WO2025232425A1 - 一种基于气化渣阴燃技术制备富co燃气的方法 - Google Patents

一种基于气化渣阴燃技术制备富co燃气的方法

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Publication number
WO2025232425A1
WO2025232425A1 PCT/CN2025/087655 CN2025087655W WO2025232425A1 WO 2025232425 A1 WO2025232425 A1 WO 2025232425A1 CN 2025087655 W CN2025087655 W CN 2025087655W WO 2025232425 A1 WO2025232425 A1 WO 2025232425A1
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Prior art keywords
temperature
smoldering
gasification
oxygen
gasification slag
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English (en)
French (fr)
Inventor
黄经春
马仑
乔瑜
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/30—Fuel charging devices
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/55—Slag

Definitions

  • This invention belongs to the field of solid waste treatment technology, specifically relating to a method for preparing CO-rich fuel gas based on gasification slag smoldering technology.
  • coal my country's energy structure, characterized by "abundant coal, scarce oil, and limited gas," dictates that coal remains the primary energy source.
  • Coal gasification a core technology for the clean and efficient utilization of coal, is hailed as the leading technology in the modern coal chemical industry and is widely used in fields such as steel, machinery, chemicals, and building materials.
  • coarse gasification ash In the coal gasification process, coarse gasification ash is usually discharged directly from the bottom of the furnace. Its composition is similar to that of boiler ash, with a low carbon content, and it is mostly used as a blending material for road construction or for backfilling. Fine gasification ash, however, has a high carbon content and high loss on ignition, failing to meet national and industry standards for building admixtures. It is difficult to use directly in construction and road projects, and there is a lack of effective large-scale disposal methods; it is mostly disposed of through stockpiling or landfilling. However, the landfilling or stockpiling of high-carbon fine gasification ash causes serious resource waste, occupies a large amount of land, generates dust causing air pollution, and leachate from prolonged stockpiling or landfilling pollutes soil and water bodies.
  • the present invention provides a method for preparing CO-rich fuel gas based on the smoldering technology of gasification slag.
  • This method can realize the gasification of gasification slag and produce high-concentration CO fuel gas based on the principle of smoldering, realize the full utilization of combustible substances in gasification slag, and solve the environmental problems caused by the inability to dispose of and utilize gasification slag on a large scale.
  • the present invention provides a method for preparing CO-rich fuel gas based on gasification slag smoldering technology. This method is carried out in a smoldering reactor and includes the following steps:
  • the moisture content of the gasification slag is controlled between 10% and 90%; the particle size of the inert medium is between 1 and 3 mm, and the mass ratio of the gasification slag to the inert medium is between 1:1 and 1:6.
  • the reaction gas is introduced from the bottom of the smoldering reaction device and ignited to start the smoldering reaction of the mixture.
  • a high-temperature high-oxygen oxidation zone, a high-temperature low-oxygen oxidation zone, a low-oxygen pyrolysis zone and a low-temperature low-oxygen drying zone are formed from bottom to top in the smoldering reaction device to complete the high-temperature oxidation process, high-temperature gasification process, pyrolysis process and drying process of the gasified slag at different locations of the smoldering reaction device respectively.
  • the Darcy velocity of the reactant gas is controlled at 1 cm/s to 15 cm/s, and the oxygen concentration is 10% to 30%, ensuring that the core reaction temperature in the high-temperature and high-oxygen oxidation zone is not lower than 900°C, and the oxygen concentration at the end of the high-temperature and high-oxygen oxidation zone is controlled at 2% to 6%; the gasification reaction temperature in the high-temperature and low-oxygen oxidation zone is controlled above 800°C, and the oxygen concentration at the end of the high-temperature and low-oxygen oxidation zone is controlled below 1%.
  • the flue gas is discharged from the exhaust port from the top of the smoldering reaction device to obtain CO-rich low-oxygen fuel gas.
  • the gasification slag is a gasification coarse slag with a moisture content of less than 30%, and its mass ratio with the inert medium is between 1:1 and 1:3.
  • the gasification slag is a fine gasification slag with a moisture content of more than 30%, and its mass ratio with the inert medium is between 1:2 and 1:5.
  • the inert medium is quartz sand or sand.
  • the low-oxygen pyrolysis zone includes a high-temperature low-oxygen pyrolysis zone, a medium-temperature low-oxygen pyrolysis zone, and a low-temperature low-oxygen pyrolysis zone formed sequentially from bottom to top, with the temperature ranges of the three zones being no less than 800°C, 500 ⁇ 800°C, and 200 ⁇ 500°C, respectively.
  • the CO-rich low-oxygen fuel gas obtained has a CO concentration of not less than 10% and an oxygen concentration of less than 1%.
  • the reaction gas fed into the smoldering reaction device is mixed with CO2 in a concentration range of 0 to 85%.
  • a residue zone is provided at the bottom of the smoldering reaction device, which is located below the high temperature and high oxygen oxidation zone, for discharging the gasification residue after the oxidation reaction.
  • the core reaction temperature in the high-temperature and high-oxygen oxidation zone is controlled at 900-1100°C.
