CN113200517B - Solar thermochemical energy conversion system with electric furnace dust as circulating medium - Google Patents

Solar thermochemical energy conversion system with electric furnace dust as circulating medium Download PDF

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CN113200517B
CN113200517B CN202110484538.4A CN202110484538A CN113200517B CN 113200517 B CN113200517 B CN 113200517B CN 202110484538 A CN202110484538 A CN 202110484538A CN 113200517 B CN113200517 B CN 113200517B
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gas
subsystem
oxidation reactor
storage tank
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CN113200517A (en
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楼波
梁证隆
余争晓
闫睿
杨维枝
黎俊杰
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C01B3/105—Cyclic methods
    • 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
    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/08—Ferroso-ferric oxide [Fe3O4]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S20/00—Solar heat collectors specially adapted for particular uses or environments
    • F24S20/30—Solar heat collectors for heating objects, e.g. solar cookers or solar furnaces
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • General Engineering & Computer Science (AREA)
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Abstract

The invention discloses a solar thermochemical energy conversion system taking electric furnace dust as a circulating medium, which comprises a material conveying subsystem, a reduction reaction subsystem, a zinc treatment subsystem and an iron treatment subsystem, wherein the material conveying subsystem is used for conveying materials required by the reaction of the reduction reaction subsystem; the reduction reaction subsystem comprises a reduction reactor for receiving the materials conveyed by the material conveying subsystem and for carrying out reduction reaction in the material conveying subsystem; the zinc treatment subsystem comprises a first oxidation reactor and a gas storage tank; the iron treatment subsystem includes a second oxidation reactor, a hydrogen storage tank, a second grinder, and a magnetic separator. According to the invention, the electric furnace dust is taken as a circulating medium, solar energy is stored in the gas fuel, a reduction reactor and an oxidation reactor are utilized to obtain high-grade Fe3O4, CO, H2 and other combustible gases, and the combination of recycling treatment and utilization of the electric furnace dust is completed, so that the energy consumption of the system process is low, and the system is environment-friendly, clean and free of environmental pollution.

Description

Solar thermochemical energy conversion system with electric furnace dust as circulating medium
Technical Field
The invention relates to the technical field of electric furnace dust treatment and the field of solar energy storage, in particular to a solar thermochemical energy conversion system taking electric furnace dust as a circulating medium.
Background
The electric furnace steelmaking dust yield in China is large, the recovery value is high, the electric furnace steelmaking dust yield in China at present exceeds 100 ten thousand tons, most of the electric furnace steelmaking dust is piled up and buried, and only a small part of the electric furnace steelmaking dust is recovered. The electric furnace dust contains a large amount of Fe and Zn, and if the electric furnace dust can be fully recycled, the condition that the current resources in China are increasingly tense can be relieved. The recovery processing method of the electric furnace dust comprises the following steps: solidification and stabilization techniques, return sintering, wet extraction, and pyrogenic processes, which are relatively mature compared to other processes, but require the use of coke or the like to provide a source of heat.
Solar energy is a renewable energy source and has large reserves, although the energy radiated to the earth atmosphere is only 22 parts per million of the total radiation energy, the energy is up to 173000TW, which is equivalent to 500 ten thousand tons of coal, and if the solar energy can be effectively utilized, the current coal burning requirement of China can be reduced properly, and the current situation of energy shortage is relieved. The solar photo-thermal utilization is to absorb solar energy through solar energy collecting devices such as a flat plate type heat collector, a vacuum tube heat collector, a focusing heat collector and the like, and then transfer heat to heat conduction oil or hot water for utilization. The solar thermal chemical conversion system is to make the solar thermal energy promote chemical reaction of some matters and store the solar conversion chemical energy into fuel.
Patent publication No. CN210087413U discloses an amino solar thermochemical cycle power generation system. The system focuses solar energy through the dish-type parabolic condenser, so that ammonia gas and hydrogen gas react to synthesize NH (NH) 3 High-pressure gaseous NH generated 3 Then the air enters a turbine to do work, and a generator is driven to generate power.
Patent publication No. CN210374744U discloses a solar photo-thermal power generation system based on a metal oxide thermochemical energy storage system. The system uses solar energy as energy source and Co 3 O 4 and/CoO is used as a circulating medium to realize the organic combination of a metal oxide thermochemical energy storage system and solar photo-thermal power generation.
Raw material NH adopted by the system 3 And Co 3 O 4 CoO, is costly, and affects its commercial use.
The electric furnace dust is used as a circulating medium of the solar thermochemical energy conversion system, solar energy is stored in the gas fuel, the combination of the recycling treatment of the electric furnace dust and the utilization of renewable energy solar energy is realized, and the electric furnace dust has better application prospect.
Disclosure of Invention
The invention provides a solar thermochemical energy conversion system taking electric furnace dust as a circulating medium, which realizes the combination of electric furnace dust treatment and utilization and solar energy storage.
