WO2023044858A1 - Appareil de gazéification propre à haute température et procédé permettant d'atteindre un taux élevé de conversion du carbone d'un matériau carboné - Google Patents

Appareil de gazéification propre à haute température et procédé permettant d'atteindre un taux élevé de conversion du carbone d'un matériau carboné Download PDF

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WO2023044858A1
WO2023044858A1 PCT/CN2021/120684 CN2021120684W WO2023044858A1 WO 2023044858 A1 WO2023044858 A1 WO 2023044858A1 CN 2021120684 W CN2021120684 W CN 2021120684W WO 2023044858 A1 WO2023044858 A1 WO 2023044858A1
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carbon
section
slag
temperature
inlet
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PCT/CN2021/120684
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English (en)
Chinese (zh)
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李红海
姜从斌
孙庆君
丁建平
高瑞恒
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航天长征化学工程股份有限公司
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Priority to CN202180102572.9A priority Critical patent/CN117980440A/zh
Priority to PCT/CN2021/120684 priority patent/WO2023044858A1/fr
Publication of WO2023044858A1 publication Critical patent/WO2023044858A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form

Definitions

  • This application relates to the technical field of harmless disposal of carbonaceous materials, in particular to a high-temperature clean gasification device and method for realizing high carbon conversion rate of carbonaceous materials.
  • landfill needs to occupy a large amount of land and is likely to cause land pollution; incineration has incomplete disposal and secondary pollution of flue gas. and other issues; co-processing of cement kilns has certain technical advantages due to high temperature and long residence time, but the disposal materials are required not to affect the quality of cement, and the disposal volume is limited; plasma melting is an emerging hazardous waste disposal technology in recent years , has the advantages of complete harmlessness and obvious reduction, and basically solves the problem of secondary pollution of solid substances, but there are also problems such as the complexity of the flue gas treatment system, which is easy to cause secondary pollution, and high disposal costs.
  • the technical solutions disclosed in Chinese patents CN104053949B and CN105605581B have basically realized the problem of vitrification of solid phase slag, but due to the existence of medium and low temperature pyrolysis, there is still the problem of incomplete gas phase treatment and easy generation of tar substances.
  • the technical scheme disclosed in Chinese patent application CN109210541A solves the problem of vitrification of solid phase slag and basically solves the problem of tars, but the content of effective gas in the synthesis gas is low, and because the gasification temperature is low (900-1000 °C), especially in the case of fluctuating furnace conditions, there is still the problem of incomplete decomposition of some toxic organic substances.
  • One purpose of this application is to make the products produced by the disposal of carbonaceous materials clean and harmless.
  • a vertical melter-gasifier for the harmless disposal of carbonaceous materials sequentially includes a low-carbon slag section, a high-carbon slag section, a flash Fast pyrolysis redox section and cooling reduction section.
  • the low-carbon slag section includes a first gasification agent inlet, a slag-supporting gas inlet and a liquid slag discharge outlet. Under normal operating conditions, pyrolytic carbon particles falling into the low-carbon slag section have cohesiveness or flowability because the carbon content is lower than a threshold.
  • the high carbon slag section includes a second gasification agent inlet.
  • the flash pyrolysis redox section includes a carbonaceous material inlet, a third gasification agent inlet, and a carbonaceous fine powder inlet. Under normal operating conditions, the carbonaceous material fed into the flash pyrolysis redox section undergoes flash pyrolysis, and part of the pyrolyzed products undergo redox reactions.
  • the temperature-lowering reduction section includes a cooling device configured to lower the temperature inside the section, and a high-temperature crude synthesis gas outlet. Under normal operating conditions, CO 2 , H 2 O in the gas entering the cooling reduction section and carbon in the carbon-containing fly ash undergo a reduction reaction to generate CO and H 2 .
  • the temperature in the flash pyrolysis redox section is 1250°C to 2500°C; the inlet temperature of the cooling reduction section is 1150°C to 2500°C, and the outlet temperature is lower than The deformation temperature of ash; the temperature in the high-carbon slag section is 1350°C to 2500°C; and the temperature in the low-carbon slag section is at least 50°C to 200°C higher than the melting point of ash.
  • the first gasification agent inlet, the second gasification agent inlet and the third gasification agent inlet are configured to inject pure oxygen or oxygen-enriched air and are all provided with a flow regulating device , the flow regulating device can adjust the injection amount of the first, second and third gasification agents according to the content of CO 2 in the gas discharged from the high-temperature crude synthesis gas outlet, the slagging temperature and the temperature in the furnace.