  • the initial reaction temperature of the high-temperature low-oxygenation zone is controlled above 850°C
  • the final reaction temperature of the high-temperature low-oxygenation zone is controlled above 800°C.
  • the monitoring of the temperature of each reaction zone in the smoldering reaction device is achieved by arranging multiple thermocouples at intervals from bottom to top inside the device.
  • the method for preparing CO-rich gas based on the smoldering technology of gasification slag in this invention is carried out in a smoldering reaction device.
  • a smoldering reaction device By combining the smoldering treatment technology with the processes of drying, dehydration, pyrolysis, gasification, and oxidation of gasification slag, and controlling the corresponding reaction conditions, CO-rich gas with low oxygen concentration can be obtained in the end. This achieves efficient utilization and harmless treatment of gasification slag, effectively improves the efficiency of coal resource development and utilization, and avoids waste of resources.
  • the method for preparing CO-rich fuel gas based on gasification slag smoldering technology in this invention is carried out in a low-oxygen, strong reducing atmosphere for most of the processing. This can effectively inhibit the generation of nitrogen oxides, effectively ensure the cleanliness of the fuel, and avoid environmental pollution when the fuel is used.
  • the method for preparing CO-rich gas based on the smoldering technology of gasification slag in this invention further enhances the gasification reaction of carbon in gasification slag by mixing a certain concentration of CO2 gas into the gas introduced into the smoldering reaction device, thereby further improving the gasification effect and the CO concentration in the outlet flue gas, and improving the quality of the gas produced.
  • the method for preparing CO-rich gas based on the smoldering technology of gasification slag in this invention has simple steps and convenient control.
  • the gasification slag can be efficiently treated and CO-rich gas with low oxygen concentration can be obtained.
  • the combustible components in the gasification slag are fully recovered, the resource is recycled and utilized, and the usability of the recycled resources is fully guaranteed, which has extremely high economic value.
  • Figure 1 is a schematic diagram of a system for preparing CO-rich fuel gas using gasification slag in an embodiment of the present invention.
  • center In the description of this invention, it should be understood that the terms “center,” “longitudinal,” “lateral,” “length,” “width,” “thickness,” “upper,” “lower,” “front,” “rear,” “left,” “right,” “vertical,” “horizontal,” “top,” “bottom,” “inner,” “outer,” “clockwise,” “counterclockwise,” “axial,” “radial,” and “circumferential” indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.
  • first and second are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated.
  • a feature defined as “first” or “second” may explicitly or implicitly include at least one of that feature.
  • a plurality of means at least two, such as two, three, etc., unless otherwise explicitly specified.
  • the terms “installation,” “connection,” “linking,” and “fixing,” etc. should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.
  • “above” or “below” the second feature can mean that the first feature is in direct contact with the second feature, or that the first feature is in indirect contact with the second feature through an intermediate medium. Furthermore, “above,” “over,” and “on top” of the second feature can mean that the first feature is directly above or diagonally above the second feature, or simply that the first feature is at a higher horizontal level than the second feature. "Below,” “below,” and “under” the second feature can mean that the first feature is directly below or diagonally below the second feature, or simply that the first feature is at a lower horizontal level than the second feature.
  • the preferred embodiment of the present invention describes a method for preparing CO-rich fuel gas based on gasification slag smoldering technology. This method utilizes smoldering technology and synergistically combines gasification slag drying and dehydration with gasification/oxidation decarbonization to prepare CO-rich fuel gas.
  • the integrated method for preparing CO fuel gas includes the following steps:
  • the gasification slag is preferably fine gasification slag or coarse gasification slag, with its moisture content preferably controlled between 10% and 80%.
  • Coarse gasification slag is the water-containing slag discharged from the bottom slag hopper of the gasifier after the slurry coal particles have undergone melting, quenching, and condensation processes under high temperature and pressure conditions in the gasifier. Its residual carbon content varies considerably depending on the coal type, gasifier type, and gasifier operating conditions, generally ranging from 10% to 30%, with particle sizes concentrated between 16 mesh and 4 mesh.
  • Fine gasification slag is generally the water-containing slag carried out from the top of the gasifier by the flow of coarse coal gas, and obtained after preliminary washing, purification, and sedimentation. It has a higher residual carbon content, generally exceeding 30%, and a particle size of less than 16 mesh, with approximately one-third being less than 200 mesh.
  • the inert medium is preferably quartz sand or sand with a particle size between 1 and 3 mm, and its moisture content when used in combination is preferably controlled below 20%.
  • the mass ratio of gasification slag to inert medium is preferably between 1:1 and 1:6, and the specific ratio is preferably determined by the particle size characteristics of the gasification slag (mainly by the moisture content and calorific value).
  • the mass ratio between the fine gasification slag and the inert medium is preferably controlled between 1:2 and 1:5.
  • the optimal mass ratio of coarse gasification slag to inert medium is preferably controlled between 1:1 and 1:3.
  • the preheating temperature (ignition temperature) of the mixture is preferably 250°C to 400°C, and more preferably 300°C.
  • the reaction gas is introduced from the bottom of the smoldering reaction device and ignited to start the smoldering reaction of the porous mixture.
