CN111647442B - Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage - Google Patents

Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage Download PDF

Info

Publication number
CN111647442B
CN111647442B CN202010634297.2A CN202010634297A CN111647442B CN 111647442 B CN111647442 B CN 111647442B CN 202010634297 A CN202010634297 A CN 202010634297A CN 111647442 B CN111647442 B CN 111647442B
Authority
CN
China
Prior art keywords
synthetic gas
hydrogen
garbage
plastic
catalytic pyrolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010634297.2A
Other languages
Chinese (zh)
Other versions
CN111647442A (en
Inventor
王凯军
槐衍森
常风民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN202010634297.2A priority Critical patent/CN111647442B/en
Publication of CN111647442A publication Critical patent/CN111647442A/en
Application granted granted Critical
Publication of CN111647442B publication Critical patent/CN111647442B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • 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
    • 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
    • C01B3/02—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
    • 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
    • C01B3/34—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 by reaction of hydrocarbons with gasifying agents
    • C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • 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
    • C10J3/72—Other features
    • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C10J3/845—Quench rings
    • 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
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046—Purification by cryogenic separation
    • 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
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—Carbon dioxide
    • 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
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • 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
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • 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
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention provides a method and a device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage, and the method for preparing the hydrogen-rich synthetic gas by the two-step catalytic pyrolysis mainly comprises the following steps: 1) The high-plastic garbage is conveyed into a first-stage pyrolysis furnace through a continuous closed conveying system to carry out medium-temperature anaerobic pyrolysis (450 ℃ to 600 ℃), and volatile products (condensing and non-condensing components) are mainly produced; 2) The volatile product is directly introduced into a secondary catalytic pyrolysis reaction furnace filled with a perovskite composite catalyst, and condensing components, water vapor, CO 2 and the like in the volatile product are catalytically converted into hydrogen-rich synthetic gas (H 2/CO) on the surface of the composite catalyst. According to the invention, the high-plastic inert garbage is converted into the hydrogen-rich synthetic gas through two-step catalytic pyrolysis, so that the problems of energy utilization and hazard of inert garbage pyrolysis liquid mainly comprising light plastics separated from kitchen/kitchen waste are mainly solved, and the purification investment and secondary pollution of the high-quality synthetic gas are reduced.

