catalyst life and realizes higher conversion rate.
Further, at least one of the following technical features is included: 1) The oxidizing gas includes at least one selected from carbon dioxide, oxygen, and water vapor;
2) The oxidizing gas is derived from the reduction of the catalyst by methane;
3) The pressure of the catalytic cracking reaction is 0.1MPa to 1.6MPa;
4) The gas comprising methane can be derived from waste recycling, and is obtained by the following method: performing anaerobic recovery treatment on the waste;
5) The catalyst is a catalyst for methane catalytic cracking reaction, and specifically the catalyst can be selected from one or more of iron ore, natural sand, iron ore and natural sand composite catalyst, nickel-based catalyst, iron-based catalyst, nickel-iron binary composite catalyst and nickel-iron containing multi-component composite catalyst. Wherein, the cost of the iron ore, the natural sand, the iron ore and the natural sand composite catalyst is low.
6) The volume concentration of the oxidizing gas is 0.1-8%. The volume concentration of the oxidizing gas refers to the percentage of the volume of the oxidizing gas to the total gas volume in the reactor.
7) The temperature of the catalytic cracking reaction is 500-800 ℃.
8) The methane concentration in the methane-containing gas is > 90% by volume.
More preferably, the gas comprising methane is obtained by: and (3) purifying and/or separating and purifying the waste after the anaerobic recovery treatment.
Even more preferably, the waste is subjected to anaerobic recovery treatment and then sequentially subjected to purification and/or separation and purification.
More preferably, the waste is subjected to anaerobic recovery treatment, and at least one method selected from the group consisting of anaerobic fermentation of wet waste, rapid treatment of low-temperature biomass in the wet waste and anaerobic pyrolysis of waste high-molecular organic matters can produce gas with high methane ratio, namely the volume content of methane in the produced gas is more than or equal to 40%, and the volume content is more than or equal to 60%. More preferably, the anaerobic recovery treatment of the waste is anaerobic pyrolysis of waste high molecular organic matters, the waste high molecular organic matters are epoxy resin carbon fiber composite material waste, the weight content of resin in the waste is 30-50%, and the weight content of carbon fiber is 50-70%.
The invention provides an integrated system for co-production of hydrogen-carbon nano materials by high-valued utilization of wastes, which comprises raw material gas preparation equipment, a methane catalytic cracking reactor, hydrogen purification equipment and carbon nano material unloading equipment; the raw material gas preparation equipment is used for preparing raw material gas, and the raw material gas comprises methane;
the raw material gas preparation equipment is communicated with the methane catalytic cracking reactor;
the methane catalytic cracking reactor is respectively communicated with the hydrogen purification equipment and the carbon nano material discharging equipment.
Preferably, the integrated system further comprises at least one of the following technical features:
a1 The raw material gas preparation equipment can prepare raw material gas comprising methane, preferably a waste anaerobic recovery treatment equipment, and recycling waste;
a2 The methane catalytic cracking reactor is an internal spiral methane continuous catalytic cracking moving bed reactor;
a3 The methane catalytic cracking reactor is provided with a nozzle type jet hole for introducing gas containing methane;
a4 The hydrogen purification equipment is membrane separation equipment;
a5 The carbon nano material discharging equipment is automatic conveying and discharging equipment for step-by-step decompression;
a6 A purifying device and/or a separation and purification device are arranged between the raw material gas preparation device and the methane catalytic cracking reactor;
a7 The integrated system further comprises a heating device for supplying heat to the methane catalytic cracking reactor;
a8 The integrated system further comprises a hydrogen storage device, the hydrogen purification device being in communication with the hydrogen storage device.
More preferably, the integrated system further comprises at least one of the following technical features:
a11 In the a 1), the waste anaerobic recovery treatment equipment comprises at least one selected from a wet garbage anaerobic fermentation device, a wet garbage middle-low temperature biomass rapid treatment device and a high molecular organic matter anaerobic cracking treatment device, and when the equipment comprises more than two devices, the devices are connected in parallel, so that the waste can be recycled, and the waste is utilized to produce high methane ratio raw gas;
a41 In the feature a 4), the membrane separation apparatus uses a membrane material having palladium copper as a main component;
a61 In feature a 6), the purification device is a filtration device;
a62 In the feature a 6), the separation and purification device is a feed gas selective separation and purification device;
a63 In the feature a 6), when the purification device and the separation and purification device are provided between the raw material gas preparation device and the methane catalytic cracking reactor, the raw material gas preparation device, the purification device, the separation and purification device and the methane catalytic cracking reactor are sequentially communicated;
a71 In the feature a 7), the heating device is a heating device for supplying heat from a heating device or renewable energy source to the raw material gas or the produced hydrogen gas;
a81 In feature a 8), the hydrogen storage device is a direct compressed gas hydrogen storage device, a liquid hydrogen storage device, a solid hydrogen storage device, or an organic liquid hydrogen storage device.