  • the smoldering reaction device is formed from bottom to top in the following order: high temperature and high oxygen oxidation zone, high temperature and low oxygen oxidation zone, low oxygen pyrolysis zone (high temperature and low oxygen pyrolysis zone, medium temperature and low oxygen pyrolysis zone, low temperature and low oxygen pyrolysis zone), low temperature and low oxygen drying zone and fresh mixture replenishment zone.
  • the mixture located in the lower layer of the smoldering reaction device undergoes an oxidation reaction in a high-oxygen environment with a core reaction temperature of not less than 900°C, forming a high-temperature, high-oxygen oxidation zone, which produces high-temperature, low-oxygen, high-concentration CO2 flue gas, referred to as the first flue gas.
  • the temperature of the first flue gas is not less than 850°C, and the oxygen concentration in it is between 4% and 6%.
  • the oxygen concentration in the initial stage of the zone is controlled at above 15%, and the oxygen concentration in the final stage is controlled at 2%–6%. More preferably, the oxygen concentration in the initial stage is controlled between 10% and 30%.
  • the highest temperature in the core reaction zone within the high-temperature, high-oxygen oxidation zone is preferably controlled at above 900°C.
  • the oxygen content of the gas fed into the smoldering reactor is between 10% and 30%, and the Darcy velocity of the gas to be between 1 cm/s and 15 cm/s; correspondingly, the reaction temperature in the high-temperature, high-oxygen oxidation zone is maintained at 900–1100°C.
  • the adjustment of this reaction temperature can be achieved by changing the oxygen concentration in the supplied gas, which will not be elaborated upon here.
  • the CO2 in the flue gas and the carbon in the gasification slag undergo a gasification reaction in a high temperature and low oxygen environment.
  • the temperature of this gasification reaction is above 800°C, generating high temperature and low oxygen flue gas rich in CO.
  • the core reaction temperature is above 800°C.
  • the oxygen concentration is relatively high, ranging from 2% to 6%; at this point, the initial reaction temperature in this zone is preferably controlled above 850°C.
  • the oxygen in the flue gas is further consumed.
  • the oxygen concentration is below 1%, and this flue gas is referred to as the second flue gas.
  • the competition between the above-mentioned reaction (1) and reaction (2) will take place. If the oxygen concentration in this zone is too high and the temperature is lower than the gasification reaction temperature, the oxidation reaction (1) will be significantly stronger than the gasification reaction (2), resulting in a low CO concentration in the second flue gas at the end of the high-temperature low-oxygen oxidation zone, which will not achieve the purpose of producing CO-rich fuel gas.
  • the oxygen concentration in the flue gas (second flue gas) further decreases, but the flue gas temperature remains in a relatively high range (not lower than 800°C).
  • a high-temperature, low-oxygen pyrolysis zone, a medium-temperature, low-oxygen pyrolysis zone, and a low-temperature, low-oxygen pyrolysis zone are formed sequentially above the high-temperature, low-oxygenation zone.
  • the temperature ranges in the three zones are not lower than 800°C, 500–800°C, and 200–500°C, respectively.
  • the concentration of pollutants such as nitrogen oxides in the flue gas can always be kept at a relatively low level.
  • the third flue gas flows upward and comes into contact with the fresh mixture fed from above.
  • the residual heat of the third flue gas is used to dry the fresh mixture, forming a low-temperature, low-oxygen drying zone of a certain thickness inside the smoldering reactor, and finally obtaining a moist flue gas rich in CO.
  • the final humid flue gas is sent out from the exhaust port of the smoldering reactor. After subsequent condensation and dehydration, a low-oxygen fuel gas rich in CO can be obtained.
  • the CO concentration in the final combustible flue gas is not less than 10%, and the oxygen concentration therein is less than 1%.
  • the core reaction temperature in the high-temperature and high-oxygen oxidation zone can be effectively controlled to be no less than 900°C, and the CO concentration in the obtained flue gas can be guaranteed to be no less than 10%.
  • the mixing concentration of CO2 gas is preferably 0-85%, and more preferably 30%.
  • a residue zone is formed at the bottom of the smoldering reaction device, which is located below the high-temperature and high-oxygen oxidation zone.
  • the residue after the oxidation reaction is discharged through the discharge port set in the residue zone.
  • the technical solution of the aforementioned preferred embodiment combines the drying, dehydration, pyrolysis, gasification, and oxidation processes of the gasification slag with smoldering treatment technology. It utilizes the heat generated by the smoldering reaction of the gasification slag itself as a heat source to remove moisture from the slag and dry it. This achieves a self-sustaining reaction without the need for external auxiliary energy, resulting in low energy consumption. Furthermore, through optimized design of the corresponding control conditions, the formation of the appropriate region within the smoldering reaction device can be completed, producing high-concentration CO from the gasification slag to obtain high-quality fuel gas, thus fully realizing the harmless treatment and energy recovery of the gasification slag.
  • the raw materials used in the preparation of the mixture in process (1) include gasification coarse slag with a moisture content of 36% and quartz sand with a particle size of 1 to 1.5 mm.