Description

Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage
Technical Field
The invention belongs to the technical field of solid waste treatment, relates to recycling utilization of solid waste with high plastic material content, and in particular relates to a method and a device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage.
Background
In the garbage classification process, the problems of garbage separation before mixing, kitchen garbage mixed incineration and the like often occur due to insufficient capacity of a rear-end treatment facility, and the implementation effect of garbage classification is seriously retarded. Wherein, the fine treatment and recycling quality improvement utilization of kitchen waste are key links of smooth implementation of waste classification. At present, garbage classification is in a primary stage, a large number of plastic bags, cutlery boxes and the like are still mixed in the kitchen garbage after classification, and the disposal of inert garbage mainly made of plastics, which is selected in the pretreatment and biological treatment processes, becomes a difficult problem.
The high-plastic inert garbage can generate liquid phase fuel (commonly called tar) with a larger proportion in the middle-temperature pyrolysis process, is a complex mixed substance composed of hundreds of organic matters, has a heat value of about 50% of that of petroleum products, has poor stability and is difficult to directly use. Meanwhile, the tar is an acidic viscous liquid substance, and is extremely easy to adhere to the inner walls of pipelines and equipment in actual engineering operation, so that the pipelines are blocked and the equipment is corroded, and the normal operation of a system is influenced. At present, the research on pyrolysis refining of tar also has a plurality of problems and bottlenecks, and has a certain distance from large-scale industrialized application.
Disclosure of Invention
In order to overcome the defects of the prior art and promote the application and popularization of the high-plastic inert garbage pyrolysis technology, the invention aims to provide a method and a device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage, which can realize continuous feeding and discharging in a closed state and convert the high-plastic inert garbage into the hydrogen-rich synthetic gas.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The method for preparing the hydrogen-rich synthetic gas by the two-step catalytic pyrolysis of the high-plastic inert garbage is characterized by comprising the following steps of:
1) Conveying the high-plastic inert garbage into a first-stage medium-temperature pyrolysis furnace through a continuous closed conveying device to carry out medium-temperature anaerobic pyrolysis at 450-600 ℃ to generate volatile products taking condensable and non-condensable gases as main components;
2) And directly introducing the obtained volatile product into a secondary high-temperature catalytic pyrolysis furnace filled with a perovskite composite catalyst to carry out catalytic pyrolysis at 800-1000 ℃, and carrying out catalytic conversion of condensed components, water vapor and CO 2 in the volatile product into hydrogen-rich synthetic gas on the surface of the perovskite composite catalyst.
The high-plastic inert garbage is inert garbage rich in plastics, in particular to light materials which are separated from kitchen/kitchen waste in the pretreatment or biological treatment process and take plastic bags and cutlery boxes as main components.
The perovskite composite catalyst is a composite catalyst which takes perovskite as a main material and is provided with trace Ni/Co, and the condensation components, water vapor and CO 2 in the volatile products are promoted to generate hydrogen-rich synthetic gas through catalytic conversion reaction.
In the perovskite composite catalyst, the loading of Ni/Co is 6% -7% of the total mass of the catalyst, wherein the doping proportion of Ni is 60% -80%, and the doping proportion of Co is 20% -40%.
The reaction residence time in the primary medium-temperature pyrolysis furnace is 30-40 min, the residence time of the secondary high-temperature catalytic reaction is not controlled generally, the condensable components, water vapor and CO 2 generated in the primary medium-temperature pyrolysis furnace are introduced into the secondary high-temperature catalytic pyrolysis furnace, the steam catalytic reforming is generated through mixed combustion, the reaction time is very short and is generally less than 10s, and the catalytic hydrogen-rich synthetic gas is discharged.
The water content of the inert garbage is regulated to be below 15%, and condensed components, water vapor and CO 2 in volatile products generated by primary medium-temperature pyrolysis are catalytically converted into the needed synthesis gas in a proper proportion.
The invention also provides a device for preparing the hydrogen-rich synthetic gas by the two-step catalytic pyrolysis of the high-plastic inert garbage, which comprises a first-stage medium-temperature pyrolysis furnace 3 with a built-in screw conveying mechanism 2, wherein a closed feeding device 1 is connected with a feeding port of the first-stage medium-temperature pyrolysis furnace 3 to supply the high-plastic inert garbage to the first-stage medium-temperature pyrolysis furnace, a volatile product outlet of the first-stage medium-temperature pyrolysis furnace 3 is directly communicated with an inlet of a second-stage high-temperature catalytic pyrolysis furnace 6 through a closed pipeline, a perovskite composite catalyst 7 is filled in the second-stage high-temperature catalytic pyrolysis furnace 6, and an outlet of the second-stage high-temperature catalytic pyrolysis furnace 6 is connected with a gas-liquid separator 8.