The third aspect of the invention provides an integrated method for co-producing hydrogen-carbon nanomaterial, comprising the following steps:
1) Preparing a feed gas comprising methane;
2) Carrying out catalytic cracking reaction on the raw material gas to obtain gas containing hydrogen and a material containing carbon nano materials;
3) Purifying the gas comprising hydrogen to obtain purified hydrogen;
4) And discharging the material containing the carbon nano material to obtain the material containing the carbon nano material.
Preferably, the integration method further comprises at least one of the following technical features:
b1 The integration method adopts the integration system;
b2 In step 1), the raw material gas is obtained by anaerobic recovery treatment of waste;
b3 In the step 2), the catalytic cracking reaction is carried out under the condition of introducing oxidizing gas;
b4 In the step 2), the pressure of the catalytic cracking reaction is 0.1MPa to 1.6MPa;
b5 In the step 2), the catalyst used in the catalytic cracking reaction is selected from one or more of iron ore, natural sand, iron ore and natural sand composite catalyst, nickel-based catalyst, iron-based catalyst, nickel-iron binary composite catalyst and nickel-iron containing multi-component composite catalyst;
b6 In step 2), the temperature of the catalytic cracking reaction is 500-800 ℃;
b7 In step 2), the methane concentration in the methane-comprising gas is > 90% by volume;
b8 In step 3), the gas comprising hydrogen is separated by a membrane to obtain purified hydrogen;
b9 In the step 4), the materials comprising the carbon nano materials are discharged through automatic transportation of step-by-step decompression;
b10 In the step 2), the raw material gas is purified and/or separated and purified and then is subjected to catalytic cracking reaction;
b11 In step 2), heat is supplied to the catalytic cracking reaction;
b12 In step 3), hydrogen storage is performed on the purified hydrogen gas.
More preferably, the integration method further comprises at least one of the following technical features:
b21 In the b 2), the waste is subjected to anaerobic recovery treatment, and at least one method selected from the group consisting of anaerobic fermentation of wet garbage, rapid treatment of low-temperature biomass in the wet garbage and anaerobic pyrolysis of waste high-molecular organic matters is carried out;
b31 In feature b 3), the oxidizing gas includes at least one selected from the group consisting of carbon dioxide, oxygen, and water vapor;
b32 In feature b 3), the oxidizing gas is derived from the reduction of the catalyst by methane;
b33 In feature b 3), the volume concentration of the oxidizing gas is 0.1% to 8%;
b81 In the feature b 8), a membrane material containing palladium and copper as main components is used for membrane separation.
More preferably, the hydrogen/carbon nanomaterial co-production method further includes at least one of the following technical features:
b101 In feature b 10), the purifying is filtering;
b102 In the b 10), the separation and purification is selective separation and purification of the raw material gas;
b103 In the characteristic b 10), the raw material gas is subjected to catalytic cracking reaction after being sequentially purified, separated and purified.
More preferably, the integration method further comprises at least one of the following technical features:
b111 In feature b 11), the feed gas or the produced hydrogen is self-heating or renewable energy heating;
b121 In feature b 12), the hydrogen storage is direct compressed gas hydrogen storage, liquid hydrogen storage, solid hydrogen storage, or organic liquid hydrogen storage.
The technical scheme has the following remarkable effects that:
(1) The invention can introduce exogenous or endogenous oxidizing gas during catalytic cracking reaction, optimize cracking performance, prolong catalyst life and realize higher conversion rate;
(2) The invention provides a complete integrated system and a complete integrated method for co-producing hydrogen-carbon nano materials, which can recycle waste resources, such as raw gas with high methane ratio, which is generated by anaerobic fermentation treatment of wet garbage, rapid treatment of wet garbage by medium-low temperature biomass and anaerobic pyrolysis treatment of waste high molecular organic matters (such as epoxy resin), and are efficient and environment-friendly.
(3) The invention can continuously co-produce the hydrogen-carbon nano material, has high hydrogen purity (more than 99%), low cost, high benefit and low energy consumption, accords with national sustainable development strategy, has the characteristics of automation and easy scale, and further provides a brand new and ideal practical technology for the efficient recycling of wastes such as wet garbage and waste high polymer organic matters.