  • the slag-supporting gas inlet is configured to be used for injecting combustion-supporting gas or inert gas, and is provided with a flow regulating device, which can adjust the combustion-supporting gas or inert gas according to the slag discharge condition and the temperature in the furnace. The amount of gas injected.
  • the carbonaceous material inlet communicates with the continuous feeding device and is vertically located between the second gasification agent inlet and the third gasification agent inlet.
  • the carbon-containing fine powder inlet is configured for injecting carbon-containing fine powder and is provided with a flow regulating device, which can be based on the content of CO in the gas discharged from the high-temperature raw syngas outlet. and the inlet temperature of the cooling reduction section to adjust the injection amount of carbon-containing fine powder.
  • the cooling device includes a cooling medium injection port configured to inject cooling medium into the inner space of the temperature reduction reduction section and/or a circulating cooling system provided in the furnace wall of the temperature reduction reduction section. system.
  • the fine powder quickly reacts to generate small molecular gases mainly CO, CO 2 , H 2 and H 2 O, and entrains carbon-containing fly ash and possible residual macromolecular organics into the cooling reduction section, and the pyrolytic carbon falls under the action of gravity into the high-carbon slag section;
  • the second gasification agent stirs the falling pyrolytic charcoal to decompose and break up, and an exothermic redox reaction occurs , the generated high-temperature gas entrains the carbon-containing fly ash produced by crushing into the flash pyrolysis redox section, and at the same time, the pyrolytic charcoal becomes low-carbon molten slag and falls to the low-carbon the slag section;
  • the first gasification agent stirs the slag and reacts with combustible substances in the slag to release heat, further reducing the melting
  • the residual carbon in the slag is homogeneously vitrified, and the vitrified slag is discharged from the slag discharge port.
  • the step of pretreating the carbonaceous material is further included before the step of feeding the carbonaceous material, and the pretreated carbonaceous material meets the homogenization requirement.
  • the following steps are further included: putting slag-producing materials into the melter-gasifier, passing through the slag-supporting gas inlet and the first gasification agent The inlet is sprayed with supporting gas and the first gasification agent, so that the combustion reaction of the supporting gas and the first gasification agent occurs, and the slag-producing material is heated and melted until a stable molten pool is established, each section in the furnace reaches the predetermined temperature, and the slagging conditions are met. .
  • the method further includes the following steps: by adjusting the amount of combustion-supporting gas or inert gas injected from the inlet of the slag-supporting gas and the amount of the first gasification gas injected from the inlet of the first gasification agent
  • the amount of the agent is such that the temperature of the low-carbon slag section is at least 50°C to 200°C higher than the melting point of the ash under normal operating conditions.
  • the temperature in the high-carbon slag section is 1350°C to 2500°C.
  • the temperature in the flash pyrolysis redox section is 1250°C to 2500°C
  • the temperature at the inlet of the cooling reduction section (D) is 1150°C to 2500°C.
  • the cooling device includes a cooling medium injection port configured to inject cooling medium into the inner space of the temperature reduction reduction section and/or a circulating cooling system provided in the furnace wall of the temperature reduction reduction section. system, by adjusting the cooling device so that the outlet temperature of the cooling reduction section is lower than the deformation temperature of the ash under normal operating conditions.
  • the cooling medium is selected from the group consisting of water mist, water vapor, cooled syngas, carbon dioxide gas, and combinations thereof.
  • the carbonaceous fines have a particle size of less than 200 microns, preferably less than 100 microns.
  • the first gasification agent, the second gasification agent and the third gasification agent are all pure oxygen or oxygen-enriched air.
  • the total molar ratio of carbon to oxygen in the furnace materials is 0.9 to 1.3, preferably 0.95 to 1.2, and more preferably 1, by adjusting the amounts of various furnace materials.
  • the supporting gas is fuel gas or atomized fuel oil.
  • shaft melter-gasifier refers to a furnace whose longitudinal axis is in the vertical direction, which is used to burn and gasify combustibles in the materials fed into it and to heat and melt ash and non-combustibles. stove.
  • carbonaceous materials refers to materials at least partially including carbonaceous combustibles, such as coal, petroleum, coke, biomass, plastics, rubber, domestic waste, pharmaceutical residues, oil sludge and the like.
  • the term “cohesiveness” means that the particles have a tendency to agglomerate and grow and adhere to each other with the slag.
  • the term "flowability" means that the particles have become liquid, merged with the slag, and can flow like a liquid, but the carbon content in it is still higher than 1% and does not constitute a qualified slag .
  • flash pyrolysis refers to pyrolysis in which the temperature rise is greater than 5000 degrees per second and the end temperature of pyrolysis exceeds 1000 degrees.