The primary medium temperature pyrolysis furnace 3 and the secondary high temperature catalytic pyrolysis furnace 6 share a system control cabinet 5, and the reaction temperature and the feeding start and stop of the two are controlled by the system control cabinet 5.
The gas phase outlet of the gas-liquid separator 8 is connected with a water condenser 9, the gas phase outlet of the water condenser 9 is connected with an alkaline water tank 10, and the gas phase outlet of the alkaline water tank 10 is connected with a purifier 12 through a pipeline with an induced draft fan 11.
Compared with the prior art, the invention firstly converts the high-plastic garbage into volatile products (non-condensable and condensable mixed gas) through medium-temperature pyrolysis, and then converts the volatile products into the hydrogen-rich synthesis gas which can be directly utilized through high-temperature catalysis, thereby realizing the utilization of pyrolysis liquid, relieving the harm of the pyrolysis liquid and reducing the purification investment and secondary pollution of the high-quality synthesis gas.
Drawings
FIG. 1 is a schematic diagram of the structure of a device for preparing hydrogen-rich synthesis gas by two-step catalytic pyrolysis of high-plasticity inert garbage.
FIG. 2 is a schematic diagram of the effect of loading different proportions of Ni and Co on hydrogen generation for the perovskite composite catalyst of the invention.
Detailed Description
The following detailed description of specific methods and apparatus of the present invention is provided in connection with specific examples, which are intended to be exemplary of the invention, but not limiting. All other examples, which are obtained without inventive effort by a person skilled in the art, are within the scope of the present invention.
The invention relates to a method for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage, which mainly comprises the following steps:
1) Conveying inert garbage rich in plastics, such as light materials such as plastic bags, cutlery boxes and the like which are separated from kitchen/kitchen waste in the pretreatment or biological treatment process, into a first-stage medium-temperature pyrolysis furnace through a continuous closed conveying device for medium-temperature anaerobic pyrolysis (450-600 ℃) to generate volatile products (mainly condensing and non-condensing gases);
2) The volatile product is directly connected into a secondary high-temperature catalytic pyrolysis furnace filled with a perovskite composite catalyst to carry out catalytic pyrolysis at 800-1000 ℃, and condensable components, water vapor, CO 2 and the like in the volatile product are catalytically converted into hydrogen-rich synthetic gas (H 2/CO) on the surface of the perovskite composite catalyst.
In the invention, the high-plastic inert garbage is inert garbage rich in plastics, in particular to light materials which are separated from kitchen/kitchen garbage in the pretreatment or biological treatment process and take plastic bags and cutlery boxes as main components.
Fig. 1 shows a specific device structure for realizing the method of the invention, which comprises a primary medium-temperature pyrolysis furnace 3 with a built-in screw conveying mechanism 2, wherein a closed feeding device 1 is connected with a feeding port of the primary medium-temperature pyrolysis furnace 3 to supply high-plastic inert garbage to the primary medium-temperature pyrolysis furnace, and a discharging device 4 is arranged at the tail end of the primary medium-temperature pyrolysis furnace 3. The volatile product outlet of the primary medium temperature pyrolysis furnace 3 is directly communicated with the inlet of the secondary high temperature catalytic pyrolysis furnace 6 through a closed pipeline, a perovskite composite catalyst 7 is filled in the secondary high temperature catalytic pyrolysis furnace 6, the outlet of the secondary high temperature catalytic pyrolysis furnace 6 is connected with a gas-liquid separator 8, the gas phase outlet of the gas-liquid separator 8 is connected with a water condenser 9, the gas phase outlet of the water condenser 9 is connected with an alkaline washing water tank 10, the gas phase outlet of the alkaline washing water tank 10 is connected with a purifier 12 through a pipeline with an induced draft fan 11, the outlet of the purifier is connected with a gas storage tank 13, the primary medium temperature pyrolysis furnace 3 and the secondary high temperature catalytic pyrolysis furnace 6 can share a system control cabinet 5, and the reaction temperature, time and feeding start and stop of the two are controlled by the system control cabinet 5.
In the embodiment, the first-stage medium-temperature pyrolysis furnace 3 adopts a pipeline pyrolysis furnace, materials are conveyed by virtue of the screw conveying mechanism 2, the main body of the closed feeding device 1 is a feeding reserve tank, and a feeding port and a discharging port of the feeding reserve tank are both provided with valves.
The specific steps for preparing the hydrogen-rich synthetic gas by carrying out two-step catalytic pyrolysis on the high-plastic inert garbage by using the device are as follows:
1. The preparation method mainly comprises the steps of preparing a perovskite/perovskite composite catalyst with trace Co/Ni and the like, taking a proper amount of the perovskite composite catalyst to be filled in a secondary high-temperature catalytic pyrolysis furnace 6, and adjusting to enable the primary medium-temperature pyrolysis furnace 3 and the secondary high-temperature catalytic pyrolysis furnace 6 to be in an optimized stable state.
The perovskite composite catalyst is a composite catalyst which takes perovskite as a main material and is provided with trace Ni/Co and the like, and can promote condensation components, water vapor, CO 2 and the like in volatile products to generate hydrogen-rich synthetic gas through catalytic conversion reaction. The supported perovskite catalyst is prepared by adopting a lemon complexation impregnation method, and the loading amount of Ni/Co is 6% -7% of the total mass of the catalyst, wherein the doping proportion range of Ni is 60% -80%, and the doping proportion range of Co is 20% -40%. By comparing Ni and Co loaded in different proportions, it is found that doping 80% Ni and 20% Co has higher selectivity to hydrogen generation. The experimental results are shown in FIG. 2, in which the A, B site of the LaNiO 3/γ-Al2O3 catalyst is doped with Ni/Co according to 6% mass fraction.
2. When the furnace temperature of the primary medium temperature pyrolysis furnace 3 reaches a medium temperature state (450-600 ℃), and the furnace temperature of the secondary high temperature catalytic pyrolysis furnace 6 reaches a high temperature state (800-900 ℃), the dried high-plastic inert garbage (with the water content of 10-20%) is taken and placed into the closed feeding device 1.
3. And opening the upper feed inlet valve of the closed feed device 1, allowing materials to enter the feed storage box, opening the lower discharge outlet valve, closing the upper feed inlet valve, and ensuring that the closed feed device 1 is in a sealed state.
4. The temperature controller and the conveying motor of the screw conveying mechanism 2 are regulated by the system control cabinet 5, and the furnace temperature of the primary medium-temperature pyrolysis furnace 3 is controlled to be in a medium-temperature state and the proper material residence time (30 min-40 min).
5. Volatile products (condensing and non-condensing gases) generated by pyrolysis in the primary medium temperature pyrolysis furnace 3 directly enter the secondary high temperature catalytic pyrolysis furnace 6, the furnace temperature of the secondary high temperature catalytic pyrolysis furnace 6 is controlled to be in a high temperature state through a secondary temperature controller, the retention time of the secondary high temperature catalytic reaction is generally not controlled, the condensing components, water vapor and CO2 generated in the primary medium temperature pyrolysis furnace are introduced into the secondary high temperature catalytic pyrolysis furnace, steam catalytic reforming is generated through mixed combustion, the reaction time is very short, and is generally less than 10 seconds, and the catalytic hydrogen-rich synthetic gas is discharged.
6. The moisture content of the inert garbage is regulated to be below 15%, so that condensed components, water vapor and CO 2 in volatile products generated by primary medium-temperature pyrolysis are catalytically converted into needed synthesis gas;
7. The synthesis gas generated by the secondary catalytic pyrolysis enters a gas storage tank 13 through a gas-liquid separator 8, a water condenser 9, an alkaline water tank 10 and a purifier 12 (deep purification drying box), and can be directly used as fuel gas or high-quality chemical raw materials.
Taking plastic garbage separated from kitchen waste/kitchen waste as an example, the kitchen waste high-plastic inert garbage is heated at the temperature of 900 ℃ in a first stage and the temperature of the pyrolysis reaction furnace is 500 ℃/30min, and under the action of a perovskite composite catalyst, the gas proportion of hydrogen-rich synthetic gas (H 2 +CO) is more than 90%, wherein the H 2 proportion is more than 70%.
According to the invention, thermogravimetric analysis (plastics, bones and degradation-resistant substances) of kitchen waste sorting substances with different component ratios are respectively compared, and a thermogravimetric experiment shows that all the components are not reduced in weight at 600 ℃, so that the sample organic matter is considered to be basically cracked at 600 ℃. The materials used in the experiment are taken from a kitchen waste treatment center in certain city, and organic wastes after kitchen waste separation in a normal state are adopted. The primary pyrolysis temperature was controlled at 600 ℃, at which point all components had been completely cracked. The experiment mainly compares the yields of H 2 at different catalysts and different catalytic temperatures, and the results are as follows:
From the experimental results, the H 2/CO yield gradually increased with increasing temperature, and the synthesis gas (H 2 +co) ratio in the gas phase product reached a maximum of 98% and the H 2 maximum yield was 72% with LaNi 0.8Co0.2O3/γ-Al2O3 catalyst at 900 ℃.
In conclusion, the high-plastic inert garbage is converted into the hydrogen-rich synthetic gas through two-step catalytic pyrolysis, so that the problems of energy utilization and hazard of the inert garbage pyrolysis liquid mainly comprising light plastics separated from kitchen/kitchen waste are mainly solved, and the purification investment and secondary pollution of the high-quality synthetic gas are reduced.