The invention provides a solar thermochemical energy conversion system taking electric furnace dust as a circulating medium, which comprises a material conveying subsystem, a reduction reaction subsystem, a zinc treatment subsystem and an iron treatment subsystem,
the material conveying subsystem is used for conveying materials required by the reaction of the reduction reaction subsystem;
the reduction reaction subsystem comprises a reduction reactor for receiving the materials conveyed by the material conveying subsystem and for carrying out reduction reaction in the material conveying subsystem, and a solar condenser is used for providing heat to form a temperature required by reduction when the reduction reaction occurs in the reduction reactor;
the zinc treatment subsystem comprises a first oxidation reactor and a gas storage tank, wherein a mixed gas inlet of the first oxidation reactor is communicated with the reduction reactor, solid products in the first oxidation reactor are returned to the material conveying subsystem for circulation, and a gas product outlet of the first oxidation reactor is communicated with the gas storage tank;
the iron treatment subsystem comprises a second oxidation reactor, a hydrogen storage tank, a second grinder and a magnetic separator, wherein a solid material inlet of the second oxidation reactor is communicated with a solid product outlet of the reduction reactor, a gas product outlet of the second oxidation reactor is communicated with the hydrogen storage tank, an inlet of the second grinder is communicated with a solid product outlet of the second oxidation reactor, and an iron oxide outlet of the magnetic separator is communicated with the material conveying subsystem.
Preferably, the material conveying subsystem comprises a first fan, a methane storage tank for providing methane, a first solid material storage tank for storing solid material generated in the first oxidation reactor, an electric furnace dust storage tank for providing electric furnace dust and a second solid material storage tank for storing iron solid material generated in the second oxidation reactor, wherein the first solid material storage tank, the methane storage tank, the first solid material storage tank, the electric furnace dust storage tank and the second solid material storage tank are all communicated with the reduction reaction subsystem through pipelines, and the stored material is conveyed to the reduction reaction subsystem under the wind force of the first fan.
Preferably, the reduction reactor comprises a mixed material inlet pipeline and a separation cavity communicated with the mixed material inlet pipeline, an incident window for incidence of solar energy is arranged on the mixed material inlet pipeline, a gas product outlet and a solid product outlet which are communicated with an outlet of the mixed material inlet pipeline are arranged on the separation cavity, and a filter screen is arranged at an inlet of the gas product outlet pipeline so as to prevent solid materials from being carried out of the separation cavity by a gas material flow.
Preferably, the mixed material inlet pipeline is a spiral pipeline, the included angle between the pipeline and the horizontal line is 30-40 degrees, the radian of an arc pipeline connected between the two pipelines is 90 degrees, the incident window is positioned on the concentrating center line of the solar concentrator, and the incident window can absorb solar energy when exposed, so that the high-temperature condition required by the reduction reaction is provided for the mixed material inlet pipeline. The solar energy condenser can effectively collect solar energy by reflecting sunlight, and the concentration center line is positioned at the incident window of the reduction reactor, so that the reduction reactor can reach a high-temperature environment.
Preferably, the reduction reaction subsystem further comprises a first cooler and a first gas lock, and a solid product outlet on the reduction reactor is communicated with the second oxidation reactor through the first cooler and the first gas lock in sequence.
Preferably, the zinc treatment subsystem further comprises a second gas lock in communication with the solid product outlet of the first oxidation reactor and a first grinder connected to the second gas lock.
Preferably, the zinc treatment subsystem further comprises a second cooler and a first gas-water separator, wherein the second cooler is communicated with the gas product outlet of the first oxidation reactor, the second cooler is connected with the separation inlet of the first gas-water separator, and the separation outlet of the first gas-water separator is connected with the gas storage tank.
Preferably, the iron treatment subsystem further comprises a third cooler and a second gas-water separator connected to the third cooler, the second oxidation reactor gas product outlet is in communication with the inlet of the third cooler, and the separation outlet of the second gas-water separator is in communication with the hydrogen storage tank.
Preferably, the first oxidation reactor and the second oxidation reactor comprise an inner cylinder, an outer cylinder, a filter plate group and a solid product outlet pipeline, the inner cylinder and the outer cylinder are coaxially arranged,
the inner cylinder is fixedly arranged, the outer cylinder is positioned at the outer side of the inner cylinder and driven by the gear mechanism to rotate, the outer cylinder rotates, the inner cylinder is static, and the inner cylinder and the outer cylinder are fixed in different supporting modes;
the top of the inner cylinder is provided with a solid product collecting area, the bottom of the inner cylinder is communicated with the inner cavity of the outer cylinder through an opening, and the inner cylinder is provided with a gas inlet, a water inlet pipeline, a solid product outlet pipeline and a gas product outlet, wherein the material inlet on the first oxidation reactor is a mixed gas inlet, and the material inlet on the second oxidation reactor is a solid material inlet;
the filter plate group is positioned between the outer cylinder and the inner cylinder, and comprises a plurality of filter plates, one end of each filter plate is fixedly connected with the inner wall of the outer cylinder, and each filter plate is obliquely arranged and is not fixed near the other end of the inner cylinder;
the inlet end of the solid product outlet pipeline is communicated with a solid product collecting area at the top of the inner cylinder.