  • pure oxygen refers to a gas with a volume content of oxygen greater than or equal to 90%
  • oxygen-enriched air refers to air with a volume content of oxygen greater than or equal to 22%
  • homogenization requirements refers to the characteristic indicators (such as calorific value, ash composition, content amount of water) varies by no more than 6%, more preferably no more than 3%.
  • the term "slag-producing material” refers to the material put into the melter-gasifier to help establish a stable molten pool before the melter-gasifier enters normal operating conditions, including but not limited to coke, firewood, coal, and ash.
  • Fig. 1 is a schematic structural diagram of a vertical melter-gasifier according to some embodiments of the present application.
  • Fig. 2 is a flowchart of a method for melting and gasifying carbonaceous materials according to some embodiments of the present application.
  • Words such as “connected” or “connected” are not limited to physical or mechanical connections, and may include electrical connections, whether direct or indirect.
  • “Multiple” includes two, equivalent to at least two. It should be understood that although the terms first, second, third, etc. may be used in the present invention to describe various information, the information should not be limited to these terms. These terms are only used to distinguish information of the same type from one another. For example, without departing from the scope of the present invention, first information may also be called second information, and similarly, second information may also be called first information.
  • a vertical melter-gasifier 100 according to an embodiment of the present application will be described below with reference to FIG. 1 , which schematically shows the structure of the furnace.
  • the melter gasifier is used for harmless disposal of various carbon-containing materials, especially carbon-containing waste.
  • the melter-gasifier includes a low-carbon slag section A, a high-carbon slag section B, a flash pyrolysis redox section C and a cooling reduction section D from bottom to top.
  • the low-carbon slag section A includes a first gasification agent inlet 11 , a slag-supporting gas inlet 1 and a liquid slag discharge outlet 10 .
  • the high-carbon slag section B includes a second gasification agent inlet 2 .
  • the pyrolytic carbon particles falling into the high-carbon slag section B are not cohesive or flowable because the carbon content is higher than the threshold value.
  • the threshold depends on the specific composition of the material to be treated and is usually between 10 wt% and 35 wt%.
  • the flash pyrolysis redox section C includes a carbonaceous material inlet 3 , a third gasification agent inlet 4 , and a carbonaceous fine powder inlet 9 .
  • the temperature-lowering reduction section D includes a cooling device for lowering the temperature inside this section, and a high-temperature crude synthesis gas outlet 7 .
  • CO 2 , H 2 O in the gas entering the cooling reduction section D and carbon in the carbon-containing fly ash undergo a reduction reaction to generate CO and H 2 .
  • the low-carbon slag section A, the high-carbon slag section B, the flash pyrolysis redox section C, and the cooling reduction section D are set up to cooperate with each other and work together, so that the Carbonaceous materials can be finally transformed into vitrified liquid slag and CO and H2 -based gas phase products that do not contain macromolecular organic substances, so as to meet the requirements of cleanliness and harmlessness.
  • the vitrified slag since the vitrified slag has a high density and can be used as a building material, reduction and resource utilization are achieved.
  • the residual carbon content in the slag discharged from the above-mentioned melter-gasifier can reach an extremely low level, such as less than 1%, so that a high carbon conversion rate can be achieved, that is, a high rate of carbon in the carbonaceous material is converted into CO , CO 2 and other small molecule carbon-containing gases.
  • the volume content of effective gas (CO and H 2 ) in the gas phase product can reach more than 80% after being processed by the melter-gasifier of the present application (compared with the prior art, it is greatly improved) , and does not contain macromolecular organic matter, and can be further processed conveniently and pollution-free to become industrially valuable raw material gas (CO+H 2 ) or to further react the CO in it to generate H 2 , which can be filled as a product for external use. Sales, thereby greatly reducing the gas emissions to the environment, realizing the reduction of emissions and the resource utilization of products.
  • the first gasification agent inlet 11, the second gasification agent inlet 2 and the third gasification agent inlet 4 are used to inject gasification agent, wherein the first gasification agent inlet 11
  • the position is set so that it can inject gasification agent into the middle and lower part of the molten pool.
  • the gasification agent used is a gas with an oxygen content greater than or equal to 90% by volume (hereinafter referred to as pure oxygen), such as a gas with an oxygen content of 92%, 95%, 98%, or 99%.
  • the gasification agent used is air with a volume content of oxygen greater than or equal to 22% (hereinafter referred to as oxygen-enriched air).