Claims (4)

1. The method for preparing the hydrogen-rich synthetic gas by the two-step catalytic pyrolysis of the high-plastic inert garbage is characterized by comprising the following steps of:
1) Conveying high-plastic inert garbage into a first-stage medium-temperature pyrolysis furnace through a continuous closed conveying device for medium-temperature anaerobic pyrolysis at 600 ℃ to generate volatile products taking condensable and non-condensable gases as main components, wherein the high-plastic inert garbage is inert garbage rich in plastics;
2) And directly introducing the obtained volatile product into a secondary high-temperature catalytic pyrolysis furnace filled with a perovskite composite catalyst to carry out catalytic pyrolysis at 900 ℃, wherein condensing components, water vapor and CO 2 in the volatile product are catalytically converted into hydrogen-rich synthetic gas on the surface of the perovskite composite catalyst, the perovskite composite catalyst is LaNi 0.8Co0.2O3/γ-Al2O3, the ratio of the hydrogen-rich synthetic gas in the gas-phase product reaches 98%, the yield of H 2 is 72%, and the hydrogen-rich synthetic gas is H 2 and CO.
2. The method for preparing the hydrogen-rich synthetic gas by the two-step catalytic pyrolysis of the high-plastic inert garbage, which is disclosed in claim 1, is characterized in that the high-plastic inert garbage is a light material which is separated in the pretreatment or biological treatment process of kitchen/kitchen garbage and takes plastic bags and cutlery boxes as main components.
3. The method for preparing the hydrogen-rich synthetic gas by the two-step catalytic pyrolysis of the high-plastic inert garbage according to claim 1, wherein the reaction residence time in the primary medium-temperature pyrolysis furnace is 30-40 min.
4. The method for preparing the hydrogen-rich synthetic gas by the two-step catalytic pyrolysis of the high-plastic inert garbage according to claim 1, wherein the water content of the inert garbage is regulated to be below 15%.
CN202010634297.2A 2020-07-02 2020-07-02 Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage Active CN111647442B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010634297.2A CN111647442B (en) 2020-07-02 2020-07-02 Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010634297.2A CN111647442B (en) 2020-07-02 2020-07-02 Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage

Publications (2)

Publication Number Publication Date
CN111647442A CN111647442A (en) 2020-09-11
CN111647442B true CN111647442B (en) 2024-07-09

Family

ID=72352577

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010634297.2A Active CN111647442B (en) 2020-07-02 2020-07-02 Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage

Country Status (1)

Country Link
CN (1) CN111647442B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113322089A (en) * 2021-05-28 2021-08-31 重庆大学 Pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics
CN113913203A (en) * 2021-10-18 2022-01-11 郭洋 Method for preparing hydrogen from organic garbage