Preferably, the included angle between each filter plate and the tangent line of the inner wall of the outer cylinder at the joint is 40-50 degrees.
The first gas lock and the second gas lock respectively have the function of preventing external air from entering the second oxidation reactor and the reduction reactor to be mixed with high-temperature combustible gas, so that the reaction process is influenced.
Wherein the first gas-water separator and the second gas-water separator are respectively used for separating water and combustible gas in gas oxidation products generated in the first oxidation reactor and the second oxidation reactor so as to collect high-grade combustible gas CO and H 2 。
The first cooler, the second cooler and the third cooler have the functions of heating materials and water by recycling waste heat in the reaction process in a countercurrent heat exchange mode, so that the heat utilization rate is improved.
Wherein the magnetic separator can collect Fe generated in the second oxidation reactor through magnetic separation 3 O 4 Separating the unavailable waste residues to a waste residue storage tank, and Fe 3 O 4 And feeding the waste water into a second solid material storage tank for continuous recycling.
Wherein the first grinder and the second grinder are respectively used for grinding solid oxidation products ZnO and Fe generated in the first oxidation reactor and the second oxidation reactor 3 O 4 Grinding coarse particles into fine particles, increasing solid contact area, and facilitating recycling of ZnO and Fe 3 O 4 Is subjected to magnetic separation.
The outer cylinder is positioned outside the inner cylinder and can rotate relative to the inner cylinder;
the top of the inner cylinder is provided with a solid product collecting area, the bottom of the inner cylinder is provided with a fan-shaped opening which is communicated with the inner cavity of the outer cylinder, and the inner cylinder is provided with a material inlet, a solid product outlet and a gas product outlet, wherein the material inlet on the first oxidation reactor is a mixed gas inlet, and the material inlet on the second oxidation reactor is a solid material inlet;
the filter plate group is positioned between the inner wall of the outer cylinder and the inner cylinder, one end of the filter plate group is fixedly connected with the inner wall of the outer cylinder, and the other end of the filter plate group is flexibly contacted with the inner cylinder but not fixed;
the inlet end of the solid product outlet pipeline is communicated with a solid product collecting area on the inner cylinder. After Zn steam reacts with water to produce solid ZnO, a filter plate group fixed on a rotary outer cylinder is brought to a high position and falls to an inclined solid product collecting area of the inner cylinder, and then zinc oxide is discharged out of the first oxidation reactor through a solid product outlet pipeline.
Compared with the prior art, the invention has at least the following beneficial effects:
the reduction reactor is heated by solar heat collection to achieve the purpose of the reactorThe energy consumption can be reduced, and the reaction is clean and pollution-free under the high-temperature condition required by the reaction; the high reduction performance of methane is utilized, the methane and electric furnace dust are mixed and preheated and react in a reduction reactor, and the methane, CO and H can be recovered in the circulating process 2 And combustible gas; the reaction products in the circulating system are easy to process and collect, and have little harm to the environment; the system is provided with a plurality of countercurrent heat exchangers, so that waste heat in the reaction process can be fully utilized to preheat materials, and the heat utilization efficiency is improved.
The invention uses electric furnace dust to replace amino and metal oxide as circulating medium, realizes the production of gas fuel by solar thermochemical energy storage, has the combination of the recycling treatment of electric furnace dust (Fe 2O3 and ZnO) and the utilization of renewable energy source solar energy, and has better application prospect.
Drawings
FIG. 1 is a schematic diagram of a solar thermal chemical energy conversion system using electric furnace dust as a recycling medium according to the present invention.
FIG. 2 is a schematic structural view of a reduction reactor according to the present invention.
FIG. 3 is a cross-sectional view of a reduction reactor according to the present invention.
FIG. 4 is a cross-sectional view of a first oxidation reactor according to the invention.
FIG. 5 is a right side view of the inner and outer drums of the first oxidation reactor of the present invention.
Fig. 6 is a cross-sectional view taken along A-A in fig. 4.
Fig. 7 is a sectional view taken along the direction B-B in fig. 4.
In the figure: 1. a methane storage tank; 2. a first fan; 3. a first solid material storage tank; 4. an electric furnace dust storage tank; 5. a second solid material storage tank; 6. a reduction reactor; 7. a first cooler; 8. a first air lock; 9. a second oxidation reactor; 10. a second grinder; 11. a magnetic separator; 12. a waste residue storage tank; 13. a third cooler; 14. a second gas-water separator; 15. a hydrogen storage tank; 16. a first oxidation reactor; 17. a second air lock; 18. a first grinder; 19. a second cooler; 20. a first gas-water separator; 21. a gas storage tank; 22. a second water pump; 23. a water storage tank; 24. a first water pump; 25. solar concentrator, 26, third fan, 27, second fan.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings.
A solar thermochemical energy conversion system taking electric furnace dust as a circulating medium comprises a material conveying subsystem, a reduction reaction subsystem, a zinc treatment subsystem, an iron treatment subsystem and a cooling subsystem.