Drawings
Fig. 1 is a schematic diagram of an integrated system for co-producing hydrogen-carbon nanomaterial according to a second embodiment of the present invention.
Fig. 2 is a schematic diagram of an integrated system for co-producing hydrogen-carbon nanomaterial according to a third embodiment of the present invention.
FIG. 3 is a photograph showing the commercial T300 epoxy resin carbon fiber composite material of the embodiment 1 of the present invention before and after the anaerobic cracking treatment of the polymer organic matters by the raw material gas preparation equipment, wherein a is before the treatment, and b is after the treatment.
Fig. 4 shows a gas production analysis chart and an X-ray photoelectron spectrum of a nanocarbon product in example 3 of the present invention, wherein a is gas production analysis data of a methane catalytic cracking reactor by using an on-line gas chromatograph, and b is full-scan spectrum data of the X-ray photoelectron spectrum of the nanocarbon product after acid treatment.
Reference numerals
1. Raw material gas preparation equipment
2. Methane catalytic cracking reactor
3. Hydrogen purification equipment
4. Carbon nanomaterial unloading equipment
5. Purification device
6. Separation and purification equipment
7. Heating apparatus
8. Hydrogen storage device
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
The first embodiment of the invention provides a method for preparing a hydrogen-carbon nanomaterial by catalytic pyrolysis of methane, comprising the following steps:
the gas comprising methane is subjected to catalytic cracking reaction in the presence of a catalyst to obtain hydrogen and carbon nanomaterial, wherein the catalytic cracking reaction is performed in the presence of an oxidizing gas, and the specific oxidizing gas can be introduced from an external source or introduced from an internal source, for example, generated in a cracking system.
In a specific embodiment, a method for obtaining and utilizing a gas comprising methane is provided: performing anaerobic recovery treatment on the waste; then specifically, the waste is subjected to anaerobic recovery treatment and then is purified and/or separated and purified; then, specifically, the waste is subjected to anaerobic recovery treatment and then is sequentially purified and/or separated and purified; and more specifically, the waste is subjected to anaerobic recovery treatment, and at least one method selected from the group consisting of anaerobic fermentation of wet garbage, rapid treatment of low-temperature biomass in the wet garbage and anaerobic pyrolysis of waste high-molecular organic matters. More specifically, for example, the pyrolysis gas obtained by performing anaerobic recovery treatment on the epoxy resin carbon fiber composite material waste is the gas containing methane, or the pyrolysis gas is processed to obtain the gas containing methane; the anaerobic cracking temperature is selected according to the waste, for example, T300 epoxy resin carbon fiber composite material waste obtained by Shanghai Zhi solid alloy science and technology Co., ltd is cracked in an anaerobic state at about 340-430 ℃, specifically, for example, 360-400 ℃, methane obtained by cracking can reach more than 43% in gas component proportion, the cracking gas comprising methane in the proportion can be purified or extracted by purifying equipment with mature technology, and then is conveyed to the subsequent technology, and catalytic cracking reaction is carried out in the presence of a catalyst to obtain hydrogen and carbon nano materials.
In one embodiment, the catalytic cracking reaction is performed in the presence of an oxidizing gas; specifically, the oxidizing gas includes at least one selected from the group consisting of carbon dioxide, oxygen, and water vapor; of course, the oxidizing gas may also result from the reduction of methane by a metal oxide catalyst, e.g., niO@Al 2 O 3 When the catalyst is used, methane and NiO can react to generate carbon monoxide and/or carbon dioxide with oxidability in the catalytic reaction process, and the specific catalyst NiO@Al 2 O 3 The mass content of NiO is 40-65%. In a specific embodiment, the oxidizing gas has a volume concentration of 0.1% to 8%, alternatively a volume concentration of 0.1% to 1%,1% to 2%,2% to 5%, or 5% to 8%. In general, the oxidizing gas obtained by reacting methane with the metal oxide can be maintained at 0.1% to 1% or 1% to 2%, without additional introduction of the oxidizing gas.
In a specific embodiment, the methane concentration in the methane-containing gas is > 90%, preferably > 95%, more preferably >99% by volume.
In a specific embodiment, the gas including methane is subjected to catalytic cracking reaction in the presence of a catalyst to obtain hydrogen and carbon nanomaterial, wherein the pressure of the catalytic cracking reaction is 0.1MPa to 1.6MPa, optionally 0.1MPa to 0.2MPa,0.2MPa to 0.8MPa, or 0.8MPa to 1.6MPa.
In one embodiment, the catalytic cracking reaction is carried out at a temperature of 500 to 800 ℃, alternatively 500 to 600 ℃,600 to 700 ℃, or 700 to 800 ℃.