  • the gasification coarse slag and quartz sand are mixed in a mass ratio of 1:2 to obtain a mixture with porous characteristics.
  • the mixed materials are filled into a laboratory-scale smoldering furnace reactor.
  • the reactor has an inner diameter of 15 cm and a height of 20 cm.
  • Thermocouples are arranged at 3 cm intervals along the height of the reactor to collect temperature data.
  • the bottom electric heating device is turned on for preheating.
  • the electric heating device is turned off, the air supply system is turned on to supply gas and ignite; in this embodiment, the composition of the gas intake is controlled to be 21% O2 and 79% N2 , the Darcy flow rate of the gas is 5 cm/s, and the reaction begins.
  • each thermocouple along the height of the material monitors the temperature inside the material, with the thermocouple at the bottom having the highest temperature, which is 1050°C.
  • the raw materials used in the preparation of the mixture in process (1) include gasification fine slag with a moisture content of 56% and quartz sand with a particle size of 1 to 1.5 mm.
  • the gasification fine slag and quartz sand are mixed in a mass ratio of 1:4 to obtain a mixture with porous characteristics.
  • the mixed materials are filled into a laboratory-scale smoldering furnace reactor.
  • the reactor has an inner diameter of 15 cm and a height of 20 cm.
  • Thermocouples are arranged at 3 cm intervals along the height of the reactor to collect temperature data.
  • the bottom electric heating device is turned on for preheating.
  • the electric heating device is turned off, the air supply system is turned on to supply gas and ignite; in this embodiment, the composition of the gas intake is controlled to be 21% O2 and 79% N2 , the gas Darcy flow rate is 5 cm/s, and the reaction begins.
  • each thermocouple along the height of the material monitors the material temperature at its respective location, with the thermocouple at the bottom having the highest temperature, which is 1200°C.
  • the main components of the dried flue gas were: 0.73% O2 , 67.13% N2 , 9.92% CO2 , 22.06% CO, and 82ppm NOx .
  • the method in the preferred embodiment can produce CO-rich fuel gas with low oxygen concentration, effectively control the nitrogen oxide content in the final flue gas, increase the calorific value of the produced fuel gas, and achieve efficient treatment of gasification slag.