The material conveying subsystem is used for conveying materials required by the reaction of the reduction reaction subsystem.
In one embodiment of the invention, the material conveying subsystem comprises a methane storage tank 1, a first solid material storage tank 3, an electric furnace dust storage tank 4, a second solid material storage tank 5 and a first fan 2, wherein the methane storage tank 1, the first solid material storage tank 3, the electric furnace dust storage tank 4 and the second solid material storage tank 5 are communicated with the reduction reaction subsystem through pipelines, and the stored materials are conveyed to the reduction reaction subsystem under the wind power of the first fan 2. The methane storage tank 1 is used for storing methane, and the first fan 2 blows the methane into the pipeline; after the materials in the first solid material storage tank 3, the electric furnace dust storage tank 4 and the second solid material storage tank 5 fall into a pipeline and are mixed with methane fed into the pipeline by the first fan 2, preheating is carried out by the first cooler 7, and the materials are fed into the reduction reactor 6 through the pipeline for reduction reaction, so that various reactions such as Fe2O3+3CH4=2Fe+3CO+6H2, znFe2O4+4CH4=Zn+2Fe+4CO+8H2, znO+CH4=Zn+CO+2H2 and the like occur; wherein the mass ratio of methane to the sum of the other materials is about 1:7.
the reduction reaction subsystem comprises a solar concentrator 25 and a reduction reactor 6 for receiving the material conveyed by the material conveying subsystem and for carrying out a reduction reaction inside the reduction reactor 6, wherein the solar concentrator 25 provides the temperature required for the reduction reaction when the reduction reaction occurs in the reduction reactor 6. The reduction reaction subsystem also comprises a first cooler 7 and a first air lock 8, and a solid product outlet on the reduction reactor 6 is communicated with a second oxidation reactor 9 through the first cooler 7 and the first air lock 8 in sequence.
At the bookIn one embodiment of the invention, the reduction reactor 6 comprises a mixed material inlet pipeline 6-2 and a separation cavity 6-6 communicated with the mixed material inlet pipeline 6-2, wherein the mixed material inlet pipeline 6-2 is a place where reduction reaction occurs. The mixed material inlet pipeline 6-2 is provided with an incident window 6-1 for incident solar energy, the incident window 6-1 is positioned on a condensation center line of the solar condenser 25, and the separation cavity 6-6 is provided with a gas product outlet and a solid product outlet which are communicated with the outlet of the mixed material inlet pipeline 6-2. The solid product outlet is fixedly provided with a first solid product outlet pipeline 6-4, the gas product outlet is fixedly provided with a first gas product outlet pipeline 6-3, and the inlet of the first gas product outlet pipeline 6-3 is provided with a filter screen 6-7 to prevent solid materials from being carried out by gas material flow. The solar energy condenser 25 provides the high temperature above 1100K environment needed by the reduction reaction for the mixed material inlet pipeline 6-2 through the incident window 6-1, the proportion of the reaction products around the temperature is proper, the reaction can be ensured, the produced zinc is ensured to be in a gaseous state, and the mixed material is subjected to the main reduction reaction in the mixed material inlet pipeline 6-2; the reaction product is separated into a gas product CH in a separation cavity 6-6 of the reduction reactor 6 4 、H 2 、H 2 O、CO、CO 2 Zn and solid product iron oxide and other impurities. The subsequent gaseous products will be discharged through the first gaseous product outlet conduit 6-3 and the solid products will be discharged through the first solid product outlet conduit 6-4 into the first oxidation reactor 16 and the second oxidation reactor 9, respectively.
In one embodiment of the invention, the wall of the mixed material inlet pipeline 6-2, the cavity wall of the separation cavity 6-6, the wall of the first gas product outlet pipeline 6-3 and the wall of the first solid product outlet pipeline 6-4 are provided with heat insulation layers 6-5 to play a role in heat insulation and reduce heat loss.
In one embodiment of the invention, the mixture inlet conduit 6-2 is a serpentine conduit. Compared with the straight pipe, the spiral pipeline is adopted, so that the occupied space of the pipeline can be reduced, and the material can be ensured to have enough heating time.
In one embodiment of the invention, the included angle between the spiral pipeline and the horizontal line is 30-40 degrees, and a certain inclination angle can prevent the pipeline from being blocked by the mixed materials, and the radian of an arc pipeline connected between two adjacent pipelines in the spiral pipeline is 90 degrees so as to prevent the material from being blocked at the spiral joint. Wherein the diameter and length of the coiled tubing is determined by the amount of material in the actual reactant and the tube diameters of the first gas product outlet tubing 6-3 and the first solid product outlet tubing 6-4 are determined by the amount of reaction product material.