In a specific embodiment, the catalyst is selected from one or more of iron ore, natural sand, iron ore and natural sand composite catalyst, nickel-based catalyst, iron-based catalyst, nickel-iron binary composite catalyst, and nickel-iron containing multi-component composite catalyst.
The second embodiment of the invention provides an integrated system for the high-valued utilization of waste and co-production of hydrogen-carbon nano materials, which is shown in figure 1 and comprises a raw material gas preparation device 1, a methane catalytic cracking reactor 2, a hydrogen purification device 3 and a carbon nano material discharging device 4; the raw material gas preparation equipment 1 is used for preparing raw material gas, wherein the raw material gas comprises methane;
the raw material gas preparation equipment 1 is communicated with the methane catalytic cracking reactor 2;
the methane catalytic cracking reactor 2 is respectively communicated with a hydrogen purification device 3 and a carbon nano material discharging device 4.
The raw material gas preparation device 1 is used for preparing raw material gas, the raw material gas comprises methane, the raw material gas can be prepared by only the device capable of preparing the raw material gas comprising methane, the raw material gas preparation device 1 is preferably waste anaerobic recovery treatment device for recycling waste, the specific waste anaerobic recovery treatment device comprises at least one selected from a wet garbage anaerobic fermentation device, a low-temperature biomass rapid treatment device in wet garbage and a polymer organic matter anaerobic cracking treatment device, and when the device comprises more than two devices, the devices are connected in parallel.
The methane catalytic cracking reactor 2 may be a fixed bed type reactor, a moving bed type reactor, a fluidized bed type reactor, a molten liquid metal type reactor, or the like. In a preferred embodiment, the methane catalytic cracking reactor 2 is an internal spiral methane continuous catalytic cracking moving bed reactor, has an internal spiral design, can optimize mass transfer (including gas and solid), heat transfer and carbon nanomaterial delivery, utilizes the internal spiral optimization design to furthest promote and utilize the performance of the catalyst, and transfers the carbon nanomaterial and the deactivated catalyst covered by carbon out through the internal spiral, thereby realizing continuous production.
In a preferred embodiment, the methane catalytic cracking reactor 2 is provided with nozzle-type jet holes for introducing methane-containing gas to achieve a better contact surface of methane with the catalyst, i.e. to optimize the gas-solid interface reaction.
In a preferred embodiment, the hydrogen purification device 3 is a membrane separation device, and the subsequent membrane separation device does not require additional energy consumption to provide extreme conditions under the high temperature and high pressure conditions already achieved in the methane catalytic cracking reactor 2.
In a preferred embodiment, the membrane separation device uses a membrane material with palladium copper as a major component.
In a preferred embodiment, the carbon nanomaterial discharge apparatus 4 is a step-wise depressurized automated transport discharge apparatus.
In a preferred embodiment, a purification device 5 and/or a separation and purification device 6 is provided between the feed gas production device 1 and the methane catalytic cracking reactor 2.
In a preferred embodiment, the purifying device 5 is a filtering device, filtering out easily floatable solid particles, etc., and may be a filter screen, etc.
In a preferred embodiment, the separation and purification device 6 is a raw gas selective separation and purification device, such as a biogas pressure swing adsorption separation device commonly used in industry.
In a preferred embodiment, when the purification apparatus 5 and the separation and purification apparatus 6 are provided between the raw material gas preparation apparatus 1 and the methane catalytic cracking reactor 2, the raw material gas preparation apparatus 1, the purification apparatus 5, the separation and purification apparatus 6 and the methane catalytic cracking reactor 2 are sequentially communicated;
in a preferred embodiment, the integrated system further comprises a heating device 7 for supplying heat to the methane catalytic cracking reactor 2, the heat energy may originate from a gas source for combustion heat supply or from a combination of renewable energy sources, not limited to chemical energy conversion into heat energy, but also chemical energy-electric energy-heat energy conversion heat supply. The specific heating device 7 is a heating device for heating raw gas or produced hydrogen from the heating device through catalytic combustion or renewable energy sources.
In a preferred embodiment, the hydrogen/carbon nanomaterial co-production system further comprises a hydrogen storage device 8, the hydrogen purification device 3 being in communication with the hydrogen storage device 8. Specifically, the hydrogen storage device 8 may be a direct compressed gas hydrogen storage device, a liquid hydrogen storage device, a solid hydrogen storage device or an organic liquid hydrogen storage device, which can store hydrogen with high efficiency.
The third embodiment of the invention provides an integrated system for co-producing hydrogen-carbon nano materials, which is shown in fig. 2, and comprises a raw material gas preparation device 1, a methane catalytic cracking reactor 2, a hydrogen purification device 3, a carbon nano material unloading device 4, a purification device 5, a separation and purification device 6, a heating device 7 and a hydrogen storage device 8; the raw material gas preparation equipment 1, the purification equipment 5, the separation and purification equipment 6 and the methane catalytic cracking reactor 2 are sequentially communicated; the methane catalytic cracking reactor 2 is respectively communicated with a hydrogen purification device 3 and a carbon nano material discharging device 4; the heating device 7 supplies heat to the methane catalytic cracking reactor 2; the hydrogen purification device 3 communicates with the hydrogen storage device 8.
The fourth embodiment of the invention provides an integrated method for co-producing hydrogen-carbon nanomaterial, which adopts the integrated system and specifically comprises the following steps:
1) Preparing a feed gas comprising methane;
specifically, the raw material gas is obtained by anaerobic recovery treatment of waste, and the waste is purified and/or separated and purified after anaerobic recovery treatment; then, specifically, the waste is subjected to anaerobic recovery treatment and then is sequentially purified and/or separated and purified; and more specifically, the waste is subjected to anaerobic recovery treatment, and at least one method selected from the group consisting of anaerobic fermentation of wet garbage, rapid treatment of low-temperature biomass in the wet garbage and anaerobic pyrolysis of waste high-molecular organic matters. More specifically, for example, the cracking gas obtained by performing anaerobic recovery treatment on the epoxy resin carbon fiber composite material waste is the gas containing methane, preferably, the epoxy resin carbon fiber composite material waste contains 30-50% of resin by weight and 50-70% of carbon fiber by weight. More specifically, the anaerobic cracking temperature is selected according to the waste, for example, the T300 epoxy resin carbon fiber composite material waste obtained by Shanghai Zhi solid alloy science and technology Co., ltd is cracked in an anaerobic state at about 340-430 ℃, methane obtained by cracking can reach more than 43% in the proportion of gas components, and the cracked gas comprising methane in the proportion can be purified or extracted by a purification device with mature technology process, and then is conveyed to the subsequent process: and then carrying out catalytic cracking reaction in the presence of a catalyst to obtain the hydrogen and carbon nano material.
2) Carrying out catalytic cracking reaction on the raw material gas to obtain gas containing hydrogen and a material containing carbon nano materials;
specifically, the catalytic cracking reaction is carried out under the condition of introducing exogenous oxidizing gas or is carried out endogenously, for example, the oxidizing gas is generated endogenously by a system, for example, the oxidizing gas is generated by reducing a metal oxide catalyst by methane, and for example, a catalyst NiO@Al is adopted 2 O 3 The catalyst can react methane with NiO in the catalytic reaction process to generate carbon monoxide and/or carbon dioxide with oxidability. In a specific embodiment, the oxidizing gas has a volume concentration of 0.1% to 8%, alternatively a volume concentration of 0.1% to 1%,1% to 2%,2% to 5%, or 5% to 8%. In general, the oxidizing gas obtained by reacting methane with the metal oxide can be maintained at 0.1% to 1% or 1% to 2%, without additional introduction of the oxidizing gas.
In a specific embodiment, the methane concentration in the methane-containing gas is > 90%, preferably > 95%, more preferably >99% by volume.
In a specific embodiment, the gas including methane is subjected to catalytic cracking reaction in the presence of a catalyst to obtain hydrogen and carbon nanomaterial, wherein the pressure of the catalytic cracking reaction is 0.1MPa to 1.6MPa, optionally 0.1MPa to 0.2MPa,0.2MPa to 0.8MPa, or 0.8MPa to 1.6MPa.
In one embodiment, the catalytic cracking reaction is carried out at a temperature of 500 to 800 ℃, alternatively 500 to 600 ℃,600 to 700 ℃, or 700 to 800 ℃.
In a specific embodiment, the catalyst is selected from one or more of iron ore, natural sand, iron ore and natural sand composite catalyst, nickel-based catalyst, iron-based catalyst, nickel-iron binary composite catalyst, and nickel-iron containing multi-component composite catalyst.
In one embodiment, the raw material gas is purified and/or separated and purified and then subjected to catalytic cracking reaction; the heat is supplied to the catalytic cracking reaction, more specifically, the raw gas or produced hydrogen is supplied from a heat source or renewable energy source.