  • the use of pure oxygen or oxygen-enriched air as a gasification agent is beneficial to promote the combustion reaction of combustibles, generate high-temperature gas, quickly establish a high-temperature environment, and is conducive to increasing the effective gas content. It should be understood, however, that other gasifying agents may also be used.
  • the first gasification agent inlet 11, the second gasification agent inlet 2 and the third gasification agent inlet 4 are respectively provided with flow regulating devices 1101, 201, 401, and these flow regulating devices can The injection amounts of the first, second and third gasification agents are adjusted according to the content of CO2 in the gas discharged from the high-temperature crude synthesis gas outlet 7, the slag discharge temperature and the temperature in the furnace.
  • these flow regulating devices are connected in communication with a controller, and the controller receives signals from the gas composition analysis sensor and the temperature sensor and sends an instruction for regulating flow to these flow regulating devices according to the signals.
  • the slag gas-supporting inlet 1 is used to inject combustion-supporting gas or inert gas, wherein the combustion-supporting gas can be any combustible gas (i.e. fuel gas), such as natural gas, liquefied petroleum gas, propane, It can also be atomized fuel oil; the inert gas can be any gas that does not react with liquid slag, such as CO 2 , N 2 .
  • the slag gas-supporting inlet 1 is provided with a flow regulating device 101, which can adjust the injection amount of supporting gas or inert gas according to the slag discharge condition and the temperature in the furnace.
  • the carbonaceous material inlet 3 is in communication with a continuous feeding device 302 (for example, a screw feeding device).
  • a continuous feeding device 302 for example, a screw feeding device.
  • carbonaceous materials that meet the requirements of homogenization after pretreatment such as coal, petroleum, coke, biomass, plastics, rubber, domestic garbage, pharmaceutical residues, and oil sludge are mixed according to the indicators
  • the carbonaceous material inlet 3 is located between the second gasification agent inlet 2 and the third gasification agent inlet 4 in the vertical direction.
  • flash pyrolysis occurs immediately after the carbonaceous material enters the furnace, and it is decomposed into falling pyrolytic carbon and rising pyrolysis gas, and the pyrolysis process needs to absorb heat, so it needs to continuously oxidize for flash pyrolysis Reduction section C supplements heat, otherwise the temperature of this section will drop and cannot meet the requirements of flash pyrolysis.
  • the second gasification agent injected from the second gasification agent inlet 2 has an exothermic reaction with the pyrolytic carbon falling from the flash pyrolysis redox section C, and the generated high-temperature gas enters the flash pyrolysis redox section C, Provide heat supply for flash pyrolysis of carbonaceous materials, so that the temperature near the inlet 3 of carbonaceous materials always meets the requirements of flash pyrolysis.
  • the third gasification agent injected from the third gasification agent inlet 4 located above the carbon material inlet 3 is mainly used to control the temperature of the rising gas phase to ensure that the temperature of the gas phase entering the cooling reaction section D meets the requirements above 1150°C, and at the same time
  • the oxygen in the third gasification agent reacts quickly with the rising macromolecular organic matter, which is beneficial to eliminate the macromolecular organic matter as soon as possible.
  • the carbon-containing fine powder inlet 9 is used for injecting carbon-containing fine powder and is provided with a flow regulating device 901, which can control CO 2 in the gas discharged from the high-temperature crude synthesis gas outlet 7.
  • the content and the inlet temperature of the cooling reduction section D are used to adjust the injection amount of carbon-containing fine powder.
  • the carbonaceous fines have a particle size of less than 200 microns, preferably less than 100 microns. Carbon-containing fine powder with small particle size has a larger residual carbon surface area, so it is easier to react with CO 2 and H 2 O, resulting in a faster heating rate and ensuring the complete pyrolysis of carbon-containing materials.
  • the cooling device of the cooling reduction section D includes a cooling medium injection port 8 for injecting cooling medium into the internal space of this section and a circulating cooling system arranged in the furnace wall of this section .
  • the cooling medium injection port 8 and the cooling medium channel of the circulating cooling system are arranged near the high-temperature crude synthesis gas outlet 7, so as to cool down the gas near the outlet.
  • the cooling medium injection port 8 is provided with a flow regulating device 801, which can adjust the injection amount of the cooling medium.
  • the cooling medium injected from the cooling medium injection port 8 may be water mist, water vapor, cooled syngas, carbon dioxide gas or one or more of them reaching a predetermined temperature.
  • the circulating cooling medium can be low-temperature fluids such as water and oil.