During operation, gas products in the reduction reactor 6 enter the first gas product outlet pipeline 6-3, the temperature of the first oxidation reactor 16 is kept above 450K, the temperature of the gas products in the reduction reactor 6 is kept above 1190K and is introduced into the first oxidation reactor 16, and the liquid surface of the first oxidation reactor 16 is flushed through the material inlet pipeline 16-1 to perform oxidation reaction main reaction; wherein the molar amount of the reactant liquid water is 4 times the molar amount of the substance to be oxidized; oxidation reaction to produce gaseous product CH 4 、H 2 、H 2 O, and solid products ZnO, C, where ZnO: c=1:1.2.
During operation, solid products in the reduction reactor 6 enter the first cooler 7 through the first solid product outlet pipeline 6-4 to be cooled to 500K, and enter the second oxidation reactor 9 after passing through the first gas lock 8, wherein the working principle of the second oxidation reactor 9 is consistent with that of the first oxidation reactor 16, the reactor temperature of the second oxidation reactor 9 is kept above 400K, and oxidation reaction main reaction occurs in the second oxidation reactor 9. Wherein the molar amount of liquid water is 4 times the molar amount of the substance to be oxidized; oxidation reaction to produce gaseous product H 2 、H 2 O, solid product C, fe 3 O 4 And other waste residues.
In one embodiment of the invention, the zinc treatment subsystem comprises a first oxidation reactor 16, a second cooler 19, a first gas-water separator 20, a second fan 27, a gas storage tank 21, a second gas lock 17 and a first grinder 18, wherein the second gas lock 17 is communicated with a solid product outlet of the first oxidation reactor 16, an input port of the first grinder 18 is connected with the second gas lock 17, and an output port of the first grinder 18 is communicated with the first solid material storage tank 3; the second cooler 19 communicates with the gaseous product outlet of the first oxidation reactor 16, said second cooler 19 being connected to a separate inlet of a first gas-water separator 20, a separate outlet of the first gas-water separator 20 being connected to said gas storage tank 21. A second fan 27 is also provided between the separation outlet of the first gas-water separator 20 and the inlet of the gas storage tank 21. The gas product generated in the reduction reactor 6 enters the first oxidation reactor 16 to perform oxidation reaction with water, the generated fuel gas CO, H2 and water vapor enter the second cooler 19 through the second gas product outlet pipeline 16-3 to be cooled down, after the temperature is reduced to room temperature, the gas product enters the first water separator 20 to perform gas-water separation, and the gas product is sent to the gas storage tank 21 for storage through the second fan 27; the ZnO solid product generated by the oxidation reaction is sent to the first solid material storage tank 3 through the second gas lock 17 and the first grinder 18, and then is returned to the material conveying subsystem for circulation. The provision of the second fan 27 ensures that the generated gas can flow under pressure.
In one embodiment of the present invention, the first gas-water separator 20 may be a baffle-type water separator, which performs gas-water separation by inertia.
The reduction reactor and the first oxidation reactor are both provided with combustible gas in a high temperature state, so that the gas lockers (the first gas locker and the second gas locker) are arranged in a solid product pipeline which can exchange gas with the external environment, solid discharge is ensured, and meanwhile, the explosion caused by leakage of external combustion-supporting gas is prevented, and the safety of the system is improved.
In one embodiment of the invention, the iron treatment subsystem comprises a second oxidation reactor 9, a hydrogen storage tank 15, a second grinder 10, a magnetic separator 11 and a waste residue storage tank 12, wherein a solid material inlet of the second oxidation reactor 9 is communicated with a solid product outlet of the reduction reactor 6, and a gas product outlet of the second oxidation reactor 9 is communicated with the hydrogen storage tank 15; the material inlet of the second grinder 10 is communicated with the solid product outlet of the second oxidation reactor 9, the second grinder 10 is used for grinding the solid product of the oxidation reaction in the second oxidation reactor 9, the magnetic separator 11 is used for separating iron oxide from the ground solid product, the iron oxide enters the second solid material storage tank 5, and the other materials are sent into the waste residue storage tank 12.
In one embodiment of the invention, a third cooler 13 and a second gas-water separator 14 are further arranged between the gas product outlet of the second oxidation reactor 9 and the hydrogen storage tank 15 in the iron treatment subsystem, the gas product outlet of the second oxidation reactor 9 is communicated with the inlet of the third cooler 13, the second gas-water separator 14 is connected with the third cooler 13, and the separation outlet of the second gas-water separator 14 is communicated with the hydrogen storage tank 15 through a third fan 26. The oxidized gas product of the second oxidation reactor 9 enters the third cooler 13 through the gas product outlet of the second oxidation reactor 9 to be cooled, the temperature is lowered to the room temperature, the gas is separated by the second water separator 10, and the gas is extracted by the third fan 26 and enters the hydrogen storage tank 15 to be stored. By providing the third fan 26, it is ensured that the generated gas can flow under pressure.
In one embodiment of the present invention, the second gas-water separator 14 may be a baffle-type water separator that uses inertia to separate gas from water.
In one embodiment of the invention, the first oxidation reactor 16 and the second oxidation reactor 9 are substantially identical in structure, except that the feed inlet to the first oxidation reactor 16 is a mixed gas inlet and the feed inlet to the second oxidation reactor 9 is a solid feed inlet. The structure will be described below taking the first oxidation reactor 16 as an example.