  • the method for preparing CO-rich fuel gas based on the smoldering technology of gasification slag in this invention is simple in steps and convenient to control.
  • By fully combining the smoldering treatment technology with the drying, dehydration, pyrolysis, gasification, and oxidation processes of gasification slag it is possible to achieve efficient treatment of gasification slag and obtain CO-rich fuel gas with low oxygen concentration. It fully recovers the combustible components in the gasification slag, realizes resource recycling, and fully ensures the usability of the recovered resources, thus having extremely high economic value.

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  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

本发明公开了一种基于气化渣阴燃技术制备富CO燃气的方法，属于固废处理技术领域，其在阴燃反应装置中进行，通过将阴燃处置技术与气化渣干化脱水、热解、气化、氧化等过程相结合，并对相应的反应条件进行控制，最终能够得到低氧浓度的富CO燃气，以此实现对气化渣的高效利用和无害化处理。本发明中基于气化渣阴燃技术制备富CO燃气的方法，其步骤简单，控制便捷，利用阴燃处置技术与气化渣干化脱水、热解、气化、氧化等过程的充分结合，能够实现气化渣的高效处理，并得到氧浓度较低的富CO燃气，充分回收了气化渣中的可燃成分，实现了资源的回收利用，并充分保证了回收资源的可利用性，具有极高的经济价值。

Description

一种基于气化渣阴燃技术制备富CO燃气的方法 【技术领域】
本发明属于固废处理技术领域，具体涉及一种基于气化渣阴燃技术制备富CO燃气的方法。
【背景技术】
“富煤、贫油、少气”的能源结构特点决定了我国仍然以煤炭作为主要能源，而煤气化是煤炭清洁高效利用的核心技术，被誉为现代煤化工产业的龙头，广泛应用于钢铁、机械、化工、建材等领域。
在煤气化过程中，气化粗渣通常从炉底直接排出，其成分与锅炉灰渣成分相似，含碳量低，大多作为道路建材的掺混原料或做回填处理；气化细渣因含碳量高、烧失量大，不符合建筑掺混原料国家标准和行业标准，难以直接用于建筑、道路工程，缺乏有效的规模化消纳方式，多以堆放或者填埋的方式处理。然而，高含碳气化细渣的填埋或者堆放会造成严重的资源浪费，占用大量土地资源，扬尘造成大气污染且长时间堆置或填埋后渗滤液还会污染土壤和水体。
正因如此，如何有效利用气化渣成为了目前研究人员的重点关注方向，采用合理有效方式规模化消纳气化细渣，不仅可减轻其对环境的影响，还能同时回收利用其中的能源，从而保障煤化工企业可持续发展。目前，针对气化渣中能量的回收通常采用的是燃烧法，该方法主要针对的是气化细渣，其虽然能够利用气化细渣的能量，但为了维持燃烧设备稳定运行只能进行低比例掺烧，且由于其高含水特性往往导致燃烧过程不稳定，无法实现气化细渣的大规模消纳利用，如需大规模进行掺烧，还需要进行额外的脱水干化处理，能耗高设备系统复杂，经济性极差。
【发明内容】
针对现有技术的以上缺陷或改进需求中的一种或者多种，本发明提供了一种基于气化渣阴燃技术制备富CO燃气的方法，能够基于阴燃的原理实现气化渣的气化并制取高浓度CO燃气，实现气化渣中可燃物质的充分利用，解决气化渣因无法大规模消纳利用所导致的环境问题。
为实现上述目的，本发明提供一种基于气化渣阴燃技术制备富CO燃气的方法，该方法在阴燃反应装置中进行，并包括如下过程：
(1)将气化渣与惰性介质混合制备具有多孔特性的混合物料；
所述气化渣的含水率控制在10％～90％之间；所述惰性介质的粒径处于1～3mm之间，且所述气化渣与所述惰性介质的质量比处于1:1～1:6之间；
(2)将混合物料填充至所述阴燃反应装置中，启动阴燃反应装置的底部加热组件对装置最下层物料进行预热，直至最下层物料的温度达到点火温度后停止加热；
(3)从阴燃反应装置的底部送入反应气体并点火，启动所述混合物料的阴燃反应，并在所述阴燃反应装置中由下至上依次形成高温高氧氧化区、高温低氧气化区、低氧热解区和低温低氧干化区，分别完成阴燃反应装置不同位置处气化渣的高温氧化过程、高温气化过程、热解过程和干化过程；
所述反应气体的气体达西流速控制在1cm/s～15cm/s，其中的氧浓度为10％～30％，并使得所述高温高氧氧化区中的核心反应温度不低于900℃，且该高温高氧氧化区结束段处的氧浓度控制在2％～6％；所述高温低氧气化区中的气化反应温度控制在800℃以上，且该高温低氧气化区结束段处的氧浓度控制在1％以下；
(4)从所述阴燃反应装置的顶部将烟气从排气口导出，得到富含CO的低氧燃气。
作为本发明的进一步改进，所述气化渣为含水率低于30％的气化粗渣，其与惰性介质混合时的质量比范围介于1:1～1:3之间；
或者
所述气化渣为含水率高于30％的气化细渣，其与惰性介质混合时的质量比范围介于1:2～1:5之间。
作为本发明的进一步改进，所述惰性介质为石英砂或者沙子。
作为本发明的进一步改进，所述低氧热解区包括由下至上依次形成的高温低氧热解区、中温低氧热解区和低温低氧热解区，三个区域中的温度范围分别为不低于800℃、500～800℃、200～500℃。