  • the deformation temperature of common ash is 900°C to 1200°C), so that the ash loses its viscosity and avoids sticking in the high-temperature crude syngas outlet 7 and subsequent pipelines cause blockage. This allows the melter-gasifier to run for extended periods of time without frequent shutdowns for cleaning. Since the circulating cooling system can also lower the temperature of the gas in the cooling reduction section D, the amount of cooling medium injected from the cooling medium injection port 8 can be reduced. In addition, there is another advantage of setting up a circulating cooling system, that is, it can recover high-quality waste heat through the heat exchange between the circulating cooling medium and high-temperature gas, and improve the thermal efficiency of the system.
  • cooling medium injection port 8 and the circulating cooling system can replace each other, but are not necessarily provided at the same time. In some embodiments, only the cooling medium injection port 8 is provided without a circulating cooling system in the furnace wall of this section. In other embodiments it is just the opposite.
  • FIG. 1 only schematically illustrates one possible shape of a melter-gasifier according to some embodiments.
  • the melter-gasifier has the shape of a cylinder with the longitudinal axis in the vertical direction, but it will be understood that it may also have other shapes.
  • the melter-gasifier has a cylindrical shape with a polygonal (eg, quadrilateral, pentagonal, or hexagonal) cross-section.
  • the melter-gasifier has a truncated circular shape with a cross-sectional area gradually changing in the vertical direction.
  • some or all of the various sections of the melter-gasifier have different shapes from each other.
  • low-carbon slag section A high-carbon slag section B
  • flash pyrolysis redox section C flash pyrolysis redox section C
  • cooling reduction section D are only rough functional divisions, and there are no strict physical boundaries. There is at least partial overlap between adjacent segments.
  • the heights and proportions of the above-mentioned sections can be determined by those skilled in the art, for example, according to the nature and quantity of the materials to be processed, which are not limited in this application.
  • Fig. 1 only schematically shows the approximate positions of each inlet and outlet, and each inlet and outlet only schematically shows one, but those skilled in the art can adjust each The location and number of entrances and exits.
  • multiple inlets and outlets can be arranged at intervals in the circumferential direction of the furnace, and multi-layer inlets and outlets can also be arranged in the height direction of the furnace.
  • some inlets can even overlap.
  • the carbonaceous material inlet 3 and the third gasification agent inlet 4 can be the same port, and the carbonaceous material and the third gasification agent are injected into the same port through the pipe with double channels. agent.
  • the melter-gasifier may also include various sensors at appropriate positions, such as temperature sensors, gas composition analysis sensors, flow sensors, etc., for The signals are transmitted to the controller, and the controller controls the flow regulating devices at each inlet according to these signals, so that the injection amount and injection timing of various substances injected into the furnace are as optimal as possible, so that the melting and gasification The furnace is running at its best.
  • FIG. 2 is a schematic flowchart of a method according to some embodiments of the present application. It should be understood that although the various steps in the flow chart of FIG. 2 are displayed sequentially as indicated by the arrows, these steps are not necessarily executed sequentially in the order indicated by the arrows. Unless otherwise specified herein, the execution of these steps is not strictly limited in order, but may be executed in other orders.
  • steps in the figure may include multiple sub-steps or multiple stages, these sub-steps or stages are not necessarily executed at the same time, but may be executed at different times, and the execution order is not necessarily sequential Instead, it may be performed alternately or alternately with at least a part of other steps or sub-steps or stages of other steps.
  • the method includes the following steps:
  • Step S1 The carbonaceous material is continuously fed into the flash pyrolysis redox section C through the carbonaceous material inlet 3, and the third gasification agent and the carbonaceous fine powder inlet 9 are respectively injected into the third gasification agent
  • Carbon fine powder, flash pyrolysis of carbon-containing materials to generate pyrolysis gas may include CO, H 2 , CO 2 , CH 4 , H 2 S, etc.
  • Step S2 CO 2 , H 2 O in the gas entering the cooling reduction section D from the flash pyrolysis redox section C undergoes a reduction reaction with the carbon in the carbon-containing fly ash to generate CO and H 2 , and possibly residual macromolecules Organic matter continues to decompose;
  • Step S3 Spray a second gasification agent into the high-carbon slag section B through the second gasification agent inlet 2, and the second gasification agent stirs the falling pyrolytic charcoal to decompose and break up, and an exothermic redox reaction occurs , the generated high-temperature gas entrains the carbon-containing fly ash produced by crushing and enters the flash pyrolysis redox section C.
  • the pyrolytic carbon becomes low-carbon molten slag and falls to the low-carbon slag section as the carbon content in it continues to decrease.
  • Step S4 Spray the first gasification agent into the low-carbon slag section A through the first gasification agent inlet 11.