The first oxidation reactor 16 is an inner and outer cylinder structure with an outer cylinder rotating and an inner cylinder fixed, and comprises an inner cylinder 16-7, an outer cylinder 16-5, a filter plate group 16-8 and a second solid product outlet pipeline 16-4, wherein the inner cylinder 16-7 and the outer cylinder 16-5 are coaxially arranged, the outer cylinder 16-5 is positioned outside the inner cylinder 16-7, and the outer cylinder 16-5 can rotate relative to the inner cylinder 16-7; the top of the inner cylinder 16-7 is provided with a solid product collecting area, the bottom of the inner cylinder is provided with an opening, and the inner cylinder 16-7 is provided with a material inlet, a solid product outlet and a gas product outlet, wherein the material inlet on the first oxidation reactor 16 is a mixed gas inlet, and the material inlet on the second oxidation reactor 9 is a solid material inlet; the filter plate group 16-8 is positioned between the outer cylinder 16-5 and the inner cylinder 16-7, and one end of the filter plate group 16-8 is fixedly connected with the inner wall 16-6 of the outer cylinder 16-5; the inlet end of the second solid product outlet conduit 16-4 communicates with a solid product collection zone on the inner drum 16-7.
Wherein the material inlet, the solid product outlet and the gas product outlet are respectively positioned at two sides of the inner cylinder 16-7. The material inlet is provided with a material inlet pipeline 16-1, the solid product outlet is provided with a second solid product outlet pipeline 16-4, and the gas product outlet is provided with a second gas product outlet pipeline 16-3. The outer tub 16-5 is not closed on both sides so as to conveniently provide the second solid product outlet pipe 16-4, the second gaseous product outlet pipe 16-3, and the material inlet pipe 16-1 so that the pipes do not interfere with the rotation of the outer tub 16-5.
In one embodiment of the present invention, the rotation of the outer barrel 16-5 is accomplished by the motor 16-13 driving the gear set 16-11. Specifically, the gear set 16-11 includes a gear fixed to the drive shaft 16-12 of the motor 16-13 and a meshing tooth fixedly provided on the outer wall of the outer cylinder 16-5 in the circumferential direction for meshing connection with the gear, and the meshing tooth is provided in the middle of the outer cylinder 16-5. When the rotary electric machine works, the motor 16-13 is started, and the motor 16-13 drives the gear to rotate through the transmission shaft 16-12, so that the outer cylinder 16-5 is driven to rotate relative to the inner cylinder 16-7 through the meshing teeth.
Preferably, the ratio of the number of teeth of the engaging teeth provided on the outer wall of the outer cylinder 16-5 to the number of teeth of the gear fixed to the drive shaft 16-12 is designed to ensure that the rotational speed of the outer cylinder is 0.2-0.4rpm, so that the material is sufficiently reacted.
In one embodiment of the present invention, a thermal insulation layer 16-9 is further provided between the inner wall 16-6 and the outer wall of the outer barrel 16-5.
In one embodiment of the present invention, the outer cylinder 16-5 is cylindrical, hollow in the inside and open at both ends, the cross section of the inner cylinder 16-7 is fan-shaped, the filter plate is a rectangular plate, one end of which is welded to the inner wall 16-6 of the outer cylinder, and rotates relative to the inner cylinder 16-7 as the outer cylinder 16-5 rotates. The other end of each filter plate is not fixed and is in flexible contact with the outer wall of the inner cylinder 16-7. In one embodiment of the present invention, the filter plate group 16-8 includes a plurality of filter plates, one end of which is circumferentially fixed to the inner wall 16-6 of the outer cylinder 16-5, and each of which is disposed obliquely. Preferably, the included angle between the filter plate and the tangent line of the inner wall 16-6 of the outer cylinder at the joint is 40-50 DEG
In one embodiment of the present invention, the inner barrel 16-7 is further provided with a water inlet, and the water inlet is correspondingly provided with a water inlet pipe 16-2. The water required for the reaction can be conveniently added through the water inlet pipe 16-2. The water inlet pipeline 16-2 is filled with water at a certain height below the outer cylinder, and the water height can close the opening of the inner cylinder.
In operation, water required for the reaction can be injected into the outer cylinder 16-5 through the water inlet pipeline 16-2, and the gas product of the reduction reactor 6 is introduced into the first oxidation reactor 16 through the material inlet pipeline 16-1 to perform oxidation reaction main reaction with the water of the first oxidation reactor 16. The oxidized solid product of the first oxidation reactor 16 is deposited below the liquid level and is sunk on the inner wall 16-6 of the outer cylinder, and the motor 16-13 drives the transmission shaft 16-12 to rotate so as to drive the gear set 16-11 to rotate, thereby driving the outer cylinder 16-5 to rotate, and the filter plate fixedly connected with the inner wall 16-6 of the outer cylinder also moves along with the rotation of the filter plate. When the solid product is moved to the lower end of the outer barrel 16-5, the filter plate 16-8 drives the solid product with the oxidation reaction to the upper end of the outer barrel 16-5 along with the rotation of the outer barrel 16-5, the oxidized solid product falls into a solid product collecting area 16-10 on the inner barrel 16-7 under the action of gravity, then is discharged out of the first oxidation reactor 16 through a second solid product outlet pipeline 16-4 communicated with the solid product collecting area, passes through a second air lock 17, passes through the grinding action of a first grinder 18, is introduced into a first solid material storage tank 3 for storage, and then is subjected to the circulation of the next round under the action of a first fan 2.