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104388105A (en) * 2014-11-06 2015-03-04 清华大学 Device and method for producing synthetic gas by continuous two-stage catalytic pyrolysis
CN107245435A (en) * 2016-10-28 2017-10-13 王凯军 A kind of apparatus and method of the difficult biochemical biochemical coupling methane phase of organic solid waste pyrolysis
CN212770593U (en) * 2020-07-02 2021-03-23 清华大学 Device for preparing hydrogen-rich synthesis gas by two-step catalytic pyrolysis of high-plasticity inert garbage

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR200233102Y1 (en) * 2001-03-13 2001-10-08 현대 알 디 에프 산업 주식회사 No oxygan sparation gab use RDF only on boiler
IE86375B1 (en) * 2009-12-22 2014-04-09 Cynar Plastics Recycling Ltd Conversion of waste plastics material to fuel
CN109575970A (en) * 2019-01-18 2019-04-05 北京山水青源环保科技有限公司 A kind of oily sediment waste plastics pyrolytic process and device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104388105A (en) * 2014-11-06 2015-03-04 清华大学 Device and method for producing synthetic gas by continuous two-stage catalytic pyrolysis
CN107245435A (en) * 2016-10-28 2017-10-13 王凯军 A kind of apparatus and method of the difficult biochemical biochemical coupling methane phase of organic solid waste pyrolysis
CN212770593U (en) * 2020-07-02 2021-03-23 清华大学 Device for preparing hydrogen-rich synthesis gas by two-step catalytic pyrolysis of high-plasticity inert garbage

Also Published As

Publication number Publication date
CN111647442A (en) 2020-09-11

Similar Documents

Publication Publication Date Title
CN102341485B (en) Process and system for thermochemical conversion of biomass
CN101208264B (en) Compact reforming reactor
CN111647442B (en) Method and device for preparing hydrogen-rich synthetic gas by two-step catalytic pyrolysis of high-plastic inert garbage
Zeng et al. Microwave catalytic co-pyrolysis of waste cooking oil and low-density polyethylene to produce monocyclic aromatic hydrocarbons: Effect of different catalysts and pyrolysis parameters
CN111039258B (en) Methanol-water reforming hydrogen production system based on solar fuel
CN103979491A (en) Method and device for producing hydrogen by blending and gasifying sludge and biomass
CN100999677B (en) Process of preparing rich furol biological oil by biomass microwave catalytic pyrolysis
CN102963866B (en) Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis
CN212770593U (en) Device for preparing hydrogen-rich synthesis gas by two-step catalytic pyrolysis of high-plasticity inert garbage
EP3311969A1 (en) Device for thermally decomposing polyethylene and polypropylene waste
CN106336879A (en) Biomass pyrolysis-reforming hydrogen production method
CN107245435B (en) Device and method for producing methane through pyrolysis-biochemical coupling of organic solid wastes difficult to biochemically produce
CN102226095A (en) Device and method for preparing fuel and chemicals by gradient pyrolysis of biomass and step-by-step collection
EP3312223B1 (en) Method for thermally decomposing polyethylene and polypropylene waste
CN103672907A (en) Garbage treatment system and method
CN104388105A (en) Device and method for producing synthetic gas by continuous two-stage catalytic pyrolysis
CN204265697U (en) The device of a kind of continous way two sections of catalyse pyrolysis preparing synthetic gas
WO2020082377A1 (en) Process for using garbage to prepare liquid-state fuel and chemical products, and garbage catalytic pyrolysis system
CN109111935B (en) Oil shale circulating fluidized bed dry distillation method and system based on methane-rich mixed gas
CN2223297Y (en) Apparatus for producing gasoline diesel oil and carbon black from waste rubber
CN103880266A (en) Hydrothermal-process sludge dehydrating method and hydrothermal-process sludge dehydrating device
CN212769855U (en) System for preparing hydrogen by pyrolyzing waste plastics
CN206173333U (en) Difficult biochemical organic solid waste pyrolysis device of methane is produced in biochemical coupling
CN203558989U (en) Extraction system for polyoxymethylene dimethyl ether preparation device
CN102234518A (en) Direct thermo-chemical technology for converting sewage sludge into oil

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant