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CN105349161A - Method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass - Google Patents

Method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass Download PDF

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Publication number
CN105349161A
CN105349161A CN201510753625.XA CN201510753625A CN105349161A CN 105349161 A CN105349161 A CN 105349161A CN 201510753625 A CN201510753625 A CN 201510753625A CN 105349161 A CN105349161 A CN 105349161A
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CN
China
Prior art keywords
biomass
pyrolysis
junked tire
hydrogen
carbon nanotubes
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Pending
Application number
CN201510753625.XA
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Chinese (zh)
Inventor
沈伯雄
刘丽君
吴撼明
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Hebei University of Technology
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Hebei University of Technology
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Priority to CN201510753625.XA priority Critical patent/CN105349161A/en
Publication of CN105349161A publication Critical patent/CN105349161A/en
Pending legal-status Critical Current

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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
    • 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
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1853—Steam reforming, i.e. injection of steam only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Provided is a method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass. Waste tyres and biomass are crushed and mixed according to a certain ratio,then the mixture is subjected to pyrolysis at a temperature of 450-650 DEG C without air, water vapour is added in the pyrolytic gas generated from pyrolysis, catalytic reforming is carried out at a temperature of 800-900 DEG C, and the employed catalyst is composed of Al2O3 carriers, a NiO main catalyst and a MgO cocatalyst through mixing. The product masses of hydrogen and carbon nanotubes count for 5-15% and 20-40% of the raw material total amount respectively. The method is advantageous in that waste tyres and biomass are mixed, the raw materials are subjected to pyrolysis, pyrolytic gas is obtained, the pyrolytic gas is subjected to catalytic reforming, thus the products transfer to hydrogen and carbon nanotubes with a high additional value, and the method has an important innovation meaning.