The cooling subsystem is used for providing cooling water for the cooler. The cooling subsystem comprises a water storage tank 23, a first water pump 24 being arranged between the water storage tank 23 and the second cooler 19, and a second water pump 22 being arranged between the water storage tank 23 and the third cooler. Part of the water in the water storage tank enters the preheating of the second cooler 19, is heated to the reaction temperature (373K, for example), and then is introduced into the first oxidation reactor 16 through the water inlet pipeline 16-2 to perform the oxidation reaction. The other part of water in the water storage tank 23 enters the third cooler 13 for preheating, is heated to the reaction temperature (373K, for example), and then is introduced into the second oxidation reactor 9 for oxidation reaction.
The solar thermochemical energy conversion system taking the electric furnace dust as the circulating medium utilizes the electric furnace dust (mainly Fe 2 O 3 And ZnO mixture) as a circulating medium in CH 4 As reducing agent, absorbing solar energy and reacting in a reduction reactor at high temperature above 1190K to generate H 2 CO and gaseous Zn, and further passing the gaseous reaction product Zn into a first oxidation reactor 16 to react with water to produce H 2 Wherein, the gaseous working medium Zn can collect the solid product ZnO after the reaction in the first oxidation reactor 16, and then is mixed into the reduction reactor 6 for reaction after being ground by the first grinder to be used as the thermochemical energy conversion cycle working medium. The solid reaction product after the reaction in the reduction reactor 6 is mainly Fe and the oxide thereof, and is sent into a second oxidation reactor to react with 9 water to generate gaseous fuel H 2 After the reacted solid material is ground by a second grinder 10, high-grade Fe can be collected by a magnetic separator 11 3 O 4 . Solar energy is stored into CO and H in the circulating process of the system 2 In the gaseous fuel, the chemical energy grade of the fuel is improved. The system disclosed by the invention realizes the organic combination of electric furnace dust treatment and utilization and solar energy storage, and has the characteristics of energy consumption reduction, environmental protection, cleanness, no environmental pollution and the like.
The invention and its embodiments have been described above with no limitation, and the construction of the invention is not limited to the embodiments shown in the drawings. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.

Claims (8)

1. A solar thermochemical energy conversion system taking electric furnace dust as a circulating medium is characterized in that: comprises a material conveying subsystem, a reduction reaction subsystem, a zinc processing subsystem and an iron processing subsystem,
the material conveying subsystem is used for conveying materials required by the reaction of the reduction reaction subsystem;
the reduction reaction subsystem comprises a reduction reactor (6) for receiving the materials conveyed by the material conveying subsystem and for carrying out reduction reaction in the reduction reactor (6), and a solar condenser (25) provides heat to form a temperature required for reduction when the reduction reaction occurs in the reduction reactor (6);
the zinc treatment subsystem comprises a first oxidation reactor (16) and a gas storage tank (21), wherein a mixed gas inlet of the first oxidation reactor (16) is communicated with the reduction reactor (6), solid products in the first oxidation reactor (16) are returned to the material conveying subsystem for circulation, and a gas product outlet of the first oxidation reactor (16) is communicated with the gas storage tank (21);
the iron treatment subsystem comprises a second oxidation reactor (9), a hydrogen storage tank (15), a second grinder (10) and a magnetic separator (11), wherein a solid material inlet of the second oxidation reactor (9) is communicated with a solid product outlet of the reduction reactor (6), a gas product outlet of the second oxidation reactor (9) is communicated with the hydrogen storage tank (15), an inlet of the second grinder (10) is communicated with a solid product outlet of the second oxidation reactor (9), and an iron oxide outlet of the magnetic separator (11) is communicated with the material conveying subsystem;
the reduction reactor (6) comprises a mixed material inlet pipeline (6-2) and a separation cavity (6-6) communicated with the mixed material inlet pipeline (6-2), wherein the mixed material inlet pipeline (6-2) is a spiral pipeline, an incident window (6-1) for enabling solar energy to enter is formed in the mixed material inlet pipeline (6-2), and a gas product outlet (6-3) and a solid product outlet (6-4) which are communicated with the outlet of the mixed material inlet pipeline (6-2) are formed in the separation cavity;
the first oxidation reactor (16) and the second oxidation reactor (9) have the same structure and comprise an inner cylinder (16-7), an outer cylinder (16-5), a filter plate group (16-8) and a second solid product outlet pipeline (16-4), the inner cylinder (16-7) and the outer cylinder (16-5) are coaxially arranged,
the inner cylinder (16-7) is fixedly and statically arranged, the outer cylinder (16-5) is positioned at the outer side of the inner cylinder (16-7), and the outer cylinder (16-5) can rotate relative to the inner cylinder (16-7);
the top of the inner barrel (16-7) is provided with a solid product collecting area, the bottom of the inner barrel is communicated with the inner cavity of the outer barrel (16-5) through an opening, and the inner barrel (16-7) is provided with a material inlet pipeline (16-1), a water inlet pipeline (16-2), a second solid product outlet pipeline (16-4) and a second gas product outlet pipeline (16-3), wherein a material inlet on the first oxidation reactor (16) is a mixed gas inlet, and a material inlet on the second oxidation reactor (9) is a solid material inlet;
the filter plate group (16-8) is positioned between the outer cylinder (16-5) and the inner cylinder (16-7), the filter plate group (16-8) comprises a plurality of filter plates, one end of each filter plate is fixedly connected with the inner wall (16-6) of the outer cylinder, and each filter plate is obliquely arranged;
the inlet end of the second solid product outlet pipe (16-4) is communicated with a solid product collecting zone (16-10) at the top of the inner cylinder (16-7).
2. A solar thermal chemical energy conversion system with electric furnace dust as a recycling medium according to claim 1, characterized in that: the material conveying subsystem comprises a first fan (2), a methane storage tank (1) for providing methane, a first solid material storage tank (3) for storing solid materials generated in a first oxidation reactor (16), an electric furnace dust storage tank (4) for providing electric furnace dust and a second solid material storage tank (5) for storing iron solid materials generated in a second oxidation reactor (9), wherein the methane storage tank (1), the first solid material storage tank (3), the electric furnace dust storage tank (4) and the second solid material storage tank (5) are communicated with the reduction reaction subsystem through pipelines, and the stored materials are conveyed to the reduction reaction subsystem under the wind power of the first fan (2).
3. A solar thermal chemical energy conversion system with electric furnace dust as a recycling medium according to claim 1, characterized in that: the mixed material inlet pipeline (6-2) is a spiral pipeline, the included angle between the pipeline and the horizontal line is 30-40 degrees, the radian of an arc pipeline connected between the two pipelines is 90 degrees, and the incident window (6-1) is positioned on the concentrating center line of the solar concentrator.
4. A solar thermal chemical energy conversion system with electric furnace dust as a recycling medium according to claim 1, characterized in that: the reduction reaction subsystem also comprises a first cooler (7) and a first air lock (8), and a solid product outlet on the reduction reactor (6) is communicated with a second oxidation reactor (9) through the first cooler (7) and the first air lock (8) in sequence.
5. A solar thermal chemical energy conversion system with electric furnace dust as a recycling medium according to claim 1, characterized in that: the zinc treatment subsystem further comprises a second gas lock (17) and a first grinder (18), the second gas lock (17) is communicated with the solid product outlet of the first oxidation reactor (16), and the first grinder (18) is connected with the second gas lock (17).
6. A solar thermal chemical energy conversion system with electric furnace dust as a recycling medium according to claim 1, characterized in that: the zinc treatment subsystem further comprises a second cooler (19) and a first gas-water separator (20), the second cooler (19) is communicated with the gas product outlet of the first oxidation reactor (16), the second cooler (19) is connected with the separation inlet of the first gas-water separator (20), and the separation outlet of the first gas-water separator (20) is connected with the gas storage tank (21).
7. A solar thermal chemical energy conversion system with electric furnace dust as a recycling medium according to claim 1, characterized in that: the iron treatment subsystem further comprises a third cooler (13) and a second gas-water separator (14) connected with the third cooler (13), a gas product outlet of the second oxidation reactor (9) is communicated with an inlet of the third cooler (13), and a separation outlet of the second gas-water separator (14) is communicated with a hydrogen storage tank (15).
8. A solar thermal chemical energy conversion system with electric furnace dust as a recycling medium according to claim 1, characterized in that: the included angle between each filter plate and the tangent line of the inner wall (16-6) of the outer cylinder at the joint is 40-50 degrees.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5013532A (en) * 1988-12-15 1991-05-07 Iit Research Institute Method for recycling electric arc furnace dust
WO2014067664A2 (en) * 2012-11-05 2014-05-08 Eth Zurich Methods and systems for reducing metal oxides
CN109486532A (en) * 2018-09-21 2019-03-19 华中科技大学 System for recovering dangerous solid waste by focusing solar energy at high temperature

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5013532A (en) * 1988-12-15 1991-05-07 Iit Research Institute Method for recycling electric arc furnace dust
WO2014067664A2 (en) * 2012-11-05 2014-05-08 Eth Zurich Methods and systems for reducing metal oxides
CN109486532A (en) * 2018-09-21 2019-03-19 华中科技大学 System for recovering dangerous solid waste by focusing solar energy at high temperature

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