作为本发明的进一步改进，得到的富含CO的低氧燃气中，CO的浓度不低于10％，且其中的氧浓度低于1％。
作为本发明的进一步改进，在送入阴燃反应装置的反应气体中混掺有浓度范围为0～85％的CO2。
作为本发明的进一步改进，在所述阴燃反应装置的底部设置有残渣区，其位于所述高温高氧氧化区的下方，用于经过氧化反应后的气化渣残渣的排出。
作为本发明的进一步改进，所述高温高氧氧化区中的核心反应温度控制在900～1100℃。
作为本发明的进一步改进，所述高温低氧气化区的初始段反应温度控制在850℃以上，且该高温低氧气化区的结束段反应温度控制在800℃以上。
作为本发明的进一步改进，所述阴燃反应装置中对应各反应区域温度的监控，在装置的内部由下至上依次间隔设置有多个电热偶。
上述改进技术特征只要彼此之间未构成冲突就可以相互组合。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，具有的有益效果包括：
(1)本发明中基于气化渣阴燃技术制备富CO燃气的方法，其在阴燃反应装置中进行，通过将阴燃处置技术与气化渣干化脱水、热解、气化、氧化等过程相结合，并对相应的反应条件进行控制，最终能够得到低氧浓度的富CO燃气，以此实现对气化渣的高效利用和无害化处理，有效提升煤炭资源开发利用的效益，避免资源的浪费。
(2)本发明中基于气化渣阴燃技术制备富CO燃气的方法，其大部分处理过程均在低氧强还原性氛围中进行，能够有效抑制氮氧化物的生成，有效保证燃料的清洁性，避免后续燃气使用时对环境的污染。
(3)本发明中基于气化渣阴燃技术制备富CO燃气的方法，其通过在通入阴燃反应装置中的气体中混掺一定浓度的CO2气体，进一步强化了气化渣中碳的气化反应，从而进一步提高了气化效果和出口烟气中的CO浓度，提升了制得燃气的品质。
(4)本发明中基于气化渣阴燃技术制备富CO燃气的方法，其步骤简单，控制便捷，利用阴燃处置技术与气化渣干化脱水、热解、气化、氧化等过程的充分结合，能够实现气化渣的高效处理，并得到氧浓度较低的富CO燃气，充分回收了气化渣中的可燃成分，实现了资源的回收利用，并充分保证了回收资源的可利用性，具有极高的经济价值。
【附图说明】
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例中利用气化渣制备富CO燃气的系统示意图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系，除非另有明确的限定。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征“上”或“下”可以是第一和第二特征直接接触，或第一和第二特征通过中间媒介间接接触。而且，第一特征在第二特征“之上”、“上方”和“上面”可是第一特征在第二特征正上方或斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”可以是第一特征在第二特征正下方或斜下方，或仅仅表示第一特征水平高度小于第二特征。
实施例：
请参阅图1，本发明优选实施例中的基于气化渣阴燃技术制备富CO燃气的方法，其基于阴燃技术来实现，通过气化渣干化脱水、气化/氧化脱碳的工艺协同来制备富CO燃气，该制备CO燃气的一体化方法包括如下步骤：
(1)制备混合物料；
实际作业时，优选将气化渣与惰性介质按照一定比例均匀混合，形成具有多孔特性的混合物料。
在优选实施例中，气化渣优选为气化细渣或者气化粗渣，其含水率优选控制在10％～80％之间。其中，气化粗渣为浆化煤炭颗粒在气化炉高温高压条件下经熔融、激冷、凝结等流程，并由气化炉底部排渣锁斗排出的含水渣，残碳量随煤种、气化炉种类、气化炉操作条件波动较大，一般在10％～30％之间，粒径集中分布在16目至4目之间。气化细渣一般为从气化炉顶部由粗煤气气流携出并经初步洗涤净化、沉淀得到的含水渣，残碳量较高，一般可达30％以上，粒径均小于16目，其中约三分之一小于200目。
同时，优选实施例中的惰性介质优选为石英砂或者沙子，其粒径处于1～3mm之间，其在混合使用时的含水率优选控制在20％以下。
更详细地，在优选实施例中，气化渣与惰性介质的质量比范围优选处于1:1～1:6之间，具体的比例选择优选由气化渣的粒径特性决定(主要由含水率和热值决定)。
其中，当气化渣为气化细渣时，其含水率通常在30％以上，此时，气化细渣与惰性介质之间的质量比范围优选控制在1:2～1:5之间。
相应地，当气化渣为气化粗渣时，其含水率为30％以下，此时，气化粗渣与惰性介质的最优质量比范围优选控制在1:1～1:3之间。
(2)将混合燃料送入对应规格的阴燃反应装置中，启动阴燃反应装置的底部加热组件对反应装置最下层的物料进行预热，直至最下层物料的温度达到点火温度后停止加热；
在优选实施例中，混合物料的预加热温度(点火温度)优选为250℃～400℃，进一步优选为300℃。
(3)从阴燃反应装置的底部送入反应气体并点火，启动多孔特性混合物料的阴燃反应，并在阴燃反应装置中由下至上依次形成高温高氧氧化区、高温低氧气化区、低氧热解区(高温低氧热解区、中温低氧热解区、低温低氧热解区)、低温低氧干化区和新鲜混合物料补充区。
具体地，在阴燃反应过程中，位于阴燃反应装置下层的混合物料在核心反应温度不低于900℃的高氧环境下进行氧化反应，形成高温高氧氧化区，产生高温低氧高浓度CO2烟气，记其为第一烟气，该第一烟气的温度不低于850℃，其中的氧浓度处于4％～6％之间。
在高温高氧氧化区中，混合物料进行的氧化反应如下：
C+O2→CO2                (1)
为保证高温高氧氧化区中氧化反应进行的准确性，在实际控制反应条件时，将高温高氧氧化区的初始段氧浓度控制在15％以上，且高温高氧氧化区的结束段氧浓度控制在2％～6％；进一步优选地，前述初始段的氧浓度控制在10％～30％之间。同时，在高温高氧氧化区内，核心反应区的最高温度优选控制在900℃以上。