Description

A kind of junked tire and biomass pyrolytic produce the method for hydrogen and carbon nanotube
Technical field
The invention belongs to reclamation of solid wastes treatment technology, be specifically related to a kind of method of junked tire and biomass pyrolytic production hydrogen and carbon nanotube.
Background technology
Junked tire output has become an important problem, the accumulation land occupation of junked tire, contaminate environment, and harm humans is healthy, is very important trade waste.Traditional treatment process as: burn, landfill and renovation etc. have certain shortcoming, the development that govern junked tire in varying degrees and recycle.Countries in the world launch the research of junked tire pyrolysis all in succession.Research finds, junked tire pyrolysis processing not only eliminates junked tire, and can reclaim all product-gas of pyrolysis, oil product and solid residue, achieves the recycling of junked tire maximum resource.But in traditional junked tire pyrolytic process, define liquid oil medium viscosity larger, form benzene homologues comparision contents high simultaneously, be not too applicable to being directly used in fuel oil.Adopt catalyse pyrolysis junked tire, the carbon black of formation, easily at catalyst surface carbon distribution, is unfavorable for the normal operation of system.
Biomass energy refers to the energy be fixed up with biomass form by the energy of solar radiation by the photosynthesis of plant.Mainly comprise agricultural wastes, waterplant, oilseed plant and city organic waste etc.The energy grade of biomass fuel is higher, hydrogeneous abundant, wherein combustible portion mainly Mierocrystalline cellulose, hemicellulose, xylogen.Generally speaking, Mierocrystalline cellulose accounts for the 40-50% of biomass weight, and hemicellulose accounts for the 20-40% of biomass weight, and xylogen accounts for the 10-25% of biomass weight.Biomass are a kind of containing the higher material of oxygen, containing annular material in the product liquid formed in pyrolytic process, and the product liquid that formed higher than junked tire pyrolysis of its oxygen functional group simultaneously.
Biomass and junked tire change C, H, O ratio of thermal decomposition material by the different ratio of raw material, and then change the composition of product, generate the target product standing on utilization.Because biomass and junked tire all belong to fertile absorber, make full use of this kind of material to protection of the environment, to save limited fossil resource significant.
The invention discloses a kind of method adopting junked tire and biomass two sections of pyrolysis combination producing hydrogen and carbon nanotube, junked tire and biomass are adopted to carry out the method mixed, raw material first obtains pyrolysis gas through pyrolysis, pyrolysis gas is again through the method for catalytic reforming, make product to the hydrogen of high added value and carbon nanotube transfer, the method has important innovative significance.
Summary of the invention
The object of the invention is for above-mentioned existing problems, there is provided a kind of junked tire and biomass pyrolytic to produce the method for hydrogen and carbon nanotube, can be applicable to that recycling treatment is carried out to junked tire and biomass and obtain the high hydrogen of attached value and the product of carbon nanotube.
Technical scheme of the present invention:
Junked tire and biomass pyrolytic produce a method for hydrogen and carbon nanotube, and step is as follows:
1) mix after junked tire and biomass fragmentation according to a certain percentage, the mass ratio of junked tire and biomass is 6-9:1, and then isolated air carries out pyrolysis at 450-650 DEG C;
2) add water vapor in the pyrolysis gas above-mentioned pyrolysis produced, at 800-900 DEG C of temperature, carry out catalytic reforming, amount of steam is the 10-25% of junked tire and biomass total mass, and the catalyzer of employing is by Al 2o 3carrier, NiO Primary Catalysts and MgO promotor mixing composition, in catalyzer, the mass percent of each component is as follows: NiO Primary Catalysts is 10-15%, MgO promotor is 0-8%, Al 2o 3carrier is surplus, and the product quality obtaining hydrogen and carbon nanotube accounts for 5-15% and 20-40% of raw material total amount respectively.
Advantage of the present invention is: the present invention adopts junked tire and biomass to carry out the method mixed, raw material first obtains pyrolysis gas through pyrolysis, pyrolysis gas, again through the method for catalytic reforming, makes product to the hydrogen of high added value and carbon nanotube transfer, has important innovative significance.
Embodiment
Embodiment 1:
Junked tire and biomass pyrolytic produce a method for hydrogen and carbon nanotube, and step is as follows:
1) mix after junked tire and biomass fragmentation, the mass ratio of junked tire and biomass is 6:1, and then isolated air carries out pyrolysis at 650 DEG C;
2) add water vapor in the pyrolysis gas above-mentioned pyrolysis produced, at 900 DEG C of temperature, carry out catalytic reforming, amount of steam is 25% of junked tire and biomass total mass, and the catalyzer of employing is by Al 2o 3carrier and NiO Primary Catalysts mixing composition, in catalyzer, the mass percent of each component is as follows: NiO Primary Catalysts is 10%, Al 2o 3carrier is 90%, and the product quality obtaining hydrogen and carbon nanotube accounts for 15% and 20% of raw material total amount respectively.
Embodiment 2:
Junked tire and biomass pyrolytic produce a method for hydrogen and carbon nanotube, and step is as follows:
1) mix after junked tire and biomass fragmentation, the mass ratio of junked tire and biomass is 9:1, and then isolated air carries out pyrolysis at 450 DEG C;
2) add water vapor in the pyrolysis gas above-mentioned pyrolysis produced, at 800 DEG C of temperature, carry out catalytic reforming, amount of steam is 10% of junked tire and biomass total mass, and the catalyzer of employing is by Al 2o 3carrier, NiO Primary Catalysts and MgO promotor mixing composition, in catalyzer, the mass percent of each component is as follows: NiO Primary Catalysts is 15%, MgO promotor is 8%, Al 2o 3carrier is 77%, and the product quality obtaining hydrogen and carbon nanotube accounts for 5% and 40% of raw material total amount respectively.
Embodiment 3:
Junked tire and biomass pyrolytic produce a method for hydrogen and carbon nanotube, and step is as follows:
1) mix after junked tire and biomass fragmentation, the mass ratio of junked tire and biomass is 8:1, and then isolated air carries out pyrolysis at 550 DEG C;
2) add water vapor in the pyrolysis gas above-mentioned pyrolysis produced, at 850 DEG C of temperature, carry out catalytic reforming, amount of steam is 15% of junked tire and biomass total mass, and the catalyzer of employing is by Al 2o 3carrier, NiO Primary Catalysts and MgO promotor mixing composition, in catalyzer, the mass percent of each component is as follows: NiO Primary Catalysts is 10%, MgO promotor is 5%, Al 2o 3carrier is 85%, and the product quality obtaining hydrogen and carbon nanotube accounts for 10% and 35% of raw material total amount respectively.