  • the first gasification agent stirs the slag and reacts with the combustible substances in the slag to release heat, further reducing the melting temperature.
  • the residual carbon in the slag is homogeneously vitrified, and the vitrified liquid slag is discharged from the liquid slag discharge port 10.
  • the flash pyrolysis redox section C has a high temperature environment (in some embodiments, up to 1250°C to 2500°C), so that the carbonaceous material fed in is pyrolyzed instantaneously (that is, flash pyrolysis), generating pyrolysis gas, pyrolytic carbon and carbon-containing fly ash.
  • pyrolysis gas and carbon-containing fly ash and the third gasification agent injected from the third gasification agent inlet 4 a small amount of carbon-containing fine powder injected from the carbon-containing fine powder inlet 9, and the high-carbon melting
  • the high-temperature gas generated in the slag section B is rapidly mixed and reacted in the high-temperature environment of the flash pyrolysis redox section C to generate small molecular gases mainly including CO, CO 2 , H 2 and H 2 O.
  • the carbon fly ash and possible residual macromolecular organic matter enter the cooling reduction section D that also has a high temperature environment (in some embodiments, the inlet temperature of this section is 1150°C to 2500°C, and the outlet temperature is lower than the deformation temperature of the ash), wherein CO 2 , H 2 O and the carbon in the carbon-containing fly ash undergo a reduction reaction to generate CO and H 2 , and the possible residual macromolecular organic matter continues to decompose into small molecular gas at high temperature, which greatly increases the residual carbon content in the fly ash.
  • the inlet temperature of this section is 1150°C to 2500°C, and the outlet temperature is lower than the deformation temperature of the ash
  • CO 2 , H 2 O and the carbon in the carbon-containing fly ash undergo a reduction reaction to generate CO and H 2
  • the possible residual macromolecular organic matter continues to decompose into small molecular gas at high temperature, which greatly increases the residual carbon content in the fly ash.
  • the gas that is reduced and finally discharged from the high-temperature crude synthesis gas outlet 7 contains more than 80% (volume ratio) of CO and H 2 , a small amount of CO 2 (less than 10% by volume, and less than 5% when the working condition is stable) and H 2 O, a very small amount of CH 4 , H 2 S, N 2 and other small molecular gases, and a small amount of fly ash, without any macromolecular organic matter, thus effectively avoiding tar substances in the process of conventional combustion and medium and low temperature pyrolysis
  • the production of benzene, phenols, and dioxins is avoided from the source, and the harmlessness of the gas phase is realized.
  • the content of effective gas i.e.
  • CO and H 2 ) in the gas discharged from the high-temperature crude synthesis gas outlet 7 is significantly improved, so that it can be processed afterward (not shown in the accompanying drawings of the application)
  • Subsequent processing equipment becomes industrially valuable raw material gas (CO+H2) or further reacts CO in it to generate H2 , which is filled and sold as a product, realizing the resource utilization of the product.
  • Only a very small amount of CO 2 and H 2 O is finally discharged into the atmosphere, thereby greatly reducing the impact on the environment.
  • the pyrolytic charcoal (solid phase) generated by flash pyrolysis falls into the high-carbon slag section B that also has a high-temperature environment (in some embodiments, up to 1350°C to 2500°C) under the action of gravity.
  • the pyrolytic charcoal is further decomposed and broken under the agitation of the second gasification agent injected from the second gasification agent inlet 2 and in a high-temperature environment, and a redox reaction occurs, a large amount of heat is released, and the generated high temperature Gas (mainly CO, CO 2 , temperature up to 1500°C-3000°C) entrains and breaks the carbon-containing fly ash into the flash pyrolysis redox section C.
  • low-carbon slag section A where the temperature changes greatly, but the lowest temperature is 50°C to 200°C higher than the melting point of ash, and the highest temperature may exceed 2500°C.
  • the pyrolytic charcoal melts into a liquid state and fuses with the slag, and the first gasification agent injected from the first gasification agent inlet 11 stirs the slag and combines with the carbon in the slag, etc.
  • the reaction of combustible substances releases heat, further reduces the residual carbon in the slag and makes it homogeneously vitrified, and effectively solidifies the heavy metals, thereby realizing the harmlessness of the solid slag.
  • the vitrified slag has a high density and can be used as a building material, volume reduction and resource utilization are achieved.
  • the long residence time of the solid phase in the high-temperature environment in the furnace (sequentially passing through the flash pyrolysis redox section C, high-carbon slag section B, and low-carbon slag section A) and under the agitation of the gasification agent
  • the mixing is sufficient and the reaction is thorough, so most of the carbon in it is finally converted into small molecule carbon-containing gases such as CO and CO 2 , and the residual carbon content in the slag is less than 1wt%, thus achieving a high carbon conversion rate. This can be achieved even with poorly reactive materials.
  • the above method also includes the step of pretreating the carbonaceous material, for example, after drying several different materials, they are mixed according to the index, so that the carbonaceous material after pretreatment meets the requirements of homogeneity.
  • Chemical requirements that is, in the process of material transportation, the change in the characteristic indicators (such as calorific value, ash composition, water content) of the material passing through a certain cross-section in the first minute and the material passing in the next minute shall not exceed 6%, which is better ground is not more than 3%.
  • the melter-gasifier can also handle more kinds of carbonaceous materials, which has a wide range of application.
  • the S0 step is also included before the S1 step, and in the S0 step, slag-producing materials (such as coke, firewood, coal, ash, etc.) are put into the melter-gasifier, through
  • the slag gas-supporting gas inlet 1 and the first gasification agent inlet 11 are sprayed into the gas-supporting gas (such as any combustible gas such as natural gas, liquefied gas, propane, or atomized fuel oil) and the first gasification agent (such as pure Oxygen, oxygen-enriched air), so that the combustion gas and the first gasification agent have a combustion reaction, and the slagging material is heated and melted until a stable molten pool is established, each section in the furnace reaches the predetermined temperature, and the slagging conditions are met.
  • the gas-supporting gas such as any combustible gas such as natural gas, liquefied gas, propane, or atomized fuel oil
  • the first gasification agent such as pure Oxygen, oxygen-enriched air
  • the carbonaceous material to be disposed is sent into the furnace and a predetermined amount of corresponding substances are sprayed into the above-mentioned various inlets to cause the above-mentioned various reactions to occur. Since these reactions are mostly exothermic reactions, a large amount of Therefore, under normal operating conditions, the temperature in flash pyrolysis redox section C can be maintained at 1250°C to 2500°C, and the temperature in high-carbon slag section B can be maintained at 1350°C to 2500°C.
  • the temperature in the slag section A is at least 50°C to 200°C higher than the melting point of the ash (the slag-supporting gas is injected through the slag-supporting gas inlet 1 to adjust the slag discharge temperature), and the inlet temperature of the cooling reduction section D is 1150 °C to 2500 °C, the outlet temperature is lower than the deformation temperature of the ash (realized by the cooling device).
  • the slag-supporting gas is injected through the slag-supporting gas inlet 1 to adjust the slag discharge temperature
  • the inlet temperature of the cooling reduction section D is 1150 °C to 2500 °C
  • the outlet temperature is lower than the deformation temperature of the ash (realized by the cooling device).
  • only a small amount of supporting gas is needed during normal operation, or only inert gas needs to be introduced to keep the orifice unblocked.
  • the amount of assisted gas injected from the slag assisted gas inlet 1 can be appropriately increased so that it can reach a suitable chemical equivalent ratio with the first gasification agent (for example, the chemical equivalent of complete combustion Ratio), thereby increasing the slag discharge temperature.
  • a suitable chemical equivalent ratio with the first gasification agent for example, the chemical equivalent of complete combustion Ratio
  • the injection amount of oxidant gas can be reduced or the oxidant gas can be switched to inert gas, and it is enough to keep the inlet unblocked.
  • the calorific value of the carbon-containing material fed into the melter-gasifier is low or the temperature in the furnace fluctuates so that the temperature cannot meet the requirements, it can be increased by increasing the amount of assisted gas injected from the slag-assisted gas inlet 1. To ensure the high temperature environment in the furnace.
  • the method also includes the following steps: by adjusting the amount of various materials entering the furnace (that is, all materials entering the furnace, including combustion-supporting gas, gasification agent, carbon-containing materials, and carbon-containing fine powder), so that the furnace
  • the total molar ratio of carbon and oxygen in the material is 0.9 to 1.3, preferably 0.95 to 1.2, more preferably 1.
  • a higher cooling efficiency that is, the ratio of the calorific value of the effective gas produced by the same amount of materials fed into the furnace to the heat value of the materials fed into the furnace
  • the economy is improved.
  • Example 1 A melting gasifier capable of processing 240 tons of solid materials per day, wherein the inner diameter of the low-carbon slag section A and the high-carbon slag section B is 2200mm, and the total height is 2400mm, and the flash pyrolysis redox section C and The inner diameter of the cooling reduction section D is 2800 mm, and the total height is 11500 mm.
  • the material fed into the furnace is a mixture of pretreated domestic waste and tar residue, with a calorific value of 25634 Kj/kg.
  • the specific components are shown in Table 1:
  • the high-temperature crude syngas generated after the carbonaceous material is processed by the melter-gasifier does not contain any macromolecular organic matter, and the effective gas (CO and H 2 ) content is as high as 94.79%, the thermal efficiency of the by-product steam is high, the solid slag contains low carbon and is glass body, which realizes the requirement of harmless disposal of solid waste, that is, solves the problem of harmless solid phase slag and gas phase after disposal problem.
  • Example 2 A melter-gasifier capable of processing 360 tons of solid material per day, wherein the inner diameter of the low-carbon slag section A and the high-carbon slag section B is 2400 mm, the total height is 2800 mm, and the flash pyrolysis redox section C and The inner diameter of the cooling and reducing section D is 3000mm, and the total height is 13500mm.
  • the material fed into the furnace is pretreated domestic waste, and the calorific value is 20285Kj/kg.
  • the specific composition is shown in Table 3:
  • the high-temperature crude syngas generated after the carbonaceous material is processed by the melter-gasifier does not contain any macromolecular organic matter, and the effective gas (CO and H 2 ) content is as high as 87.01%, the thermal efficiency of the by-product steam is high, the solid slag contains low carbon and is glass body, which realizes the requirement of harmless disposal of solid waste, that is, solves the problem of harmless solid phase slag and gas phase after disposal problem.
  • the melter-gasifier and the method for harmless disposal of carbonaceous materials provided by the embodiment of the present application have many advantages and broad application prospects, especially the harmless disposal process can be realized. , material reduction and resource utilization.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Four vertical de gazéification par fusion (100) et procédé de traitement inoffensif de matériaux carbonés. Le four comprend successivement, de bas en haut, une section laitier à faible teneur en carbone (A), une section laitier à haute teneur en carbone (B), une section pyrolyse éclair-rédox (C) et une section de réduction par refroidissement (D). La section laitier à faible teneur en carbone comprend une entrée (11) pour un premier agent de gazéification, une entrée (1) pour un gaz facilitant la combustion du laitier et un orifice (10) d'évacuation du laitier liquide. La section laitier à haute teneur en carbone comprend une entrée (2) pour un deuxième agent de gazéification. La section pyrolyse éclair-rédox comprend une entrée (3) pour une matière carbonée, une entrée (4) pour un troisième agent de gazéification et une entrée (9) pour une poudre fine carbonée. La section réduction par refroidissement comprend un appareil de refroidissement utilisé pour abaisser la température à l'intérieur du segment et une sortie (7) pour le gaz de synthèse brut à haute température. Dans les conditions normales de fonctionnement, les particules de carbone pyrolytique tombant dans la section laitier à haute teneur en carbone ne présentent aucune cohésivité ni aucune fluidité, du fait qu'elles ont une teneur en carbone supérieure à un seuil. Les particules de carbone pyrolytique tombant dans la section laitier à faible teneur en carbone présentent une cohésivité et une fluidité du fait qu'elles ont une teneur en carbone inférieure au seuil. Le matériau carboné chargé dans la section pyrolyse éclair-rédox subit une pyrolyse éclair, et la partie pyrolysée du produit subit une réaction rédox. Le CO2 et le H2O se trouvant dans le gaz pénétrant dans la section de réduction par refroidissement subissent une réaction de réduction avec le carbone se trouvant dans les cendres volantes carbonées pour produire du CO et du H2.
PCT/CN2021/120684 2021-09-26 2021-09-26 Appareil de gazéification propre à haute température et procédé permettant d'atteindre un taux élevé de conversion du carbone d'un matériau carboné WO2023044858A1 (fr)

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PCT/CN2021/120684 WO2023044858A1 (fr) 2021-09-26 2021-09-26 Appareil de gazéification propre à haute température et procédé permettant d'atteindre un taux élevé de conversion du carbone d'un matériau carboné

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1312662A2 (fr) * 2001-05-07 2003-05-21 Cirad-Foret Procédé de gazéification de biomasse, appareil et utilisation
CN105542805A (zh) * 2015-12-15 2016-05-04 广西高远环境工程有限公司 生活垃圾立卧式干馏气化裂解三段集成制气的装置与工艺

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1312662A2 (fr) * 2001-05-07 2003-05-21 Cirad-Foret Procédé de gazéification de biomasse, appareil et utilisation
CN105542805A (zh) * 2015-12-15 2016-05-04 广西高远环境工程有限公司 生活垃圾立卧式干馏气化裂解三段集成制气的装置与工艺

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