对于上述控制条件而言，若初始段的氧浓度太低，则反应(1)中的氧化放热反应强度会相对较弱，反应温度放热不足以产生900℃以上的高温环境，导致后续气化反应相对较弱，CO浓度较低，达不到产生富CO燃气的目的。同时，若结束段的氧浓度太高，则会使得高温低氧气化区内气化渣中的碳快速发生燃烧反应，燃烧反应(即前述氧化反应(1))会显著强于预计的气化反应，导致烟气中CO浓度相对较低，达不到产生富CO燃气的目的。
为了达到上述目的，在实际操作时，优选控制送入阴燃反应装置中的气体含氧量处于10％～30％，且气体达西流速控制在1cm/s～15cm/s；相应地，高温高氧氧化区中的反应温度维持在900～1100℃。对于该反应温度的调节，可以通过改变送气中的氧气浓度来实现，在此不做赘述。
进一步地，第一烟气产生后向上流动至上层相邻的干物料时，烟气中的CO2与气化渣中的碳在高温低氧环境下发生气化反应，该气化反应的温度在800℃以上，生成富含CO气体的高温低氧烟气。
在高温低氧气化区中，混合物料与第一烟气发生的气化反应如下：
C+CO2→2CO              (2)
在高温低氧气化区中，核心反应温度处于800℃以上。在高温低氧气化区的初始段(靠近高温高氧氧化区的一侧)，氧浓度相对较高，处于2％～6％；此时，该区域的初始段反应温度优选控制在850℃以上。相应地，经过气化区的气化反应，烟气中的氧气进一步消耗，在高温低氧气化区的结束段形成的富含CO高温低氧烟气中，氧浓度在1％以下，记该烟气为第二烟气。
在高温低氧气化区中，会进行上述反应(1)与反应(2)之间的竞争，如果该区域中氧浓度过高、温度低于气化反应温度，则氧化反应(1)会显著强于气化反应(2)，导致高温低氧气化区结束段处的第二烟气中CO浓度较低，无法达到产生富CO燃气的目的；另外，倘若高温低氧气化区结束段处的氧浓度过高，则会使得下一阶段的热解区内产生的部分挥发分气体与氧气快速发生燃烧反应，从而导致烟气中的可燃气体浓度降低，并使得气化渣中的部分碳在该阶段被消耗，进而降低高温高氧氧化区、高温低氧气化区中参与反应的碳含量，影响氧化区中的放热量和气化区中的气化效果。
经过高温低氧气化区以后，烟气(第二烟气)中的氧浓度进一步降低，但烟气温度仍然保持在较高的范围(不低于800℃)，此后，随着烟气在阴燃反应设备中进一步向上流动，在高温低氧气化区的上方依次形成高温低氧热解区、中温低氧热解区和低温低氧热解区，三个区域中的温度范围分别为不低于800℃、500～800℃、200～500℃，利用烟气与各热解区中混合物料的相互接触和作用，使得气化渣中的部分挥发分先后释放并进入烟气中，得到可燃气体含量进一步提高的第三烟气，此时，第三烟气的温度已经降至200℃以下。
实际作业时，由于烟气处于高CO、低氧的状态，故而烟气中的氮氧化物等污染物浓度能够始终保持在相对较低的水平。
进一步地，经过三段热解区以后，第三烟气进一步向上流动，与上方补充送料的新鲜混合物料接触，利用第三烟气的余热将新鲜混合物料干化，在阴燃反应装置的内部形成一定厚度的低温低氧干化区，并得到最终富含CO的含湿烟气。
(4)利用完第三烟气中的余热后，将最终的含湿烟气从阴燃反应装置上的排气口送出，后续经冷凝除水等作业后，便可得到富含CO的低氧燃气。
在优选实施例中，最终导出的可燃烟气中的CO浓度不低于10％，且其中的氧浓度低于1％。
对于优选实施例中的方法而言，通过调节气化渣与惰性介质之间的混合比例以及向阴燃反应装置中送气的气体达西流速和气体中的氧气浓度，可以有效控制高温高氧氧化区中的核心反应温度不低于900℃，并保证得到的烟气中CO浓度不低于10％。
更详细地，为了提升高温低氧气化区中的气化效果以及增加出口烟气中的CO浓度，优选在送入阴燃反应装置的气体中掺混一定浓度的CO2气体，其掺混浓度优选为0～85％，进一步优选为30％。
进一步地，在阴燃反应装置的底部形成有残渣区，其位于高温高氧氧化区的下方，经过氧化反应后的残渣通过设置于残渣区中的出料口排出。
对于现有的气化渣处理方法而言，由于气化渣含水，其热处置过程(如焚烧)中需要消耗大量的能源用于干化，与此同时气化渣热值相对较低，稳燃效果较差，导致其资源化效率非常低。
与之相比，在前述优选实施例的技术方案中，通过将气化渣的干化脱水、热解、气化、氧化过程与阴燃处置技术相结合，利用气化渣自身阴燃反应产生的热量作为热源，将气化渣水分进行脱出干化，无需外部辅助能量干化气化渣，即可实现自持反应，能耗低。而且，通过相应控制条件的优选设计，可以完成阴燃反应装置中相应区域的形成，通过气化渣制取高浓度CO，得到高品质燃气，充分实现气化渣的无害化处理和能量回收。
为了进一步补充说明本发明优选实施例中技术方案的优点和技术效果，通过如下两个具体实施例对其进行补充说明。
具体实施例1：
在该实施例中，过程(1)中制备混合物料所采用的原料包括含水率为36％的气化粗渣和粒径为1～1.5mm的石英砂，气化粗渣与石英砂之间以质量比例1:2进行混合，得到具有多孔特性的混合物料。
进一步地，将混合后的混合物料填充至实验室规模阴燃炉反应器内，该反应器的内腔直径为15cm，高度为20cm，按间距3cm沿反应器高度方向依次布置热电偶采集温度。完成混合物料的填充后(物料填满)，开启底部电加热装置进行预热。
此后，待物料底部热电偶温度到达350℃时，关闭电加热装置，开启供风系统进行供气并点火；在该实施例中，控制进气的组分组成为21％O2、79％N2，气体的达西流速为5cm/s，反应开始启动。
随着阴燃反应向上传递，物料内沿高度方向的各热电偶分别监测物料内的温度，且位于最下方的热电偶温度最高，其为1050℃。
相应地，通过对反应器尾端排出的烟气成分进行检测，发现尾部烟气干化后的主要组分为：0.98％O2、70.72％N2、8.12％CO2、20.09％CO、80ppm NOx。
具体实施例2：