3) Purifying the gas comprising hydrogen to obtain purified hydrogen;
specifically, the gas containing hydrogen is subjected to membrane separation to obtain purified hydrogen; more specifically, the membrane separation uses a membrane material having palladium copper as a main component. More specifically, the raw material gas is sequentially purified, separated and purified and then subjected to catalytic cracking reaction, more specifically, the purification is filtration, the separation and purification is selective separation and purification of the raw material gas, more specifically, the raw material gas is sequentially purified, separated and purified and then subjected to catalytic cracking reaction;
in a specific embodiment, the purified hydrogen is subjected to hydrogen storage, more specifically, the hydrogen storage is direct compressed gas hydrogen storage, liquid hydrogen storage, solid hydrogen storage or organic liquid hydrogen storage.
4) And discharging the material containing the carbon nano material to obtain the material containing the carbon nano material.
Example 1
As shown in fig. 3 a, a commercially available T300 epoxy resin carbon fiber composite material is provided, the composite material is put into a raw material gas preparation device 1 (anaerobic cracking treatment device), the composite material is started by an internal superheated steam cracking program in the device, the temperature in a cavity of the device reaches 340-430 ℃ and is in an anaerobic state, and the treated composite material is collected. As shown in fig. 3 b, the polymer or epoxy coating of the composite material with a smooth surface prior to treatment has clearly disappeared after treatment. From this, it can be proved that the anaerobic cracking treatment device for the polymer organic matters in the raw material gas preparation equipment 1 is effective for recycling the solid waste of the organic polymer.
Example 2
The raw material gas is prepared by using T300 epoxy resin carbon fiber composite material waste (the weight content of resin in the waste is 35 percent and the weight content of carbon fiber is 65 percent) obtained by Shanghai Zhi Shi alloy science and technology Co Ltd, specifically, the waste is filled into ton-grade raw material gas preparation equipment 1 (anaerobic cracking treatment device), the equipment is started by an internal superheated steam cracking program in the equipment, the temperature in the equipment cavity reaches 380 ℃ and is in an anaerobic state, and the generated cracking gas (namely the raw material gas of a subsequent recycling process) is collected at fixed time and analyzed by utilizing a gas chromatography-mass spectrometer. Specifically, when the tail gas sampling analysis at the first time point is performed immediately after the temperature reaches 380 ℃, and when the tail gas sampling analysis at the second time point is performed after the temperature is stabilized at 380 ℃, as shown in table 1, the device can be found to effectively generate pyrolysis gas mainly comprising methane and hydrogen when the organic polymer waste is treated under the treatment process conditions by comparing and analyzing with a blank gas cylinder sample and three standard samples (std-1, std-2 and std-3), and the methane content of the methane is up to 43%. After the treatment, the resin in the T300 epoxy resin carbon fiber composite material waste is completely converted into gas.
TABLE 1 Tail gas analysis of T300 epoxy resin carbon fiber composite organic Polymer waste treated by anaerobic pyrolysis
Furthermore, the pyrolysis gas containing methane is purified or extracted by the purification equipment 5 with mature technical process, and then is conveyed to the subsequent recycling process (namely the methane catalytic cracking reactor 2), so that the co-production of hydrogen and the high-value recycling of nano carbon can be realized.
In addition, experiments prove that exogenous carbon dioxide gas is additionally added into the reaction system, so that carbon deposition on the surface of the catalyst can be better eliminated, the service life of the catalyst is prolonged, and high conversion rate is realized.
Example 3
The catalyst adopts NiO@Al with the mass fraction of 59.4 percent of NiO 2 O 3 The catalyst is then introduced into methane catalytic cracking reactor 2 to make catalytic cracking reaction. Tool withThe methane may be obtained by purifying and separating the raw material gas by a purifying apparatus 5 (specifically, a filtering apparatus) and a separating and purifying apparatus 6 (specifically, a raw material gas selective separating and purifying apparatus). Specifically, the internal spiral methane continuous catalytic cracking moving bed reactor can be used as a methane catalytic cracking reactor, and is provided with a nozzle jet hole for introducing gas containing methane. The pressure of the catalytic cracking reaction is 0.1-0.15 MPa, the temperature of the catalytic cracking reaction is 700 ℃ (the temperature is provided by the heating equipment 7), and the hydrogen and the nano carbon material are obtained after the catalytic cracking reaction. As shown in fig. 4 a, gas chromatography directly demonstrates the generation of hydrogen, which is one of the main products, and purification or extraction can be directly performed by the hydrogen purification device 3 (the hydrogen purification device 3 may specifically be a membrane separation device of a membrane material with palladium copper as a main component) which is mature in the technical process, and then the hydrogen is stored by the hydrogen storage device 8, so that the purity of the obtained hydrogen is greater than 99%. The obtained nanocarbon is shown in a graph b in fig. 4, and the obtained solid product is directly proved to mainly contain carbon elements by performing X-ray photoelectron spectroscopy analysis on the nanocarbon material after the acid treatment, so that the effect of the methane catalytic cracking reactor 2 in an integrated device is verified.
In summary, the invention provides a complete integrated system and method for co-producing hydrogen-carbon nano materials, which can recycle waste resources, such as raw gas with high methane ratio, which is generated by anaerobic fermentation treatment of wet garbage, rapid treatment of wet garbage by medium-low temperature biomass and anaerobic pyrolysis treatment of waste high molecular organic matters (such as epoxy resin), is efficient and environment-friendly, and can carry out continuous co-production of hydrogen-carbon nano materials after purifying the raw gas, thus having low cost, high benefit and low energy consumption, meeting national sustainable development strategy, having the characteristics of automation and easy scale, and further providing a brand new and ideal practical technology for efficient recycling of waste such as wet garbage and waste high molecular organic matters.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (13)
1. The method for preparing the hydrogen-carbon nanomaterial by methane catalytic pyrolysis is characterized by comprising the following steps of:
and carrying out catalytic cracking reaction on the gas comprising methane in the presence of a catalyst to obtain hydrogen and carbon nanomaterial, wherein the catalytic cracking reaction is carried out under the condition of introducing oxidizing gas.
2. The method for preparing hydrogen-carbon nanomaterial by catalytic cracking of methane as claimed in claim 1, comprising at least one of the following technical features:
1) The oxidizing gas includes at least one selected from carbon dioxide, oxygen, and water vapor;
2) The oxidizing gas is derived from the reduction of the catalyst by methane;
3) The pressure of the catalytic cracking reaction is 0.1MPa to 1.6MPa;
4) The gas comprising methane is obtained by the following method: performing anaerobic recovery treatment on the waste;
5) The catalyst is selected from one or more of iron ore, natural sand, iron ore and natural sand composite catalyst, nickel-based catalyst, iron-based catalyst, nickel-iron binary composite catalyst and nickel-iron containing multi-component composite catalyst;
6) The volume concentration of the oxidizing gas is 0.1% -8%;
7) The temperature of the catalytic cracking reaction is 500-800 ℃;
8) The methane concentration in the methane-containing gas is > 90% by volume.
3. The method for producing a hydrogen-carbon nanomaterial according to claim 2, wherein the gas including methane is obtained by the following method: and (3) purifying and/or separating and purifying the waste after the anaerobic recovery treatment.
4. The method for preparing hydrogen-carbon nanomaterial by catalytic pyrolysis of methane as claimed in claim 3, wherein the waste is subjected to anaerobic recovery treatment and then to purification and/or separation and purification in sequence.
5. The method for preparing the hydrogen-carbon nanomaterial by catalytic pyrolysis of methane according to claim 2, wherein the waste is subjected to at least one method selected from anaerobic fermentation of wet garbage, rapid treatment of low-temperature biomass in the wet garbage and anaerobic pyrolysis of waste high-molecular organic matters.
6. An integrated system for co-producing hydrogen-carbon nano materials by utilizing high-valued waste is characterized by comprising raw material gas preparation equipment (1), a methane catalytic cracking reactor (2), hydrogen purification equipment (3) and carbon nano material unloading equipment (4);
the feed gas preparation device (1) is used for preparing feed gas, and the feed gas comprises methane;
the raw material gas preparation equipment (1) is communicated with the methane catalytic cracking reactor (2);
the methane catalytic cracking reactor (2) is respectively communicated with the hydrogen purification device (3) and the carbon nano material discharging device (4).
7. The integrated system of claim 6, further comprising at least one of the following features:
a1 The raw material gas preparation equipment (1) is waste anaerobic recovery treatment equipment;
a2 The methane catalytic cracking reactor (2) is an internal spiral methane continuous catalytic cracking moving bed reactor;
a3 The methane catalytic cracking reactor (2) is provided with a nozzle jet hole for introducing gas containing methane;
a4 The hydrogen purification device (3) is a membrane separation device;
a5 The carbon nano material discharging equipment (4) is automatic conveying and discharging equipment for step-by-step decompression;
a6 A purifying device (5) and/or a separating and purifying device (6) are arranged between the raw material gas preparation device (1) and the methane catalytic cracking reactor (2);
a7 -the integrated system further comprises a heating device (7) for supplying heat to the methane catalytic cracking reactor (2);
a8 The integrated system further comprises a hydrogen storage device (8), the hydrogen purification device (3) being in communication with the hydrogen storage device (8).
8. The integrated system of claim 7, further comprising at least one of the following features:
a11 In the a 1), the waste anaerobic recovery treatment equipment comprises at least one selected from a wet garbage anaerobic fermentation device, a wet garbage middle-low temperature biomass rapid treatment device and a high polymer organic matter anaerobic cracking treatment device, and when the equipment comprises more than two devices, the devices are connected in parallel;
a41 In the feature a 4), the membrane separation apparatus uses a membrane material having palladium copper as a main component;
a61 In feature a 6), the purification device (5) is a filtration device;
a62 In the feature a 6), the separation and purification device (6) is a feed gas selective separation and purification device;
a63 In the feature a 6), when the purification device (5) and the separation and purification device (6) are arranged between the raw material gas preparation device (1) and the methane catalytic cracking reactor (2), the raw material gas preparation device (1), the purification device (5), the separation and purification device (6) and the methane catalytic cracking reactor (2) are sequentially communicated;
a71 In the feature a 7), the heating device (7) is a heating device for supplying heat from a heating device or renewable energy source for raw gas or produced hydrogen;
a81 In the feature a 8), the hydrogen storage device (8) is a direct compressed gas hydrogen storage device, a liquid hydrogen storage device, a solid hydrogen storage device, or an organic liquid hydrogen storage device.
9. An integrated method for co-producing hydrogen-carbon nano materials is characterized by comprising the following steps:
1) Preparing a feed gas comprising methane;
2) Carrying out catalytic cracking reaction on the raw material gas to obtain gas containing hydrogen and a material containing carbon nano materials;
3) Purifying the gas comprising hydrogen to obtain purified hydrogen;
4) And discharging the material containing the carbon nano material to obtain the material containing the carbon nano material.
10. The integration method of claim 9, further comprising at least one of the following features:
b1 -said integration method employs an integrated system according to any one of the claims 3 to 5;
b2 In step 1), the raw material gas is obtained by anaerobic recovery treatment of waste;
b3 In the step 2), the catalytic cracking reaction is carried out under the condition of introducing oxidizing gas;
b4 In the step 2), the pressure of the catalytic cracking reaction is 0.1MPa to 1.6MPa;
b5 In the step 2), the catalyst used in the catalytic cracking reaction is selected from one or more of iron ore, natural sand, iron ore and natural sand composite catalyst, nickel-based catalyst, iron-based catalyst, nickel-iron binary composite catalyst and nickel-iron containing multi-component composite catalyst;
b6 In step 2), the temperature of the catalytic cracking reaction is 500-800 ℃;
b7 In step 2), the methane concentration in the methane-comprising gas is > 90% by volume;
b8 In step 3), the gas comprising hydrogen is separated by a membrane to obtain purified hydrogen;
b9 In the step 4), the materials comprising the carbon nano materials are discharged through automatic transportation of step-by-step decompression;
b10 In the step 2), the raw material gas is purified and/or separated and purified and then is subjected to catalytic cracking reaction;
b11 In step 2), heat is supplied to the catalytic cracking reaction;
b12 In step 3), hydrogen storage is performed on the purified hydrogen gas.
11. The integration method of claim 10, further comprising at least one of the following features:
b21 In the b 2), the waste is subjected to anaerobic recovery treatment, and at least one method selected from the group consisting of anaerobic fermentation of wet garbage, rapid treatment of low-temperature biomass in the wet garbage and anaerobic pyrolysis of waste high-molecular organic matters is carried out;
b31 In feature b 3), the oxidizing gas includes at least one selected from the group consisting of carbon dioxide, oxygen, and water vapor;
b32 In feature b 3), the oxidizing gas is derived from the reduction of the catalyst by methane;
b33 In feature b 3), the volume concentration of the oxidizing gas is 0.1% to 8%;
b81 In the feature b 8), a membrane material containing palladium and copper as main components is used for membrane separation.
12. The integration method of claim 10, further comprising at least one of the following features:
b101 In feature b 10), the purifying is filtering;
b102 In the b 10), the separation and purification is selective separation and purification of the raw material gas;
b103 In the characteristic b 10), the raw material gas is subjected to catalytic cracking reaction after being sequentially purified, separated and purified.
13. The integration method of claim 10, further comprising at least one of the following features:
b111 In feature b 11), the feed gas or the produced hydrogen is self-heating or renewable energy heating;
b121 In feature b 12), the hydrogen storage is direct compressed gas hydrogen storage, liquid hydrogen storage, solid hydrogen storage, or organic liquid hydrogen storage.
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