Claims (1)

1. produce a method for hydrogen and carbon nanotube with junked tire and biomass pyrolytic, it is characterized in that: step is as follows:
1) mix after junked tire and biomass fragmentation according to a certain percentage, the mass ratio of junked tire and biomass is 6-9:1, and then isolated air carries out pyrolysis at 450-650 DEG C;
2) add water vapor in the pyrolysis gas above-mentioned pyrolysis produced, at 800-900 DEG C of temperature, carry out catalytic reforming, amount of steam is the 10-25% of junked tire and biomass total mass, and the catalyzer of employing is by Al 2o 3carrier, NiO Primary Catalysts and MgO promotor mixing composition, in catalyzer, the mass percent of each component is as follows: NiO Primary Catalysts is 10-15%, MgO promotor is 0-8%, Al 2o 3carrier is surplus, and the product quality obtaining hydrogen and carbon nanotube accounts for 5-15% and 20-40% of raw material total amount respectively.
CN201510753625.XA 2015-11-06 2015-11-06 Method for producing hydrogen and carbon nanotubes through pyrolysis of waste tyres and biomass Pending CN105349161A (en)

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Application Number Priority Date Filing Date Title
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Publication Number Publication Date
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106185863A (en) * 2016-07-06 2016-12-07 上海绿人生态经济环境保护研究所 The technique that CNT prepared by the combustible gas utilizing junked tire thermal cracking to produce
CN107699265A (en) * 2017-10-16 2018-02-16 广州宝狮无线供电技术有限公司 A kind of method and device for handling junked tire
CN110844900A (en) * 2019-11-11 2020-02-28 天津大学 Method for preparing carbon nano tube by taking waste tire as raw material
CN111634902A (en) * 2020-06-01 2020-09-08 南京博岭节能环保研究院有限公司 Method for preparing carbon nano tube by secondary catalytic reforming of lignin pyrolysis gas
CN113457575A (en) * 2021-06-07 2021-10-01 东南大学 System and method for preparing carbon nanofibers and hydrogen through microwave continuous pyrolysis
CN116588941A (en) * 2023-05-18 2023-08-15 昆明理工大学 Method for comprehensively utilizing yellow phosphorus slag

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030147802A1 (en) * 2001-11-21 2003-08-07 William Marsh Rice University Process for making single-wall carbon nanotubes utilizing refractory particles
CN101054159A (en) * 2007-06-01 2007-10-17 西北大学 Method of preparing high-purity hydrogen gas and cooperatively growing carbon nano-tube
CN101476176A (en) * 2009-01-09 2009-07-08 深圳大学 Method for gas-phase growth of carbon fibre
CN101707864A (en) * 2007-06-06 2010-05-12 琳德有限公司 Integrated processes for generating carbon monoxide for carbon nanomaterial production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030147802A1 (en) * 2001-11-21 2003-08-07 William Marsh Rice University Process for making single-wall carbon nanotubes utilizing refractory particles
CN101054159A (en) * 2007-06-01 2007-10-17 西北大学 Method of preparing high-purity hydrogen gas and cooperatively growing carbon nano-tube
CN101707864A (en) * 2007-06-06 2010-05-12 琳德有限公司 Integrated processes for generating carbon monoxide for carbon nanomaterial production
CN101476176A (en) * 2009-01-09 2009-07-08 深圳大学 Method for gas-phase growth of carbon fibre

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106185863A (en) * 2016-07-06 2016-12-07 上海绿人生态经济环境保护研究所 The technique that CNT prepared by the combustible gas utilizing junked tire thermal cracking to produce
CN107699265A (en) * 2017-10-16 2018-02-16 广州宝狮无线供电技术有限公司 A kind of method and device for handling junked tire
CN110844900A (en) * 2019-11-11 2020-02-28 天津大学 Method for preparing carbon nano tube by taking waste tire as raw material
CN110844900B (en) * 2019-11-11 2022-05-24 天津大学 Method for preparing carbon nano tube by taking waste tire as raw material
CN111634902A (en) * 2020-06-01 2020-09-08 南京博岭节能环保研究院有限公司 Method for preparing carbon nano tube by secondary catalytic reforming of lignin pyrolysis gas
CN113457575A (en) * 2021-06-07 2021-10-01 东南大学 System and method for preparing carbon nanofibers and hydrogen through microwave continuous pyrolysis
US11760635B2 (en) 2021-06-07 2023-09-19 Southeast University System and method for preparing carbon nanofiber and hydrogen through continuous microwave pyrolysis
CN116588941A (en) * 2023-05-18 2023-08-15 昆明理工大学 Method for comprehensively utilizing yellow phosphorus slag
CN116588941B (en) * 2023-05-18 2024-04-30 昆明理工大学 Method for comprehensively utilizing yellow phosphorus slag

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Application publication date: 20160224