在该实施例中，过程(1)中制备混合物料所采用的原料包括含水率为56％的气化细渣和粒径为1～1.5mm的石英砂，气化细渣与石英砂之间以质量比例1:4进行混合，得到具有多孔特性的混合物料。
进一步地，将混合后的混合物料填充至实验室规模阴燃炉反应器内，该反应器的内腔直径为15cm，高度为20cm，按间距3cm沿反应器高度方向依次布置热电偶采集温度。完成混合物料的填充后，开启底部电加热装置进行预热。
此后，待物料底部热电偶温度到达350℃时，关闭电加热装置，开启供风系统进行供气并点火；在该实施例中，控制进气的组分组成为21％O2、79％N2，气体达西流速为5cm/s，反应开始启动。
随着阴燃反应向上传递，物料内沿高度方向的各热电偶分别监测各位置处的物料温度，且位于最下方的热电偶温度最高，其为1200℃。
相应地，通过对反应器尾端排出的烟气成分进行检测，发现尾部烟气干化后的主要组分为：0.73％O2、67.13％N2、9.92％CO2、22.06％CO、82ppm NOx。
显然，在两个具体实施例中，利用优选实施例中的方法，均可以制得氧浓度较低的富CO燃气，并有效控制最终烟气中的氮氧化物含量，提升制得燃气的热值，完成气化渣的高效处理。
本发明中基于气化渣阴燃技术制备富CO燃气的方法，其步骤简单，控制便捷，利用阴燃处置技术与气化渣干化脱水、热解、气化、氧化等过程的充分结合，能够实现气化渣的高效处理，并得到氧浓度较低的富CO燃气，充分回收了气化渣中的可燃成分，实现了资源的回收利用，并充分保证了回收资源的可利用性，具有极高的经济价值。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，该方法在阴燃反应装置中进行，并包括如下过程：
    (1)将气化渣与惰性介质混合制备具有多孔特性的混合物料；
    所述气化渣的含水率控制在10％～90％之间；所述惰性介质的粒径处于1～3mm之间，且所述气化渣与所述惰性介质的质量比处于1:1～1:6之间；
    (2)将混合物料填充至所述阴燃反应装置中，启动阴燃反应装置的底部加热组件对装置最下层物料进行预热，直至最下层物料的温度达到点火温度后停止加热；
    (3)从阴燃反应装置的底部送入反应气体并点火，启动所述混合物料的阴燃反应，并在所述阴燃反应装置中由下至上依次形成高温高氧氧化区、高温低氧气化区、低氧热解区和低温低氧干化区，分别完成阴燃反应装置不同位置处气化渣的高温氧化过程、高温气化过程、热解过程和干化过程；
    所述反应气体的气体达西流速控制在1cm/s～15cm/s，其中的氧浓度为10％～30％，并使得所述高温高氧氧化区中的核心反应温度不低于900℃，且该高温高氧氧化区结束段处的氧浓度控制在2％～6％；所述高温低氧气化区中的气化反应温度控制在800℃以上，且该高温低氧气化区结束段处的氧浓度控制在1％以下；
    (4)从所述阴燃反应装置的顶部将烟气从排气口导出，得到富含CO的低氧燃气。
  2. 根据权利要求1所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，所述气化渣为含水率低于30％的气化粗渣，其与惰性介质混合时的质量比范围介于1:1～1:3之间；
    或者
    所述气化渣为含水率高于30％的气化细渣，其与惰性介质混合时的质量比范围介于1:2～1:5之间。
  3. 根据权利要求2所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，所述惰性介质为石英砂或者沙子。
  4. 根据权利要求1～3中任一项所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，所述低氧热解区包括由下至上依次形成的高温低氧热解区、中温低氧热解区和低温低氧热解区，三个区域中的温度范围分别为不低于800℃、500～800℃、200～500℃。
  5. 根据权利要求1～3中任一项所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，得到的富含CO的低氧燃气中，CO的浓度不低于10％，且其中的氧浓度低于1％。
  6. 根据权利要求1～3中任一项所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，在送入阴燃反应装置的反应气体中混掺有浓度范围为0～85％的CO2。
  7. 根据权利要求1～3中任一项所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，在所述阴燃反应装置的底部设置有残渣区，其位于所述高温高氧氧化区的下方，用于经过氧化反应后的气化渣残渣的排出。
  8. 根据权利要求1～3中任一项所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，所述高温高氧氧化区中的核心反应温度控制在900～1100℃。
  9. 根据权利要求1～3中任一项所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，所述高温低氧气化区的初始段反应温度控制在850℃以上，且该高温低氧气化区的结束段反应温度控制在800℃以上。
  10. 根据权利要求1～3中任一项所述的基于气化渣阴燃技术制备富CO燃气的方法，其特征在于，所述阴燃反应装置中对应各反应区域温度的监控，在装置的内部由下至上依次间隔设置有多个电热偶。
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JP2004307682A (ja) * 2003-04-08 2004-11-04 Nippon Steel Corp 可燃性廃棄物のガス化方法および装置
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